Federal Guidelines
Pretreatment of Discharges
to Publicly Owned Treatment Wor
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U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF WATER PROGRAMS OPERATIONS
WASHINGTON, D.C. 20460
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Federal Guidelines
Pretreatment of Discharges
to Publicly Owned Treatment Works
US EPA
Headquarters and Ciemicai Libraries
EPA West Bfap Room 3340
ivlaiicode 3404T
1301 Goosli uifon Ave NW
Washington DC 20004
202-566-0556
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF WATER PROGRAMS OPERATIONS
WASHINGTON, D.C. 20460
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NOTICE
These guidelines are proposed by the U.S.Environmental Pro-
tection Agency pursuant to the authority in Section
304 (f) (1) of the Federal Water Pollution Control Act Amend-
ments of 1972 (Public Law 92-500)
Interested parties are encouraged to submit written comments,
views, or data concerning the guidelines to the Director,
Municipal Wastewater Systems division, Environmental Protection
Agency, Washington, D.C. 20460. All such submissions received
prior to the date given in the notice in the Federal Register will
be considered.
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TABLE OF CONTENTS
Page No.
SECTION I INTRODUCTION 1
1. Purpose 1
2. Authority 1
3. Definitions 2
4. The Federal Water Pollution Control 2
Amendments of 1972
SECTION II EFFLUENT LIMITATIONS AND NPDES PERMITS 4
5. NPDES Municipal Permits 4
6. Effluent Limitations for Publicly 5
Owned Treatment Works
SECTION III JOINT TREATMENT AND PRETREATMENT 6
7. Joint Treatment 6
8. Pretreatment Policy 7
9. Federal Pretreatment Standards 7
SECTION IV STATE AND LOCAL PRETREATMENT 10
REQUIREMENTS
10. Objectives 10
11. Pretreatment Information 10
12. Pretreatment Ordinance 13
13. Example Calculations 14
14. Other Considerations 15
APPENDIX A Pretreatment Standards (40 CFR 128) A-1
APPENDIX B Secondary Treatment Information B-1
(40 CFR 133)
APPENDIX C
Information on Materials Which Inhibit C-1
Biological Treatment Systems
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TABLE OF CONTENTS
(cont i nued)
Page No.
APPENDIX D Information on Pretreatment Unit D-1-1
Operat ions
Annex
1-Paper and Allied Products
0-1-1
Annex
2-Dairy Products
D-2-1
Annex
3-Text iles
0-3-1
Annex
^-Seafoods
D-1+-1
Annex
5-Pharmaceuticals
D-5-1
Annex
6-Leather Tanning and
D-6-1
Finishing
Annex
7-Sugar
D-7-1
Annex
8-Petroleum Refining
0-8-1
Annex
9-Meat Products
D-9-1
Annex
10-Grain Hi 11ing
D-10-1
Annex
11-Fruit and Vegetable
D-11-1
Annex
12-Beverages
D-12-1
Annex
13-Plastic and Synthetic
D-13-1
Materials
Annex
1^-Blast Furnaces, Steel Works,
D-1i+-1
and Rolling and Finishing
Annex
15-0rganic Chemicals
D-15-1
Annex
16-Metal Finishing
D-16-1
Annex
17-Other Industries
D-17-1
Inorganic Ferti1izer
D-17-2
Electric and Steam
D-17-k
Generation
A1umi num
D-17-6
Flat Glass, Cement,
D-17-8
Lime, Concrete
Products, Gypsum,
and Asbestos
Inorganic Chemicals
D-1 7-10
Industrial Gas Products
D-17-12
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Federal Guidelines
Pretreatment of Discharges
to 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 1ty
Authority for these guidelines is contained In Section 304 (f)
(1) of the Federal Water Pollution Control Act Amendments of
1972 (the Act), which states:
"For the purpose of assisting States In carrying out
programs under Section 402 of this Act, the Adminis-
trator shall publish . . . guidelines for pretreatment
of pollutants which he determines are susceptible to
treatment by publicly owned treatment works. Guidelines
under this subsection shall be established to control
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and prevent the discharge ... of any pollutant which
interferes with, passes through, or otherwise is in-
compatible with such works".
3 • Def i ni t ions
Compatible Pollutant:
Biochemical oxygen demand, suspended solids, pH, and fecal
coli form bacteria.
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.
Pretreatment:
Treatment of wastewaters from sources before introduction
into the joint treatment works.
Source:
Any building, structure, facility, or installation from which
there is or may be the discharge of pollutants.
k. The Federal Water Pollution Control Act Amendments of 1972
The Act establishes a national system for preventing, reducing,
and eventually eliminating water pollution. The ultimate goal
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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 304 and implemented under
Section 308 of the Act.
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SECTION I I
EFFLUENT LIMITATIONS AND NPDES PERMITS
NPDES Municipal Permits
Procedures developed under Section 402 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
guide J ines.
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 in cases where the failure of an industry to
provide such pretreatment would cause a publicly owned treat-
ment works to violate its effluent limitations.
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 discharges into such works of pollutants from
any source which would be a new source as defined
in Section 306 of the Act if such source were dis-
charging pollutants.
b. New discharges 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 discharged into such works by a source
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already discharging pollutants into such works at the
time the permit is issued.
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 kO2 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. Secondary Treatment Information (Appendix B).
b. Toxic Effluent Standards or Prohibitions (Section 307
(a) of the Act).
c. Water Quality Standards (Section 303 of the Act).
The most stringent limitation for each pollutant will govern.
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SECTION I I I
JOINT TREATMENT AND PRETREATMENT
7. Joint Treatment
Joint treatment of industrial and municipal wastewaters in the
same treatment works is generally a desirable practice. Treat-
ment of the combined wastewaters can benefit the environment,
the municipality, and industry if properly designed and oper-
ated.
Some of the advantages of joint treatment are:
a.
b.
c.
d.
e.
f.
Increased flow which can result in reduced ratios of
peak to average flows.
Savings in capital and operating expenses due to the
economics of large-scale treatment facilities.
Better use of manpower and land.
Improved operation (larger plants are potentially
better operated than smaller plants).
Increased number of treatment modules with resultant
gains in reliability and flexibility.
More efficient disposal of sludges resulting from
treatment of wastewaters containing compatible
pol1utants.
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 other than biochemical oxygen demand, suspended
solids, pH, and fecal coliform bacteria is by definition incom-
patible. This Section is applicable only to "major contrib-
uting 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 304 (b) of
the Act. Provision is made however, to permit a less stringent
pretreatment standard for an incompatible pollutant if the
municipality is committed in its NPDES permit to remove a
specified percentage of the incompatible pollutant. These re-
quirements are based on the premise that incompatible pollu-
tants introduced into a publicly owned treatment works should
not pass through such works in amounts greater than would be
permitted for direct discharge.
The four pollutants which are defined as compatible are those
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 limitations 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, it 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 the treatment works is designed to
remove incompatible pollutants by virtue of effluent limitations
based on water quality standards or toxic effluent standards,
or if there is some removal of incompatible pollutants in the
treatment works which occurs as an incident to the removal of
compatible pollutants. In the latter case, it must be deter-
mined that the incidental removal can be relied upon and will
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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 oper-
ation 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 containing
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 permitted effluent
1 imitations.
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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 concent rat ions 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
wi11 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. 20^02. 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
Dai ry Products
Text i1es
Seafoods
Pha rmaceut i cal s
Leather Tanning and Finishing
Suga r
Petroleum Refining
Meat Products
Grain Mi 11 ing
Fruit and Vegetables
Beverages
Plastic and Synthetic Materials
Blast Furnaces, Steel Works, and Rolling and Finishing
Organi c Chemicals
Metal Finishing
Inorganic Fertilizers
Electric and Steam Generation
A1uminum
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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CI ass i fi cat i on
Waste Extremely
Const i tuents Low Average High High
BOD , mg/L <200 200-300 300-1,000 >1,000
COD, mg/L <300 300-450 450-1,500 >1,500
SS, mg/L < 200 200-300 300-1,000 >1,000
Temp., C < 15 15-25 >25
pH <6 (acid) 6-9 > 9 (alkaline)
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
Pretreatment requ^ements 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. Example Calculations
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 then 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
Wastewater flow
200 tons/day
1 MGD
Wastewater contains incompatible pollutant 1
The guidelines for best practicable control technology
currently available for pollutant I are:
Industry X
Industry Y
1.0 pounds/ton
1.5 pounds/ton
The Federal pretreatment standards for the major contributing
industries would be as follows (the municipality is not
committed in its NPDES permit to remove any percentage of the
incompatible pollutant I):
Industry X: 100 tons/day * 1.0 pound/ton = 100 pounds/day
Industry Y: 200 tons/day * 1.5 pound/ton = 300 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 =
(280) = 70 pounds/day
Pollutant I Allocation to Industry Y =
14. 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.
Total
400 pounds/day
(280) = 210 pounds/day
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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 1 apse.
(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
. , _ . w IMM |
ENVIRONMENTAL PROTECTION
AGENCY
[40 Cn Part 123 2
POLLUTANTS IN PUBLICLY OWNED
TREATMENT WORKS
Pretreatment Standards
Pursuant to the authority delegated
In section 307(b) of the Federal Water
Pollution Control Act Amendments of
1972 (Public Law 92-500), notice Is
hereby given that the Environmental
Protection Agency proposes to issue
standards for pretreatment of pollutant*
Introduced into publicly owned treat-
ment worts.
Under section 307
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to enable compliance with NPDES per-
mits Issued to publicly owned treatment
works.
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. When published, the
guidelines will be made available through
the Environmental Protection Agency
P.c-giOtiul Offices.
Interested parties are encouraged to
submit written comments, views, or data
concerning the regulations proposed
herein, to the Director, Municipal Waste
Water Systems Division, Environmental
Protection Agency, Washington, D.C.
20460. All such submissions, received on
or before September 4, 1973, will be con-
sidered prior to promulgation of final
regulations. If, during the period for
written submissions, It la deemed neces-
sary that public hearings be held notice
of such hearings will be published In the
Federal Register.
Robert W. Fri,
Acting Administrator.
Julv 13, 1D73.
PART 123—PRETREATMENT STANDARDS
Seo.
128 100 Purpose.
128.201 Applicability.
128.110 State or local law.
123.120 Definitions.
128.1'Jl Compatible pollutant.
128.122 Incompatible pollutant.
123.123 Joint treatment works.
128.124 Major contributing industry.
128.125 Pretreatment.
1U3.130 Pretreatment standards.
128.131 Prohibitions.
128.132 Compatible pollutant*.
128.133 Incompatible pollutant*.
128.140 Time for compliance.
§ 1215.100 Purpose.
The provisions of this part Implement
section 307(b) ot the Federal Water Pol-
lution Control Act Amendment* of 1972
(Public Law 82-500) hereinafter referred
to aa ''the Act".
S 123.101 Aujilifii bility.
The standards set forth in S 123.131
apply to all non-domestic users of pub-
licly oxnetl treatment works. The stand-
ard set forth In H 128.133 applies only
to major contributing industries.
§ 1:28.1 If, State or lo<*ul law.
."»oi;hln« 'n this part shall affect any
ivctreatment requirement established by
im;,- otacc or local law not In conflict with
any standard established pursuant to
this Part. In particular coses, a State or
municipality, in order to meet the efflu-
ent limitations In a NPDES permit for a
publicly owned treatment works may find
U iyjre."iary to Impose pretreatment re-
quirements stricter than those contained
herein.
§ 128.120 Definition*.
Definitions of terms used In tills part
"vc i«s follows:
PROPOSED RULES
§ 128.121 Compatible pollutant.
For purposes of establishing Federal
requirements for pretreatment pursuant
to 5 128.133, the term "compatible pol-
lutant" means biochemical oxygen de-
mand, suspended solids, pH and fecal
coliform bacteria.
§ 123.122 Incompatible pollutant.
The term "incompatible pollutant"
means any pollutant which is not a
compatible pollutant as defined In
5 128.121.
§ 128.123 Joint treatment worlts.
Treatment works for both non-Indus-
trial and Industrial wastewater.
§ 128.124 Major contributing industry.
A major contributing Industry Is one
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 receiv-
ing the waste; (c) has In Its waste, a
toxic pollutant In toxic amounts as de-
fined in standards issued under section
307(a) of the Act, or (d) Is found by the
permit Issuance authority, In connection
with the Issuance of an NPDES permit
to the publicly 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 qual-
ity of effluent from that treatment works.
§ 128.123 Pretreatment.
Treatment of wastewaters from
sources before Introduction into the Joint
treatment works.
g 128.130 Pretreatment standards.
