DRAFT DEVELOPMENT DOCUMENT
for the
ELECTRICAL AND ELECTRONIC COMPONENTS
POINT SOURCE CATEGORY
Douglas M. Costle
Administrator
Eckardt C. Beck
Assistant Administrator
for Water and Waste Management
Steven Schatzow
Deputy Assistant Administrator
for Water Planning and Standards
Robert B. Schaffer
Director, Effluent Guidelines Division
G. Edward Stigall
Chief, Inorganic Chemicals Branch
Richard J. Kinch
Senior Project Officer
Frank H. Hund
Project Officer
October , 1980
Effluent Guidelines Division
Office of Water and Waste Management
U.S. Environmental Protection Agency
Washington, D. C. 20460
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TABLE OF CONTENTS
SECTION TITLE
I CONCLUSIONS AND SUMMARY
II RECOMMENDATIONS
III INTRODUCTION
IV SUBCATEGORIZATION
V DRY PRODUCTS SUBCATEGORY
Switchgear and Fuses
Resistance Heaters
Ferrite Electronic Parts
Motors and Generators
Fuel Cells
Alternators
Insulated Wire and Cuble,
Non-Ferrous
VI CARBON AND GRAPHITE PRODUCTS
Products i
Size of Industry
Manufacturing Processes
Materials
Water Usage
Production Normalizing Parameters
Waste Characterization and
Treatment-In-Place
Potential Polluant Parameters
Applicable Treatment Technologies
Benefit Analysis
VII DIELECTRIC MATERIALS SUBCATEGORY
Products
Size of Industry
Manufacturing Processes
Materials
Water Usage
Production Normalizing Parameters
Waste Characterization and
Treatment-In-Place
Potential Pollutant Parameters
Applicable Treatment Technologies
Benefit Analysis
III-l
IV-1
V-l
V-l
V-2
V-4
V-6
V-8
V-10
V-l 2
VI-1
VI-2
VI-4
VI-6
VI-9
VI-11
VI-13
VI-36
VI-43
VI-48
VII-1
VII-5
VII-6
VII-11
VII-16
VII-19
VII-22
VII-42
VII-42
VII-63
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TABLE OF CONTENTS
(Continued ]f
SECTION
VIII
IX
X
TITLE
ELECTRIC LAMP SUBCATEGORY
Products
Size of the Industry
Manufacturing Processes
Materials
Water Usage
Production Normalizing Parameters
Waste Characterization and
Treatment-In-Place
Potential Pollutant Parameters
Applicable Treatment Technologies
Benefit Analysis
ELECTRON TUBE SUBCATEGORY
Products
Size of the Industry
Manufacturing Processes
Materials
Water Usage
Production Normalizing Parameters
Waste Characterization and
Treatment-In-Place
Potential Pollutant Parameters
Applicable Treatment Technologies
Benefit Analysis
SEMICONDUCTOR SUBCATEGORY
Products
Size of the Industry
Manufacturing Processes
Materials
Water Usage
Production Normalizing Parameters
Waste Characterization and
Treatment-In-Place
Potential Pollutant Parameters
Applicable Treatment Technologies
Benefit Analysis
PAGE
VIII-1
VIII-3
VIII-5
VIII-16
VIII-19
VIII-20
VIII-24
VIII-59
VIII-67
VIII-77
IX-1
IX-6
IX-7
IX-13
IX-15
IX-15
IX-18
IX-68
IX-77
IX-93
X-l
X-2
X-3
X-9
X-13
X-l 5
X-16
X-87
X-88
X-97
11
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TABLE OF CONTENTS
(Continued)
SECTION TITLE PAGE
XI CAPACITOR SUBCATEGORY
Products XI-1
Size of the Industry XI-3
Manufacturing Processes XI-3
Materials XI-17
Water Usage XI-18
Production Normalizing Parameters XI-18
Waste Characterization and XI-22
Treatment-In-Place
Potential Pollutant Parameters XI-46
Applicable Treatment Technologies XI-47
Benefit Analysis XI-67
XII CONTROL AND TREATMENT TECHNOLOGY
Introduction XII-1
Transfer of Performance XII-3
Individual Treatment Technologies XII-68
In-Process Treatment Techniques XII-128
XIII COST OF WASTEWATER CONTROL AND TREATMENT
Introduction XIII-1
Cost Estimation Methodology XIII-1
Cost Estimates for Individual XIII-15
Treatment Technologies
Energy and Non-Water Quality Aspects XIII-56
XIV ACKNOWLEDGEMENTS XIV-1
XV REFERENCES XV-1
XVI GLOSSARY XVI-1
iii
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SECTION I
TO BE PREPARED BY EPA
1-1
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SECTION III
INTRODUCTION
GUIDELINE DEVELOPMENT SUMMARY
The Electrical and Electronic Components (E&EC) Category is des-
cribed in terras of the Standard Industrial Classifications
(SIC's) as defined in Table 3-1. This document encompasses the
following E&EC product areas:
Carbon and Graphite .
Switchgear and Fuses
Resistance Heaters
Incandescent Lamps
Fluorescent Lamps
Electron Tubes
Cathode and TV Tubes
Insulators - Mica
Insulators - Plastic and Laminates
. Capacitors
Semiconductors (Simple)
Semiconductors (Complex)
Electric and Electronic Components
Wet Transformers
Effluent guidelines for the E&EC Category were developed from
data obtained from previous EPA studies, literature searches,
and plant surveys and evaluations. Initially, all existing
information from EPA records and available literature was re-
viewed to determine the production processes performed, raw
materials utilized, wastewater treatment practices, water uses
and wastewater characteristics. In addition to providing a
description of the E&EC Category, this existing information
also identified both the need to acquire additional information
and potential plants to contact for this information.
Approximately 160 plants were contacted by phone and letters to
obtain additional data on the E&EC Category. Thirty-nine of
these plants were visited for an on-site study of their manu-
facturing processes, water use and wastewater treatment. In
addition, wastewater samples were collected at twenty-four of
the visited plants. Sampling was utilized to determine the
source and quantity of pollutants in the raw process wastewater
and Jbreated effluent from a cross-section of plants in the E&EC
Category.
Utilizing both existing data and sampling data collected during
this study, the wastewater characteristics of the E&EC Category
were assessed to determine possible uniformity from plant to
plant and thus the applicability of one set of discharge stan-
dards. Since the discharge characteristics of all plants in the
III-l
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TABLE 3-1
E&EC CATEGORY
SIC 3612 - Power, Distribution, and Specialty Transformers
SIC 3613 - Switchgear and Switchboard Apparatus
SIC 3621 - Motors and Generators
SIC 3622 - Industrial Controls
SIC 3623 - Welding Apparatus, Electric
SIC 3624 - Carbon and Graphite Products
SIC 3629 - Electrical Industrial Apparatus, Not Elsewhere
Classified
SIC 3631 - Household Cooking Equipment
SIC 3632 - Household Refrigerators and Home and Farm Freezers
SIC 3633 - Household Laundry Equipment
SIC 3634 - Electric Housewares and Fans
SIC 3635 - Household Vacuum Cleaners
SIC 3639 - Household Appliances, Not Elsewhere Classified
SIC 3641 - Electric Lamps
SIC 3643 - Current-Carrying Wiring Devices
SIC 3644 - Noncurrent-Carrying Wiring Devices
SIC 3645 - Residential Electric Lighting Fixtures
SIC 3646 - Commercial, Industrial, and Institutional Electric
Lighting Fixtures
SIC 3647 - Vehicular Lighting Equipment
SIC 3648 - Lighting Equipment, Not Elsewhere Classified
SIC 3651 - Radio and Television Receiving Sets, Except
Communication Types
SIC 3652 - Phonograph Records and Pre-recorded Magnetic Tape
SIC 3661 - Telephone and Telegraph Apparatus
SIC 3662 - Radio and Television Transmitting, Signaling, and
Detection Equipment and Apparatus
Radio and Television Receiving Type Electron Tubes,
Except Cathode Ray
SIC 3672 - Cathode Ray Television Picture Tubes
SIC 3673 - Transmitting, Industrial, and Special Purpose
Electron Tubes
SIC 3674 - Semiconductors and Related Devices
SIC 3675 - Electronic Capacitors
SIC 3676 - Resistors, for Electronic Applications
SIC 3677 - Electronic Coils, Transformer and Other Inductors
SIC 3678 - Connectors, for Electronic Applications
SIC 3679 - Electronic Components, Not Elsewhere Classified
SIC 3693 - Radiographic X-Ray, Fluoroscopic X-Ray, Therapeutic
X-Ray, and Other X-Ray Apparatus and Tubes; Electro-
medical and Electrotherapeutic Apparatus
SIC 3694 - Electrical Equipment for Internal Combustion Engines
SIC 3699 - Electrical Machinery, Equipment, and Supplies, Not
Elsewhere Classified
SIC 3671 -
III-2
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data base were not uniform, it was necessary to establish sub-
categories for which the wastewater characteristics of each
subcategory were uniform. The initial subcategorization of the
E&EC Category was made by product type as follows:
Transformers
Switchgear and Fuses
Carbon and Graphite
Resistance Heaters
Electric Lamps
Insulators
Electron Tubes
Semiconductors
Capacitors .
The manufacturing processes associated with some products in the
above areas do not generate wastewaters. In addition, the manu-
facturing processes of some products are already covered by
existing regulations (for example metal finishing). Therefore,
the initial approach to subcategorization was modified to a
combined product/manufacturing process basis. This modified
approach encompasses only those products and manufacturing
processes unique to the E&EC Category where wastewater is
generated. This modification resulted in the establishment of
the following subcategories for which,effluent limitations are
required:
Dielectric Materials
Carbon and Graphite Products
Electric Lamps
Picture Tubes
Semiconductors
Capacitors
Further subdivision of the subcategories may be required to
account for variations in wastewater characteristics requiring
treatment resulting from different basis materials, production
processes, product types and their attendant wastewater
characteristics.
Once the subcategorization approach was established, all of the
data collected were analyzed to determine wastewater generation
and raw waste characteristics for each subcategory. In addition,
the full range of control and treatment technologies existing
within the E&EC Category was identified. This technology
review was accomplished by considering the pollutants to be
treated and the chemical, physical and biological characteristics
of these pollutants. Special attention v/as paid to in-process
technology such as the recovery and reuse of process solutions,
the recycle or reuse of process water and the curtailment of
water use.
III-3
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The information as outlined above was then evaluated in order to
determine applicable treatment technology for each subcategory.
In evaluating these technologies, various factors were con-
sidered. These included demonstrated performance, the total
cost of application of the technology in relation to the pollu-
tant reduction benefits to be achieved, the age of equipment
and facilities involved, the processes employed, the engineering
aspects of the application of various types of control tech-
niques, process changes, and non-water quality environmental
impact (including energy requirements).
Sources of Industry Data
Data on the E&EC Category were gathered from literature
studies, contacts with EPA regional offices, previous industry
studies by the EPA, plant surveys and evaluations, and inquiries
to waste treatment equipment manufacturers. These data sources
are discussed below.
Literature Study - Published literature in the form of books,
reports, papers, periodicals, promotional materials, Dun and
Bradstreet surveys and Department of Commerce Statistics was
examined; the most informative sources are listed in Section
XIII. The researched material included product descriptions
and uses, manufacturing processes utilized, raw materials con-
sumed, waste treatment technology and the overall characteristics
of plants in the E&EC Category concerning number of plants,
employment levels and production.
EPA Regional Office Contacts - All 10 EPA regional offices were
telephoned for assistance in identifying E&EC plants in their
respective regions.
EPA Studies - A previous preliminary and unpublished EPA study
of the E&EC Category was reviewed. This information included
sampling data from nine plants, visit trip reports from 21
plants, and data from phone surveys of 81 E&EC plants. Visit
trip report and survey data included information on products
manufactured, manufacturing processes performed, water use, and
wastewater treatment for each plant. A summary of these visits
and phone contacts is presented in Table 3-2 for each E&EC
product area. The only stream data available from these previous
EPA studies came from sampling visits to nine plants.
Plant Survey and Evaluation - Three types of data collection were
used to supplement available information pertaining to facilities
in the E&EC Category. First, approximately 160 plants were
contacted by phone and/or letter to obtain basic information re-
garding products, manufacturing processes performed, wastewater
generation and waste treatment. Second, based upon this in-
formation, 39 plants were visited to view their operations and
discuss their products, manufacturing processes, water use and
wastewater treatment. Finally, 24 plants were selected for
III-4
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sampling visits to determine the pollutant characteristics of their
wastewater. Table 3-3 summarizes these plant contacts for each
E&EC product area.
The sampling program at each plant consisted of up to three days
of sampling. Prior to any sampling visit all available dataf such
as layouts and diagrams of the selected plant's production processes
and waste treatment facilities, were reviewed. In most cases, a
visit to the plant to be sampled was made prior to thev actual
sampling visit to finalize the sampling approach. Representative
sample points were then selected. Finally, before conducting a:
visit, a detailed sampling plan showing the selected sample points
and all pertinent sample data to be obtained was generated and
reviewed.
For all sampling, flow proportioned composite samples or the equi-
valent (for batch discharge) were taken over the daily time period
the plant was in operation. Sample points typically included a
total raw waste sample, a final treated effluent sample, and a
sample of a particular process step that was of interest. For
example, a typical semiconductor sampling visit included samples
of the final effluent, total raw waste, and wet air scrubber
discharge streams.
All of the samples collected were kept on ice throughout each day
of sampling. At the end of the sampling day, the composite
samples were divided into several bottles and preserved according
to EPA protocol.
All samples were subjected to three levels of analysis depending
on the stability of the parameters to be analyzed. On-site
analysis, performed by the sampler at the facility, determined
flow rate, pH, and temperature. Five liters of water from each
sample point for each sampling day were delivered to a laboratory
in the vicinity of the subject plant and analyzed for total
cyanide, fluoride, total organic carbon, biological oxygen demand,
oil and grease, phenols, and total suspended solids. This analysis
was performed by these local laboratories within 24 hours after
each sample was collected. Because of the sensitive nature of
the cyanide and phenols analysis procedures, a quality assurance
questionnaire was completed by all laboratories performing this
analysis.
III-5
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TABLE 3-2
SUMMARY OF PREVIOUS EPA E & EC CATEGORY
CONTACTS
Product Area
Phone Contact
Resistance Heaters -
Switchgear & Puses 10
Transformers 5
Insulators 15
Electron Tubes 14
Carbon & Graphite Products 13
Semiconductors 10
Capacitors 5
Electric Lamps 9
Totals
81
Plant Visit Data Sample Data
1
1
3
1
5
5
5
IT
1
3
2
2
III-6
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TABLE 3-3
PLANT SURVEY & EVALOATION SUMMARY
Product Area
Transformers
Switchgear
and Fuses
Carbon and
Graphite
Resistance
Heaters
Electric Lamps
Insulators
Electron Tubes
Semiconductors
Capacitors
Totals
Phone Contact
25
14
5
2
23
18
12
41
23
163
Plant Visit Data
4
Sample Data
1
6
1
5
10
8
3?
4
1
2
9
4
I?
III-7
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The remainder of the composite samples collected each day were
analyzed by an IFB organics laboratory and an IPS metals laboratory,
These two laboratories were selected by the Sample Control Center
prior to the plant visit, ail organic samples were shipped on ice
to the organics laboratory daily, and all metals samples were
shipped at the end of the sampling visit. Analyses performed
at the IPS laboratories were in accordance with EPA protocol.
Waste Treatment Equipment Manufacturers - Various manufacturers
of waste treatment equipment were contacted by phone or visited
to obtain cost and performance data on specific technologies.
Information collected was based both on manufacturer's research
and on in-situ operation at plants that were not E&EC manufacturers
but had similar wastewater characteristics of primarily heavy
metals wastes.
UTILIZATION OF INDUSTRY DATA
Data collected from the previously described sources are used
throughout this report in the development of a base for limitations
and standards for each E&EC subcategory. Previous EPA studies,
the literature, and plant visits provided the information used to
describe the E&EC Category in terms of its products as presented
later in this section. This same information also provided the
basis for the subcategorization approach discussed in Section IV.
Raw wastewater characteristics and effluent data presented for
each subcategory in Section VI through XI were obtained from
previous EPA sampling data as well as sampling conducted .during
this study. Based on these sampling data, pollutant parameters
requiring control in each subcategory were selected and are
presented in Sections VI through XI for each subcategory.
Applicable treatment technologies for control of these pollutants
are also presented in Section XII. The applicability of each
technology is supported by its use in the E&EC Category as well as
data from treatment manufacturers or its use in other industries
with similar wastes. The cost and performance of treatment
(both individual technologies and systems) are also presented in
Section XIII for each subcategory. These costs are based
primarily on data from equipment manufacturers. Specific systems
for each subcategory are detailed in the individual subcategory
presentations (Sections VI through XI). Actual performance based
on sampling data and performance of observed treatment based
on data from many industrial areas with similar wastes and
treatment are also presented.
XII-8
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SECTION IV
INDUSTRY SUBCATEGORIZATION
INTRODUCTION
The purpose of industry subcategorization is to establish group-
ings within the Electrical and Electronic Components (E&EC)
Point Source Category such that each group has a uniform set of
effluent limitations. Subcategorization should be based on raw
waste characteristics and the factors that affect the raw waste
characteristics of a plant. Thus, if the raw wastewater
characteristics for plants within a group are similar, a uniform
effluent will result for a given wastewater treatment system for
that group. Such a group is designated as a subcategory. This
section presents the subcategories and discusses the factors
considered as a basis for E&EC subcategorization.
Due to the breadth of the E&EC Category and the wide variety of
products manufcictured, subcategorization of the electrical and
electronic components is approached in three stages:
1. Identify the various product areas encompassed
by the E&EC Category. (Reference Table 3-1)
2. Identify those products using no wet processes
in their manufacture and those products using
wet processes that are covered by existing or
projected regulations governing other point
source categories.
3. Identify those products using wet processes that
are unique to the manufacture of E&EC products
and are not covered by existing or proposed
regulations. This latter group of products will
be further investigated to establish a final set
of subcategories, each of which has a uniform
set of wastewater characteristics.
Several products may be excluded from this study because there is
no wastewater generated in their manufacture or the wastewater
produced is covered by other point source categories. Table 4-1
presents the products that will be excluded from this document
because their manufacture is dry. Products covered under other point
source categories are discussed in more detail in Section V of this
document and are also listed in Table 4-1.
Deleting those products whose manufacture does not utilize
manufacturing process water unique to E&EC manufacturing
results in the establishment of the following subcategories:
1V-1
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TABLE 4-1
E&EC PRODUCTS
USING DRY PROCESSES OR NON-UNIQUE WET PROCESSES
Products whose manufacture uses only dry processes
Product
Capacitors; non metal case, paper, film or
metallized film dielectric
Incandescent lamps
Reflector lamps
Metal vapor lamps using glass envelopes
Photoflash lamps
Insulators, epoxy and phenolic
Products using wet processes addressed by other
Point Source Categories
Transformer (dry)
Switchgear
Carbon and graphite brushplates
Resistance heaters stove/oven burner units
Small electric appliance
Rigid, encased heaters
Flexible heaters
Bare wire heaters
Electric comfort heaters
IV-2
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TABLE 4-1 Con't
E&EC PRODUCTS
USING DRY PROCESS OR NON-UNIQUE WET PROCESSES
Product
2. Con't
Other flexible heaters strips, bands, cables ,
Paper film or metallized film dielectric
Household cooking equipment
Electric motors and generators
Industrial controls
Welding apparatus
Household refrigerators and freezers
Household laundry equipment
Electric housewares and fans
Household vacuum cleaners
Current carrying wiring devices
Non-current carrying wiring devices "._ i
' •- ' )
Residential commercial, industrial, and institutional
electric lighting fixtures
Vehicular lighting equipment
Phonograph records and prerecorded magnetic tape
Telephone and telegraph apparatus
x-ray tubes and equipment
Electrical equipment for internal combustion engines
Electrical equipment, machinery, and supplies not else-
where classified
IV-3
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Carbon and Graphite Products
Dielectric Materials
Electric Lamps
Electron Tubes
Semiconductors
Capacitors
SUBCATEGORIZATION DEVELOPMENT
A study of the E&EC Category indicates that more than one subcategory
is required because of the variety of wastewater characteristics
generated by the manufacture of the different product types. The
remainder of this section describes the subcategorization of E&EC
products to establish groupings such that each group has a uniform
set of wastewater characteristics.
After considering the nature of the E&EC products, the follow-
ing subcategorization bases were considered plausible:
1.
2.
3.
4.
5.
6.
Products
Products
Manufacturing Processes
Raw or Process Materials Used
Size of Plant
Age of Plant
Geographic Location
A review of each of these factors reveals that product type is
the principal factor affecting the wastewater characteristics of
plants within the E&EC Category. Product type determines both
the raw and process material requirements and the number and type
of manufacturing processes used. Groups of products using the same
wet processes produce wastewater with similar characteristics. The
different products vary widely in wet manufacturing processes
used, and this results in major differences in the wastewater
characteristics associated with each product. The major source
of wastewater results from clean-up and rinsing activities
associated with each of these manufacturing processes. A product
subcategorization results in the following nine subcategories:
1. Transformers
Two types are manufactured, wet (filled
with dielectric fluid) and dry.
Both types use standard metal working
and metal finishing processes covered
by the Metal Finishing Category.
Wet processes unique to the product are
detergent dielectric fluid clean up and
management of residual PCB fluids.
IV-4
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Switchgear &
Fuses
Carbon &
Graphite
4. Resistance
Heaters
5. Electric Lamps -
All types use processes included in the
metal finishing and plastics processing
categories«
All wet processes used in the manu-
facture of switchgear and fuses are
addressed by the Metal Finishing
Category.
Products range from contacts and motor
brushes weighing ounces to metallurgical
electrodes weighing several tons.
Wet processes unique to the product are
extrusion and impregnation quenches used
at some plants manufacturing large
products. Some plants also use contact
water in carbon machining and wet air
scrubber processes.
Three types of resistance heaters are
made; rigid encased elements used for
electric stoves and ovens, bare wire
heaters used in toasters and hair
dryers, and insulated flexible heater
wire that is incorporated into blankets
and heating pads.
All wet processes used in the manu-
facture of resistance heaters are in-
cluded in the Metal Finishing Category.
Five major product types are manufac-
tured: incandescents, flash bulbs,
fluorescents, glow lamps, and lamp
parts.
Incandescent and flash bulb manufacture
use dry processes only.
Fluorescent lamp manufacture uses a wet
glass washing process. In addition, a
few plants use a wet process to apply
phosphors.
Neon glow lamps use a lead cleaning pro-
cess using an acid cleaner and its sub-
sequent water rinses which are covered
by the Metal Finishing Category. Some
quartz envelope vapor lamps receive a
final cleaning using an acid process.
IV-5
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6.
Dielectric
Materials
7. Electron Tubes -
8. Semiconductors -
Manufacture of lamp bases uses wet,
processes addressed by the Metal Finish-
ing Category.
Filament manufacture uses
a unique wet process to dissolve the
mandrels on which filaments are wound.
Three types of non-glass and non-
ceramic insulators are used: mica,
epoxy, and phenolic.
Epoxy and phenolic insulators use no
wet processes.
Mica insulation manufacture is analogous
to paper making and uses a wet process
unique to the product.
Four basic types of electron tubes are
produced: TV and cathode ray picture
tubes, receiving tubes, power tubes,
and light sensing tubes.
Receiving, power, and light sensing
tube manufacture uses' wet processes al-
ready addressed by the Metal Finishing
Category.
TV and cathode ray picture tube manu-
facture use the same metal finishing
processes as receiving, power, and light
sensing tubes in addition to wet pro-
cesses associated with glass etching,
photolithography, and phosphor
deposition.
The industry manufactures many different
types of devices used in electronic
circuitry.
Product types are based on several dif-
ferent material technologies.
Manufacture involves similar processes
for all products. Many wet processes
are used such as wafer cutting and lap-
ping, fume scrubbing associated with
layer generation and doping, deposition
of conducting layers by evaporation,
application and removal of photolitho-
graphic masks, removal of layers by acid
etching, and preparation and use of
deionized water for rinsing.
IV-6
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9. Capacitors - Approximately a dozen type of capa-
citors are manufactured to cover a wide
range of sizes,^operating voltages,
and environments associated with
electric motors, electric power
handling, fluorescent lighting and
electronic equipment.
- The different types require different
materials and processes.
- Some types use all dry manufacturing
processes. These are non-metal case
types using paper, film, or metallized
dielectrics.
- Metal case versions of the above types
may use wet processes in the case
manufacture. These processes are ad-
dressed by the Metal Finishing Category.
- The remaining types use wet processes
unique to the product during the
manufacture of the electrodes and/or
dielectric and during encapsulation.
As can be seen from the above, product subcategorization does
not adequately address differences in raw wastes produced by
some processes within the same subcategory. For example, in
the capacitor industry ceramic capacitors are manufactured .
utilizing the same manufacturing processes as other capacitor
types except for the use of a ball milling operation. This
operation produces wastes that differ from wastes produced by
other capacitor manufacturing. These wastes also require
different treatment technologies for pollutant removal-. For this
reason, two different wastewater treatment systems are required
to treat wastewaters from ceramic ball milling and from capacitor
manufacturing processes excluding ball milling.
Manufacturing Processes
Subcategorization by manufacturing process could adequately de-
fine waste characteristics for the E&EC Category. However,
this subcategorization would be overly complex in determining
the waste loads and effluent limitations due to the number of
processes that exist in this category. In addition, subcate-
gorization on the basis of manufacturing process is not uniquely
suited to define waste characteristics since many operations
generate the same waste constituents.
Subcategorization by both product type and by manufacturing
process is necessary in some instances in the E&EC Category.
IV-7
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This subcategorization basis will account for differences in
raw wastes produced by the subcategory without being overly complex,
This product/manufacturing process subcategorization results in
the following subcategories:
1. Transformers - The only wet processes that is unique
to E&EC are the clean-up and management
of residual dielectric fluid. These
processes will be considered in the
dielectric materials subcategory.
2.
3.
4.
5.
6.
Switchgear and Fuses - (no further subcategorization
is necessary)
Carbon and Graphite - quenching processes
machining processes
Resistance Heaters - (no further subcategorization
is necessary)
Electric Lamps - filament manufacturing
fluorescent lamp manufacturing
Dielectric
Materials
The only wet process that is unique to
E&EC is the manufacture of mica paper
dielectric. Mica paper dielectric
manufacture will be included in the
dielectric materials subcategory.
7. Electron Tubes - electron tube manufacturing
aperture mask manufacturing
8. Semiconductors - (no further subcategorization is necessary)
9. Capacitors - ball milling operations
capacitor manufacture (excluding ball milling)
(Production of some types of capacitors in-
cludes the use of dielectric fluid. This
dielectric fluid use will be included in the
dielectric materials subcategory).
Raw or Process Materials Used
There is a wide variation in basis materials, process materials,
and process chemicals used within this industry, and all waste-
water constituents are a direct result of this material usage.
Therefore, they are intrinsically accounted for since the selec-
ted product subcategories are directly related to the physical
and chemical properties of the raw materials used (e.g., basis
materials/ solvents, process chemicals).
Size of Facility
The nature of the manufacturing processes for the E&EC Category
is the same in all facilities regardless of their size. Size
alone is an insufficient categorization criterion since the
waste characteristics of a plant depend on the raw materials and
the manufacturing processes employed.
IV-8
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Age of Facility
The relative age of plants is important but is not a suitable
basis for categorizing the industry because it does not consider
those items which affect the effluent wastewater discharged. The
age of a plant has no bearing on the resulting wastewater charac-
teristics or the required waste treatment. Therefore, plant age
is an inappropriate basis on which to categorize.
Geographic Location
There is not a basis for subcategorization by geograohic location
alone. Manufacturing processes are not affected by the physical
location of the facility, except for availability of usable
process water. The price of water may affect the amount of
modification to procedures employed in each plant. However,
procedural changes can affect the volume of pollutants discharged
but not the characteristics of the constituents. The waste
treatment components described in Section XII can be utilized in
any geographical area. In the event of a limitation in the
availability of land space for constructing a waste treatment
facility, the in-process controls and rinse water conservation
techniques described in Section XII can be adopted to minimize
the land space required for the end-of-process treatment
facility. Often, a compact package unit can easily handle end-
of-process waste if good in-process techniques are utilized to
conserve raw materials and water.
SUMMARY OF SUBCATEGORIZATION
The subcategorization of the E&EC industry is summarized as
follows:
1.
Subcategorizing raw waste characteristics by product
type for unique water using processes not covered
under other point source categories produces tfie fol-
lowing subcategories: j
Carbon and Graphite Products <
Dielectric Materials
Electric Lamps
Electron Tubes
Semiconductors
Capacitors
IV-9
-------
2. Further subcategorization by manufacturing process pro-
duces the following subdivisions within the subcategories;
Carbon and Graphite Products
Quenching operations
Machining, grinding, scrubbing operations
. Dielectric Materials
Dielectric fluid use
Mica paper dielectric manufacture
. Electric Lamps
Fluorescent lamp manufacture
Filament manufacture
Electron Tubes
Electron tube manufacture
Aperture mask manufacture
. Semiconductors
(no further breakdown is required)
Capacitors
Capacitor manufacturing operations
excluding ball milling
Ceramic ball milling operations
Some manufacturing processes used in the manufacture of E&EC
products are covered under existing or proposed regulations
while other processes used in the manufacture of the same
products are unique to this industry. The discussion of all of
these processes is found in the appropriate product subcategory
sections which follow.
IV-10
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SECTION V
DRY PRODUCTS SOBCATEGORY
INTRODUCTION
The dry products subcategory includes those electrical and
electronic components that do not require manufacturing process
water unique to the E & EC industry. Rather, any process waste-
water results from manufacturing operations in the Metal Finishing
Category. Electronic products considered in this dry products
subcategory are:
Switchgear and Fuses
Resistance Heaters
Ferrite Electronic Parts
Motor and Generators
Fuel Cells
Alternators
Insulated Wire and Cable, Non-ferrous
Sources of information for this subcategory include phone surveys
of plants in the various product areas and literature reviews.
This section includes discussion of the various products, size
of the industry, manufacturing processes and materials used, and
process water usage. A table is presented for each product area
which summarizes the manufacturing processes and basis materials
used.
SWITCHGEAR AND FUSES
Products
The switchgear industry manufactures products used to control
electrical flow and to protect equipment from electrical power
surges and short circuits. The major switchgear products are:
Electrical power distributors, controls, and
metering panel assemblies.
Circuit breakers - Circuit breakers /are automatic
load sensitive switches used to protect equipment
from short circuits and power surges by dis-
connecting the equipment from the power source.
Circuit breakers may be of the arq quenching
(air or gas) or oil filled quenching types.
Relays - Control relays (low voltage), power relays
(high voltage), and magnetically abtuated switches.
V-l
-------
Switches - Manual current controlling devices.
Puses - Electronic current controlling devices.
Unlike circuit breakers, they may be used only once.
Size of Industry
Switchgear manufacture is classified under SIC 3613. It is
estimated that approximately 84,000 production workers are employed
in the manufacture of switchgear and that between 572 and 678 manu-
facturing firms are engaged in this business. The mean
employment level is estimated to be 135 production employees per
plant. Employment levels in the plants contacted range from 35
to 2,500 production employees.
Manufacturing Processes and Materials
Table 5-1 is a listing of switchgear products and typical manu-
facturing processes. This information was gathered from actual
plant visits and phone surveys of 24 switchgear manufacturers.
[ No wet manufacturing processes unique to the manufacture of
I switchgear have been identified. The manufacture of oil-filled
' circuit breakers does not involve wet processing. The use of
I this circuit breakerioil, a petroleum based, naphthenic dielectric
ji fluid, is covered in'the dielectric fluids Section VI of this
; report.
Process Water Usage
All switchgear manufacturing processes involving the use or dis-
charge of process water are metal finishing processes. These
processes and associated water and wastewater are therefore covered
by the Metal Finishing Category Development Document and will not
be discussed further in this report.
RESISTANCE HEATERS !
Products
Resistance heaters convert electrical energy into usable heat
energy,
The major resistance heater products are:
Rigid, metal encased heater elements which are
used in stoves, ovens, and small appliances.
Bare wire heaters which are used in toasters
and space heaters and utilize a wire or
ribbon to 'convert the electrical energy to heat.
V-2
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TABLE 5-1
PROCESSES AND MATERIALS USED IN SWITCHGE^R AND FUSE MANUFACTURE
PRODUCT
Circuit Breakers
Buss Bars
Fuses
Switches
Regulators
(Voltage, Power)
Assemblies
Enclosures
METAL, FINISHING PROCESSES
Chemical Milling, Stamping,
Milling, Molding, Assembly
Chemical Milling, Assembly,
Stamping, Molding, Grinding
Chemical Milling, Electroplat-
ing, Assembly, Milling,
Molding, Soldering, Machining
Conversion Coating, Plating,
Chemical Milling, Milling,
Stamping, Machining, Grinding,
Assembly
Chemical Milling, Electroplat-
ing, Grinding, Welding,
Soldering, Machining,
Polishing, Assembly
Chemical Milling, Electroplat-
ing, Conversion Coating,
Grinding, Welding, Soldering,
Solvent Degreasing, Machining,
Painting, Polishing
Chemical Milling, Electroplat-
ing, Conversion Coating,
Welding, Soldering, Solvent
Degreasing, Machining,
Assembly, Polishing, Grinding
BASIS MATERIALS
Plastic, Steel, Cooper,
Brass, Aluminum,
Nickel, Zinc
Copper, Aluminum, Brass
Copper, Brass, Plastic,
Steel
Steel, Copper, Brass,
Zinc '
Copper, Brass, Steel,
Plastic
Aluminum, Steel, Zinc,
Plastic, Fiberglass
Steel, Aluminum,
Plastic
V-3
-------
Flexible insulated wire heaters which are used
in electrical heating cables, electric heating
pads, and electric blankets.
s- ' ' '
Size of Industry
Resistance heater manufacture consists of portions of SIC 3631,
Household Cooking Equipment and SIC 3634, Electric Housewares
and Pans. It is estimated that approximately 11,000 production
workers are employed in the manufacture of resistance heaters
and that between 154 and 160 plants are engaged in this business.
The mean employment level is estimated to be 71 production employees
per plant. However, review of plant listings indicates that in the
majority of plants, the manufacture of resistance heaters is an
integral part of the manufacture of another finished product. Re-
latively few plants manufacture resistance heaters as their final
product.
Manufacturing Processes and Materials
Table 5-2 is a listing of resistance heater products and typical
manufacturing processes. This information has been gathered from
phone surveys of 10 plants. No manufacturing processes unique to
the manufacture of resistance heaters have been identified.
Process Water Usage
All resistance heater manufacturing processes involving the use or
discharge of process water are metal finishing processes. These
processes and associated water and wastewater are therefore
covered by the Metal Finishing Category Development Document and
will not be discussed further in this report.
FERRITE ELECTRONIC PARTS
Products
The ferrite electronic parts subcategory includes electronic
products utilizing metallic oxides. The metallic oxides have
ferromagnetic properties that offer high resistance, making cur-
rent losses extremely low at high frequencies. Ferrite electronic
products include:
. Magnetic recording tape
Magnetic tape transport heads
. Electronic and aircraft instruments
Microwave connectors and components
. Electronic digital equipment
V-4
-------
TABLE 5-2
PROCESSES AND MATERIALS USED IN RESISTANCE HEATER MANUFACTURE
PRODUCT
Rigid
Heater
Elements
Bare Wire
Heaters
Flexible Insulated
Wire Heaters
METAL FINISHING PROCESS
Plating, Chemical Milling,
Welding, Rolling, Molding,
Swaging, Machining
Plating, Soldering,
Welding
Plating, Descaling,
Machining, Molding, Welding
BASIS MATERIALS
Steel, Nickel, Copper,
Plastic, Insulating
Material, Ceramic
Material
Steel, Nickel, Copper,
Insulating Material
Copper, Steel, Nickel,
Rubber, Plastic,
Insulating Material
V-5
-------
Size of Industry
Perrite electronic parts manufacture is classified under SIC 3679,
It is estimated that 10,000 production workers are employed in
ferrite electronics parts manufacturing. Between 35 and 40
manufacturing firms are engaged in this business. The mean
employment level is estimated to be 270 production employees
per plant.
Manufacturing Processes and Materials
Table 5-3 is a listing of ferrite products and typical manu-
facturing processes. The information presented was gathered
from the literature and a phone survey of 10 facilities.
Process Water Usage
Ferrite manufacturing processes and associated water usage
and wastewater generation are covered in the Metal Finishing
Category Development Document and will not be discussed further
in this report.