The following sections set forth pre-
treatment standards for pollutants In-
troduced into publicly owned treatment
works.
§ 128.131 Prohibition*.
No discharge to publicly owned treat-
ment works shall contain the following
described materials:
(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.
(c) Solid or viscous substances In
amounts which would cause obstruction
to the flow In sewers, or other Interfer-
ence with the proper operation of the
publicly owned treatment works.
(d) Wastewaters at a How rate and/or
pollutant discharge rate which Is exces-
sive oyer relatively short time periods so
that there is. a treatment process upset
and subsequent loss of treatment effi-
ciency.
§ 128.132 Compatible poHutunU.
Except as required by 3123.131, pre-
treatment for removal of compatible
pollutants lrf not required by these regu-
19237
latlons. However, States and munici-
palities may require such pretreatment
pursuant to section 307(b) (4) of the Act.
§ 128.133 Incompatible pollutants.
In addition to the prohibitions set forth
in 5128.131, the pretreatment standard
for incompatible pollutants Introduced
into a publicly owned treatment works
by a major contributing industry shall
be best practicable control technology
currently available as defined by the Ad-
ministrator pursuant to section 304(b)
of the Act; provided that, if the publicly
owned treatment works which receive*
the pollutants is committed. In its NPDES
permit, to remove a specified percentage
of any incompatible pollutant, the pre-
treatment standard applicable to users
of such treatment works shall be cor-
respondingly reduced for that pollutant.
§ 128.140 Time for compliance.
Any owner or operator of any source
to which the pretreatment standards re-
quired by this Part are applicable, shall
be In compliance with such standards
within three years from the date of
promulgation of this part
[FR Doc.71-14791 Piled 7-18-73:8:4* am]
-------
AP8!oNDAY, APRIL 30, 1973
WASHINGTON, D.C.
Volume 38 ¦ Number 82
Page* 10615-1C698
PART I
(r;:rt II begins on page 10681)
vFirt III be pins on page 10685)
WATER POLLUTION—EPA propoMt effluent limitation*
for publicly owned treetment works; comments by
6-29-73 10642
B-1
-------
10612
PROPOSED RULES
ENVIRONMENTAL PROTECTION
AGENCY
[ 40 CFR Part 133 j
SECONDARY TREATMENT INFORMATION
Notice of Proposed Rulemaking
Section 30 (d)(1) of the Federal
Water Pollution Control Act Amend-
ments of 1972 (the Act) requires the pub-
lication of information, In terms of
amounts of constituents and chemical,
physical, and biological characteristics of
pollutants, on the degree of effluent re-
duction attainable through the applica-
tion of secondary treatment. Section
301(b)(1)(B) of the Act requires that
effluent limitations, based on secondary
treatment, be achieved for all publicly
owned treatment works in existence on
July 1, 1917, or approved for a construc-
tion grant prior to June 30, 1974 (for
which construction must be completed
within 4 years of approval). Grants for
treatment works construction projects
made from fiscal year 1975 or later funds
will require that each project Include
the application of the best practicable
waste treatment technology. The follow-
ing regulations are proposed pursuant to
these sections of the Act.
The level of effluent quality attainable
by secondary treatment is expressed in
terms of biochemical oxygen demand,
suspended solids, fecal coliform bacteria,
and pH. Because there is a great variety
of secondary treatment processes, and a
variety of conditions under which these
processes operate, it is not possible to
define a single attainable level of effluent
quality with respect to biochemical oxy-
gen demand and suspended solids by sec-
ondary treatment at all publicly owned
treatment works. Accordingly, with re-
spect to these pollutants, the level of ef-
fluent quality attainable by a publicly
owned treatment works through the ap-
plication of secondary treatment has
been defined in the proposed regulation
in terms of a minimum level.
The secondary treatment processes at
some publicly owned treatment works
may have been designed to attain a
higher level of effluent quality than the
levels herein specified. In such cases, the
level of effluent quality which will be re-
quired with respect to biochemical oxy-
gen demand and suspended solids, will
be set during permit issuance proceed-
ings pursuant to section 402 of the Act.
For existing treatment works, it is an-
ticipated that any level required In the
permit higher than the levels specified
in this regulation, will be based on an
evaluation of performance data. For new
treatment works, such levels of effluent,
quality higher than the levels set forth
herein will be based on an evaluation of
performance data from existing treat-
ment works of similar design and oper-
ating under similar conditions. If such
data are not available, such levels will
be based on a conservative engineering
analysis of its performance capabilities.
In all such cases specific effluent limita-
tions setting a level of effluent quality
higher than the levels specified herein
will be for the purpose of ensuring proper
operation and maintenance of the pub-
licly owned treatment works. Permits so
written will not provide a basis for re-
quiring construction of additional facili-
ties or material changes in the applica-
tion of technology.
It should be noted that It Is intended
that permits will be Issued to publicly
owned treatment works which may im-
pose effluent limitations applicable to pol-
lutants other than biochemical oxygen
demand, suspended solids, pH, and fecal
coliform. Such limitations will reflect
and take into consideration preireatment
requirements that may be Imposed upon
specific discharges pursuant to section
307, and such pretreatment requirements
will take into account levels of reductions
which will be attainable by a given mu-
nicipal treatment plant by secondary
treatment.
For publicly owned treatment works
treating a substantial portion of extreme-
ly high strength (in terms of biochemical
oxygen demand and suspended solids)
Industrial waste waters, provision Is made
for adjustment of the secondary treat-
ment level of effluent quality to account
for the difficulty In treating such waste
waters.
The regulations recognize that there
are certain conditions which will upset a
secondary treatment process resulting in
a temporary increase in pollutant dis-
charge in excess of that attainable by
secondary treatment. Procedures for
notice and review of upset incidents will
be specified in permits Issued for publicly
owned treatment works pursuant to sec-
tion 402 of the Act.
The level of effluent quality set forth
in the regulations is based on a sampling
of performance data for well designed
and operated secondary treatment works.
Water quality standards and toxic ef-
fluent standards, pursuant to sections 303
and 307(a) of the Act, are applicable to
publicly owned treatment works when ef-
fluent limitations based on secondary
treatment would not be sufficient to at-
tain or maintain acceptable water quality
or prevent the discharge of toxic pol-
lutants in toxic amounts.
Interested parties are encouraged to
submit written comments, views, or data
concerning the regulations proposed
herein to the Director, Municipal Waste
Water Systems Division, Environmental
Protection Agency, Washington, D.C.
20460. All such submissions, received
on or before June 29, 1973, will be con-
sidered prior to promulgation of final
regulations.
William D. Ruckelshaus,
Administrator.
April 23,1973.
PART 133—SECONDARY TREATMENT
INFORMATION
Sec.
133.100 Purpose.
133.101 Authority.
133.103 Secondary treatment.
133.103 Special considerations.
§ 133.100 Purpose.
This part provides information on the
degree of pollutant reduction or 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 Federal
Water Pollution Control Act Amend-
ments of 1972 (the Act).
§ 133.102 Secondary treatment.
The level of effluent reduction attain-
able by a publicly owned treatment
works through the application of sec-
ondary treatment is a reduction at least
down to the following levels of effluent
quality:
Unit of Monthly WeekJy
measurement average average
BiochemWal oxy^n inn/5 30 45
demand (*> (lit?).
Suspended solids tmk./I. 30 46
lrVcal coliforo bac- N uniOrr/lOU 200 400
terin. nil.
pH units WJUlin limits o!6.0
u> » o.
FEDERAL REGISTER, VOl. 31, NO. •>—MONDAY, APRIL 30, 1*73
B-2
-------
PROPOSED RULES
10643
(a) The monthly average, other than
for fecal conform bacteria, is the arith-
metic mean of the 24-hour composite
samples collected In a 1-month period.
The monthly average for fecal coliform
bacteria Is the geometric mean of
samples collected in a 1-month period.
(b) The weekly average, other than
for fecal coliform bacteria, is the arith-
metic mean of the 24-hour composite
samples collected during a 1-week pe-
riod. The weekly average for fecal con-
form bacteria Is the geometric mean of
samples collected In a 1-week period.
(c) A 24-hour composite sample con-
sists of several effluent portions collected
in a 24-hour period and composited ac-
cording to flow. For fecal collform bac-
teria, a sample consists of one t '.iuent
portion collected during a 24-hour
period.
(d) Chemical oxygen demand
-------
APPENDIX C
INFORMATION ON MATERIALS WHICH INHIBIT
BIOLOGICAL TREATMENT PROCESSES
Prepared by
Roy F. Weston, Inc.
Env!ronmenta1
Scientists and Engineers
West Chester, Pennsylvania
-------
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.
Kalabfna, 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 ZnSO^ 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 2.0 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 mg/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 adversely
affected the performance of aerobic metabolism. However,
Rudolfs (1) indicated that boron in raw sewage affected the
C-2
-------
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 um
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 compari son.
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^ 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 sluiges. 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.
Ammon i a
Drague, et al (21) reported that ammonia concentrations in
the range of 1,500-3,000 mg/L inhibited the anaerobic digestion
process. When the ammonia concentration reached 3,000 mg/L,
the feed sludge became strongly toxic to the digestion process.
C-4
-------
This is in agreement with the values reported by Rudolfs (1).
The concentration of ammonia refers to that present in the
influent to the digesters of accumulated in the digesters.
Sodium Chloride
The presence of sodium chloride in raw sewage or in the
digester has been reported to produce deleterious effects
both in aerobic biological systems and in anaerobic digesters.
Rudolfs has indicated that the gas production in anaerobic
digestion will be greatly reduced when the NaCl concentration
reaches 50,000 mg/L in digesters (1). Studies conducted by
Kincannon (22) indicated that the laboratory-scale aerobic
biological system was greatly affected at NaCl concentrations
of 10,000 mg/L in raw wastewater. Similar results were reported
by Lawton and Eggert (23) in the case of trickling filters.
Chi proform
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 concert trat i on 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 (24,25). 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 (Na4", K*, Ca+, and Mq++)
Malina (27) has presented data on the effects of several
cations on anaerobic digestion. The results indicated that:
Ca++ strongly inhibited anaerobic digestion at a concen-
tration of 8,000 mg/L; Mg++ at a concentration of 2,000 mg/L;
K+ at 12,000 mg/L; and Na+ at 8,000 mg/L. These results were
in close agreement with those reported by Kugelman and
McCarty (28).
C-5
-------
Chlorinated Organic Compounds
The effect of several chlorinated organic compounds, at very
low concentrations, on anaerobic digestion of biological
sludges is marked, and constitutes a warning that a close
watch must be kept on the disposal of these compounds.
Jackson, et al (29) have summarized the results on toxicity
of various chlorinated organic compounds, as indicated in
Table 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 Bioloaical Sewaqe 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
0946).
6. McDermott, G.N., et al, "Zinc in Relation to Activated Sludge and
Anaerobic Digestion", Proc. 17th Industrial Waste Conference,
Purdue University, Rafayette, Ind., 461-475 (1962).
7. "The Effect of Industrial Wastes on Sewaqe Treatment", Publication
No. TR-13, New England Interstate Water Pollution Control Commission,
Boston, Mass. (1965).
8. Nemerow, N.L., "Theories and Practices of Industrial Waste Treatment",
Addison-Wiley Publi shing Company, Reading, Mass. (1963).
9. Air and Water News, 5. 40, 8-9 (October 11, 1971)-
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. Banerjl, 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. Whlteland, A.B., et al, "Pilot Plant Experiments on the Effects of
Some Constituents of Industrial Wastewaters on Sewage Treatment",
Water Pol 1utlon 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, 23, 522-524 (1949).
17. "Control!inq 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 Rang, 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-
rnent," Proc. 19th Ind. Waste Conf., 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, 42, 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
Pi ants." 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 of 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-8
-------
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,
Doug las, Isle of Man, England (1969).
30. McCarty, P. L., "Anaerobic Waste Treatment Fundamentals;
Part 3, Toxic Materials and Their Control." Jour. Public
Works (Nov. 196*0.
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. Puri f. , No. 6 (1971).
32. Pettet, A. E. J., and Mills, E. V., "Biological Treatment of
Cyanide with and without Sewage." Jour. Appl. Chem. , h
(Aug. 195*0.
C-9
-------
Table C-1
Information on Materials Which Inhibit Biological
Treatment Processes
Po11utant
Copper
Z i nc
Chromium < Hexava lent -
Chromium 'Trivalcnt,
Total Chromium
Nickel
Lead
Boron
Cadm i urn
S i Iver
Va nad i um
Su1f ides ' S !