MOTOR AND GENERATORS
Products
The motor manufacturing industry produces devices that convert
electric energy into mechanical energy. The generator manufactur-
ing industry produces devices which convert an input mechanical
energy into electrical energy. The major motor and generator
products are:
Electric motors and generators
Motors and generators
Variable speed drives and gear motors
. Fractional horsepower motors
Hermetic motor parts
. Appliance motors
, Special purpose electric motors
Size of Industry
Motor and generator manufacture is classified under SIC 3621. It
is estimated that 75,100 production workers are employed in the
V-6
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TABLE 5-3
PROCESSES AND MATERIALS USED IN
FERRITE ELECTRONIC PARTS MANUFACTURE
PRODUCT
Magnetic Recording
Tape
Magnetic Tape
Transport Heads
Electric and Air-
craft Instruments
Electronic Digital
Equipment, Microwave
Connectors and Com-
ponents
PROCESSES
Shearing, Slitting,
Assembling
Metal Producing,
Welding, Fabrication,
Machining
Forming, Shearing,
Slitting, Fabrica-
tion, Machining
BASIS MATERIAL
Aluminum, Magnesium,
Castings, Stampings
Bronze, Brass,
Aluminum Extrusions,
Epoxies-quartz
Aluminum Reels, Iron
Rods & Bars, Tubing,
Extrusions
V-7
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manufacture of motors and generators. The 1977 Census of
Manufactures lists 448 manufacturers of motors and genera1
tors. The mean employment level is estimated 'to be 170 pro-
duction employees per plant.
Manufacturing Processes and Materials
Table 5-4 is a listing of motor and generator products and typi-
cal manufacturing processes. The information was gathered
from phone surveys of 11 motor and/or generator manufacturers
and from a literature investigation.
Process Water Usage
All motor and generator manufacturing processes involving the
use or discharge of process wastewater are metal finishing pro-
cesses. These processes and associated water usage and waste-
water generation are covered by the Metal Finishing Category
Development Document and will not be discussed further in this
report.
FUEL CELLS
Products
The fuel cell industry manufactures products that are electro-
chemical generators in which the chemical energy from a reaction
of air (oxygen) and a conventional fuel is converted directly
into electricity.
The major fuel cell industry products, basically in research and
development stages, are:
Fuel cells for military applications (Low power
equipment, < 10 kW)
Fuel cells for power supply for vehicles
(Medium power sources, 10 to 150 kW)
Fuel cells used as high power sources,
> 150 kW for:
- railway traction, including shunting engines
- naval propulsion
- power stations, basic and emergency
- space applications
V-8
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TABLE 5-4
PROCESSES AND MATERIALS USED IN MOTOR AND GENERATOR MANUFACTURE
PRODUCT
Appliance Motors
Special Purpose
Electric Motors,
Electric Motors,
Fractional Horse-
power Motors, Her-
metic Motor Parts
Motors and
Generators,
Variable Speed
Drivers and Gear
Motors
PROCESSES
Casting, Forging, Stamp-
ing, Blanking, Drawing,
Shearing, Slitting,
Welding, Heat Treating,
Surface Fnishing,
Assembly, Machining
Casting, Stamping,
Blanking, Drawing, Shear-
ing, Slitting, Forming,
Welding, Machining, Heat
Treating, Assembly
Die Casting, Stamping,
Blanking, Drawing,
Shearing, Welding,
Machining, Heat Treat-
ing, Surface Finishing,
Assembly
Casting, Stamping,
Blanking, Drawing,
Shearing, Slitting,
Machining, Assembly
BASIS MATERIALS
Carbon Steel Alloys
and Tool Steel,
Copper Wire, Aluminum,
Iron Sheets
Carbon Steel Sheets,
Rods, Bars, Strips,
Coils, Stainless Steel
Rods and Bars, Copper
Wire
Aluminum Casting Sheets,
Iron Castings, Steel
Plates, Slabs, Rods,
Bars, Carbon Steel Rods,
Bars, Strips, and Coil
Carbon Steel Sheets,
Rods and Bars
V-9
-------
Low temperature - low pressure fuel cells with
carbon electrodes
Size of Industry
The fuel cell industry is classified under SIC 3674 (Solid State
Fuel Cells) and SIC 3629 (Electrochemical Generators). It is
estimated that 1000 to 5000 production workers are employed
in the manufacture of fuel cells under SIC 3629. The number
of employees under SIC 3674 is unavailable. Between 5 and 10
manufacturing firms are engaged in the production of fuel cells.
The mean employment level is estimated to be 500 production
employees per plant.
Manufacturing Processes and Materials
Table 5-5 is a listing of fuel cell products and typical manu-
facturing processes. The information presented was gathered from
phone surveys of 3 fuel cell manufacturers and from a literature
survey.
Process Water Usage
All fuel cell manufacturing processes involving the use or dis-
charge of process wastes are metal finishing processes. These
processes and associated water usage and wastewater genera-
tion are covered by the Metal Finishing Category Development
Document and will not be discussed further in this report.
ALTERNATORS
Products
The alternator industry manufactures products that convert
mechanical energy into electrical energy in the form of an
alternating current.
The major alternator products are:
Electric equipment for internal combustion engines
Automobile electrical parts
Flywheel alternators, solid state voltage regulators,
overvoltage controls
Size of Industry
Alternator manufacture is classified under SIC 3694. It is
estimated that 8750 production workers are employed in the manu-
facture of alternator products. Between 65 and 75 manufacturers
are engaged in this business. The mean employment level is
estimated to be 125 production employees per plant.
V-10
-------
TABLE 5-5
PROCESSES AND MATERIALS USED IN FUEL CELL MANUFACTURES
PRODUCT
Low Temperature -
Low Pressure Fuel
Cells with Carbon
Electrode
Fuel Cells Used
as High Power
Sources for Mili-
tary Applications,
as Power Supply for
Vehicles
PROCESSES
Extrusion, Gas-baking,
Heat treating, Testing,
Assembly, Molding,
Catalyzation with Heavy
Metals Salts, Sintering
Machining, Heat Treating,
Sintering, Molding,
Carbonizing, Testing,
Assembly
BASIS MATERIALS
Base Carbo-n, Binders
Metal (oxide) Cata-
lysts, Wax or Paraffin
Compounds, Chlorapla-
tinic Acid, Teflon,
Polyethylene, Nickel,
Plastics
Graphite, Resins,
Plastic, Teflon,
Electronic Components,
Cutting Fluids
v-n
-------
Manufacturing Processes and Materials
Table 5-6 is a listing of alternator products and typical
manufacturing processes. The information presented was gathered
from a literature survey and phone survey of 7 alternator
manufacturers.
Process Water Usage
All alternator manufacturing processes involving the use or dis-
charge of process waters are metal finishing processes. These
processes and associated water usage and wastewater genera-
tion are covered by the Metal Finishing Category Development
Document and will not be discussed further in this report.
INSULATED WIRE AND CABLE, NON-FERROUS
The insulated wire and cable industry manufactures products where
a conductor is covered with a non-conductive material to eliminate
shock hazard. The major insulated wire and cable industry pro-
ducts are:
Insulated non-ferrous wire
Drawn and tinned copper wire
Auto wiring systems
Magnetic wire
Bulk cable appliances
Marine cable appliances
Marine wiring
Camouflage netting
Fine insulated wire
Size of Industry
The insulated wire and cable industry is classified under SIC 3357,
Estimates of the number of employees and the number of firms
manufacturing insulated wire and cable are not available.
Manufacturing Processes and Materials
Table 5-7 is a listing of insulated wire and cable products and
typical manufacturing processes. The information presented was
gathered from a literature survey and phone survey of 8
insulated wire and cable manufacturers.
V-12
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TABLE 5-6
PROCESSES AND MATERIALS USED IN ALTERNATOR MANUFACTURE
PRODUCT
Electric Equipment
for Internal Com-
bustion Engines
Auto Electrical
Parts
Flywheel Alterna-
tors, Solid State
Voltage Regulators,
Overvoltage Controls
PROCESSES
Stamping, Blanking,
Drawing, Welding,
Fabricating, Machining,
Heat Treating, Surface
Finishing, Assembly
Stamping, Blanking,
Drawing, Fabrication,
Assembly
Casting, Stamping,
Blanking, Drawing,
Welding, Fabrication,
Machining, Heat Treat-
ing, Surface Finishing,
Assembly
BASIS MATERIALS
Carbon Steel Sheets,
Rods, Bars, Tubing
and Pipe, Stainless
Steel, Brass-Bronze,
Aluminum, Iron Rods,
Zinc Ingots, Mica
Paper
Steel Sheet, Copper
Wire, Brass Rods
and Sheets
Carbon Steel Rods,
Bars, Strips, and
Coils; Aluminum
Ingots, Pigs, Bullets,
Strips and Coils;
Zinc Ingots
V-13
-------
TABLE 5-7
PROCESSES AND MATERIALS USED IN INSULATING
WIRE AND CABLE MANUFACTURE
PRODUCT
Drawing & Insulat-
ing of Non-Ferrous
Wire, Camoflage Net-
ting, and Fine insu-
lated Wire
Drawing and Tinning
Copper Wire and
Insulated Male
Cable
Auto Wiring Systems,
Magnet Wire, Marine
Wiring and Insulated
Bulk Cable
Appliances
PROCESSES
BASIS MATERIALS
Drawing, Spot Welding Copper Wire
Drawing, Stranding,
Heat Treating
Die Casting, Stamping
Blanking, Drawing,
Shearing, Slitting,
Forming, Welding, Heat
Treating, Assembly
Carbon, Stainless
Steel, Steel, Copper
Carbon Steel, Brass-
Bronze Strips, Coils,
Stainless Steel-Wire,
Copper-Rods and Bars,
Aluminum Wire
V-14
-------
Process Water Usage
All insulated wipe and cable manufacturing processes involving
the use or discharge of process waters are metal finishing
process. These processes and associated water usage and waste-
ewater generation are covered by the Metal Finishing Category
Development Document and will not be discussed further in this
report.
V-15
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-------
SECTION VI
CARBON AND GRAPHITE SUBCATEORY
INTRODUCTION
This discussion of the Carbon and Graphite subcategory consists of
the following major sections:
Products
Size of Industry
Manufacturing Processes
Materials
Water Usage
Production Normalizing Parameters
Waste Characterization and Treatment in Place
Potential Pollutant Parameters
Applicable Treatment Technologies
Benefit Analysis
Data contained in this section were obtained from several sources.
Engineering visits were made to 6 plants within the subcategory. Of
these 6 plantst wastewater samples were collected from four of these
facilities. A total of 16 Carbon and Graphite plants were contacted
by telephone in this survey. A literature survey was also conducted
to ascertain differences between types of Carbon and Graphite products,
process chemicals used, and typical manufacturing processes.
PRODUCTS
Elemental carbon in its amorphous and anisotropic crystalline forms
exhibits unique electrical, thermal, physical, and nuclear proper-
ties. Manufacturing techniques permit control of these properties
over very wide ranges. Thus, both carbon (the amorphous form) and
graphite (the anisotropic crystalline form) are used, in hundreds
of products manufactured for use by many industries. Most carbon
and graphite produdts are electrical conductors of one form or
another; hence, the manufacture of most carbon and graphite pro-
ducts is included within the E&EC Category.
The major carbon and graphite product areas are carbon electrodes
for aluminum smelting and graphite furnace electrodes for electric
steel production. Carbon electrodes for aluminum smelting are made
primarily by the aluminum industry for consumption within that
-industry. Their manufacture is covered by existing regulations for
the aluminum industry.
VI-1
-------
Graphite furnace electrodes for electric steel production are made
by the carbon and graphite products industry. In addition to
graphite furnace electrodes, th*is study of the Carbon and Graphite
subcategory also includes the following products:
. Graphite molds and crucibles for metallurgical
applications.
Graphite anodes for electrolytic cells used for produc-
tion of materials such, as caustic soda, chlorine,
potash, and sodium chlorate
Carbon and graphite for structural, refractory, nuclear,
and other non-electrical applications
. Carbon and graphite brushes, brush stock contacts and
other products for electrical applications (Brushes are
used to make continuous electrical contact between ro-
tating and stationary members of electrical machines)
Carbon and graphite specialties such as jigs and fixtures,
battery carbons, seals and rings, and rods for electric
arc lighting, welding, and metal cutting
Carbon and graphite products are contained in SIC 3624. The major
subclassifications of SIC 3624 are electrodes for electric furnace
and electrolytic cell use and carbon and graphite products (except
electrodes). Carbon and graphite products include brushes, elec-
trodes and other carbon and graphite products (electrical, mechan-
ical, aerospace, nuclear, metallurgical and refractory).
SIZE OF INDUSTRY
The size of the Carbon and Graphite subcategory is presented in the
following paragraphs in terms of number of plants, number of produc-
tion employees, and production rate. Each of these figures represent
an estimate based upon data collected from visited facilities, tele-
phone surveys, and literature surveys.
It is estimated that approximately 70 plants are engaged in the manu-
facture of carbon and graphite products. These estimates are based
upon the 1977 Dun and Bradstreet listing of companies engaged in
business in SIC 3624. Known non-manufacturing firms (distributors)
and known manufacturers of non-carbon and graphite products (brush-
plates) were removed from the listing. From this modified lis-
ting, 70 plants are estimated to be engaged in the manufacture of
carbon and graphite products.
Vl-2
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The Department of Commerce 1977 Census of Manufactures (Preliminary
Statistics) was also reviewed. After removal of plants believed to
be engaged in the manufacture of non-carbon and graphite products
(brushplates), 70 plants were estimated to be engaged in the manu-
facture of carbon and graphite products.
The Department of Commerce 1972 Census of Manufactures was also
compared to the above sources. 70 plants were estimated to be
engaged in the manufacture of carbon and graphite products.
Number of Employees
It is estimated that between 8,300 and 9,000 production employees
are engaged in the manufacture of carbon and graphite products.
These estimates are based on the Department of Commerce 1972 Census
of Manufactures which lists 8,600 production employees engaged in
the manufacture of carbon and graphite products and on the Depart-
ment of Commerce 1977 Census of Manufactures Preliminary Statistics
which lists 9,000 production employees. Employees believed to be
engaged in the manufacture of non-carbon and graphite products
(brushplates) were subtracted from the total number of production
employees listed in the SI-C. The resulting estimate based on the
1977 census is that approximately 8,300 employees are engaged in
the manufacture of carbon and graphite products.
Typical plants either surveyed by telephone or visited have numbers
of production employees ranging from 30 to 800. The majority of
plants employ between 60 and 350 production employees. Only six
plants employ more than 300 production employees*
Production Rate
Total production of carbon and graphite products is not available.
However, the following partial information is presented from the
Department of Commerce 1977 Census of Manufactures (Preliminary
Statistics) to profile the industry:
Electrodes for electric
and electrolytic cell use
Carbon
Graphite
All other carbon and
graphite products
Other products not
elsewhere classified
Millions of Kg.
Per Year (1977)
782.76 (355.8)
832.48 (378.4)
N/A
N/A
% Total Annual
Dollar Value (1977)
12%
42
44
VI-3
-------
A typical medium sized plant, employing 260 production workers and
360 total people, produces 15,800 metric tons/year of large carbon
and graphite electrodes. A typical large plant, employing 650 to-
tal employees, produces 68,000 metric tons/year of graphite.
MANUFACTURING PROCESSES
Due to its high triple point, 3750 _+ 50°C and 125 + 15 atm, carbon
cannot be melted and cast to form finished products. At ambient
pressure carbon does not melt; it sublimes (at 3370 4- 25°C). Thus
the manufacturing process for carbon and graphite products is one
of aggregating small particles together, followed by heat treating
to develop the desired microstructure and physical properties.
Carbon products, called "baked carbon" in the industry, require
baking at approximately 1000°C. Graphite products also known as
"synthetic graphite", "graphitized products", or "electrographite",
require one or more additional heat treating cycles at high tempera-
tures to develop the anisotropic crystalline structure that is
unique to graphite. This process is called "graphitizing".
The flow of materials and the major unit operations in the produc-
tion of baked carbon and electrographite are presented schematically
in Figure 6-1. This schematic most closely defines the process for
producing carbon or graphite of large dimensions for molds, struc-
tural, and furnace electrode applications. Many of the steps out-
lined are also followed in producing different grades of material
for special applications, such as anodes and motor brushes.
The process starts with weighing the required quantities of
calcined carbon filler, binders and additives; combining them as
a batch in a heated mixer; and then forming the resulting "green"
mixture by compression molding or by extrusion. In some plants
green carbon forms are quenched in large water-filled tanks to
harden the material for subsequent handling. Following inspection
and testing for defects, acceptable green bodies are readied for
baking.
Green bodies are carefully packed in materials such as sand,
coke granules, or charcoal. Packing supports the green body (which
softens during the early stages of baking), distributes heat more
uniformly, absorbs excess tar or pitch binder, and protects the
green bodies from oxidation. Baking takes place within a gas or
oil fired furnace, reaching a peak temperature of approximately
1000°C. The process continues for several weeks. When the
furnace has cooled down to approximately 400°C, the resulting
baked carbon bodies are unpacked, stripped of packing material,
and cleaned.
VI-4
-------
Raw Materials
Process Materials
Extrusion Aids
Water
Packing
Extrusion
Or Molding
•—- Denotes Wastewater Flow Path
FIGURE 6-1
PRODUCTION OF CARBON AND GRAPHITE SUBCATEGORY
VI-5
-------
Baked carbon is one of the most difficult refractory materials to
machine. It is hard, brittle and very abrasive, owing to small
carbide inclusions formed from impurities during the baking
process. Hence, manufacturing to final shape and finish is
performed by grinding with'diamond wheels. Cooling and dust
control are achieved either by air pickup with bag-house filtering
or by wet grinding using contact cooling water.
For graphite production the baked carbon is placed in an electric
furnace. The baked carbon is packed with metallurgical coke,
graphite or charcoal to facilitate current flow at the
start of heating. As the temperature rises, the baked carbon
itself becomes the resistor material. Peak temperature is
controlled to 2700 + 500°C, the precise value having an important
effect on the physical and electrical properties of the final
product. Duration of the graphitizing process is approximately
two weeks. After unpacking, finished graphite is allowed to air
cool to room temperature. The density of electrographite can be
increased by impregnating the graphite with such materials as
coal tar pitch or petroleum oil, either prior to or subsequent to
initial graphitizing, and then recycling through the graphitizing
furnace. Impregnation generally occurs in a pressure or vacuum
autoclave. In some plants the impregnated material is quenched in
water-filled tanks to facilitate subsequent handling.
The resulting graphite is soft and nonabrasive. It can be machined
with conventional wood working or metal working tools. Machining
lubricants are unnecessary and undesirable, because the porosity
of the graphite may cause absorption of the lubricants which would
alter the electrical characteristics of the piece.
MATERIALS
Materials required to manufacture carbon and graphite products
may be classified as raw materials and process materials. Raw
materials, which generally become part of the product, may be
subdivided into fillers, binders, additives, and impregnants.
Process materials such as packing materials, contact water, and
extrusion aids do not generally enter the product, but they are
necessary to perform certain operations.
Filler Materials
Several different raw carbon filler materials are used depending
on the product to be manufactured. These filler materials are:
. Petroleum Coke - A byproduct of petroleum cracking,
petroleum coke is a refining residue from which most
VI-6
-------
Binders
of the volatiles have been driven off. Formation of
crystallites during coking promotes subsequent graphi-
tizing. Petrole-im coke still contains approximately
5 to 15% volatile organics. These must be driven off
by calcining prior to mixing with the other raw materials.
Anthracite Coal - Anthracite coal is used for baked
carbon products only, not for graphitized products.
Ash content must be reduced from 12% to approximately
6%r which is generally achieved by washing or other
benefincation processes, including electric calcining.
Wood Charcoal - Used for specialty carbon products and
brushes, wood charcoal imparts desirable high electrical
contact resistance to carbon compositions. Wood charcoal
does not graphitize.
Carbon Black - A product of incomplete petroleum
combustion, carbon black is used in a wide variety of
carbon and graphite products, especially brushes.
Natural Graphite - Used to increase the density and
conductivity of carbon and graphite formulations, natural
graphite is used as a filler in brushes and other
products. Natural abrasives, which are always present,
are useful in controlling the self-cleaning action of
brushes.
Pitch Coke - The result of coking coal tar pitch, pitch
coke is higher in ash content and is more abrasive than
petroleum coke. Its use is limited to specialty carbon
and graphite products.
Binder materials are^used to cement the aggregated filler material
particles together during the "green" stage. Binder materials are
required to bond with carbon during the baking process to con-
tribute to the uniformity of the microstructure of the finished
product. Binder materials include:
Coal Tar Pitch - A byproduct of coal tar distillation
and the production of metallurgical coke, coal tar
pitch is the primary binder used in the manufacture of
carbon and graphite products.
Phenol Formaldehyde - This and other related thermo-
setting plastics are used in applications where
extra durability is required.
VT-7
-------
Additives
Additives are used to alter the electrical and physical properties
of the product. They are non-carbonaceous and include:
. Sulfur - Sulfur is sometimes used to dehydrogenate the
binder to promote coking of the binder.
Iron Oxide - Iron oxide is used to limit volumetric
expansion during graphitizing to help avoid structural
defects.
Metals - Silver or copper powders are used to increase
electrical conductivity of certain brush and electrical
contact formulations.
Impregnants
Impregnants are sometimes applied to graphite products prior to final
graphitizing to increase density and reduce porosity. Impregnants
include:
Coal Tar Pitch - Coal tar pitch is the most common
impregnant used. Impregnant grades of pitch are less
viscous and have lower melting points than binder pitches,
but they are derived from the same sources.
. Oils - Petroleum oil is also used as an impregnant because
of its low viscosity, low melting point, and absence of
solid particles. Other oils are used in some plants to
control the off gassing of volatiles into the atmosphere
during this process.
Process Materials
Packing materials, extrusion lubricants, contact water, and scrubber
water comprise the process materials used in the manufacture of carbon
and graphite products.
Packing Materials— "Green" body packing materials
consist of sand, charcoal, and granulated coke. They
are used singly or in combination to support the green
body during baking, to protect the body from oxidation,
and to distribute the furnace heat uniformly.
Graphitizing furnace packing materials consist of
graphite, metallurgical coke, and charcoal. They are
used to protect against oxidation and to conduct furnace
current during initiation of heat-up.
71-8
-------
Extrusion Lubricants - Small quantities of materials
such as petroleum oil may be added to the green mixture
to facilitate extrusion.
Contact Water - Contact water is used in some plants
to quench the hot green carbon after extrusion.
Contact water may also be used to quench hot baked
carbon following its impregnation with graphitizing
materials.
Contact water may also be used in conjunction with the
final machining and finishing of baked carbon products.
The water is used for flushing chips and for cooling
the diamond grinding wheels.
Scrubber Water - One visited facility re~processes the
baking oven packing sand by air scrubbing the carbon
from the sand. The carbon-laden air is subsequently
. scrubbed of carbon particulates with a wet air scrubber.
WATER USAGE
Prom the 1972 Census of Manufactures, gross water usage is estimated
to be 102.2 million liters per day (27 million gallons per day) for
the carbon and graphite products industry. Based on plants visited,
approximately 58% is recycled and 42%, or 42.8 million liters per
day (11.3 million gallons/day), is discharged. Process water is
approximately 18% of the gross water usage, or 18.5 million liters
per day (4.9 million gallons/day). (The remaining 82% includes sanitary.
use, boiler blowdown, etc.) Process water use appears to be unevenly
divided over the 70 plants estimated to be involved in carbon and
graphite production. Many smaller plants, employing up to approxi-
mately 150 total employees, report no use of contact cooling water
at all. Five visited medium and large plants reported contact
water in amounts ranging between approximately 302,000 and 2,650,000
liters per day (80,000 to 700,000 gallons per day). This contact
water use includes the use of wet air scrubber water at one visited
facility.
Wastewater
Of the 42.8 million liters/day (11.3 million gallons/day) discharged,
it is estimated that approximately 14.4 million liters/day (3.8 mil-
lion gallons/day) are treated, and the balance is discharged untreated,
Treatment is not consistent in the carbon and graphite products indus-
try. Observations regarding treatment from six visited plants are
summarized in Table 6-1.
VX-9
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PRODUCTION NORMALIZING PARAMETERS
Production normalizing parameters are used to relate the pollutant
mass discharge to the production level of a plant. Regulations expres-
sed in terms of this productiqn normalizing parameter are multiplied
by the value of this parameter at each plant to determine the allowable
pollutant mass that can be discharged. Meaningful production
normalizing parameters that have been considered for Carbon and
Graphite industry include:
Size, complexity and other product attributes that
affect the amount of pollution generated during
manufacture of a unit.
Manufacturing processes, but differences in pro-
cesses for the same product result in differing
amounts of pollution.
Production records, but lack of applicable data
may impede determination of production rates in
terms of desired normalizing parameters.
Several other broad strategies that have been developed to determine
normalizing parameter are as followsj
The process approach - In this approach, the production
normalizing parameter is a direct measure of the produc-
tion rate for each wastewater producing manufacturing
operation. These parameters may be expressed as sq.m.
processed per hour, kg of product processed per hour,
etc. This approach requires knowledge of all the wet
processes used by a plant because the allowable pollu-
tant discharge rates for each process are added to
determine the allowable pollutant discharge rate for
the plant. Regulations based on the production norma-
lizing parameter are multiplied by the value of the
parameter for each process to determine allowable dis-
charge rates from each wastewater producing process.
Concentration limit/flow guidance - This strategy
limits effluent concentration. It can be applied
to an entire plant or to individual processes. To
avoid compliance by dilution, concentration limits
are accompanied by flow guidelines. The flow guide-
lines, in turn, are expressed in terms of the produc-
tion normalizing parameter to relate flow discharge
to the production rate at the plant.
There are four wet processes used in the carbon and graphite sub-
category. They were introduced earlier in this section, but will
be expanded here to develop production normalizing parameters. The
four wet processes are:
Vl-11
-------
Extrusion Quenching - Some plants, making large
electrodes for metals smelting, extrude the mixed
raw materials for the electrode in paste or "green"
carbon form. The hot green carbon is cooled by im-
mersion in large, open water tanks to cool and harden
them, so that they can be handled in the subsequent
baking steps. These baking steps transform the "green"
carbon to a hard form, called "baked" carbon.
Pollutants are leached from the surface of the
green carbon during extrusion quenching. Hence,
an applicable production normalizing factor for this
process would be" surface area of the extruded pieces.
Impregnation Quenching - Baked carbon is con-
verted to graphite by subsequent heating. Electrical
and physical properties of the graphite can be altered
by impregnating the baked carbon with additional
graphitizing materials.
Impregnation occurs within a vacuum or pressure
autoclave, which is flooded with impregnant and then
emptied once each impregnation cycle. Impregnant is
absorbed into the graphite as a function of the sur-
face area. Some plants impregnate prior to the first
graphitizing cycle, which is followed by quenching the
warm, impregnated, baked carbon in large, open water
tanks to facilitate subsequent handling.
As with extrusion quenching, pollutants are leached
from the. surface of the impregnated graphite during
subsequent quenching. An applicable production norma-
lizing parameter for impregnation quenching is surface
area. Therefore, effluents from extrusion and impreg-
nation quench will be considered together in the
development of production normalizing parameters.
Machining and Grinding - Baked carbon is a hard, abrasive
material that is best machined using diamond grinding
wheels^ Water is used as a machining lubricant and
coolant as well as for dust control. Machining opera-
tions range from smoothing or finishing operations on
large electrodes in which less than 1% of the rough
electrode is removed to complex machined shapes in which
the majority of the rough stock is machined away. How-
ever, complete recycling of machining process water has
been achieved in this industry, which results in zero
discharge. Zero discharge is recommended for machining
and grinding processes, and this eliminates the need for
defining a production normalizing parameter for the
machining process.
VI-12
-------
Scrubbing - Air scrubbers have not been reported to be
-Ln wide use in the carbon and, graphite industry. They
have been observed at only one plant, 15606, where they
are used in a sand recycling process. The sand, used
to pack the baking furnace, is stripped of excess carbon
by an air blast which is subsequently cleaned with- a
wet air scrubber. Scrubbing washes the pollutant laden
air stream with a flow of water. Analysis of raw waste-
water shows that raw scrubber wastewater is similar to
raw machining process wastewater and therefore will be
considered along with machining and grinding. Zero
discharge is recommended for scrubbing processes, and
this eliminates the need for defining a production
normalizing parameter for the scrubber process.
The carbon and graphite industry can therefore be considered to have
two types of process wastewaters. Quench waters used for extrusion
and impregnation are similar in pollutant constituents and concentra-
tions. Machining (or grinding) and wet air scrubbing of carbon
and graphite products represents the second type of effluent.
While quench waters tend to contain oils, machined wastes and sand
scrubbing contain suspended solids.
WASTE CHARACTERIZATION AND TREATMENT IN PLACE
This section presents the sources of waste in the Carbon and Graphite
subcategory and the analytical results of samples of this wastewater.
The in-place waste treatment systems are also discussed and effluent
sample data from these systems for the four sampled Carbon and Graphite
plants is presented.
Sources of Wastewater
The following four wet processes are used by the carbon and graphite
industry:
Post-extrusion quench
Post-impregnation quench
Machining
. Scrubbing •
These wet processes are not universally used by the industry.
Table 6-2 summarizes the use of wet processes at plants contacted
during this study. A review of this table indicates that:
Zero or moderate discharge versions of all four wet
processes presently exist and are in use by the in-
dustry.
Manufacturers of large products generally use wet
processes, although no one plant has been found to
use all four wet processes.
Vl-13
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Large products, such as electrodes and anodes, are
made in medium to large plants.
Small plants make small products, such as electric
motor brushes and s^al rings, and generally use no
wet processes.
Post-Extrusion Quench
At four visited plants, this process is associated only with large
products such as electrodes or anodes. These products range from
3 to 5 meters long, 40 to 72 cm (16 to 28 inches) in diameter,
and,weigh several metric tons. Quenching typically occurs in large
open, concrete tanks that are filled with contact cooling water.
Observed tank capacities range from 42,000 liters to 110,000 liters
(11,000 to 29,000 gallons). Large products may require several hours
in the tank to cool down. Extrusion aids may be used in the batch
formulations of the product. In one plant, extrusion aids form an
oil film on the surface of the cooling water. This oil film was
removed by skimming and contractor hauled.
The post-extrusion quench process uses a straight-through water flow,
with no recirculation or cooling. Flows of 62,000, 364,000, 662,000,
and 1,744,000 liters/day (16,400, 96,000, 175,000, and 461,000 GPD)
have been observed at visited plants.
Zero discharge extrusion quench was not observed. All four visited
plants discharge extrusion quench water. By contrast, four other
plants surveyed that make small, molded products do not use
quenching at all. These products are allowed to air cool with no
water usage.
Post-Impregnation Quench - This process, observed at three visited
plants, is associated with large graphite products such as electro-
des and occurs only if impregnation precedes initial graphitizing.
The quench typically occurs in large open, concrete tanks that are
filled with contact cooling water. Tanks of 165,000 liters
(11,500 gallons) capacity have been observed. Some impregnants
form an oil film on the surface of the cooling water. This oil
film is removed prior to further processing of the product.
The simplest post-impregnation quench process uses a straight-
through flow with no recirculation. A quench flow rate of 200,000
liters/day (53,000 GPD) was observed at one plant using this process.
A zero discharge, post impregnation process was observed at two
other plants. Incoming water is used to make up evaporation losses
and maintain bath temperature at 30-35°C (85-95°F). No oil film was
observed. No recirculating processes or zero-discharge processes
using oil skimming were observed.
When impregnation of large graphite products occurs subsequent to
initial graphitizing, the impregnated product is allowed to air
Vl-15
-------
cool. Quenching in water would cause too rapid a cooling rate,
and product cracking may result.
Machining - The machining operations that use water are associated
with both large and small products, but some carbon and graphite
product manufacturers also use dry machining. When water is used,
it is used to control dust and to cool the diamond grinding wheels.
In two of four plants visited using wet machining processes,
settling and recycling of the water was observed, resulting in
zero discharge. Carbon sludge was dewatered and hauled. Recircu-
lation rates ranged from 11,000 to 18,000 liters/day (3,000 to
4,800 GPD).
One other plant has an agreement to discharge 73,000 I/day (19,000
GPD) to the local POTW without any pretreatment. The carbon solids
in the water are useful to the POTW as a flocculant. Other plants
surveyed use dry machining processes, employing vacuum pick-up and
bag house filtering of carbon dust.
Scrubbers - One visited plant recycles the baking oven packing sand
by stripping the carbon dust from the sand with air. The air stream
is subsequently cleaned in a scrubber, which discharges 64,000
liters/day (17,000 GPD) of water. No other scrubber processes have
been observed.
Wastewater Analysis Data
Raw waste characteristics from the four wet processes were obtained
by sampling a total of eight waste streams in four carbon and graphite
plants. The samples were analyzed for the pollutants listed in
Table 6-3, which contains the 129 toxic pollutants and 26 non-toxic
pollutants.
Table 6-4 presents sampling analysis data for detected parameters
in raw process wastewaters and Table 6-6 for treated effluents for
those plants sampled within the 'carbon and graphite subcategory.
Pollutant parameters are grouped according to toxic organics,
toxic metals, non-toxic metals, and other pollutants. Total
pollutant concentrations are presented as well as mass loadings
of those pollutant parameters. Mass loadings were derived by
multiplying concentration by the flow rate and the hours per day
that a particular process is operated. Some entries were left
blank for one of the following reasons: the parameter was not
detected; the concentration used for the kg/day calculation is less
that the lower quantifiable limits or not quantifiable. The kg/day
is not included in, totals for calcium, magnesium, and sodium. The
kg/day is not applicable to pH. Totals do not include values
preceded by "less , than."
Table 6-4 lists the raw waste streams sampled for the carbon and
graphite subcategory. The following considerations were made in
presenting the data:
. Trace Levels - Pollutants detected at levels too
low to measure are reported at less than (<) the
minimum threshold of- measurement for the test
method used.
VI-16
-------
TABLE 6-3
POLLUTANT PARAMETERS ANALYZED
TOXIC ORGANICS
001 Acenaphthene
002 Acrolein
003 Acrylonitrile
004 Benzene
005 Benzidine
006 Carbon tetrachloride
(tetrachloromethane)
007 Chlorobenzene
008 1,2,4-trichlorobenzene
009 Hexachlorbenzene
010 1,2-dichlorethane
011 1,1,1-trichloroethene
012 Hexachloroethane
013 1,1-dichloroethane
014 1,1,2,2-tetrachloroethane
015 1,1,2,2-tetrachloroethane
016 Chloroethane
017 Bis(chloromethyl)ether
018 Bis(2-chloroethyl)ether
019 2-chloroethyl vinyl ether (mixed)
020 2-chloronaphthalene
021 2,4,6-trichlorophenol
022 Parachlorometa cresol
023 Chlorof orm(trichloromethane)
024 2-chlorophenol
025 1,2-dichlorobenzene
026 1,3-dichlorobenzene
027 1,4-dichlorobenzene
028 3,3-dichlorobenzidine
029 1,1-dichloroethylene
030 1,2-trans-dichloroethylene
031 2,4-dichlorophenol
032 1,2-dichloropropane
033 1,2-dichloropropylene
(1,3-dichloropropene)
034 2,4-dimethylphenol
035 2,4-dinitrotoluene
036 2,6-dinitrotoluene
037 1,2-diphenylhydra
038 Ethylbenzene
039 Pluoranthene
040 4-chlorophenyl phynyl ether
041 4-bromophenyl phenyl ether
042 Bis(2-chloroisopropyl)ether
043 Bis(2-chloroethoxy) methane
044 Methyle'ne chloride
(dichloromethane)
045 Methyl Chloride (chloromethane)
046 Methyl bromide (bromoethene)
047 Bromoform (tribromomethane)
048 Dichlorobromomethane
049 Trichlorofluoroethane
050 Dichlorodifluoromethane
051 Chlorodibromomethane
052 Hexachlorobutadiene
053 Hexachlorocyclopentadiene
054 Isophorone
055 Naphthalene
056 Nitrobenzene
057 2-nitrophenol
058 4-nitrophenol
059 2,4-dinitrophenol
0 60 4,6-dinitro-o-cresol
061 N-nitrpsodimethylamine
062 N-nitrosodipheynylamine
063 N-nitrosodi-n-propylamine
064 Pentachlorophenol
065 Phenol
066 Bis(2-ethylhexyl) phthalate
067 Butyl benzyl phthalate
068 Di-tt-butyl phthalate
069 Di-n-ocityl phthalate
070 Diethyl phthalate
071 Dimethyl phthalate
072 1,2-benzanthracene
(benzo(a)anthracene)
073 Benzo(a)pyrene (3,4-benzopyrene)
0 74 3,4-benzofluoranthene
(benzo(b)fluoranthene)
075 11,124aenzofluoranthene
(benzo{k)fluoranthene)
076 Chrysene
077 Acenaphthylene
078 Anthracene
079 1,12-benzoperylene
(benzo(ghi)perylene)
080 Fluorene
081" Phenanthrene
082 1,2,5,6-dibenzanthracene
,(dibenzo (a, h) anthracene)
Vl-17
-------
TABLE 6-3 (Continued)
POLLUTANT PARAMETERS ANALYZED
TOXIC ORGANICS
083 Indeno (1,2,3-CD) Pyrene
(2,3-o-phenylene pyrene)
084 Pyrene
085 Tetrachloroethylene
086 Toluene
087 Trichloroethylene
088 Vinyl chloride (Chlorethylene)
089 Aldrin
090 Dieldrin
091 Chlordane (technical mixture
and metabolites)
092 4,4'-DDE
093 4,4'-DDE (p,p'-DDX)
094 4,4'-ODD (p,p'-TDE)
095 Alpha-endosulfan
096 Beta-endosulfan
097 Endosulfan sulfate
098 Endrin
099 Endrin aldehyde
100 Heptachlor
101 Heptachlor epoxide (BHC-Hexa-
chlorocyclohexane)
102 Alpha-BHC
103 Beta-BHC
104 Gamma-BBC (Lindane)
105 Delta-BHC (PCG-polychlorinated
biphenyls)
106 PCB-1242 (Arochlor 1242)
107 PCB-1254 (Arochlor 1254)
108 PCB-1221 (Arochlor 1221)
109 PCB-1232 (Arochlor 1232)
110 PCB-1248 (Arochlor 1248)
111 PCB-1260 (Arochlor 1260)
112 PCB-1016 (Arochlor 1016)
113 Toxaphene
129 2,3,7,8-tetrachlorodibenzo-p-
dioxin (TCDD)
Xylenes
Alkyl epoxides
TOXIC METALS
114 Antimony
117 Beryllium
118 Cadmium
119 Chromium
120 Copper
121 Cyanide
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
TON-TOXIC METALS
Calcium
Magnesium
Aluminum
Manganese
Vanadium
Boron
Barium
Molybdenum
Tin
Yttrium
Cobalt
Iron
Titanium
OTHER POLLUTANTS
Oil and Grease
Total Organic Carbon
Biochemical Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
pH
VI-18
-------
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VI-19
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VI-23
-------
Incoming Water Analysis - In some instances samples
were taken of incoming plant water. Pollutants were
found -in some of these incoming streams at essential-
ly the same levels as in the output streams, indi-
cating that the incoming water is the source of the
pollutant. These pollutant levels were not subtracted
from the total pollutant level of the affected streams.