Sulfates 1 SO^
Ammon i a
Sod i um 1Na ^
Po v ss i um ! K ')
Co ic i um ' Ca ' ')
Magnesi um < Ma '
Ac ry Ion i t r i te
bcmftic
Carbon 7etrach loride
h 1 o r"v form
¦Me thy I f-ne Ch lor i de
r\' i r rach ioropheno i
, , 1 '! r i c h loroe thane
i '• ich Icrof 1 uoromethane
Tr i chIorot r i fI noroethane
C/a n i •'
Aerobic Processes
1.'
0. '
1 <>
IP.O
Concentration , mg 7L
Anaerobic Digestion N i t r i f i cat i on
I .o
'¦.o
r>. o
. 00 '
-j t r'o le um origin)
100
5 00 ,,
1r. .XV
5r)0o
-',r)00
OS 00
100^
o.p
r3C.^
10''
o.]
! .0
. ii.
I., 0'
0.7
. 0"
1.0
'.0
References
P)>V)
(1)' ]..'?)
(1U)
('¦¦<:)
<;"))
( L0)C 19)f ¦'<>)
C i.o) (i7)nfi)f i9)f ?o)
(1T)(18)'30)
f?T){r.fi)f;o)
f''T)'°8)'?0)
( :'T)'"'f.)'?0)
(
'•'"?)
(°9)
-------
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-chemica1, and
de i nki ng)
Pulp Washing and Screening
Stock Preparation
Paper Maki ng
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
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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
pret rea tment:
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 hemieel 1u1ose).
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 nq
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
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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 organlcs
and the type of cooking liquor will determine the characteristics
of the wastewater.
D-1-3
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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-
vesti gati on.
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
(A-0-60 percent BOD removal). This has been at-
tributed primarily to high organic loading and filter
clogging with fibers (4).
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
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Pretreatment
The pretreatment unit operations which may be necessary fo
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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Table 0-1-1
Wastewater Characteristics
Paper and Allied Products
Characteri st t cs
Mechan ? ca1 Pu1p i ng
(Bleached & Unbleached^
Chemical Pulping
(Unbleached)
Chemical Pulping
(B1eached)
De i nk i ng
Pulp
Paper and
Pape rboa rd
But 1 d ? n g
Products
Industry Operation
Vea r-round
Yea r-round
Yea r-round
Yea r-round
Yea r-round
Yea r- round
Flow
Conti nuous
Cont i nuous
Cont inuous
Cont i nuous
Cont i nuous
Conti nuous
BOD
EXTREMELY HIG
AVERAGE-EXT.
HIGH AVERAGE-EXT .UGH
HIGH
AVERAGE-HIGH
EXTREMELY HIGH
TSS
HIGH
LOU-HiGH
LOW-HIGH
HIGH
AVERAGE-HIGH
EXTREMELY H 5 GH
TOS
, i
/-we rage
HIGH
HIGH
HIGH
Low-average
Low
COD
HIGH
HIGH
HIGH
HIGH
HIGH
HIGH
Grit
PRESENT
PRESENT
PRESENT
PRESENT
PRESENT
PRESENT
Cyan i de
Absent
Absent
Absent
Absent
Absent
Absent
Chlorine Demand
HIGH
HIGH
HIGH
HIGH
HIGH
HIGH
PH
Neut ra 1
ACID-ALKALINE
ACIDIC
ALKALINE
neut ra'
Neut raI
Color
Low
H i gh
H i gh
Low
Low
Low
Turbi dt ty
H i gh
Hi gh
Hi gh
Hi gh
H i gh
VERY HIGH
Explosives
Absent
Absent
Absent
Absent
Absent
Absent
Di ssoWed Gases
Absent
P resent
Present
Absent
Absent
Absent
Oete rgen ts
Absent
Absent
Absent
Absent
Absent
Absen t
Foaming
PRESENT
PRESENT
PRESENT
PRESENT
PRESENT
PRESENT
Heavy Meta1s
ABSENT3
PRESENT
PRESENT
PRESENT
Absent
Absent
Col 1oi da 1 Soli ds
Present
Present
p resen t
presen t
p resen t
Present
Vol at i1e 0 rgani cs
Absent^
Present
present
absent
absent
Absent
Pest ici des
Absent
Absent^
absen t^4
absent
absent
Absent
Phosphorus
DEFICfENT
DEFICIENT
DEFICIENT
DEFICIENT
DEFIC1ENT
DEFICIENT
N i t rogen
DEFICIENT
DEFICIENT
DEFICIENT
DEFICIENT
DEFICf[NT
DEFICIENT
Tempe rature
high5
HIGN5
HIGH5
highS
high5
SIGH?
Phenol
Absent
Absent
Absent
Absent
Absent
Absent
SuIf i des
Absent
Absent
Absent
Absent
Absent
Absent
Oil & G rease
Present
Present
Present
Present
Present
Present
Coli form (Tota1)
Average
Average
Ave rage
Ave rage
Average
Average
^Hiah if bleaching of pulp is practiced.
Acidic if bleaching of pulp is practiced.
^Present if bleaching of pulp is practiced.
^Present only from log washing operations.
Higher temperature than domestic wastewater. May affect design but not hamfu1 to joint treatment o recesses.
NOTE: characteristics which nay require pretreatfient or are significant to joint treatnent plant dcslq- »r« snov.n ir u?PrR C'SC
The wastewater characteristics shown reflect the Industrial Practices described in Section 2.
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Table D-1-2
Pretreatment Unit Operations for the Paper and Allied Products Industry
Pretreatment
Sub-G roup
Mechanical Pulping
(Unbleached)
Mechanical Pulping
(B leached)
1
1
Chemical Pulping
(Unbleached)
Chemical Pulping
(Bleached)
1
1
Deinking Pulp
1
Paper 5- Paper Board
Building Products
Suspended Biological
System
Coarse Solids Separation
+ Grit Removal
Coarse Solids Separation
+ Grit Removal +
Neutra1i zat i on
Coarse Solids Separation
+ Grit Removal +
Neutralization
Coarse Solids Separation
+ Grit Removal +
Neutrali zat ion
Coarse Solids Separation
+ Neutra1i zat ion
Coarse Solids Separation
Coarse Solids Separation
Fixed Biological
System
Independent Physical - Chemical
System
Where pulp and paper wastewaters
constitute more than about 10 percent
of the total wastewater flow, fixed
biological systems or independent
physical chemical systems normally are
not used. Where the pulp and paper
wastewater constitute less than this
proportion, the pretreatment require-
ments will be same as for suspended
biological systems.
Equalization may be required in addition to those shown when batch pulping processes are used.
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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 arid Semichemicdi Pulp
Mill Waste," Technical Bulletin tiki, 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. 0RD 1
(July 1969).
D-1-8
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DAIRY PRODUCTS INDUSTRY
1. Industry Description
This industry includes Standard Industry Classifications (SIC)
2021, 2022, 2023, 2024, 2026, and 50^3. 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 fee
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
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The following industrial practices can have a major impact
on the wastewater characteristics:
Whey Hand 1i ng
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) (l).
C1ean 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
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(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 TDS. 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 (h). 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 norma 11y 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 recirculation rates (3).
k. 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
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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-i»
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Table D-2-1
Cha racter i sties
Industrial Operation
FLOW
BOD
TSS
TDS
COD
Grit
Cyan i de
Chlorine Demand
pH
Col o r
Turb i d i ty
Explosives
Dissolved Gases
Detergents'
Wastewater Characteristics
Dairy Products
Milk Hand 1i ng
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
Natural and Cottage
Cheese Product
Year-round (BATCH)
INTERMITTENT
EXTREMELY HIGH
Average-EXT. HIGH
HIGH
EXTREMELY HIGH
PRESENT
Absent
HIGH
ACID TO ALKALINE
HIGH
H i gh
Absent
Absent
PRESENT
Foami ng
Heavy Metals
Col 1o ida 1 Soli ds
Volatile Organics
Pest icides
PRESENT
Absent
HIGH
Absent
Absent
PRESENT
Absent
HIGH
Absent
Absent
Phosphorus
N i t rogen
Temperatu re
Phenol
Sulfides
Present
Adequate
Normal-High^
Absent
Absent
Present
DEFICIENT ,
Normal-High1*
Absent
Absent
0 i1 and G rease
Coli form
1
Present
PRESENT
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 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
UPPER CASE.
i n
Wastewater characteristics shown reflect all the Industrial
Practices described under Section D-2.
D-2-5
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Table D-2-2
Pretreatment Unit Operations for the Dairy Products Industry
Pretreatment
Sub-G roup
Mi 1k Hand 1i ng
Milk Products
Suspended Biological
System
Equali zation +
Neutra1i zat ion
Fixed Biological
Sys tern
Equa1i zati on +
Neut ra1i zat i on
Independent Physical
Chemical System
Equa1i zat i on +
Neutrali zati on
Natural and
Cottage Cheese
Products
Equali zat ion +
Neut ra1i zat ion
Equali zation +
Neutrali zation
Equa1i zat ion +
Neutrali zation
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REFERENCES
1. "Proceedinqs Second National Symposium on Food Processinq
Wastes", Denver, Colorado, Environmental Protection Agency,
Water Pollution Control Research Series 12060 (March, 1971).
2. "The Cost of Clean Water, Vol. Ill, 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 (19&5K
D-2-7
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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, carboxymethyl 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
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During scouring cotton wax and other non-cellulosic 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 arid urea, and with fire retard-
ants, such as triaziridyl phosphine oxide.
The pretreatment sub-qroups 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
concentrations.
d-3-2
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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
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Table D-3-1
Wastewater Characteristics
Text i1e Indus t ry
Cha racter i st i cs
Industrial Operation
F 1 ow
BOD
TSS
TDS
COD
Grit
Cyan i de
Chlorine Demand
pH
Color
Woo 1
Year-round (batch)
INTERMITTENT1 - Continuous
HIGH
HIGH
HIGH
HIGH
PRESENT
Absent
HIGH
BAS IC
HIGH
Cotton and Synthetics
Year-round (batch)
INTERMITTENT1 - Continuous
Ave rage-HIGH
Low-AVERAGE
HIGH
Ave rage-HIGH
Absent
Absent
HIGH
BASIC
HIGH
Tu rb i d i ty
Exp 1os i ves
Dissolved Gases
Detergents
Foami ng
Heavy Metals
Col 1oida1 Soli ds
Vol at i1e 0 rgan i cs
Pest i c i des
Phosphorus
Ni trogen
Temperature
Phenol
Su1f i des
0 i 1 and G rease
Coli form (Fecal)
High
Absent
Absent
PRESENT
Present
PRESENT
Present
Absent
Absent
PR SENT
DEFICIENT
Norma 1-H i gh^
Absent^
Absent
HIGH5
PRESENT
High
Absent
Absent
PRESENT
Present
PRESENT
Present
Absent
Absent
PRESENT
DEFICIENT
Normal-High
Absent
Absent
Absent-Present
Absent
Wastewater flow characterized by an intermittent pattern over the day.
1
Temperature equal to or higher than domestic wastewater. May affect design but not
harmful to joint treatment processes.
5,
Phenol may be present in dye carriers.
+0 i1 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.
D-3-^
-------
Table D-3-2
Pretreatment Unit Operations for the Textile Industry
Pretreatment
Sub-Group
Wool
Cotton & Synthetics
Suspended Biological
System
Coarse Solids Separation +
Grease Removal + Chemical
Precipitation (color, heavy
metals) + Equalization +
Neutrali zation
Coarse Solids Separation +
Chemical Precipitation
(color,heavy metals) +
Fixed Biological
System
Coarse Solids Separation +
Grease Removal + Chemical
Precipitation (color, heavy
metals)•+ Equalization +
Neutrali zation
Coarse Solids Separation +
Chemical Precipitation
(color,heavy metals) +
V * / ' \ ~ ' > 1 ¦ * 1 *"w ' - /
Equalization + Neutralization Equalization + Neutralization
Independent Physical - Chemical
System
Coarse Solids Separation +
Grease Removal + Chemical
Precipitation (color, heavy
metals) + Equalization +
Neut ra1i zat ion
Coarse Solids Separation +
Chemical Precipitation
(color,heavy metals) +
Equalization + Neutralization
0
1
VjJ
a
\n
-------
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 Hill Products",
Environmental Protection Agency (Unpublished)
3. "The Cost of Clean Water - Vol. Ill - Industrial Waste
Profile No. k Textile Hill 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 209b.