The presence of pollution in the incoming streams is
noted in the data.
Pollutant Loads - Pollutant loads were calculated for
measurable pollutants by multiplying concentration by
flow and daily flow durations. This procedure gives
calculated pollutant loads in kg/day for each pollu-
tant for each stream sampled.
Sample Blanks - Blank samples of organic-free distilled
water were placed adjacent to sampling points to detect
airborne contamination of water samples. These sample
blank data are not subtracted from the analysis results,
but, rather, are shown as a (B) next to the pollutant
found in both the sample and the blank. The tables show
figures for total toxic organics, total toxic and
non-toxic metals, and other pollutants.
Summary of Raw Waste Stream Data
Table 6-5 summarizes pollutant concentration data for the sampled
raw waste streams for the Carbon and Graphite Subcategory. Mini-
mum, maximum, mean, and flow weighted mean concentrations have been
determined' for sampled raw waste streams. The flow weighted mean
concentration was calculated by dividing the total mass rates (mg/
day) by the total flow rate (liters/day) for all sampled data for
each parameter. The flow weighted mean concentration of total raw
waste (includes machining, grinding, scrubber wastes, and quenches)
is also presented in Table 6-5.
Pollutant parameters listed in Table 6-5 were selected based upon
their occurrence and concentration in the sampled streams. Those
parameters not detected or at trace levels in the sampled streams
were excluded from this table.
Treatment In-Place
Table 6-1 summarized treatment in place for the carbon and graphite
industry. Wastewater treatment was observed in six of the carbon
and graphite plants visited, and consists of the following:
Oil separation prior to discharging quench water.
Settling carbon solids out of water used for
machining coolants prior to reuse.
VI-24
-------
TABLE 6-5
CARBON AND GRAPHITE SUBCATEGORY
MACHINING, GRINDING & SCRUBBER RAW WASTE STREAM DATA
Parameter
Flow Weighted
Minimum Maximum Mean Mean
Concentration Concentration Concentration Concentration
(mg/1) (mg/1)
TOXIC ORGANICS
Oil 1,1,1 Trichloroethane
044 Methylene Chloride
065 Phenol
066 Bis(2-ethylhexyl)phthalate
067 Butyl benzyl phthalate
068 Di-n-butyl phthalate
TOXIC METALS
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium
120 Copper
121 Cyanide
122 Lead
123 Mercury
124 Nickel
125 Selenium
128 Zinc
NON-TOXIC METALS
Aluminum
Manganese
Vanadium
Boron
Barium
Molybdenum
Tin
Yttrium
Cobalt
Iron
Titanium
Magnesium
0.068,(B)*
<0.01
<0.01
<0.01
<0.01
0.007
0.001
0.001
<0.003
<0.005
<0.01
<0.01
<0.005
<0.005
<0.01
0.003
0.061
0.23
0.006
0.023
0.041
0.085
0.020
0.013
<0.004
0.013
0.573
0.047
1.21
0.068(B)
0.049
0.039
0.410
0.019
<0.01
0.005
<0.01
0.019
0.054
5.3
0.065
1.7
0.002
0.146
0.08
0.237
2.18
0.071
0.121
0..424
0.878
0.445
0.208
0.007
0.051
6.689
0.338
8.296
0.068
0.023
0.025
0.11
0.013
0.01
0.003
0.004
0.008
0.028
1.67
0.03
0.483
0.001
0.062
0.025
0.125
0.942
0.05
0.075
0.193
0.48
0.167
0.085
0.005
0.038
3.285
0.145
3.79
0.068
0.0160
0.034
0.153
0.0115
0.01
0.0178
0.006
0.01
0.045
1.219
0.026
0.264
0.0025
0.046
0.015
0.178
1.783
0.061
0.105
0.347
0.524
0.358
0.171
0.005
0.049
5.5
0.273
2.07
VI-25
-------
TABLE 6-5 (Con't)
CARBON AND GRAPHITE SUBCATEGORY
MACHINING, GRINDING & SCRUBBER RAW WASTE STREAM DATA
Earameter
OTHER POIZOTANTS
Total Suspended Solids
Tbtal Organic Carbon
Biochemical Oxygen Demand
Oil and Grease
Hienols
Flow Weighted
Minimum Maximum Mean Mean
Concentration Concentration Concentration Concentration
(rag/1) (mg/1) (mg/1) (mg/1)
53
116
0.0
7.0
0.014
2988.
7222.
25
70.4
0.122
1329.
2050.3
10.13
26.73
0.04
612.
353
9.2
11.3
0.066
* Based on one stream, one day (concentration found in blanks)
VI-26
-------
TABLE 6-5 (Con't)
CARBON AND GRAPHITE SUBCATEGORY
EXTRUSION AND IMPREGNATION QUENCHING RAW KfcSTE STREAMS
Parameter
Flow Weighted
Minimum Maximum Mean Mean
Concentration Concentration Concentration Concentration
(mg/1) (mg/1) (mg/1) (mg/1)
TOXIC ORGANICS
004 Benzene <0.01 0.011
039 Pluoranthene <0.01 0.013
044 Methylene chloride <0.01 0.062
066 Bis(2-«thylhexyl)phthalate <0.01 2.1
072 1,2-Benzanthracene <0.01 0.019
073 Benzo pyrene <0.01 0.013
075 11,12 Benzoanthracene <0.01 0.011
076 Chrysene <0.01 0.011
078 Anthracene <0.01 0.013
TOXIC METALS
119 Chromium <0.01 <0.015
120 Copper <0.01 0.027
122 Lead <0.005 0.045
123 Mercury 0.0007 <0.001
124 Nickel <0.01 0.114
125 Selenium 0.002 <0.01
128 Zinc 0.023 0.11
NON-TOXIC METALS
Aluminum 0.217 0.279
Manganese 0.003 0.017
Vanadium <0.01 0.061
Boron 0.018 0.116
Barium 0.023 0.042
Molybdenum 0.005 <0.035
Yttrium <0.004 0.005
Cobalt 0.003 <0.05
Iron 0.003 0.653
Titanium <0.002 0.003
Magnesium 1.37 8.069
0.01
0.011
0.034
0.533
0.013
0.012
0.01
0.01
0.011
0.013
0.016
0.038
0.0012
0.038
0.005
0.05
0.242
0.011
0.016
0.055
0.035
0.025
0.0043
0.034
0.424
0.002
3.62
0.01
0.01
0.014
0.047
0.010
0.01
0.01
0.01
0.01
0.013
0.023
0.037
0.001
0.107
0.003
0.029
0.239
0.0038
0.03
0.062
0.018
0.008
0.003
0.01
0.104
0.002
4.23
VI-27
-------
TABLE 6-5 (Con't)
CARBON AND GRAPHITE SUBOVTEGORY
EXTRUSION AND IMPREGNATION QUENCHING RAW WASTE STREAMS
Parameter
OTHER POLLUTANTS
Total Suspended Solids
Total Organic Carbon
Biochemical Oxygen Demand
Oil & Grease
Phenols
Flow Weighted
Minimum Maximum Mean Mean
Concentration Concentration Concentration Concentration
(mg/1) (mg/1) (mg/1) (mg/1)
1.0
<1.0
2.0
3.5
<0.005
19.0
4.1
19.0
44.0
0.022
6.90
2.28
7.67
18.80
0.015
2.79
2.53
5.69
7.93
0.016
VI-28
-------
TABLE 6-5 (Con't)
CARBON AND GRAPHITE-TOTAL RAW WASTE
(MACHINING, GRINDING, SCRUBER EFFLUENT, AND
EXTRUSION AND IMPREGNATION QUENCHES)
Parameter
TOXIC ORGANICS
004 Benzene
Oil 1,1,1-trichloroethene
039 Fluoranthene
044 Methylene chloride
065 Phenol
066 Bis(2-ethylhexyl)phthalate
067 Butyl benzyl phthalate
068 Di-n-butyl phthalate
072 1,2-benzanthracene
073 Benzo(a)pyrene
075 11,12-benzofluoranthene
076 Chrysene
078 Anthracene
079 1,12-benzoperylene
TOTAL- TOXIC ORGANICS
TOXIC ORGANICS
119 Chromium
120 Copper
122 Lead
124 Nickel
128 Zinc
OTHER POLLUTANTS ,
Total Suspended Solids
Total Organic Carbon
Oil & Grease
Biochemical Oxygen Demand
Flow Weighted
Mean Concentration
(mg/1)
0.01
0.01
0.01
0.021
0.013
0.052
0.01
0.01
0.01
0.012
0.01
0.01
0.01
0.01
0.197
0.015
0.08
0.045
0.104
0.036
31.8
19.25
8.09
5.86
VI-29
-------
Oil Separation : - Oil separation was observed at one visited plant.
At this plant, the effluents from the extrusion quench and the
impregnation quench each flow through oil separators prior to
discharge.
The extrusion quench oil separation treatment was installed primarily
to handle oil leakage from the extrusion machinery and to contain
leakage from any major hydraulic system failure that might occur.
Process wastewater at the rate of 27,600 1/hr (7,292 gal/hr) enters
the tank at the bottom. Oil droplets impinge on plates placed
perpendicular to the flow direction causing the oil droplets to coa-
lesce and rise to the surface. The water leaves the tank at the
bottom of the opposite end of the tank. The oil that collects at the
top of the tank is periodically skimmed off and stored for future
use or reclaim.
The impregnation oil separation treatment is similar to the extrusion
oil separation treatment. The only significant difference is that
the impregnation quench flow is smaller at 8,357 1/hr (2,208 gal/hr).
The impregnant oil rises to the top of the tank from which it is
skimmed periodically. Skimmed oil is stored for future use or
reclaim.
Settling - Settling of carbon particles generated from machining
and wet air scrubbing processes was observed at five visited
plants. In three of these plants, carbon particles are picked up
in a water stream and sent to a settling tank. The supernatant is
recycled back to the machining process. The carbon particles are
pumped from the bottom of the settling tank as sludge and contrac-
tor removed.
There are differences between the plants in the implementation of
the settling treatment. In Plant 36173 a water flow of 757. 1/hr
(200 gal/hr) carries carbon particles to a circular clarifier that
is equipped with a conical bottom. Carbon sludge, drawn from the
clarifier, is pumped to a tank which is emptied periodically by
contract hauling. The effluent water is recycled back to the
machining processes for reuse. In Plant 30047 a water flow of 712
1/hr (188 gal/hr) carries carbon particles to a 15,140 liter (4,000
gal) lamella separator. An anionic polymer is added to the water
before it enters the lamella separator. The polymer acts as a floc-
culant, aiding the settling of carbon particles. The carbon parti-
cles are drawn off the bottom of the lamella separator as sludge,
which is dewatered in a vibrating screen dewaterer. The water from
the dewatered sludge is returned to a 16,300 liter (4,310 gal) sump
located upstream of the lamella separator, which collects the wet
machining wastes. Plant 36175 treats process wastewater in two
parallel clarifiers prior to discharging the treated effluent.
The clarifiers are regularly pumped out to maintain a low level of
carbon sludge. The treated effluent is then discharged directly
to a stream at a rate of 22710 liters per hour (6000 gallons/hr).
VI-30
-------
Plant 15606 uses a wet air scrubber to remove carbon particles from
baking operations. The scrubber water is discharged to a settling
pond where settling of carbon particles occurs. The wastewater flow
rate from this process is approximately 15897 liters/hr (4200
gallons/hr).
Treated Waste Analysis
Table 6-6 presents the sampling analysis results of treated effluents
from the quenching processes and two machining processes. Table 6-6
is based on the same considerations used in constructing Table 6-4
in reporting trace levels, incoming water analysis, and pollutant
loads. As with Table 6-4 the samples presented in Table 6-6 were
analyzed for the pollutants listed in Table 6-3. '
Actual Performance of Observed Treatment Systems
Use of raw wastewater data from Table 6-4 and treated wastewater
data from Table 6-6 permits assessment of the performance of
the following three observed treatment systems:
Extrusion oil separation prior to discharge
. Impregnation oil separation prior to discharge
. Wet machining settling and recirculation
Extrusion Oil Separation - The performance of the extrusion oil
separator at plant 36173 is presented in Table 6-7. Its oil and
grease removal effectiveness is fairly low. The low removal rate
is consistent with its primary purpose of containing, a major
hydraulic fluid spill should it occur rather than of removing small
amounts of oil adhering to the product. The concentration of metals
and organics is essentially unchanged through th\e separator. The
apparent increases in concentration of some pollutants shown in
Table 6-7 are attributed to sampling variations and are not considered
significant in light of the very low concentratio^i levels involved.
Impregnation Oil Separation - The performance of the impregnation oil
separator at plant 36173 is presented in Table 6-8.\ Oil and grease
is reduced from 44 to 6 mg/1 which is consistent with its primary
purpose of removing process impregnant from the discharge stream. As
with Table 6-7, increases in concentration of some pollutants such
as zinc are attributed to sampling variations. \
Machining Settling - The performance of the machining clarifier at
plant 36173 is presented in Table 6-9. The clarifier removes 99%
of the TSSf
-------
Plant 10 No.
Stream Description
Ftou (1/ltr)
Duration (hrs)
Sample ID No.
TOXIC ORCANICS
1 Acenaphtheni!
4 Benzene
7 Chlorobonzene
11 1,1,1-Trichloroethane
23 Chloroform
24 2-Chlorophcnol
37 l|2-Diphenylhydrazine
J8 Ethylbenzcne
39 Fluoranthene
bit Hethylene Chloride
67 Bromoforra
48 Dichlorobromomethane
51 Chlorodibromomethane
S3 Naphthalene
57 2-Nitrophenol
62 N-Nitrosodiphenylamine
65 Phenol
66 Bis(2-ethylhexyl)
phthalate)
67 Butyl benzyl phthalate
68 Di-n-butyl phthalate
69 Di-n-octyl phthalate
70 Diethylphthalatc
71 Dinethylphthalate
72 Benzanthracene
73 3,4-Bcnzopyrene
75 11,12-Benzofluoranthene
76 Chrysene
73 Anthracene
79 1,12-Bcnzoperylene
SO Fluorene
83 Ideno(l,2,3-cd)pyrene
86 Pyrene
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
96 6,6-DDE(p,p-TDE)
100 Heptachlor
102 Alpha-BHC
106 G-imia-BHC
Total Toxic Organics
TOXIC ffiTALS
116 Antimony
115 Arsenic
117 Beryllium
118 Cadmium
119 Chromium
120 Copper
121 Cyanide
122 Lead
123 Mercury
126 (ticket
125 Seleniun
126 Silver
127 Thallium
128 Zinc
Total Toxic Metals
OTHER POLLUTANTS •
TSS
TOC
BOD
Oil & Grease
Phenols
TABLE 6-6
CARBON & GRAPHITE TREATED EFFLUENT CHARACTERISTICS
Concentration Mass Load Concentration Mass Load Concenlration Mass Load
mg/liter kg/day mg/liter kg/day nig/liter kg/day
36173 36173 36173
Extrusion Quench Effluent Impregnation Quench Effluent Machining Effluent
<0.010
<0.010
<0.010
<0.010
0.090
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
0.090
0.001
0.001
<0.001
<0.005
<0.015
<0.013
0.030
<0.050
<0.001
<0.013
0.0181
<0.001
<0.001
0.135
0.185
6.0
2
2.0
11.0
0.020
27,600
26
3273
0.060
0.060
0.00066
0.00066
0.020
0.012
0.089
0.122
4.00
1.325
1.325
7.29
0.013
8357
24
3274
<0.010
<0.010
<0.010
<0.010
<0.010
0.023
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
0.033
<0.001
0.001
<0.001
<0.005
<0.015
<0.013
<0.010
<0.050
<0.001
<0.013
0.0021
<0.001
<0.001
0.041
0.044
5.0
4
7.0
6
0.014
VI-32
0.005
0.002
0.007
0.0002
0.0004
0.0082
0.0088
1.00
0.802
1.40
1.20
0.003
0.059
0.001
<0.001
<0.001
<0.005
0.043
0.158
<0.01
0.435
<0.001
<0.013
0.013
0.001
<0.001
0.027
0.682
24.0
2.0
6.0
19.0
0.010
757
24
3272
<0.010
<0.010
0.059 0.001
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
0.001
0.00002
0.0008
0.-003
0.008
0.0002
0.00002
0.0005
0.0125
0.436
0.036
0.109
0.345
0.0002
-------
TABLE 6-7
EXTRUSION QUENCH OIL SEPARATION PERFORMANCE
Plant ID 36173
SAMPLE ID NO.
3270
Raw Waste
mg/1
3273
Treated Waste
mg/1
044 Methylene Chloride .062*
072 1,2-Benzanthracene 0.011
073 3,4-Benzopyrene 0.013
075 11,12-Benzo .011
fluoranthene
076 Chrysene .011
Total Toxic Organics 0.108
125 Selenium 0.002
128 Zinc 0.023
Total Toxic Metals 0.025
TSS 5
TOC 1
- BOD 2
Oil & Grease 14
Phenols .022
.09
<.010
<.010
<.010
<.010
0.09
0.018*
0.135
0.153
6
2
2
11
.020
* Interferences present
VI-33
-------
TABLE 6-8
IMPREGNATION QUENCH OIL SEPARATION PERFORMANCE
SAMPLE ID NO.
3271
Raw Waste
mg/1
3274
Treated Waste
mg/1
044 Methylene Chloride .030*
072 1,2-Benzanthracene .019
Total Toxic Organics 0.049
115 Arsenic .001
125 Selenium .006*
128 Zinc .034
Total Toxic Metals 0.041
TSS 19
TOG <1
BOD 19
Oil & Grease 44
Phenols .019
.023
.010
0.033
.001
.002*
.041
0.044
5
4
7
6
.014
Interferences present
VI-34
-------
TABLE 6-9
MACHINING SETTLING WATER CHARACTERISTICS
SAMPLE I.D. NO.
004 Methylene Chloride
067 Butyl Benzyl Phthalate
Total Toxic Organics
114
115
119
120
122
123
124
125
128
Antimony
Arsenic
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Zinc
Total Toxic Metals
TSS
TOC
BOD
Oil & Grease
Phenols
3269
Grinding Effluent
mg/1
.049*
.019
0.068
.003
0.001
0.054
5.3
1.7
.002
0.02
.080*
0.061
7.22
2,988
188
25
20
.014
3272
Clarifier Effluent
mg/1
.059
<.010
0.059
.001
<0.001
0.043
.158
.435
<.001
<0.013
.013
.027
0.682
24
2
6
19
.010
* Interferences Present
Vl-35
-------
POTENTIAL POLLUTANT PARAMETERS
This section assesses the raw wastewater characteristics of the
carbon and graphite industry and identifies the significant pol-
lutants. The wastewater analysis of 8 raw waste streams sampled
at 6 plants were shown in Table 6-5.
The requirement for control of a particular pollutant depends upon
consideration of its presence at harmful levels and the existence
of practical technology for removing the pollutant. The process
raw waste pollutant parameters listed in Table 6-5 were reviewed
in light of these considerations. As a result of this review,
the following pollutants have been selected from machining, grin-
ding and scrubber raw waste data as significant pollutants re-
quiring control:
120 Copper
122 Lead
128 Zinc
Total Suspended
Solids
Total Organic Carbon
Oil and Grease
Iron
Aluminum
Table 6-10 lists pollutants other than the potential pollutant
parameters presented above that were analyzed in machining, grinding
and scrubber effluent raw waste streams sampled within the carbon
and graphite subcategory. Each pollutant is listed in the appropriate
group as being not detected, detected at trace levels, or at levels
too low to be effectively treated.
Review of quenching raw waste streams shows the following pollutant
as significant and requiring control:
Oil and Grease
Table 6-11 lists pollutants other than the potential pollutant
parameter listed above that were analyzed in extrusion and
impregnation quench raw waste streams sampled within the carbon
and graphite subcategory. Each pollutant is listed in the appro-
priate group as being not detected, detected at trace levels,
or levels too low to be effectively treated.
Vl-36
-------
TABLE 6-10
CARBON AND GRAPHITE SUBCATEGORY
POLLUTANT PARAMETERS NOT DETECTED IN RAW WASTE STREAMS
MACHINING, GRINDING, AND SCRUBBER
TOXIC ORGANICS
002 Acrolein
003 Acrylonitrile
005 Benzidine
006 Carbon tetrachloride
(tetrachloromethane)
007 Chlorobenzene
008 1,2,4-trichlorobenzene
009 Hexachlorobenzene
010 1,2-dichloroethane
012 Hexachloroethane
013 1,1-dichloroethane
014 1,1,2-trichloroethane
015 1,1,2,2-tetrachloroethane
016 Chloroethane
017 Bis (dhilorornethyl) ether
018 Bis(2-chloroethyl)ether
019 Ether (mixed) 2-chloroethyl vinvyl
020 2-chloronaphthalene
021 2,4,6-trichlorophenol
022 Parachlorometa cresol
025 1,2-dichlorobenzene
026 1,3-dichlorobenzene
027 1,4-dichlorobenzene
028 3,3-dichloroethylene
029 1,1-dichloroethylene
030 1,2-trans-dichloroethylene
031 2,4-dichlorophenol
032 1,2-dichloropropane
033 1,2-dichloropropylene
035 2,4-dinitrotoluene
036 2,6-<3initrotoluene
038 Ethylbenzene
040 4-chlorophenyl phenyl ether
041 4-bromophenyl phenyl ether
042 Bis(2-chloroisopropyl)ether
043 Bis(2-chloroethoxy)
045 Methyl chloride (chloromethane)
046 Methyl bromide (bromomethane)
047 Brcmoform
049 Trichlorofluoromethane
050 Dichlorodifluoromethane
051 Chlorodibromethane
052 Hexachlorobutadiene
053 Ffexachlorocyclopentadiene
054 Isophorone
056 Nitrobenzene
058 4-nitrophenol
059 2,4-dinitrophenol
061 N-nitrosodimethylamine
063 N-nitrosodi-n-propylamine
064 Pentachlorophenol
072 Benzanthracene
074 3,4-benzofluoranthene
(benzo(b)fluoranthene)
076 Chrysene
077 Acenaphthylene
079 1,12-benzoperylene
082 1,2,5,6-dibenzanthracene
083 Ideno pyrene
085 Tetrachloroethylene
088 Vinyl chloride (chloroethylene)
089 Aldrin
090 Dieldrin
091 Chlordane
092 4,4-DDT
093 4,4-DDE (pfp'-DDX)
095 Alpha-endosulfan
096 Beta-endosulfan
097 Endosulfan sulfate
098 Endrin
099 Endrin aldehyde
101 Heptachlor epoxide
(BHC-hexachlorocyclohexane)
103 Beta-BHC
104 Gamma-BHC
105 Delta-BHC (PCB-^)olychlorinated
biphenyls)
106 PCB-1242 (Arochlor 1242)
107 PCB-1254 (Arochlor 1254)
108 PCB-1221 (Arochlor 1221)
109 PCB-1232 (Arochlor 1232)
110 PCB-1248 (Arochlor 1248)
111 PCB-1260 (Arochlor 1260)
112 PCB-1016 (Arochlor 1016)
113 Toxaphene
129 2,3,1,8-tetrachlorodibenzo-p-
dioxin (TCDD)
VI-37
-------
TABLE 6-10 (Cbntinued)
POLLUTANTS DETECTED AT TRACE LEVELS
MACHINING, GRINDING, AND SCRUBBER
RAW WASTE STREAMS
TOXIC OSGANICS
001 Acenaphthene
004 Benzene
023 Chloroform
024 2-chlorophenol
034 2,4-dimethylphenol
037 1,2-diphenylhydrazine
039 Pluoranthene
048 Dichlorobromethane
055 Naphthalene
057 2-nitrophenol
062 N-nitrosodiphenylamine
068 Di-n-butyl phthalate
069 Di-n-octyl phthalate
070 Diethyl phthalate
071 Dimethyl phthalate
073 Benzo(z)pyrene
075 11,12-benzofluoranthene
078 Anthracene
080 Pluorene
081 Phenanthrene
084 Pyrene
086 Toluene
087 Trichloroethylene
094 4,4-DDE
100 Beptachlor
102 Alpha-BRC
104 Gamma-BHC
TOXIC METALS
117 Beryllium
126 Silver
127 Thallium
127 Thallium
VI-38
-------
TABLE 6-10 (Continued)
POIiUTANTS DETECTED AT LEVELS TOO LOW TO REQUIRE TREATMENT*
MACHINING, GRINDING, AND SCRUBBER EFFLUENT
Parameter
Toxic organics
Oil 1,1,1-Trichloroethane
044 Methylene Chloride
065 Phenol
066 Bis(2-ethylhexyl)Phthalate
067 Butyl Benzyl Phthalate
068 Di-n-butyl Phthalate
Toxic Metals
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium
121 Cyanide
123 Mercury
125 Selenium
Non-Toxic Metals
Barium
Tin
Yttrium
Cobalt
Titanium
Magnesium
Other Pollutants
BCD
Phenols
Mean Concentration rag/1
0.068
0.023
0.025
0.11
0.013
0.01
0.003
0.004
0.008
0.028
0.03
0.001
0.025
0.48
0.085
0.005
0.038
0.145
3.79
10.13
0.04
Flow Weighted
Mean Concentration rog/1
0.068
0.016
0.034
0.153
0.0115
0.01
0.0178
0.006
0.01
0.045
0.026
0.0025
0.015
0.524
0.171
0.005
0.049
0.273
2.07
9.2
0.066
*These parameters do not require treatment because (1) the raw waste concen-
tration is less than the daily makimum figure (See Table 6-12), or (2) no
performance data is available for treatment of these parameters.
VI-3 9
-------
TABLE 6-11
CARBON AND GRAPHITE SUBCATEGORY
POLLUTANT PARAMETERS NOT DETECTED IN RAW WASTE STREAMS
EXTRUSION AND IMPREGNATION QUENCHES
TOXIC ORGANICS
002 Acrolein
003 Acrylonitrile
005 Benzidine
006 Carbon tetrachloride
(tetrachlorcnte thane)
0 08 1,2,4-trichlorobenzene
009 Hexachlorobenzene
010 1,2-dichloroethane
012 Hexachloroethane
013 1,1-dichloroethane
014 1,1,2-trichloroethane
015 1,1,2,2-tetrachloroethane
016 Chloroethane
017 Bis(chloromethyl) ether
018 Bis(2-chloroethyl)ether
019 Ether (mixed) 2-chloroethyl vinyl
020 '2-chloronaphthalene
021 2,4,6-trichlorophenol
022 Parachlororaeta cresol
025 1,2-dichlorobenzene
026 1,3-dichlorobenzene
027 1,4-dichlorobenzene
028 3,3-dichloroethylene
029 1,1-dichloroethylene
030 1,2-trans-dichloroethylene
031 2,4-dichlorophenol
032 1,2-dichloropropane
033 1,2-dichloropropylene
(1,3-dichloropropene)
035 2,4-dinitrotoluene
036 2,6-dinitrotoluene
040 4-chlorophenyl phenyl ether
041 4-bronophenyl phenyl ether
042 Bis(2-chloroisopropyl) ether
043 Bis(2-chloroethoxy) Methane
045 Methyl chloride (chloromethane)
046 Methyl bromide (bromomethane)
049 Trichlorofluoromethane
050 Dichlorodifluoromethne
052 Hexachlorobutadiene
053 Hexachlorocyclopentadiene
054 Isophorone
056 Nitrobenzene
057 2-nitrophenol
058 4-nitrophenol
059 2,4-dinitrophenol
060 4,6-dinitro-o-cresol
061 N-nitrosodimethylamine
063 N-nitrosodi-n-propylamine
064 Pentachlorophenol
069 Di-n-octyl phthalate
074 3,4-Benzofluoranthene
(benzo(b)fluoranthene)
077 Acenaphthylene
085 Tetrachloroethylene
088 Vinyl Chloride (chloroethylene)
089 Aldrin
090 Dieldrin
091 Chlordane
092 4,4-DDT
Q93 4,4HDDE (p,p-DDX)
096 Beta-endosulfan
097 Endosulfan sulfate
098 Endrin
099 Endrin aldehyde
101 Heptachlor epoxide
(BHCHtiexachlorocyclohexane)
103 Beta-BHC
105 Delta-BHC (PCB-polychlorinated
biphenyls)
106 PC3-1242 (Arochlor 1242)
107 PCB-1254 (Arochlor 1254)
108 PCB-1221 (Arochlor 1221)
109 PCB-1232 (Arochlor 1232)
110 PCB-1248 (Arochlor 1248)
111 PCB-1260 (Arochlor 1260)
112 PCB-1016 (Arochlor 1016)
113 Toxaphene
129 2,3,7,8-tetrachlorodibenzo-p-
dioxin (TCDD)
VI-40
-------
TABLE 6-11 (Continued)
CARBON-'AND GRAPHITE SUBCATEQORY
POLLUTANT PARAMETERS DETECTED AT LOW LEVELS
EXTRUSION AND IMPREGNATION QOENCH-RAW WASTE STREAMS
Toxic Organics
001 Acenaphthene
004 Benzene
007 Chlorofoenzene
Oil 1,1,1-Trichlorethane
023 Chloroform
024 2-chlorophenol
034 2,4-dimethyl phenol
037 1,2-diphenylhydrazine
038 Ethylbenzene
047 Bronoform
048 Dichlorobronethane
051 Chlorodibromomethane
055 Naphthalene
062 N-nitrosodiphenylamine
065 Phenol
067 Butyl Benzyl Phthalate
068 Di-n-butyl phthalate
070 Diethyl phthalate
071 Dimethyl phthalate
079 1,12-benzopenylene
080 Fluorene
081 Phenanthrene
082 Dibenzo anthracene
083 Ideno pyrene
084 Pyrene
086 Ibluene
087 Trichloroethylene
094 4^4-DDE
095 2-endosulfan
100 Heptachlor
102 Alpha-BHC
104 Ganroa-BHC
Toxic Metals
114 Antimony
115 Arsenic
117 Beryllium
118 Cadmium
121 Cyanide
126 Silver
Non-Toxic Metals
Tin
VI-41
-------
TABLE 6-11 (Continued)
POLLUTANTS DETECTED AT LEVELS TOO LOW TO REQUIRE TREATMENT
EXTRUSION AND IMPREQilATION QUENCHES
Parameter
Toxic Organics
004 Benzene
039 Fluoranthene
044 Methylene Chloride
066 Bis(2-ethylhexyl)Ehthalate
072 Benzanthracene
073 3,4-Benzopyrene
075 11,12-Benzofluoranthene
076 Chrysene
078 Anthracene
Toxic Metals
119 Chromium
123 Mercury
125 Selenium
Non-Toxic Metals
Aluminum
Manganese
Vanadium
Boron
Barium
Molybdenum
Yttrium
Cobalt
Iron
Titanium
Magnesium
Other Pollutants
BOD
Ehenols
Mean Concentration mg/1
0.01
0.011
0.034
0.533
0.013
0.012
0.01
0.01
0.011
0.013
0.0012
0.005
0.242
0.011
0.016
0.055
0.035
0.025
0.0043
0.034
0.424
0.002
3.62
7.67
0.015
Plow Weighted
Mean Concentration mg/1
0.01
0.01
0.014
0.047
0.01
0.01
0.01
0.01
0.01
0.013
0.001
0.003
0.239
0.0038
0.03
0.062
0.018
0.008
0.003
0.01
0.104
0.002
4.23
5.69
0.016
* These parameters do not require treatment because (1) the raw waste concen-
tration is less than the daily maximum figure (See Table 6-12), or (2) no
performance data is available for treatment of these parameters.
VI-42
-------
APPLICABLE TREATMENT TECHNOLOGIES
These paragraphs contain a discussion of alternative treatment
schemes for reducing the pollutant levels discharged from the four
wet processes associated with the manufacture of carbon and graphite
products. All treatment alternatives presented use standard/ proven
treatment technologies which are discussed in detail in Section XII.
Recommended Treatment Systems
Two levels of treatment are presented for each water discharging
process used in carbon and graphite product manufacture. The Level
1 treatment consists of end-of-pipe schemes to reduce pollutant
loads prior to discharge. Level 2 treatment permits total recircu-
lation of process water.
Identical treatment is recommended for both extrusion and impreg-
nation quench streams. Two levels of treatment have been recom-
mended. The Level 1 treatment schematic is presented in Figure
6-2 and consists of skimming and contract hauling of sludge. Pro-
visions for settleable solids removal is also included. The
quench stream Level 2 recycle treatment schematic is presented in
Figure 6-3 and consists of a clarifier for settling with oil
skimming. Recycle presents the likelihood of increased oil and
solids concentrations requiring removal to prevent pollutant build-
up. Polymer addition is recommend for improved solids removal
for applications where high TSS is of concern.
For machining, grinding and scrubber effluent waste'waters, two
levels of treatment have been recommended. The Level 1 treatment
schematic is presented in Figure 6-4 and consists of a clarifier
with solids and oil removal. The Level 2 system schematic is pre-
sented in Figure 6-5 and is identical to Level 1 but includes re-
cycling. Recycle in this application requires polymer addition
to prevent excessive TSS build-up in the returned coolant. Level
2 without oil skimming has been observed in industry. Oil skim-
ming is recommended for those applications where increased con-
centrations of oil and grease in the returned coolant could become
absorbed by the machined carbon and affect product quality or ease
of handling.
Performance of Recommended Treatment Systems
Level 1 has been observed for extrusion and impregnation quenches
within the industry and sampling has verified separator effective-
ness in reducing oil and grease discharge levels". (Tables
6-7 and 6-8). Level 2 treatment for extrusion and impregnation
quenches achieves zero discharge of pollutants.
Vi-43
-------
011 Separator
I
SolIds Removal
011
Discharge
FIGURE 6-2
LEVEL 1 EXTRUSION AND IMPREGNATION QUENCH
TREATMENT SYSTEM FOR CARBON AND GRAPHITE
SUBCATEGORY
VI-44
-------
Recycle
Polymer.
Addition
Clarifier
T
Solids Removal
Haul Oil
FIGURE 6-3
LEVEL 2 EXTRUSION AND IMPREGNATION QUENCH
TREATMENT SYSTEM FOR CARBON AND GRAPHITE
SUBCATEGORY
VI-45
-------
Recycle
Polympf _...
Addition
»
Clarifier
f
•Haul Oil
Solids Removal
FIGURE 6-4
LEVEL 2 MACHINING, GRINDING, AND SCRUBBER EFFLUENT
TREATMENT SYSTEM FOR CARBON AND GRAPHITE
SUBCATEGORY
VI-46
-------
Polymer
Addition"
Clarifier
I
•Discharge
•Haul Oil
Solids Removal
FIGURE 6-5
LEVEL 1 MACHINING, GRINDING, AND SCRUBBER EFFLUENT
TREATMENT SYSTEM FOR CARBON AND GRAPHITE
SUBCATEGORY
VI-47
-------
Level 1 treatment of machining, grinding, and scrubber effluent
has been observed in industry without oil skimming and sampling
has verified that a clarifier without polymer addition can main-
tain a TSS level of less than 24 mg/1 (Table 6-9).