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 I968 was approximately 4 billion pounds
(cleaned), with the catch being utilized as follows: 35a.
rendered, 30% marketed fresh, 20% canned, 10% frozen, and
5/, to miscellaneous processing (1).
The seafood industry involves the processing of numerous
species of seafood including: mollusks (oysters, clams,
and 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 classes
of rendering processes are used: dry, wet, solvent
extraction, 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 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.
-------
Soli d Waste Hand!i pg
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
wash i ng.
3. Wastewater Characteristics
The characteristics of the process wastewaters from
the industry are shown in Table D-4-1.
The seafood processing industry is seasonal, but waste-
water flows are relatively constant during operation.
Wastewaters include various auxiliary sources such as
cooling water and cooling waters from refrigeration
sys terns.
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. Considerations
of significance to the Joint treatment of seafood
wastewaters and domestic waste include high chlorine
demand, the presence of surface-active agents, fecal
coliform, and high concentrations of chlorides and other
dissolved solids from sea water usage within the plant.
4. Pret reatment
The pretreatment unit operations which may be necessary
for various types of joint treatment facilities are shown
in Table 0-k-2,
Very little treatability information is available for
seafood-processing wastewaters. If seawater is used as
process water, a dilution of 3 to 1 (domestic wastewater
to process wastewater) is required so that dissolved
solids and chlorides will not cause problems in a joint
biological treatment plant. Oil separation will be a
pretreatment consideration if oily fish, such as tuna,
sardines, herring, cod, haddock, halibut, etc., are
p rocessed.
D-4-2
-------
Table D-4-1
Wastewater Characteristics
Seafood Industry
Characteri sties
C1 ass i fi cat i on
Industrial Operation
F1 ow
BOD
TSS
TDS
COD
Grit
Cyani de
Chlorine Demand
PH
Color
Turb i d i ty
Explosives
Dissolved Gases
Detergents
Foami ng
Heavy Meta1s
Colloidal Soli ds
Vol at i1e Organ ics
Pes ti c i des
SEASONAL
Cont i nuous
Average-H1GH
Average-HIGH
Average-HIGH
Average-HIGH
Absent
Absent
Average-H1GH
Neutral
Average-H
H i gh
Absent
Absent
Presen t
Absent
Absen t
Average-HI
Absen t
Absent
GH
GH
Phosphorus
Ni trogen
Temperature
Pheno1
Su1fi des
Adequate
Adequate |
Normal-Hi gh
Absent
Absent
Oil & Grease
Coli form (Fecal)
Co 1i form (Total)
Average-HIGH
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-^-3
-------
Table O-k-Z
Pretreatment Unit Operations for the Seafood Industry
Suspended Biological
System
Coarse Solids
grit removal
separat ion2
Separation +
+ oi 1
Fixed Biological
System
Coarse Solids Separation +
grit removal + oi1
3 ; 5
separat ion
Independent Physical
Chemical System
Coarse Solids Separation +
grit remova1 + o i1
separation2
o
¦
¦r
¦
¦c-
For shellfish processing.
20il separation may be required to reduce free floating oil and grease depending on
seafood processed.
-------
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).
D-lf-5
-------
PHARMACEUTICAL INDUSTRY
1 , Industry Description
This industry includes Standard Industry Classifications
(SIC) 2831, ?833, and 283^+ - The Industry produces medicinal
chemicals and pharmaceutical products, including some fine
chemicals which are marketed outside the pharmaceutical industry
-is 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 (l).
In general, the pharmaceutical industry may be divided into
two broa
-------
The pretreatment sub-groups for this industry are as follows
Synthes i5
Fermentation
2. Industrial Practices
The following industrial practices can significantly influence
the iwdiiewrfter character!; (..j ;
1. 3c i vent recovery it '• etc 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 reauired (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 wash inns,
concentration and drying procedures, and equipment washdown.
Wastewaters generated from the pharmaceutical industry can be
characterized as containing high concentrations of BOD, COO,
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-bacteria] 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
-------
4. Pre treat merit
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
Pharniaceu t i ca I Industry
Characteri sties
Syn thes i s
Ferrnen ta t i on
Industrial Operation
F1 ow
BOD
TSS
TDS
COD
Grit
Cyan i de
Chlorine Demand
pH
Color
Turb i d ity
Exp 1os i ves
Dissolved Gases
Detergents
Foami ng
Heavy Metals
Colloidal Soli ds
Volat ile Organ i cs
Pest i c i des
Phosophorus
N i trogen
Temperature
Phenol
Su1f i des
Oi 1 S- Grease
Coli form (Total)
Year-Round (BATCH)
INTERMITTENT
AVERAGE-HIGH
HIGH
AVERAGE-HIGH
AVERAGE-HIGH
Absent
PRESENT
AVERAGE-HIGH
ACID-BASIC
Av«rage-Hi gh
Average
Presen t
Absent
PRESENT
PRESENT
PRESENT
Hi gh
HIGH
Absent
DEFICIENT
DEFICIENT
Normal-Hi gh'
Absent
Absen t
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-Hi qh
Hi gh
Present
Absent
PRESENT
PRESENT
Absent
HIGH
HIGH
Absent
DEFICIENT-HIGH
DEFICIENT-HIGH
Norma 1-H i gh
Absent
Absent
Absent-Presen t
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-5-1*
-------
Table D-5-2
Pretreatment Unit Operations for the Pharmaceutical Industry
Pretreatment
Sub-Group
Synthes i s
Fermentation
Suspended Biological System
Chemical Precipitation
(Heavy Metals) + Solvent
Separation + Neutralization
+ Cyanide Oxidation
Solvent Separation + Equali-
zation + Neutralization
Fixed Biological System
Chemical Precipitation
(Heavy Metals) + Solvent
Separation + Equali-
zation + Neutralization +
Cyanide Oxidation
Solvent Separation + Equal
zation + Neutralization
Independent Physical
Chemical System
Chemical Precipitation
(Heavy Metals) + Solvent
Separation + Equali-
zation + Neutralization
+ Cyanide Oxidation
i- Solvent Separation +
Equalization + Neutral-
i zation
-------
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
1• Industry Description
This industry includes Standard Industrial Classification (SIC)
3111. This classification includes tanning, curing, and fin-
ishing hides and skins into leather. The trend in the tannery
industry is toward greater centralization near large 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-
ski n 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
Retan, color and fat liquor
k. Finishing
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 unhalred
stock for subsequent operations. The beam house operation Is
typical of hide and skin processing with cattlehlde 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
I ndustr i a 1 Practices
ln-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".
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
-------
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
genera], 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 H„S gas
in the sewer lines and the effect of reducing character Istics
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 H2S release can be mini-
mized. If the pH of the wastewater is expected to be lower,
the sulfide concentration should be reduced below 1.0 mg/L to
prevent I^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.
D-6-4
-------
k. 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
ef f luent..
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 u-6-1
Wastewater Characteristics
Leather Tanning and finishing Industry
Characteri sti cs
Chrome Tanninq
Veqetable Tanning
Industry Operation
Year-Round (Batch)
Year-Round (Batch)
F 1 ow
INTERMITTENT
INTERMITTENT
BOD
EXTREMELV HIGH
EXTREMELY HIGH
TSS
EXTREMES, HIGH
EXTREME LY HIGH
TOS
HIGH
HIGH
COD
EXTREMEL\ uluri
EXTREME LY HIGH
Gri t
PRESENT
PRESENT
Cyan!de
Absent
Absent
Chlorine Demand
High
Hi gh
pH
ACID - ALKALINE
ACID - ALKALINE
Col or
Present
Present
Turfai di ty
Present
Present
Explosi ves
Absen t
Absen t
Dissolved Gases
Present
Present
Detergents
Present
Present
Foami ng
Absent
Absent
Heavy Metals
PRESENT
Absent
Colloi dal So 1i ds
Present
Present
Volatile Organics
Present
Present
Pest i ci des
Absent
Absent
Phosphorus
DEFICIENT
DEFICIENT
Ni trogen
Adequate
Adequate
Temperature
Normal'
Normal'
Phenol
Absent
Absent
Su1f i des
Present
Present
011 & Grease
HI GH2
HIGH2
Co 1i form (Tota1)
Low
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
-------
Table D-6-2
Pretreatment Unit Operations for the Leather Tanning and Finishing Industry
Suspended Biological
System
Coarse Solids Separation +
Grit Removal + Equalization
Fixed Biological
System
Coarse Solids Separation +
Grit Removal + Equalization
Independent Physical
Chemical System
Coarse Solids Separation +
Grit Removal + Equalization
Pretreatment
Group
Chrome Tanning
+ Chemical Precipitation
(Heavy Metals) + Solids
Separation + Neutralization
Vegetable Tanning Coarse Solids Separation +
Grit Removal + Equalization
+ Neutralizat ion
+ Chemical Precipitation
(Heavy Metals) + Solids
Separation + Neutralization
Coarse Solids Separaration + Coarse Solids Separation +
Grit Removal + Equalization Grit Removal + Equalization
+ Neutrali zat ion
1. Pretreatment requirements assume fat and grease recovery as saleable by-product.
-------
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 (1967)-
2. "Activated Sludge Treatment of Chrome Tannery Wastes," Water
Pollution Control Research Series, ORD-5, U.S. Department
of the Interior, FWPCA, (1969).
3. Eye, D. J., Adldons, J. G., "Anaerobic - Aerobic Treatment
of Spent Vegetable Tan Liquors from a Sole Leather Tannery,"
Proc. 23rd Industrial Waste Conference, Purdue University,
126-139 (1968).
4. Sproul, 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, ^7-^67 (1 966).
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. 68-01-002*+ (Unpublished).
7. Wims, F. J., "Treatment of Chrome Tanning Wastes for
Acceptance by an Activated Sludge Process," Proc. 18th
Industrial Waste Conference, Purdue University, 53^-5^9
(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 kS 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 acld-llme 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
feedi ng.
Because of the similarity of the wastewaters from the sugar
industry, there are no separate pretreatment sub-groups for this
i ndustry.
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 (4,5).
The pulp press liquor and evaporator condensates can be re-
cycled for use in the flume-washing operation.
3. Wastewater Characteristics
The characteristics of the process wastewater from the industry
are shown in Table D-7—1 - Sugar plants generally operate 24
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 . Flui„a washing
2. Lime cake or slurry
3. Evaporator condensates
k. 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
0-7-2.
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.
D-7-4
-------
Table D-7-1
Wastewater Characteristics
Sugar Industry
Character i st ics
Industrial Operation
F 1 ow
BOD
TSS
TDS
SEASONAL1
Continuous-Variable
Low-EXT. HIGH
Low-EXT. HIGH
H IGH
COD
Grit
Cyan i de
Chlorine Demand
PH
Low-EXT. HIGH
PRESENT
Absent
HIGH
Neut ra1
Color
Turbidity
Exp 1os i ves
D i ssolved Gases
Dete rgents
low-high
PRESENT
Absent
Absent
Absent
Foam i ng
Heavy Metals
Col 10ida1 Sol ids
Volatile 0rgan ics
Pest i c i des
Absent
Absent
Low
Absent
Absent
Phosphorus
N i t rogen
T empe ratu re
Phenol
Su1f i des
DEFIC IENT
DEFIC IENT
H 1 GH
Absent
Absent
Oil & G rease
Coli form (Fecal)
Coli form (Total)
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 pre treatment 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
-------
Table 0-7*2
Pretreatment Unit Operations for the Sugar Industry
Suspended Biological System
coarse solids separation +
equalization + grit removal +
solids reparation (lime
siurry)^
Fixed Biological System
coarse solids separation
equalization + grit removal
+ grit removal + solids
separation (lime slurry)
I ndependen t
Physical-Chemical System
coarse solids separation
+ grit removal + solids 2
separation (lime slurry)
—i
¦
cr
1 Equalization may not be necessary, depending on specific physical-chemical processes used.
2 Grit removal and solids separation for lime slurry may be combined.
-------
REFERENCES
1. "State-of-Art, Sugarbeet Processing Waste Treatment," Water Pol-
lution Control Research Series, 12060 DSI 7/71, Environmental
Protection Agency, Washington, D.C. (1971)•
2. Force, S.L., "Beet Sugar Factory Wastes and Their Treatment -
Primarily the Find ley System," Proc. 17th Ind. Waste Conf.,
Purdue University, 116-135 (1962).
3. Rogers, H.G., and Smith, L.H., "Beet Sugar Waste Lagooning,"
Proc. 8th Ind. Waste Conf., Purdue University, 136-147 (1953).
k. Biglane, K.E., "Some Current Waste Treatment Practices in
Louisiana Industry, "Proc. 13th Ind. Waste Conf., Purdue
University, 12-20 (1958).