Level 2 treatment of extrusion and impregnation quench streams has
not been observed in industry, but discussion with industry repre-
sentatives has indicated that recycle would not affect product
quality. The only reservation expressed by industry was that the
recycled water may require cooling to prevent a build-up of heat
in the quench tank. A typical quench tank operates at 30-35°C
(85-95°F) and uses make-up water of 15-20°C (60-70°F).
Performance figures are based upon data from treatment component
performance observed in other industries. This performance data
is applicable to the Carbon and Graphite industry. Section XII
describes the treatment components and systems and the typical
performance levels achievable by each component and system.
System performance is presented in Table 6-12 for Level 1 systems,
Level 2 is total recycle.
Estimated Cost of Recommended Treatment Systems
The procedures and process assumptions for determining estimated
costs for the recommended treatment system components are discussed
in Section XII and Section XIII of this report. Tables 6-13 to
6-24 present estimated costs for each of the recommended treatment
systems previously discussed.
Costs have been estimated for two types of waste (1) machining,
grinding and scrubber wastewater and (2) quench wastewaters, for
both the Level 1 and Level 2 treatment systems. Three different
flow rates were used for each waste type to present the variation
in system costs resulting from changes in system flow rates. The
three flow rates for each waste stream are characteristic of a
small, medium, and large wastewater discharge within the Carbon
and Graphite industry for both types of waste streams.
BENEFIT ANALYSIS
This section presents an analysis of the industry-wide benefit
estimated to result from applying the two levels of treatment
previously discussed in this section to the total process waste-
water generated by the Carbon and Graphite subcategory. This
analysis estimates the total amount of pollutants that would not
be discharged to the environment if the two levels of treatment
were applied on a subcategory-wide basis. An analysis of the
benefit versus estimated subcategory-wide cost for each of the
treatment levels will also be provided.
Vl-48
-------
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VI-62
-------
Industry-wide Costs
By multiplying the cost of each level of treatment at various flow
rates by the number of plants in each flow regime in the industry,
a subcategory-wide cost figure is estimated (Table 6-25). This
figure represents the total cost of each treatment level for the
entire Carbon and Graphite subcategory. This calculation does not
make any allowance for waste treatment that is currently in-place at
Carbon and Graphite facilities.
Industry-wide Cost and Benefit
Table 6-26 presents the estimate of total cost to the Carbon and
Graphite subcategory to reduce pollutant discharge. This table also
presents the benefit of reduced pollutant discharge for the Carbon
and Graphite subcategory resulting from the application of the two
levels of recommended treatment. Benefit was calculated by multi-
plying the estimated number of gallons discharged by the subcate-
gory times the performance attainable by each of the recommended
treatment systems as shown in Table 6-12. Values are presented for
each of the selected subcategory pollutant parameters.
The column "Raw Waste" shows the total amount of pollutants that would
be discharged to the environment if no treatment was employed by any
facility in the industry. The columns under.Levels 1 and 2 show
the amount of pollutants that would be discharged if each level of
treatment were applied to the total wastewater estimated to be dis-
charged by the carbon and graphite subcategory.
The total amount of wastewater .discharged from each level of treat-
ment is also presented in this table to indicate the amount of pro-
cess wastewater to be recycled by each of the levels of treatment.
Process wastewater recycle is a major step toward water conservation
and reduction in pollutant discharge.
VI-63
-------
TABLE 6-25
Carbon and Graphite Subcategory
Industry-wide Cost Analysis
Extrusion and Impregnation Quenches
Investment*
Annual Costs
Capital Costs
Depreciation
Operation & Maint.
Energy and Power
Total Annual Cost
LEVEL 1
2429578.1
204851.45
485915.61
390493.48
0.0
1081260.6
LEVEL 2
9380265.4
790892.7
1876052.9
658505.4
57495.1
3382944.8
Machining, Grinding, and Scrubber Effluent
Investment*
Annual Costs
Capital Costs
Depreciation
Operation & Maint.
Energy and Power
Total Annual Cost
LEVEL 1
3369762.5
284123.42
673952.5
303572.15
2224.586
1263872.8
LEVEL 2
3549162.5
299247.0
709832.5
474862.7
4824.56
1488766.8
* Based on 26 plants estimated to discharge process wastewater
from these processes.
VI-64
-------
TABLE 6-26
Cartoon and Graphite Subcategory
Didustry-wide Cost and Benefit Analysis
Machining, Grinding, and Scrubber Effluent
Parameter
Plow (Million liters/year)
120 Copper
122 Lead
128 Zinc
Ibtal Suspended
Solids
total Organic
Carbon
Oil and Grease
Iron
Aluminum
Annual Cost
Extrusion and Impregnation Quenches
Plow (Million liters/year) 5980 5980
Oil and Grease 47421.4 NC
Raw Waste
kg/year
304.2
370.82
66.62
54.15
186200.0
107534.7
3437.5
1673.1
542.4
Level 1
kg/year
304.2
247.6
15.21
54.15
5414.8
NA*
3346.2
242.5
.NA
1081260.6
Level 2
304.2
%
1
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3382944
5980
Recycle-Zero Discharge
Annual Cost
1263872.8 1488766.8
NC - No Change In Concentration Due To Treatment
*NA - Not Available
VI-65
-------
-------
SECTION VII
DIELECTRIC MATERIALS SUBCATEGORY
INTRODUCTION
This discussion of the dielectric materials subcategory consists of
the following major sections:
Products
Size of Industry
Manufacturing Processes
Materials
Water Usage
Production Normalizing Parameters
Waste Characterization and Treatment in Place
Potential Pollutant Parameters
Applicable Treatment Technologies
Benefit Analysis
Data contained in this section were obtained from several sources.
Engineering visits were made to six plants within the industry.
Wastewater samples were collected from 3 facilities. A total of
63 dielectric materials manufacturing plants were contacted in
this survey by telephone. These plants include manufacturers
that use dielectric materials in wet capacitors and transformers.
A literature survey was also conducted to ascertain differences
between types of dielectric materials, process chemicals used, and
typical manufacturing processes.
PRODUCTS
This product subcategory consists of both dielectric-containing de-
vices such as oil filled transformers and capacitors in addition
to the miscellaneous dielectric products themselves (except por-
celain and glass) such as mica paper (used in fixed capacitors),
phenolics, laminates, fiberglass, polyesters, and rubbers. There
are three major wastewater producing products in the dielectric
subcategory: oil filled transformers, oil filled capacitors, and
mica paper dielectric. Only those processes unique to the E&EC
category will be discussed, other processes are considered in
other development documents, particularly, the Metal Finishing
Subcategory.
Oil Filled Transformers for Power, Distribution, and Special
Applications
Transformers can be classified into two groups, namely oil filled
("wet") transformers and non-oil filled ("dry") transformers. Most
VII-1
-------
of the larger transformers such as power and-distribution transfor-
mers are oil filled. Small high-voltage transformers such as auto-
motive ignition coils are wet while virtually all of the smaller
low-voltage transformers are dry.
Electric power is transmitted by increasing the voltage at the
generator, transmitting it to distant locations via high voltage
transmission lines, and then reducing the voltage successively at
substations, at primary feed substations, and at distribution points
to the consumption level. Thus, the transmission and distribution
of electric power requires a substantial number of transformers, al-
most all of which are oil filled. Power and distribution transformers
account for a sizable part of the transformer industry (63% of the
total dollar value of transformer sales).
Small low voltage transformers are used as fluorescent lamp bal-
lasts (accounting for 10% of the total dollar value of transformer
sales). Other common uses of low voltage transformers include
signalling and doorbell transformers, machine tool controls,
general industrial and commercial uses, power regulation, and
instrument transformers.
Production of the different classes of transformers is summarized
below in terms of percent of total annual dollar value. This in- •
formation was obtained from the 1977 Department of Commerce Census
of Manufactures (Preliminary Statistics).
% Total Annual
Dollar Value
Power and distribution
transformers
Fluorescent lamp ballasts
Specialty transformers (except
fluorescent lamp ballasts)
Power regulators, other trans-
formers , parts
(Other not specified by type)
63.0%
10.0%
16.4%
8.0%
2.6%
100.0%
The total annual value of transformer shipments for 1977 is estimated
to be $2,084,000,000.
Oil Filled Capacitors
Oil filled capacitors can be separated into two categories by size:
larger sized capacitors generally used for power factor correction
and smaller sized capacitors used for electric motor control and
in fluorescent lamps.
VII-2
-------
Production of the different classes of transformers is summarized
below in terms of percent of total annual dollar value. This in-
formation was obtained from the 1977 Department of Commerce Census
of Manufactures (Preliminary Statistics).
Shunt and series power capacitors,
units and equipment, 1/2 KVA and
above, and accessories for ,power
factor correction and other low-
frequency a,c. applications.
A.C. capacitors, except electro-
lytic; general purpose, for
motors, controls, etc.; capaci-
tors for fluorescent lamp
ballast; and other capacitors.
Capacitors for industrial use
except for electronic appli-
cations.
% Total Annual
Dollar Value
41.6%
57.7%
0.7%
100.0%
The total annual value of transformer shipments is estimated to be
$154,900,000 for 1977.
Mica Paper Dielectric
Mica paper is a dielectric material used in the manufacture of fixed
capacitors. Fixed capacitors are layered structures of conductive and
dielectric (insulating) surfaces. The layering of fixed capacitors
is either in the form of rigid plates or in the form of thin sheets
of flexible material which are rolled. Fixed capacitor types are
distinguished from each other by type of conducting material, dielec-
tric material, and encapsulating material. Mica paper is one of the
dielectrics used in fixed capacitors and is included in this section
because of the large quantities of process water required in its pro-
duction. No other mica applications have been addressed in this docu-
ment .
Miscellaneous Dielectrics
Miscellaneous dielectrics are summarized in Table 7-1. Table 7-1 al-
so presents a summary of the manufacturing processes used in the pro-
duction of miscellaneous dielectrics, process water used, and waste-
water treatment. This listing is based on telephone contacts with
32 plants. Most electrical insulators are manufactured of phenolic,
VII-3
-------
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laminates, fiberglass, polyesters, or molded dense rubber. Insula-
ting parts manufactured of rubber and various plastics are made by
molding, cutting, stamping, extruding, punching and various machine
forming operations. An undetermined amount of water is used
in quenching, spray contact cooling or wet machining. These
products and manufacturing processes are covered under existing
or proposed documents. Therefore, miscellaneous dielectrics
will not be discussed further in the E&EC category.
SIZE OF INDUSTRY
The size of the dielectric materials industry is presented in the
following paragraphs in terms of number of plants, number of produc-
tion employees, and production rate. Each of these values represents
is estimated based upon data collected from visited facilities, tele-
phone surveys and literature surveys«
Number of Plants
Transformers -• It is estimated that 280 plants are engaged in the
manufacture of both wet and dry transformers. This estimate is
based on the following three sources of information:
1977 Dun and Bradstreet listing of companies engaged
in business within the SIC 3612 category. Known non-
manufacturers (distributors) were removed from the
listing. Prom this modified listing, 350 plants are
estimated to be engaged in the manufacture of trans-
formers .
Department of Commerce 1977 Census of Manufactures
(Preliminary Statistics). A total of 280 plants were
estimated to be engaged in the manufacture of trans-
formers .
Department of Commerce 1972 Census of Manufactures.
A total of 210 plants were estimated to be engaged
in the manufacture of transformers.
Oil Filled Capacitors - It is estimated that 30 to 50 plants are
engaged xn the manufacture of oil filled capacitors. This estimate
is based on the following two sources:
Department of Commerce 1977 Census of Manufactures
(Preliminary Statistics). A total of 30 to 50
plants were estimated to be engaged in the manufac-
ture of oil filled capacitors. *
Department of Commerce 1972 Census of Manufactures.
A total of 36 to 60 plants were estimated to be en-
gaged in the manufacture of oil filled capacitors.
VII-5
-------
Mica Paper Dielectric - It is estimated that 12 to 18 plants are en-
gaged in the manufacture of mica paper. This estimate is based on a
telephone survey of manufacturers producing mica paper.
Number of Employees
Transformers - It is estimated that between 32,700 and 46,600
production employees are engaged in the manufacture of both wet
and dry transformers. These estimates are based on the follow-
ing sources:
. Department of Commerce 1977 Census of Manufactures
(Preliminary Statistics). A total of 32,700 produc-
tion workers were estimated to be engaged in the man-
ufacture of transformers.
. Department of Commerce 1972 Census of Manufactures
lists 46,620 production workers engaged in the manu-
facture of transformers.
Twenty-nine transformer plants were visited or surveyed by telephone.
Each plant employs between 35 and 4,000 production employees. The
majority of plants contacted have between 140 and 300 production em-
ployees .
Oil Filled Capacitors - It is estimated that between 2,200 and 4,800
production employees are engaged in the manufacture of oil filled
capacitors. These estimates are based on the following sources:
Department of Commerce 1977 Census of Manufactures
(Preliminary Statistics). A range of 2,200 to 3,800
production workers were estimated to be engaged in
the manufacture of oil filled capacitors.
Department of Commerce 1972 Census of Manufactures.
A range of 2,800 to 4,800 production workers were
estimated to be engaged in the manufacture of oil
filled capacitors. •
Eight oil filled capacitor plants were visited or surveyed by tele-
phone. Each plant employs between 30 and 350 production workers.
Mica Paper Dielectric - It is estimated that between 250 and 450 pro-
duction employees are engaged in the manufacture of mica paper dielec-
tric. Typical plants surveyed employ between 20 and 40 production
workers. These estimates are based on a telephone survey of manufac-
turers producing mica paper.
MANUFACTURING PROCESSES
The manufacturing processes for dielectric materials are described in
the following paragraphs. The use of dielectric fluids in wet trans-
VII-6
-------
formers and capacitors, and the manufacture of mica paper dielectric
are discussed in terms of typical production processes for each of '
these products. > , ,
Wet Transformers
Power transformers are the largest transformers made and are used at
power generating stations to increase voltages to high levels for
transmission (e.g. 765,000 volts). A typical process flow diagram
for wet power transformer manufacture is given in Figure 7-1.
The main operations in manufacturing a power transformer are common
to all transformer manufacture. They are the manufacture of a steel
core, the winding of coils, and the assembly of the coil/core on some
kind of frame or support. A significant difference between "dry" and
"wet" transformer manufacture is the need for a container or tank
to contain the dielectric fluid in the case of "wet" transformers.
In addition, the larger wet transformers have radiators attached to
air-cool the dielectric fluid. Oil filled transformers must be free
of moisture, because any water diminishes the effectiveness of the
dielectric and can lead to a short circuit failure.
Coil-winding starts with the manufacture of a cylindrical pressboard
or phenolic plastic form, which is saturated with transformer oil.
Copper wire, wound with 12-18 wraps of paper insulation, is wound
around the coil form. A series of paper and paperboard or phenolic
plastic spacers is.added to the form during winding to separate the
coils. Upon completion of winding all coils on a form, the windings
are compressed axially in a press to the required size. The wound
coil is then heated and vacuum dried to remove residual moisture.
Flooding the coil with oil impregnates the coil. Finally the coil
is compressed a second time.
In the four wet transformer plants visited, transformer oil is care-
fully handled to prevent its escape into the environment. Vacuum
impregnation processes use chamber flooding to introduce the oil
into the coil assembly. The process takes several days, and ade-
quate time is allowed to let free oil drip off the coils and hand-
ling equipment while still inside the chamber, s Minimal evidence of
oil spillage was observed anywhere in the manufacturing plants.
Solid absorbents were used for collecting the small quantities of
spilled oil.
Core fabrication starts by cutting thin strips of silicon steel to
size. These strips of steel are stacked to form the core. Coils
are then placed over legs of the core. The top yoke is placed,on
the top of the assembly. Kraft paper and/or phenolic spacers are
added to the assembly as an insulator, the complete assembly is dried
in a chamber, and transformer oil is added manually to saturate the
assembly.
VII-7
-------
Hake Coil
Hake Core
Make Tank
Assenbly
Cut Grain
Oriented Silicon
Steel
Assemble core
. By Stacking
Steel Leaves
Core
iy
)ver
Processes with uastewater
discharges are unknown
FIGURE 7-1
OIL FILLED TRANSFORMER MANUFACTURE
VII-8
-------
Tank fabrication starts by shot blasting carbon steel plates. The
plates are cut to size by shearing or burning with a torch. Smaller
steel parts are deburred in a water solution and rinsed in a rust
inhibiting solution. The tank is welded using submerged arc
welding. Radiators, bought from an outside supplier, are
welded to some tanks and bolted to others. The tank is deter-
gent washed and rinsed. An epoxy primer is applied and then baked on.
The tank is then coated with an alkyd finish coat. Core and
tank fabricating and welding process operations are discussed
further under the Metal Finishing Category.
Pans, a control unit and, in some cases, radiators are attached in
pre-assembly. The coil-core assembly is placed into the tank, con-
nections are made and bushings are attached to the unit in final
assembly. The unit is evacuated to remove any water vapor and then
filled with oil. The completed transformer is then tested.
Oil Filled Capacitors
Large oil filled capacitor containers are produced manually and
are made of steel or aluminum. Large oil filled capacitors are often
used in corrosive environments, and their containers are often pro-
tected by phosphate or chromate surface treatment and subsequent paint-
ing. Container preparation for large oil filled capacitors can dis-
charge cleaning and coating wastes. Special ceramic insulators are
used to separate the cover from the terminals.
Small oil filled capacitor containers of aluminum or steel are
fabricated on a dry automatic impact extruder. The containers for
small oil filled capacitors are usually unfinished. Hence, there is
no wastewater discharge associated with their fabrication. Figure
7-2 depicts a typical production process. In addition, small oil
filled capacitors utilize a number of automatic operations to pro-
vide insulated terminals that connect to the interior wiring. These
operations usually do not have a wastewater discharge.
The electrical leads of the winding are manually soldered to the
terminal connections on the cover of all capacitors. The covers are
welded to the capacitor container to form a sealed capacitor. There
is a fill hole in the cover that is left open for subsequent oil fil-
ling operations. The soldering and welding operations do not usually
result in a wastewater discharge.
The conditioning process for small oil filled capacitors takes place
after the sealed capacitors are loaded into a filling chamber. The
sealed capacitors are conditioned prior to filling by baking at
moderate temperatures under heavy vacuum for several hours. While
still under vacuum, the chamber is flooded with dielectric fluid.