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 (C5 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
st reams.
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
respect i ve1y.
The following specific in-plant practices are frequently
emp1oyed:
a. Sour-condensate stripping is used to remove sulfides
(as hydrogen sulfide, ammonium sulfide, and
polysuIfides) 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
-------
3. Wastewater Characteri sties
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 'clean' waters may
include pollution-free cooling waters, boiler blowdown,
and cooling tower blowdown.
The character!stics of wastewater drawn from storage tanks
will depend on the guality 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
d i1ute wa s tewa te r.
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 wastewaters,
0-8-4
-------
which cone in diiect contact wi ¦ h petroleum hydrocarbons,
contain free and o.-ulsified oil, sulfides, phenols, ammonia,
BOD, COD, heavy motais, anJ "• t ko I i n i ( y as major waste
const i tuents.
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
amnion i a
b. Spent-caustic neutralization
c. Spent-acid neutralization and recovery or disposal by
other means
d. Separate collection and disposal of acid sludges,
clay, and spent catalysts
e. Gravity separation of free oil from process effluents
Depending upon the in-plant control methods used within a
refinery it may be necessary to add sulfide removal and
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 oi1 in a municipal sewer wouid con-
stitute a fire and explosive hazard. For this reason, sewer
ordinances generally have prohibited the discharge of refinery
wastewaters to municipal facilities, h 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).
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
-------
Table D-8-1
Wastewater Characteristics"
Petroleum Refining Industry
Characteri st ics
1ndust ry Ope rat i on
Yea r-Round
F1 ow
Cont i nuous
BOD
Ave rage'
TSS
Low
TDS
HIGH
COD
HIGH
Grit
PRESENT
Cyanide
Present
Chlorine Demand
H i gh
pH
ACID -ALKALINE
Col or
Low
Turbidi ty
Low
Exp 1os i ves
PRESENT
Dissolved Gases
Present
Detergents
Low
Foami ng
Absent
Heavy Metals
PRESENT
Col 1oi da 1 Soli ds
Low
Volatile Organics
Present
Pesticides
Absent
Phosphorus
DEF1 CIENT2
Ni trogen
Adequate
Temperature
HIGH^
Phenol
HIGH
Sulfides
HIGH
Oi1 & Grease
HIGH
Coli form (Total)
Low
••After gravity oil separation (API Separators).
Whe refinery wastewaters have high COO/BOD ratios indicating the presence of biologically resistant organic chemicals.
^If cooling tower blowdown is also discharged with the process wastewater, phosphates may be present depending on water treatment.
3Temperature 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 reflect all the Industrial Practices described in Section 2.
-------
Table D-8-2
Pretreatment Unit Operations for the Petroleum Refining Industry^
Suspended Biological Fixed Biological Independent Physical Chemical
System System System
Equalization + Coagulation - Equalization + Coagulation - Equalization + Coagulation -
Solids Separation^ + Solids Separation2 + Solids Separation2 +
Neutralization Neutralization Neutralization
CJ
i
oo
'pretreatment Unit Operations Apply to API Separator Effluent
2Combined with Oil Removal to insure oil concentration below 50 mg/L
-------
REFERENCES
1. "The Cost of Clean Waters, Volume III, Industrial Waste
Profile No. 5, Petroleum Refining," U.S. Department of the
Interior, FWPCA, (1967).
2. Nemerow, N.L., "Theories and Practices of Industrial Waste
Treatment," Addison-Wes1ey Publishing Company, Inc.,
Reading, Mass. (1963).
3. Beychok, M.R., Aqueous Wastes from Petroleum and Petrochemical
Plants", John Wiley and Sons, New York, (1967).
k. "Petroleum Refining Effluent Guidelines", Environmental
Protection Agency, Washington, D.C. (Unpublished)
D-8-9
-------
MEAT PRODUCTS INDUSTRY
I . I ndustry Description
This industry includes Standard Industrial Classification
(SIC) Nos. 2011, 2013, 2014, and 209'+.
These classifications include slaughterhouses, packing-
house,. processing plant--: (beef, pou'tr/. 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 skinninq, defeatherinq 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
-------
Ren '.1 e f i r iC|
v3! i r.i^ r i nq s unit p recess irf-plant
.I,;)-! i r; ca t i o;:: ut :¦ i j i i i f i c an 11 y influence tne p re-
treatment considerations. Wet and dry rendering are
two subprocosses presently used within the industry.
• i) the wet process, the meat by-products in a batch
tank ar~ root id hy .'i reel injection of steam. Dry
tv niA.r {p , vi ! the remaining tank water
iswv he evap'; r .s \.!>' • ••'. The tank water is a
major source of organic pul lution, when sewered, and
has a BOD value of approximately 45,000 mg/L (2).
Evaporation of wet-re.;deri rig tank water and the
installation of en trainment separators on barometric
condensers may reduce the need for pre treatment of
wet-rendering process wastewaters.
Was tew ater 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 amnion i a condensers in the
refrigeration systems). Many large plants providing their
own complete or partial treatment: have found it economical
to segregate wastewaters into blood, clean water, manure-
free water, and manure waters.
3• Wastewater Characteristics
The characteristics of wastewaters from the meat products
industry are shown in Table D-9-i. 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
wastewaters (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
Meat Products
Industry Operation
Year-round ,
F1 ow
INTERMITTENT
BOD
high-ext. HIGH
TSS
HIGH
TDS
HI GH
COD
HIGH - EXT. HII
Grit
Absent
Cyan i de
Absent
Chlorine Demand
HIGH
pH
Neutral
Color
HIGH
Tu rb i d i ty
H i gh
Exp 1os i ves
Absent
Dissolved Gases
Absent
Detergents
Present
Foami ng
Absent
Heavy Metals
Absent
Co 11o i da 1 So 1 i ds
HIGH
Vo1 at ile Organ ics
Absen t
Pest i c i des
Absent
Phosphorus
Present
Ni trogen
Present ^
Temperature
Normal-Hi gh
Phenol
PRESENT3
Sulfi des
Absent
Oi1 and Grease
PRESENT
Coli form (Fecal)
PRESENT
Wastewater flow is intermittent over the day or week.
2
Temperature equal to higher than domestic wastewater; may
affect design but not harmful to joint treatment processes.
3
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.
0-9-^
-------
TABLE D-9-2
Pretreatment Unit Operations for the
Meat Products Industry
Suspended Biological System
Coarse Solids Separation +
Grease Removal2
Fixed Biological System
Coarse Solids Separation +
Grease Removal^
Independent Physical-
Chemical System
Coarse Solids Separation
+ Grease Removal
0
1
I
Assumes in-plant recovery and separate handling of blood, manure, and paunch manure.
2
Only free-floating oil and grease.
-------
REFERENCES
1 . "The Cost of Clean Water, Volume_ III, Industrial Profile
No. 8 - Meat Products1,' Federal Water Pollution Control
Administration, Washington, O.C., (September 1 96 7)-
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 (19&5).
D-9-6
-------
GRAIN MILLING INDUSTRY
Industry Description
This industry includes Standard Industrial Classification (SIC)
2041, 20kk, 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.
Industrial Practices
The following industrial practices can significantly influence
p ret reatment.
Dry Corn Mi 11 inq
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 Ml 11 Inq
The dry cleaned corn Is steeped first In circulating water
containing SO. for 30 to ko 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 11ing
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 i ce M i11i nq
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.
3. 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, BOO, 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 P-iO-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-IO-1
Wastewater Characteristics
Gra in M i ! 1 I ndust ry
Characterist ic
Industry Operation
s. ea r-Round
F t ow
CONTINUOUS
BOD
HIGH- EXT. HIGH
TSS
Low- EXT. HIGH
TDS
H i qh
COD
HIGH- EXT. HIGH
Grit
P resent
Cyan ide
Absent
Chlorine Demand
H i gh
pH
AC ID IC-ALKALINE
Color
Absent
Tu rb i d i ty
Present
Exp 1os i ves
Absent
Dissolved Gases
Absent
Detergents
Absent
Foam i ng
Absent
Heavy Metals
Absent
Collo i da 1 Solids
P resent
Vol at i1e Organ i cs
Low
Pest i c i des
Absent
Phosphorus
Low-Adequate
N i t rogen
Low-Adequate
Temperature
H i gh
Phenol
Absent
Su1f ides
Absent
0 i1 and G rease
Absent
Co 1i form (Tota1)
Present
1 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-if
-------
Table D-10-2
Pretreatment Unit Operations for the Grain Mill Industry
Suspended Biological System
Coarse Solids Separation +
Equali zation +
Neutrali zat ion
Fixed Biological System
Coarse Solids Separation
Equali zation +
Neutrali zat ion
! independent
Phys i ca 1 /'Chem ica 1 System
+ Coarse Solids Separation
Equali zation +
Neutrali zation
-------
REFERENCES
1. "Industrial Waste Studv Report - Grain Mil 1t n q Industry",
Environmental Protection Agency, Washington, D.C.,
(unpub1i shed).
2. Ling, J.T., "Pilot Investigation of Starch - Gluten Waste
Treatment", Proceedings 16th Industrial Waste Conference,
Conference, Purdue University, 515-525 (1967).
3. Wi1lenbrink, R.V., "Waste Control and Treatment by a Corn
and Soybean Processor", Proceedings 22nd Industrial Waste
Conference, Purdue University, 515-525 (1967).
b. Jeyfriend, C,F., "Purification of Starch Industry Wastewater",
Proceedings 23rd Industrial Waste Conference, Purdue
University, 1103-1119 (1968).
D-10-6
-------
FRUIT AND VEGETABLE INDUSTRY
1. Industry Description
This industry includes Standard Industrial Classification's
(SIC) 2033, 2034, 2035, and 2037. These industrial
classifications include the processing of fruits and
vegetables, including cleaning, sorting, sizing, peeling,
stabilizing, and final processing.
Because of the similarity of the wastewaters from the
various segments of the fruit and vegetable industry,
there are no separate pretreatment sub-groups for this
i ndust ry.
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,
e.g., fruit juices. 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
are generally sewered 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-l1-1
-------
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 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; therafter, the cans are cooled with water
before being labeled and packed in cartons.
2. Industrial Practices
The following industrial practices can significantly
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.
Peeling 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
establ1shments.
3. Wastewater Characteristics
The characteristics of the wastewaters from the processing
fruits and vegetables are shown In Table D—11—1. The
D-l1-2
-------
fruit and vegetable industry Is a seasonal operation,
usually corresponding to the local growing season. With-
in 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 cooked. These latter
processes are batch types. In general, 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 within
each plant will dictate the pretreatment and subsequent
treatability. 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
be a problem if the crops being processed have been
sprayed recently or 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; however, this may change as water
reuse practices increase.
D-l1-3
-------
TABLE D-l1-1
Wastewater Characteristics
Fruit and Vegetable Industry
Characteri sti cs
Industrial Operation
F low
BOD
TSS
TDS
SEASONAL (BATCH)
INTERMITTENT
Ave rage-EXT. HIGH
Average-EXT. HIGH
Average-HIGH
COD
Gri t
Cyani de
Chlorine Demand
pH
Average-EXT. HIGH
PRESENT
Absent
Average-HIGH ,
ACID-ALKALINE
Col or
Turbidi ty
Exp 1os i ves
Dissolved Gases
Detergents
Average-HIGH^
Hi gh
Absent,
Absent
PRESENT
Foaming
Heavy Metals
Col 1oidal Solids
Volatile Organi cs
Pesticides
Absent
Absent
Average
Absent
Absent-Present
Phosphorus
N i t rogen
Temperature
Phenol
Sulfi des
DEFICIENT
DEFICIENT ^
Normal-Hi gh
Absent
Absent
Oi1 & Grease
Fecal Coliform
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.
k. 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 the
industrial practices described in Section 2.
D-11-4
-------
TABLE D-lI-2
Pretreatment Unit Operations for the Fruit and Vegetable Industry
Independent Physical
Suspended Biological System Fixed Biological System Chemical System
Coarse Solids Separation + . Coarse Solids Separation + Coarse Solids Separation
Grit Removal + Neutralization GritiRemoval + Neutraliza- + Grit Removal + Neutra-
tion lization
1. Neutralization is dependent on commodity and peeling process employed.
-------
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 Cam ?ry Fruit Waste by Continuous Fermenta-
tion", Bulletin No. 207, Washington State Institute of
Technology, Pullman, Washington (March 1950).
k. "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-n-6
-------
BEVERAGES INDUSTRY
'• Industry Description
This industry includes Standard Industrial Classification
(SIC) 2082, 2083, 2084, 2085, 2086, and 2087.
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,
ma 11)
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
(essential oiIs).
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 beverages, and distilled spirits (except
industrial alcohol).
W i ne and b randy.
Bottled and canned soft drinks, and flavors and syrups.
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
mi seellaneous 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. Liqui
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 cells, 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
liquid waste and is discharged to the sewer (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:
Frult Expression:
1. Water used for washing fruits.
2. Hydraulic press clean-up.
D-12-2
-------
Evaporation:
1. Evaporator condensate.
2. Kettle wash water.
Steam Disti1lation:
1 . Boi1er b1owdown.
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 Characteristics
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 BOO,
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 and is generally discharged to sewers. 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 characteristies 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).
P retreatment
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-\2-k
-------
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-piant
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 *+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.
0-12-5
-------
TABLE b -1 2 -1
Wastewater Characteristics
Beverages Industry
C horac ten sties
Malt Beverages and
Distilled Sp i r i ts
Wiue and Grandy
So ft Drinks lio 111 i nq
1n dus try Ope rati on
F) ovt
BON
TSS
TfJS
Year-round „
1NTE RM1TTEN T-Con t i n uou s
H i GH
Low to HIGH
High
SEASONAL
INTERMITTENT
HIGH-CXT. HIGH
Low to EXT, HIGH
HI yh
Year-round
INTERMlTTENT
Average to HIGH
Low to HIGH
Low to High
COD
Gri t
Cyanide
Chlorine Demand
pH
HIGH
PRESENT
Absent
No Data
ACID-NEUTRAL
HlGH-rxT. HIGH
PRESENT
Absen t
No Data ,
ACID-ALKALINE3
Average to HIGH
PRESENT
Absent
No Data ~
ALKALINE
Co 1 or
Tu r b i d i t y
Explos i ves
b isso1ved Gases
Detergents
Present
Presen t
Absent
Present^
Present
P resen t
Presen t
Absent
Absent
Present**
Present
P resen t
Absent
Present
Present**
Foami rig
Heavy Meta1s
Colloidal So 1i ds
Vo1 at i1e Organics
Pest icides
Present
Absent
Present
Present
Absent
Present
Absent
Presen t
Present
Ab sent
Present
Absen t
Present
Presen t
Absent
Phosphorus
N i t rogen
Tempe ratu re
Phenol
Sulfides
DEFICIENT
DEFICIENT
Normal-H i gh
Absent
Absent
DEFIC 1 EN T
DEFICIENT
High
, Absent
Absent
DEFIC IENT
DEFICIENT
Normal
Absen t
Absent
011 and Grease
Co 1 i fo rtr ( Feca 1)
Co 1 ? fo rrr ( To t a 1 )
Absent
Absent
Present
Absent
Absen t
Present
Absent
Absent
Presen t
'pollutants characteristies represent only Bottling Industry; no data available for flavors and syrups.
2Malt beverages generate wastes on a continuous basis; distilled spirits waste flow wi 11 be cyclic.
3AlkaMne pH due to caustic detergents used for bottle washing.
^Surface active agents are discharged primarily from bottle washing.
5Temperature equal to or higher than domestic wastewater; may at feci design but not harmful to
joint treatment processes.
NOTE: Characteristics which may require pret reatment or are significant to joint t reatin.nt
plant design are shown in UPPER CASE.
Wastewater characteristics shown reflect the industrial practices described in
Section 2.
0-12-6
-------
TABLE D-J2-2
Pretreatment Unit Operations for the Bevaerages Industry
Pretreatment Sub-Group
Malt Beverages
Suspended
Biological System
Coarse Solids Separation
+ Grit Removal + Equal-
ization + Neutralization
F i xed
Biological System
Coarse Solids Separation
+ Grit Removal + Equal-
ization + Neutralization
Indeoendsnt Phys'cai
Chemical System
Coarse Solids Sesjaro
+ Grit Removal + Eju
i zat ion + Neutrali za
Wine and Brandy
Coarse Solids Separation
+ Grit Removal + Equal-
ization + Neutralization
Coarse Solids Separation
+ Grit Removal + Equal-
ization + Neutralization
Coarse Solids Sesara
+ Grit Removal+ Ecu a
: ze t ion -r Neutre! i ze
Soft Drinks Bottling
Grit Removal +
Neutralization
Grit Removal +
Nau t ra1ization
: Renova I +
: ra 1 :zat i on
-------
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 Industry1,1 prepared for
the Environmental Protection Agency by Aware, Inc.,
Nashville, Tennessee (unpublished).
3. "Industrial Waste Survey of the Wine Industry',1 prepared
for the Environmental Protection Agency by Aware, Inc.,
Nashville, Tennessee (unpublished).
U. "Industrial Waste Survey of Distilled Spirits Industry','
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-1 2-8
-------
PLASTIC AND SYNTHETIC MATERIALS INDUSTRY
1 . 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 character!sties and treatability
information, the industry is divided into the following pre-
treatment sub-groups:
Pretreatment Sub-Group
Rayon Fibers
Nylon Fibers
2
High- and Low-Density
Polyethylene Resins
3
Urethane Resins
Polyolefin Fibers
Polyvinyl Acetate Resins
Polyvinyl Alcohol Resins
Polyester Fibers
k
Cel1ulos ic Resins
Cellophane
Polypropylene Resins
Cellulose Acetate Fibers
Polyvinyl Chloride Resins
Polystyrene
ABS, SAN Resins
Phenolic Resi ns
Nylon Resins
Polyacetal Resins
Acrylic Fibers
D-13-1
-------
Industrial Practices
The following industrial practices can significantly influence
the wastewater characteristic-.
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 solubilization 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
thi s 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 2
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 4 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 proprietary 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
-------
TABLE D-13-1
Wastewater Characteristics
Plastic and Synthetics Industry
Characteri sties
Sub-Group 1
Sub-Group 2
Sub-Group 3
Sub-Group 3
Industry Operation
Year-Round
Year-Round
Year-Round
F1 ow
Continuous-Variable Continous
3
Cont inuous
BOD
HIGH
Low
Low
Average-HIGH
TSS
HIGH
Low
Low
Low-HIGH
TDS
HIGH
Low
Low
Low-HIGH
COD
HIGH
Low
Low
Average-HI GH
Gri t
Absent
Absent
Absent
Absent
Cyanide
Absent
Absent
Absent
Absent
Chlorine Demand
HIGH
Low
Low
AVERAGE-HIGH
PH
ACID-BASIC
ACID-BASIC
Neutral
ACID-BASIC
Col or
Low-Average
Low-Average
Low
Low-Average
Turbidi ty
Hi gh
Low
Low
Low-Hi gh
Explosives
Absent
Absent
Absent
Absent
Dissolved Gases
Absent
Absent
Absent
Absent
Detergents
Absent
Absent
Absent
PRESENT
Foami ng
Absent
Absent
Absent
Absent
Heavy Metals
PRESENT
Absent
Absent
Absent
Colloida! Sol ids
HIGH
Low
Low
Average
Volatile Organics
Absent
Present
Absent
Present
Pesticides
Absent
Absent
Absent
Absent
Phosphorus
DEFICIENT
DEFICIENT
DEFICIENT
DEFICIENT
Ni trogen
DEFICIENT
DEFICIENT
DEFICIENT
DEFICIENT
Temperature
Normal-H i gh
Normal-Hi gh
Normal-Hi gh
Norma 1 -Hi gh
Phenol
Absent
Absent
Absent
Present
Sulfides
Absent
Absent
Absent
Absent
Oil and Grease
Absent
PRESENT
Absent
Absent
Coliform (Fecal)
Absent
Absent
Absent
Absent
Products generally associated with little or no process wastewater
^Temperature equal to or higher than domestic wastewater. May affect the design but not harmful to joi
, treatment processes.
See text page D-13-3
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.
-------
TABLE D-13-2
Pretreatment Unit Operations for the Plastic and Synthetic Materials Industry
Pretreatment
Sub-Group
Suspended Biological
System
Fixed Biological
System
Independent Physica1-Chemica1
System
1
Coarse Solids Separation
Neutralization + Chemical
Precipitation (heavy
metals)
Coarse Solids Separation Coarse Solids Separation +
+ Neutralization + Chemical Neutralization + Chemical
Precipitation (heavy Precipitation (heavy
metals) metals)
Oil Separation +
Neutralization
Oil Separation +
Neutralizat ion
Oi1 Separat ion' +
Neutrali zation
Pretreatment Not Required
Pretreatment Not Required
Pretreatment Not Required
Va>
I
vn
Coarse Solids Separation +
Neutralization
Coarse Solids Separation + Coarse Solids Separation +
Neutralization Neutralization
Oil separation required to reduce mineral oil (petroleum sources) concentration below
50 mg/L.
NOTE: Publicly owned treatment works must be protected from batch dumpings of
faulty product materials.
-------
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, 1967).
0-13-6
-------
BLAST FURNACES, STEEL WORKS, AND ROLLING AND H N> 3H'NG
1. incus try Description
This i.'iJu try includes Standard Industrial Classification
(SIC) 3312.
Thi-. c 1 a ^ s i f i c
-------
In the by-product process, coal is heated in the
absence of air to a temperature at which the volatile
matter is driver off. At the end of coking eye I c.
the hot resi du.-.i r-M-o (A, 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 • -P'ved from the furnace. The
is iv r c ¦ / P'. from i.'-.o liquor in a
i ' 1 .
! I': ,'p v/o r k ' i
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.
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 cm- air is
used to refine the hot iron into steel by oxidizing
and removing silicon, phosphorus, manganese, and
carbon from the iron.
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, sheet?,
strip, skelp, and bars.
Cold Finishing
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.
D-1k-2
-------
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 liguor. 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-l*t-l.
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 2i+-hour day. The volume and
characteristics of wastewater are subject to hourly
variations from batch dumping of acid baths and still
bot toms.
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-lU-3
-------
portion of the wastewater generated contains suspended
olids 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. ? re t rt:a fmen t 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 (1). The gases (CO2, 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
0-}k-k
-------
scale-bearing waters and cooling waters containing
primarily scale and oil.
Steel pickling to remove oxides and scales is accomplished
through solutions of H2SO4, 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 fini sh.
Plating of steel products is done electrolytically, 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.
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-]k-5
-------
TABLE 0-14-1
Wastewater Characteristics
Blast Furnaces,
Steel Works,
and Ro 1 1 i ng and F i
n i sh i ng 1 ndus t ry
Charac ter is t i c s
Coke Works
1ron Works
Steel Works
Hot Forminq
Cold Finishinq
1 ndus trial Ope rat ion
Year-round
Year-round
Year-round
Year-round
Year-round
F1 ow
INTERMI7TENT
Continuous
Cont\nuous
Cont inuous
(NTERMfTTENT
BOD
Low-Average
Low-Average
Low
Low
Low-Average
TSS
Low
Low-H i gh
Average-H i qh
Low-Hi gh
Low-H i gh
IDS
Low
Low
Low
Low
High
COD
Low-Average
Low-Average
Low
Low
Low-Average
Grit
Present
Present
Absent
Absent
Absent
Cyan ide
PRESENT
Present
Absen t
Absent
PRESENT
Chlorine Demand
H i gh
LOW
Low
Low
Low
pH
Neu t ra1
Neutral
Neutral
Neutral
ACIDIC
Color
Absent
Absent
Absen t
Absen t
Absent
Tu rb i d i ty
?resen t
P resen t
Present
Present
Present
Exp ios i ves
Absen t
Absen t
Absent
Absen t
Absent
Dissolved Gases
Present
Present
Present
Absent
Absent
Detergents
Absent
Absent
Absent
Absen t
P resen t
Fo am i n g
Absent
Absent
Absen t
Ab sen t
Absent
Heavy Metals
Absent
Presen t
Present
Present
PRESENT
Cofloidal So? ids
Present
Absent
Absent
Absen t
Presen t
Vo1 at i 1e Organ i c s
Present
Ab sen t
Ab sen t
Present
Present
Pes t i c i des
Absent
Ab sen t
Absent
Absen t
Absent
Character!sties
Coke Works
1 ron Works
Steel Works
Hot Forminq
Co 1d Finishinq
Phosphorus
DEFICIENT
DEFICIENT
DEFICIENT
DEFICIENT
DEFICIENT
N11 rogen
Adequate
Adequate
DEFICIENT
DEFICIENT
DEFICIENT
Temperature
HI GH
H i gh
H i gh
High
High'
Pheno1
PRESENT
Present
Absent
Absen t
Present
Su1fi des
PRESENT
Presen t
Absent
Absent
Absent
Oi1 and Grease
Present
Absent
Absent
Present
PRE5ENT
Coli form (Total)
Absent
Absent
Absent
Absen t
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
-------
TABLE D-l4-2
Pretreatment Unit Operations for the
Blast Furnaces, Steel Works, and Rolling and Finishing Industry
Pretreatment Sub-Group
Coke Production
Suspended
Biological System
Equalization +
Solids Separation
Fixed
Biological System
Equalization +
Solids Separation
Independent Physical'
Chemical System
Equalization +
Solids Separation
Cold Finishing
Equalization + Oi1
Separation or Skimming
+ Chemical Precipita-
tion (heavy metals) +
Neutrali zation
Equalization + Oi1
Separation or Skimming
+ Chemical Precipita-
tion (heavy metals) +
Neutrali zation
Equali zat ion + Oi1
Separation or Skimming
+ Neutrali zation
-------
REFERENCES
1. Nemerow, N.L., "Theories and Practices of Industrial
Waste Treatment", Addison-Wisley 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
1. Industry Description
This industry includes Standard Industrial Classifications
(SIC) 2811, 2813, 2814, 2815, and 2818.
These classifications include the manufacture of a wide
variety of products ranging from industrial gases and
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 1969. A major portion of these chemicals
falls under Standard Industrial Classifications 2815 and
2818. The important products of the industry are those
derived from petroleum fractions.
The Organic Chemicals industry consists of such a complex
combination of processes and products that a "typical or
average" plant exists only in a statistical sense. The
product mix and output of an industry depend primarily
on the total economic activity and the demand for products.
The Organic Chemicals industry is very dynamic in develop-
ment of new products and processes.
Considering the number of products involved within the
industry (several hundred), this study has been limited
to the high-volume products, and only 27 major chemicals
are included. These products in combination represent
approximately 81 percent of the total organic chemicals
manufactured in the United States. A listing of the
products covered is shown below in the order of 1970
manufacturing volume (1):
1.
Ethylene
15. Ethanol
2.
Benzene
16. Isopropanol
3.
Propylene
17. Acetic Acid
4.
Ethylene Dichloride
18. Cumene
5.
Toluene
19. Cyclohexane
6.
Methanol
20. Phenol
7.
Ethyl benzene
21. Acetaldehyde
8.
Styrene
22. Acetic Anyhdride
9.
Formaldehyde
23. Terephthalic Acid
10.
Vinyl Chloride
24. Dimethyl Terephthalate
11.
EthyJene Oxide
25. Acetone
12.
Xylene (Mixed)
26. Ad i p i c Ac i d
13.
Butadiene
27. Aerylonitri le
14.
Ethylene Glycol
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 2/
chemicals there are 22 intermediate chemicals and five
feedstocks (i.e., ethylene, propylene, benzene, toluene,
and xy1ene).
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.
Benzene
13.
Vinyl Chloride (Monomer)
2.
To)uene
14.
Ethanol
3.
Xy1ene
15.
Acetaldehyde
k.
Cyc1ohexane
16.
Acetic Acid
5.
Ad i p i c Ac i d
17.
Acetic Anyhdride
6.
Ethyl benzene
18.
P ropy 1ene
7.
Styrene
19.
1 sop ropano1
8.
Phenol
20.
Acetone
9.
Terephthaiic Acid (TPA)2I.
Cumene
10.
Dimethyl Terephthai ate
22.
Ethylene Oxide
(DMT)
23.
Ethylene Glycol
11.
Ethy1ene
12.
Ethylene Dichloride
Sub-Group 2
1. Butad i ene
2. Methanol
3. FormaIdehyde
Sub-Group 3
Aery Ion itrile
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 0-15-].
The characteristics of wastewaters vary from plant to
plant, according tn the products and processes used. The
Organic Chemicals plants generally operate 2b 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.
Aery 1 oni t r i1e 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 oi1 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 acry1 onitri1e 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 aery 1 onitri1e
(Sub-Group 3).
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 materials.
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.
D-15-4
-------
Table D-15-1
Wastewater Characterist fcs
0rganic Chemica1s
Cha racter i sties
^nh-firnuo 1
Sub-Grouo 2
Sub-G,rOUB 3
Industrial Operation
Flow
BOD
TSS
TDS
Year-round
Continuous-Variable
Average-EXT. HIGH
Low-Hi gh
HIGH
Year-round
Continuous-Variable
AVERAGE-HIGH
Low
Low-High
Year-round
Cont1nuous-Va r iable
Low'
High
Hi gh
COD
Gr i t
C yan i de
Chlorine Demand
pH
Average-EXT. HIGH
Absent
Absent
H i gh
ACIDIC-ALKALINE
Average-HIGH
Absent
Absent
High
ACIDIC-ALKALINE
H i gh
Absent
PRESENT
H i gh
AC 1D t C
Color
Tu rb i d i ty
Explos i ves
Dissolved Gases
Detergent s
Low-Average
Low
Absent
Present
Present
Low-Average
Low
Absent
Present
Present
Low
Low
Absent
Present
Present
Fo am i n g
Heavy Metals
Collo i da 1 So lids
Vo1 at i1e Organ i cs
Pes 11c i des
Present
Present
Absent
Present
Absen t
Present
Present
Absent
Present
Absent
Present
Present
Absent
Present
Absen t
Phosphorus
N i t rogeri
Temperature
Pheno1
Su1fi des
DEFICIENT
DEFICIENT
Normal-HIGH^
Low-HIgh
Present
DEFICIENT
DEFICIENT2
HI gh3
Present
Present
DEFICIENT
Adequate
No Data
Absent
Absent
Oi I and Grease
Coli form (Total)
Iow-HIGH
Low
Low-HIGH
Low
Absent
Low
'low BOO Is probably due to the toxicity characteristics of this waste.
2
Adequate when butadiene is manufactured.
3Temperature equal to or higher than domestic wastewater; may affect design but
not harmful to jofnt 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.
-------
Table D-15-2
Pretreatment Unit Operations for the
Organic Chemicals Industry
Pretreatment Sub-Group
I
Suspended
Biological System
Oil Separation +
Equali zation +
Neutrali zation +
Spi1J Protection +
Chemical Precipita-
]
tion 1
Fi xed
Biological System
Oil Separation +
Equalization +
Neut rali zat ion +
Spi11 Protection +
Chemical Precipita-
l r
tion 1
Independent Physical-
Chemical System
Equalization +
Neutrali zation +
Chemical Precipitation'
Oil Separation^ + Oil Separation^ + Equalization +
Equalization + Equalization + Neutralization
Neutralization Neutralization
'Need for chemical precipitation depends on extent of catalyst recovery.
2
Oil separation required for butadiene manufacture only.
-------
REFERENCES
1. Chemical arid 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 07/71s Environmental Protection Agency, Research
and Monitoring (July, 1971).
D-15-7
-------
METAL FINISHING INDUSTRY
1 . Industry Description
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 typs 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, degreaslng, desmudglng,
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 chromates. Cyanides are used In case hardening.
2. Wastewater Characteristics
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 be taken Into consideration
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 a^ter
plating operations. The rinse waters constitute the major
volume of wastewaters, while spent solutions discharged Inter-
mittently add major po'lutants to the total effluent. The
D-16-1
-------
wastewaters contain, in general, spent acids, alkalis, oil and
grease, detergents, cyanides, and vanous heavy metals (Cr,
Ni, Cu, Ag, Fe, Zn, and Sn). The meta 1-finishing plants differ
from one another with respect to their processes, meta^, and
chemicals, and the characterisU5cs 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 nnstal s (1 ,2,3) •
In general, the types of wastewaters from r.ieta 1 - f i n i sh i ng in-
dustries are:
1. Ac i d wastes
2. Alka1i ne was ten
3. Heavy metals wastes
4. 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 cyanida wastes usually
are collected in a segregated sewer system in order Lo prevent
the release of toxic hydrogen cyanide gas under acidic condi-
tions. However, the cyanide wastes can be mixed with 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 generate^f rom metal-
finishing operations are cyanides, metal ions, (Cr , Ni, Fe,
Cu, Ag, and Sn), oil and grease, organic solvents, acids, 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 CO2 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-16-1
Wastewater Characteristics
Metal Finishing Industry
Character!sties
Industrial Operation
Year-round (BATCH)
F1 ow
BOO
T5S
TDS
COD
Conti nuous-VARIABLE
Low
Average-Hi gh
HIGH
Low
Grit
Cyani de
Chlorine Demand
pH
Col or
Present
HIGH
HIGH
AC IDIC
Present
Turbidi ty
Explos i ves
0 issolved Gases
Detergents
Foam'ng
Present
Absent
Present
Present
Absent
Heavy Metals
Col 1oidal Solids
Vol at i1e 0 rgan i cs
Pesticides
HIGH
Absent
Present
Absent
Phosphorus
N i t rogen
Temperatu re
Pheno'
Sulfides
Present
Present
Normal
Low
Absent
0i 1 and G rease
Coliforn (Total)
Present
Absent
^Temperature similar to domestic wastewater
NOTE: Characteristics which may require pretreatment or are
significant to joint treatment plant design are shown in
UPPER CASE.
D-l 6-4
-------
TABLE D—16—2
Pretreatment Unit Operations for the Metal Finishing Industry
0
1
CT\
VI
Suspended Biological
System
Equalization + Neu-
tralization + Cyanide
Removal + Chromian
Reduction + Chemical
Precipitat ion (Heavy
Metals)+ Solids Separation
F i xed B i o1 ag i m 1
System
Equalization +
Neutralization +
Cyanide Removal
+ Chromium Re-
duction + Chemical
Precipi tation
(Heavy Metals) +
Solids Separation
Independent Physical
Chem: ca 1 Systein
Equali zat ion +
Cyanide Removal +
Chemical Precipita-
tion + Neutralization
Chemical precipitation may not be needed, depending on the processes used in the independent physical
chemical joint treatment plant.
-------
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. 9^, 8,
(19V).
3. Nemerow, N.L., "Theories and Practices of Industrial Waste
Treatment", Addison-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 Electroplatinq Wastes", Water Pollution Control Research
Series, 12010-EIE 3/71, EPA, Washington, D.C. (1971).
6. "Ultrathin Membranes for Treating Metal Finishinq 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 3334, 3341, 3361)
4. Flat Glass, Cement, Lime, Concrete Products,
Gypsum, and Asbestos
(SIC 3211, 3241, 3274, 3275, 3292)
5. Inorganic Chemicals
(SIC 2812, 2819)
6. Industrial Gas Products
(SIC 2813)
Two tables are provided for each of these six Industries;
the first shows the wastewater characteristics, and the
other shows pretreatment unit operations for various joint
treatment processes.
D-i 7-1
-------
Table D-17-?
Wastewater Characteristics
Inorganic Fertilizer
Character i st i cs
Phosphoric Acid
Normal Super Phosphate
Triple Super Phosphate
Mono-Ammonium Phosphate
Di-Ammonium Phosphate
N-P-K Fert i1izers
Ammon i a
Ammonium Nitrate
Urea
Ammonium Sulfate
Industrial Operation
Year-Round
Year-Round
Year-Round
F1 ow
Cont i nuous
Cont i nuous
Cont i nuous
BOD
Low-Average
Low
Low-Average
TSS
Average-High
Low-Average
Low-Average
TDS
HIGH
HIGH
HIGH
COD
Low-Ave rage
Low
Low-Average
Grit
Absent
Absent
Absent
Cyan i de
Absent
Absent
Absent
Chlorine Demand
Low
Low
Low
PH
AC ID
ALKALINE
ALKALINE
Color
No Data
No Data
No Data
Turb id ity
No Data
No Data
No Data
Explosive Chemicals
Absent
Absent
Absent
Dissolved Gases
PRESENT
Absent
Absent
Detergents
Absent
Absent
Absent
Foam i ng
No Data
No Data
No Data
Heavy Metals
Absent
Absent
Absent
Colloidal Sol ids
Absent
Absent
Absent
Volatile Organics
Absent
Absent
Absent
Pesticides
Absent
Absent
Absent
Phosphorus
Adequate
DEFICIENT
Adequate
N i trogen
Adequate j
Adequate ^
Adequate
Temperature
Normal-High
Normal-High
Normal-High
Phenol
No Data
No Data
No Data
Sulfide
No Data
No Data
No Data
Oil & Grease
Absent
PRESENT2
Absent
Coli form (Total)
Absent
Absent
Absent
Temperature equal to higher than domestic wastewater; affect design but not
harmful to joint treatment.
2
Oil present in the wastewater is mineral in origin.
NOTE: Characteristics which may require pretreatment or are significant to joint
treatment plant design are shown in UPPER CASE.
D-17-2
-------
Table D-17-2
Pretreatment Unit Operations for the Inorganic Fertilizers Industry
Pretreatment Group
Phosphoric Acid
Normal Super Phosphate
Triple Super Phosphate
Mono-Ammonium Phosphate
Oi-Ammonium Phosphate
N-P-K Fertilizers
Suspended Biological
System
solids separation +
neutralization
Fixed Biological
System
sol ids separation
+ neutralization
Independent Physical-Chemical
System
solids separation +
neutralizat ion
o
¦
¦vl
I
Ammoni a
Ammonium Nitrate
Urea
Anmonium Sulfate
neutraIizat i on
oil separation
neutralization
neutra? ization +
oil separation
neutrali zat ion
neutrali zat i on
oi 1 separat ion
neutralization
-------
Tab 1e 0-18-1
Wastewater Characteristics
Electric and Steam Generation
Characteristi c
Industry Operation
F 1 ow
BOD
TSS
TD5
COD
Grit
Cyani de
Chlorine Demand
pH
Col or
Turbidi ty
Explosive Chemicals
Di ssolved Gases
Detergents
Foami ng
Heavy Metals
Colloi dal Soli ds
Vol ati1e 0rgani cs
Pest i ci des
Phosphorus
N i t rogen
Tempe ratu re
Phenol
Su 1 f.i de
Oi 1 and Grease
Coliform (Total)
Year-Round
INTERMITTENT
Low
Low
Hi gh
1
Low
Low
Present'
Low
ACIDIC-ALKALINE
Low
Low
Absent
Absent
Present
Present
PRESENT
Absent
Present
Absent
DEFICIENT
DEFICIENT
HIGH
Present'
Absent
J
Present
Absent
1Cyanide 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.
D-11-k
-------
Table D-18-2
Pretreatment Unit Operations for the Electric and Steam Generation Industry
Suspended Biological System
Equalization (cooling) +
Neutralization + Chemical
Precipitation (heavy
metals) + Cyanide
Oxi dati on
Independent Physical-
Fixed Biological System Chemical System
Equalization (cooling)
+ Neutralization +
Chemical Precipitation
(heavy metals) +
Cyanide Oxidation
Equaliation (cooling)
+ Neutralization +
Chemical Precipitation
(heavy metals) +
Cyanide Oxidation
-------
Table D-19-1
Wastewater Characteristics
Monferrous Metals - Aim mum
Bauxite Refining
Direct Chill Ingot Coating
and Foundry Rolling,
Characteri sties
Primary Smelt i nq
Drawinq and Extrudinq
1ndust ry Operat ion
Year-round
Year-round
F 1 ow
Cont i nuous
Cont inuous
BOD
Low
Low
TSS
HIGH
HIGH
TDS
Low
Low-Ave rage
COD
Low .
Low
Grit
present'
Absent
Cyan ide
Present
Absent
Chlorine Demand
Low
Low
pH
Neutral
NEUTRAL-AC ID
Col or
H i gh
Ave rage
Turb id i ty
H i gh
Ave rage
Explosive Chemicals
Absent _
Absent .
Dissolved Gases
PRESENT
PRESENT
Detergents
Absent
Absent
Heavy Metals
Present
Absent
Col 1oi da 1 Solids
Absent
Absent
Volatile Organics
Absent
Absent
Pest ic ides
Absent
Absent
Phosphorus
DEFICIENT
Deficient-Adequate
N i t rogen
DEFICIENT
DEFICIENT
Temperature
Normal-HIGH
Norma 1 —H1GH
Phenol
Absent
Absent
Sulfide
Absent
Absent r
Oi 1 and Grease
Present
Present
Col i form (Tota 1)
Absent
Absent
Present in bauxite refining wastewater.
Fluorine is generally present in scrubber water.
Chlorine is present in casting, foundry, and secondary smelting
scrubber waters.
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
-------
Table D-19-2
Pretreatment Unit Operations for the Aluminum Industry
Pretreatment
G roup
Bauxite Refining
Primary Smelting
Suspended Biological
System
solids sepa rat i on
F i xed B i olog i ca1
System
Independent Physical
Chemical System
sol i ds sepa rat ion
solids separation
Direct Chill Ingot
Casting and Foundry
Rol1ing, Drawing,
Foundry Extruding
Secondary Smelting
o 11 sepa rat ion +
neut ra1i zat ion +
chemical precipita-
tion (phosphate re-
mova 1)
oi1 separat ion +
neut ra1i zat i on +
chemical precipi-
tation (phosphate
remova1)
oi1 separat i on +
neut ra1i zat i on +
chemical precipi-
tation (phosphate
remova1)
-------
Table D-20-1
Wastewater Characteristics
Glass, Cement, Lime, Concrete Products.
Asbestos and Gypsum Products
Flat
Cement
Concrete
Asbestos
Character! st ic
Glass
Mi rrors
6- L ime
Products
S- Gypsum
Industry Operation
Year-round
Year-round
Yea r-round
Year-round
Year-round
F1 ow
Cont i nuous
Cunt i nuous
Cont i nuous
Cont i nuous
Cont i nuous
BOD
Low
Low
Low
Low
Low
TSS
Low-HIGH
HIGH
HIGH
low-high
Low-HIGH
TDS
Low-H1GH
HIGH
HIGH
LOW-HIGH
No data
COD
Low
Low
Low
Low
Low
Grit
PRESENT
PRESENT
Absent
PRESENT
Absent
Cyan i de
Absent
Absent
Absent
Absent
Absent
Chlorine Demand
No Data
f'o Data
No Data
No Data
No Data
pH
Neutral
ALKALINE
ALKALINE
ALKALINE
Neutral
Col or
Absent
Absent
Absent
Absent
Absent
Turb id i ty
P resent
Present
Present
Present
Present
Explosive Chemicals
Absent
Absent
Absent
Absent
Absent
Dissolved Gases
Absent
Absent
Absent
Absent
Absent
Dete rgents
PRESENT
PRESENT
PRESENT
PRESENT
PRESENT
Foam i ng
Absent
Absent
Absent
Absent
Absent
Heavy Metals
Absent
Present
Absent
Absent
Absent
Colloidal Sol ids
PRESENT
PRESENT
PRESENT
PRESENT
PRESENT
Vol at ile Organ ics
Absent
Absent
Absent
Absent
Absent
Pesticides
Absent
Absent
Absent
Absent
Absent
Phosphorus
PRESENT
PRESENT
DEFICIENT
DEFICIENT
DEFICIENT
N i t rogen
DEFIC1|NT
DEFIC1|NT
DEFICIENT
DEFICIENT
DEFICIENT
Temperature
Norma 1
Normal
Normal-High
Norma 1
Norma 1-HIgh
Phenol
Absent
Absent
Absent
Absent
Absent
Sulf i de
Absent.
Absent
Absent
Absent
Absent
0 i 1 and G rease
absent'
Absent
Absent
Absent
Absent
Col iform (Total)
Absent
Absent
Absent
Absent
Absent
1 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
-------
Table D-20-2
Pretreatment Unit Operations for the
Glass. Cement. Lime. Concrete Products. Asbestos, and Gypsum Products Industry
Pretreatmerit Group
Flat Glass
Mi rrors
Cement & Lime
Concrete Products
Suspended Biological System
grit remova1 +
sol ids separation
grit removaI +
neutrali zat ion
+ chemical precipitation
(heavy meta1s)
neutralization
grit remova1 +
neutralization
Fixed Biological System
grit remova1 +
sol ids sepa rat i on
grit remova1 +
neutrali zat i on
+ chemical precipitation
(heavy metals)
neut ra1izat ion
grit remova1 +
neutrali zat ion
Independent Physical
Chemical System
grit remova1 +
sol ids sepa rat i on
grit remova1 +
neutralizat ion
+ chemical precipitation
(heavy metals)
neutralizat ion
grit remova1 +
neutralizat ion
Asbestos 6 Gypsum Products
solids separation
solids separation
solids separation
-------
Table D-2 1-1
Was tewater Charac teri st i cs
Inorganic Chemicals
C harjcte r i s t i c
Ca 1 c i urn Carb i d->
Sodium Chloride
Sodium Tripoly-
phosphate
C h 1 o r i n e ,
Etc.
Hydrogen Peroxide
Sodium Dichromate
Sod i uni Su 1 f a te
A1umi num
Chloride,
Etc.
Industry Operation
Y ear-Round
Year-Round
Yea r-Round
Year-Round
F 1 ' >¦. !
Cont i nuous
Con ti nuous
Con t i nuou s
Cont i nuous
BOD
Low
Low
Low
Low
T jS
No Data
No Data
No Data
No Data
TDS
AVENGE1
HIGH
HIGH
HIGH
COD
Low
Low
Low
Low
Grit
Absent
Absen t
Ab:.en L
Absent
Cyan i de
Absent
Absen t
PRESENT2
Absen t
Chlorine Demand
Low
Low
Low
Low
p H
N -u tra 1
ACID-BASIC
ACID-BASIC
ACID-BASIC
Co 1 or
No Data
No Data
No Data
No Data
T u r b i d i t y
No Data
No Data
No Data
No Data
Exp 1os i ve Chemi ca1s
Absen t
Absen t
Absent
Absent
Dissolved Gases
Absent
Absent
Absent
Absen t
I) ;t erqents
Abs> nt
Absent
Absent
Absen t
Foam i ng
No Data
No Data
No Data
No Data
Heavy Metals
Absen t
PRESENT3
PRESENT
Absent
Colloidal Sol i ds
Vo1 a t i 1 e Organ i cs
P is t i c i des
Phosphorus
N i t rogen
Temperature
ph?no1
Su1' i de
0i ' and Grease
Co Ii:orm (Tota1)
Absen t
Absent
DEF I C I ENT^
DEFICIENT
Norma 1-h i gh
No Data
No Data
Absent
No Data
Absen t
Absen t
DEFICIENT
DEFICIENT
Norma 1-h i gh
No Data
No Data
Absent
No Data
Absent
Absent
DEFICIENT
DEFICIENT
Norma 1 -hi gh
No Data
No Data
Absent
No Data
Absent
Absen t
DU" I C ! ENT
Dl! : r ENT
Normai-high
No Data
No Data
Absent
No Data
Mad wastes have high salt concentrations.
-1
Cyanide generated by electrolytic process for hydrogen peroxide.
3
Downs cell Drocess for chlorine doesn't generate heavy metals.
'I
S;dium Triphosphate Wastewater will have very high phosphate concentration (*z2000 mg/1)
Characteristics which may require pretreatment or are significant to joint treatment
D-17-10
plant design are shown in UPPER CASE.
-------
Table D-21-2
Pretreatment Unit Operations for the Inorganic Chemicals Industry
Pretreatment
Group
Calcium Carbide
Sodium Chloride
Sodium Tripolyphosphate
Chlori ne
Sodium Hydroxide
Potassium Hydroxide
Sodium Metal
Hydrochloric Acid
Hyd rogen Pe rox i de
Sodium Dichromate
Sodium Sulfate
VJ
J^Aluminum Chloride
— Aluminum Sulfate
Hydrofluoric Acid
Nitric Acid
Sodium Bicarbonate
Sodiun Si 1icate
Sodium Sulfite
Sulfuric Acid
Sodium Carbonate
Suspended Biological
System
pretreatment not
requi red
Fixed Biological
System
pretreatment not
requi red
Independent Physical-
Chemical System
pretreatment not
requ i red
reutralization +
chemical precipitation
{heavy metals)
+ equalization
neutrali zation +
chemical precipitation
(heavy metals)
+ equali zation
neut ra!i zat ion +
chemical precipitation
(heavy fnetals)
neutali zation +
chemical precipitation
(heavy metals)
neutralization
neut ra1i zat i on +
chemical precipitation
(heavy metals)
neutralization
r.eutra 1 i zat i on +
chemical precipitation
(heavy metals)
neut ra1i zat i on
-------
Table 0-22-1
Wastewater Characteristics
Industrial Gases
Character i st i c
Industry Operation
Flow
BOD
rss
TDS
COD
Grit
Cyani de
Chlorine Demand
prl
Color
Turbi dity
Explosive Chemicals
Disc, 'i .fed Gases
Detergents
Foam i ng
Heavy Metals
Colloida1 Sol ids
Vo1 at i1e Organ i cs
Pes t ic ides
Phosphorus
Ni trogen
Temperature
Phe ol
Sulf i de
OiI and Grease
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