The dielectric enters the fill holes until the capacitors are com-
pletely filled. The chamber is then allowed to drain and the small
oil filled capacitors are removed. After removal, the fill holes are
VII-9
-------
CONTAINER
MANUFACTURE
SURFACE
TREATMENT
I
EXTERIOR
PAINTING
PHOSPHATE
OR
CHROMATE
(covered under MFC)
DIELECTRIC
OIL
FILLING
DETERGENT
WASH
I
WATER
RJNSE
1
SOLDER
LEADS
CONDITIONING
1
ELECTRICAL
EVALUATION
SHIP
*• Denotes
Wastewater
Flow Paths
. -
'-if**
FIGURE 7-2
OIL-FILLED CAPACITOR MANUFACTURE
VII-10
-------
soldered closed. Large oil filled capacitors are filled individually
with a hose. A special one way valve prevents the dielectric fluid
from escaping. These operations are dry and do not result in "a waste-
water discharge.
Oil filled capacitors are usually cleaned with solvent after filling
with dielectric fluid. The solvent is recovered, distilled, reused.
One facility cleans the exterior of the small oil filled capacitors
with a water wash which results in a wastewater discharge (this
cleaning process has been eliminated and a solvent cleaning step
has been instituted since the time of the plant visit). Large
capacitor manufacture did not result in a wastewater discharge at
any of the visited facilities.
Mica Paper Dielectric
Mica paper manufacturing requires significant quantities of process
water. This water is used for carrying mica in a slurry. Figure 7-3
depicts a typical production process.
Mica is heated in a kiln and then placed in a grinder where water
is added. The resulting slurry is passed to a double screen sepa-
rator where undersized and oversized particles are separated. The
screened slurry flows to a mixing pit and then to a vortex cleaner.
The properly sized slurry is used in a paper-making machine where
excess water is drained or evaporated. The resulting cast sheet of
mica paper is fed on a continuous roller to a radiant drying oven,
where it is cured. From there, the mica paper is wound onto rolls,
inspected and shipped.
Mica particles too fine for use are discharged in process wastewater.
All process wastewater is treated by settling.
MATERIALS
Materials used in the dielectric materials subcategory are discussed
in the following paragraphs. Materials are listed in terms of their
use in wet transformers, oil-filled capacitors, and mica paper dielectric,
Wet Transformers
Materials used in the manufacture of oil filled transformers are:
Silicon Steel - This magnetic steel is wound or
stacked in sheets to form the magnetic iron core.
Copper Wire - Used to wind the primary and secondary
coils,,of most transformers.
Aluminum Wire - Used to wind the coils of some trans-
formers.
VII-11
-------
u
VII-12
-------
Carbon Steel - Used for manufacturing transformer
tanks or casings and for making radiators used in
larger transformers.
Insulating Paper and Paperboard - Used to insulate
the coil wire and serve as spacers between windings.
Paper board is used to form the inner cylinder of
larger concentric coils or as a flat platform for
flat interleaved type coils. Kraft paper, the most
extensively used insulating paper, is made from wood
fiber;^manila paper from Manila hemp; kraftboard from
wood fiber; and pressboard from wood and cotton.
Laminated Phenolic Resin - Used for forming the inner
cylinder of some coils and used as insulating spacer
material.
Hardwood (maple) - Used as insulated support in some
power transformers.
Ceramic Bushings - Used for external connections to
the primary and secondary transformer windings.
Varnishes, Lacquers, and Shellacs - Used to coat windings
and for insulation of dry transformers to seal them from
moisture.
Enamel Coating - Used to coat some core steel before
forming the core.
Paints (Epoxys, Alkyd coatings, PVC coatings, Polyurethane
paints, etc) - Used to coat transformer cans or tanks.
Nitrogen Gas - Large transformers are filled with nitrogen
gas after the unit is tested and drained of oil. The trans-
former is shipped with N, under a slight positive pressure
to prevent leakage of air and moisture into the transformer,
Light Petroleum Distillate (similar to kerosene) — Used as
vapor to heat coil-core assemblies to drive out moisture
prior to flooding with transformer oil.
Transformer Oils - Used to impregnate insulation and
spacers of coil-core assemblies of large, "wet" trans-
formers.
Dielectric Fluid - Most oil filled transformers contain
a highly refined petroleum oil similar to low viscosity
lubricating oil. Some transformers are filled with a
gaseous dielectric fluid, e.g. perfluoroethane.
VII-13
-------
These dielectric fluids are basically organic liquids, such as lubri-
cating oil, used as an electrical dielectric (or insulator) and serve
as heat transfer media for cooling electrical components. In the
E&EC category, dielectric fluids are used in larger transformers, and
oil filled capacitors. In transformers, the quantity of fluid re-
quired varies from about 35 liters to 105,000 liters.
Previously, polychlorinated biphenyl (PCB) was used as the dielectric
fluid in practically all fluid filled capacitors and transformers.
The manufacture of PCB dielectric fluid ended in 1978. The PCB rule
prohibits PCB manufacture after July 1, 1979. Problems related to
PCB use as a dielectric fluid are discussed in Appendix >A of this
report.
Substituting other dielectric fluids for PCB is required by law.
There are several fire resistant fluids which are proposed as sub-
stitutes for PCB. Table 7-2 presents a summary of PCB substitute
dielectric fluids currently used or proposed for use in oil filled
capacitors and oil filled transformers. Di-n-octyl phthalate is
widely used in fluid filled capacitors. Silicone oils are probably
the most popular PCB substitute for transformer oils.
Oil Filled Capacitors
Materials required in the manufacture of oil filled capacitors are
similar to those of the transformers listed above. These materials
are:
Insulating Paper
Polypropylene Sheet
Aluminum Sheet
Steel Casing
Dielectric Fluids
Oil filled capacitors utilize the same dielectric fluids as trans-
formers with capacities ranging from a few milliters to as many as
25 liters. Capacitor assembly and manufacturing is another subcate-
gory.
Mica Paper Dielectric
Mica paper in its simplest form is pure mica, but for some applica-
tions, a lamination of plastic on both sides of the mica sheet may be
required. These are the only process material requirements for the
production of mica paper.
VII-14
-------
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WATER USAGE
Host manufacturers of oil filled transformers and capacitors have
eliminated the use of water from their production steps. Some of
them have accomplished this by employing solvent cleaners. Other
manufacturers require water for the cleaning of transformer and
capacitor casings prior to painting and coating. Cleaning, pain-
ting, and coating are processes included within the Metal Fini-
shing Category Document. Some manufacturers perform a cleaning
operation on transformers and capacitors after filling with dielec-
tric fluids. These manufacturing processes will be discussed in
this section.
The production of mica paper dielectric is totally dependent on pro-
cess water. Unlike oil filled transformers or capacitors, water
is used in large quantities throughout each step of production.
Transformers
From the 1972 Census of Manufactures, gross water usage is estimated
to be 198.8 million liters per day (52 million gallons per day) for
wet and dry transformer manufacture. Approximately 63% of gross
water usage is recycled. Only 3% of gross water used, 6.06 million
liters per day (1.6 million gallons per .day) is process water.
From plant contacts and visits, it was observed that most of the
manufacturing process water used is for non-contact cooling water.
From these same sources, it was found that all process water was
used in metal cleaning processes prior to coating.
From the 1972 Census of Manufactures, the amount of water discharged
which includes both process and non-process water is estimated at
33% of gross water usage or 64.7 million liters per day (17.1 mil-
lion gallons per day). Nine percent or 64.7 million liters per day
(1.5 million gallons per day) of this discharged water is estimated
to be treated. As shown in Table 7-3, most process water used is
simply discharged without treatment.
All of the visited plants made use of process water only in metal
cleaning operations and conversion coating (see Table 7-3). The
plants surveyed by phone indicated that their transformer manu-
facturing either required no process water or required use of
process water only in conjunction with metal coating or electro-
plating operations.
Oil Filled Capacitors
Some water usage was observed in oil filled capacitor manufacturing.
Table 7-4 summarizes the survey results and shows that two of the
eight plants contacted use a detergent wash upon completion of the
capacitor fill step. The single plant visited discharges 432,000
liters per day (114134 GPD) from this detergent wash process and
phosphatizing.
VII-16
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The remaining manufacturers contacted do not use process water
by either using solvent degreasing when cleaning is required or by
employing manufacturig techniques that avoid the need for cleaning
after filling. The visited capacitor facilities that used a water
wash after filling operations are now using a solvent cleaning step
and are not discharging process wastewater unique to E&EC manufac-
turing.
Mica Paper Dielectric
Water usage was observed in all mica paper dielectric manufacturing.
Table 7-5 summarizes the water usage, which ranges from 3,506,000
liters/day (926285.2 GPD) to 31,400 liters/day (8295.9 GPD). The
water is necessary first to saturate, separate, and break down the
raw mica into flakes and then :to carry the refined mica through its
^deposition onto the web of the paper machine.
PRODUCTION NORMALIZING PARAMETERS
Production normalizing parameters are used to relate the pollutant
mass discharge to the production level of a plant. Regulations ex-
pressed in terms of this production normalizing parameter are multi-
plied, by the value of this parameter at each plant to determine the
allowable pollutant mass that can be discharged. Meaningful pro-
duction normalizing parameters for dielectric materials subcategory
that have been considered are:
Size, complexity and other product attributes that affect
the amount of pollution generated during manufacture
of a unit.
Manufacturing processes, but differences in processes
for the same product result in differing amounts of
pollution.
Production records, but lack of applicable data may
impede determination of production rates in terms of
desired normalizing parameters.
Several other broad strategies which have been developed to deter-
mine normalizing parameters. They are as follows:
The process approach •- In this approach, the production
normalizing parameter is a direct measure of the produc-
tion rate for each wastewater producing manufacturing
operation. These parameters may be expressed as sq.m.
processed per hour, kg of product processed per hour, etc.
This approach requires knowledge of all the wet pro-
cesses used by a plant because the allowable pollutant
discharge rates for each process are added to determine
the allowable pollutant discharge rate for the plant.
Regulations based on the production normalizing parame-
ter are multiplied by the value of the parameter for
each process to determine allowable discharge rates from
each wastewater producing process.
VIi-19
-------
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Concentration limit/flow guidance - This strategy limits
effluent concentration. It can be applied to an entire
plant or to individual processes. To avoid compliance
by dilution, concentration limits must be accompanied by
flow guidelines. The flow guidelines, in turn, are ex-
pressed in terms of the production normalizing parameter
to relate flow discharge to the production rate at the
plant.
The following paragraphs present selected production normalizing
parameters for the dielectric materials subcategory and the rationale
used in their selection.
Wet Transformers and Oil Filled Capacitors
The manufacturing processes used in the production of wet transformers
and oil filled capacitors are similar in regard to dielectric fluid
cleanup. In both wet transformers and oil filled capacitors a waste-
water discharge results from cleaning the unit after filling. Pol-
lutants entering the waste stream are generated partly as a direct
result of the washing and rinsing of the exterior of the product to
remove excess dielectric fluid.
Much of the pollutant discharge is not directly related to production.
At one visited facility, for example, the treatment system is used
to remove residual PCB fluid from contaminated plant grounds. This
type of discharge can best be regulated by determining an allowable
pollutant discharge concentration. Therefore, use of a production
related normalizing parameter is not appropriate, and effluent
limitations should be expressed in terms of concentration only.
Mica Paper Dielectric
Based upon the nature of the mica paper manufacturing industry, the
mass of mica processed has been selected as the production normali-
zing parameter. This selection is based upon the fact that the
principal factor affecting wastewater characteristics is the amount
of mica produced.
The processes used in mica paper dielectric manufacturing requires
the use of mica and water only. As the mica is processed in-
to its final form, wastewater containing the inert mica is produced.
This wastewater production occurs only when the manufacturing proces-
ses are operating. Since several different thicknesses of mica paper
are produced, the area of the paper may not be indicative of the amount
of wastewater generated. This leaves the weight or mass of mica paper
produced as the most applicable production normalizing parameter.
These data are easily obtainable because they are collected by man-
ufacturers as a means of controlling productivity of the plant.
VII-21
-------
WASTE CHARACTERIZATION AND TREATMENT IN PLACE
This section will present the sources of wastewater in the dielectric
materials subcategory, sampling results of this wastewater, and treat-
ment currently in place at these facilities. Wastewater produced
by mica paper manufacturing will be discussed separately because
of waste characteristics and treatment technology.
Process Descriptions and Water Use
Wet Transformers - Two types of transformers are manufactured: wet
(filled with dielectric fluid) and dry. Both types of transformers
use standard metal finishing processes. Wet transformers use wet
processes unique to this subcategory of the E&EC category for
clean-up of dielectric fluid spills and management of residual
PCB fluid spills.
Oil Filled Capacitors - Oil filled capacitors require process water
that is specific to the E&EC industry. This process water is used
in the clean-up of dielectric fluid that spills or overflows when
the capacitor is filled and water used for case wash.
There are two distinct sizes of capacitors that are filled with di-
electric fluid, and the technique of filling the two categories of
capacitors differs. Larger capacitors are filled individually through
a hose connection, and smaller capacitors are batch filled in racks
within a chamber, which is evacuated and then flooded with dielectric
fluid. A small amount of spillage occurs when disconnecting the fill
hose from the larger capacitors. The spilled dielectric is generally
washed away with a solvent which is reclaimed. This procedure does
not result in any wastewater discharge.
The racks of smaller capacitors coming from the flooded chambers
are washed either by an organic solvent which can be recycled or by
a detergent wash and rinse. At Plant ID 30082 the detergent wash
may be recycled, but the rinses are discharged. This discharge
carries dielectric fluid into the environment. However, the
plant is now using a solvent washer for cleaning these capaci-
tors with no discharge to waste treatment.
Mica Paper Dielectric - The manufacture of mica paper dielectric re-
quires inert mica and water as process materials. The mica is ground
into fine particles and mixed with water into a slurry. This slurry
is then cast into a sheet on a moving belt and the water is drained
and evaporated. The mica sheet is then rolled and prepared for ship-
ment. The wastewater generated by this process comes from the drain-
age on the moving belt and from the slurry which is discarded.
VTI-22
-------
Since particle size of mica flakes is important in producing mica
paper that is both flexible and durable, the manufacturing process
rejects those particles too small and discharges them with
process wastewater. The above represent the only process
wastewater specific to mica paper dielectric production.
Wastewater Analysis Data
Process wastewater and effluent discharges from dielectric materials
manufacturing were sampled at three facilities. Samples were analyzed
for parameters identified on the list of 129 toxic pollutants,
non-toxic metals, and other pollutants presented in Table 7-6.
Tables 7-7 through 7-12 present sampling analysis data for detected
parameters in raw process wastewaters and treated effluents for
those plants sampled within the dielectric materials subcategory.
Pollutant parameters are grouped according to toxic organics,
toxic metals, non-toxic metals, and other pollutants. Total
pollutant concentrations are presented as well as mass loadings
of those pollutant parameters. Mass loadings were derived by
multiplying concentration by the flow rate and the hours per
day that a particular process is operated. Some entries were
left blank for one of the following reasons: the parameter was
not detected? the concentration used for the kg/day calculation is
less than the lower quantifiable limits or not quantifiable. The
kg/day is not included in totals for calcium, magnesium, and
sodium. The kg/day is not applicable to pH. Totals do not include
values preceded by "less than".
Only a limited amount of stream analysis data is available. Toxic
organics, toxic metals and non-toxic metals were detected at
measurable levels as well as at levels below the limit of quanti-
tative measurement. Other parameters are all reported in measurable
quantities. The following conventions were followed in presenting
the data: ^
Trace Levels - Pollutants detected at levels too low to
measure are reported as less than (<) the minimum limit
of measurement for the test method used.
Pollutant Loads - Pollutant loads are calculated for
measureable pollutants by multiplying concentration
by flow and daily flow durations. This procedure gives
calculated pollutant loads in kg/day by pollutant for
each stream sampled. ,
VI1-23
-------
TABLE 7-6
POLLUIANT PARAMETERS ANALYZED
TOXIC ORGANICS
1. Acenaphthene 46.
2. Acrolein 47.
3. Acrylonitrile 48.
4. Benzene 49.
5. Benzidine 50.
6. Carbon Tetrachloride(Tetrachloromethane) 51.
7. Chlorobenzene 52.
8. 1,2,4-Trichlorobenzene 53.
9. Hexachlorbenzene 54.
10. 1,2-Dichlorethane 55.
11. 1,1,1-Tridiloroethene 56.
12. Hexachloroethane 57.
13. 1,1-Dichloroethane 58.
14. 1,1,2-Trichlroethane 59.
15. 1,1,2,2-Tetrachloroethane 60.
16. Chloroethane 61.
17. Bis(Oiloranethyl}Ether 62.
18. Bis(2-Chloroethyl)Ether 63.
19. 2-Chloroethyl Vinyl Ether(Mixed) 64.
20. 2-Chloronaphthalene 65.
21. 2,4,6-Trichlorophenol 66.
22. Parachloroneta Cresol 67.
23. Chlorofonn(Trichloromethane) 68.
24. 2-Chlorophenol 69.
25. 1,2-Dichlorobenzene 70.
26. 1,3-Oichlorobenzene 71.
27. 1,4-Dichlorobenzene 72.
28. 3,3'-Dichlorobenzidine 73.
29. lA-Dichlocoethylene 74.
30. 1,2-Trans-Dichloroethylene 75.
31. 2.4-Dichlorophenol 76.
32. 1,2-Dichloropropane 77.
33. l,2^icMorcpropylene(l,3-^ichloropropene) 78.
34. 2,4HDimethylphenol 79.
35. 2,4-Dinitrotoluene 80.
36. 2,6-Dinitrotoluene 81.
37. 1,2-Diphenylhydrazine 82.
38. Ethylbenzene 83.
39. Fluoranthene 84.
40. 4-ChlorophenylPhynyl Ether 85.
41. 4-BroK^>henylPhenyl Ether 86.
42. Bis(2-Chloroisoprcpyl)Ether 87.
43. Bis(2-Chloroethoxy)Methane 88.
44. Methylene Chloride(Dichloromethane) 89.
45. Methyl Chloride (Chloromethane) 90.
Methylbromide (Bromomethane)
Bromoform (Tribromonethane)
Dichlorobromone thane
Trichlorofluoromethane
Dichlorcdifluoromethane
Chlorodibromome thane
Hexachlorobutadiene
Hexachlorocyclopentadiene
Isophorone
Naphthalene
Nitrobenzene
2, 4-Dinitrophenol
4, 6-Dinitro-o-cresol
N-Nitrosodimethylamine
N-^itrosodiphenylaraine
N-Nitrosodi-N-Propylamine
Pentachlorophenol
Phenol
Bis ( 2-Ethylhexyl ) Phthalate
Butyl Benzyl Phthalate
Di-N-Butyl Phthalate
Di-N-Octyl Phthalate
Diethyl Phthalate
Dimethyl Phthalate
1 , 2-Benzanthracene (Benzo (A) Anthracene )
Benzo ( A)Pyrene ( 3 , 4-Benzo-Pyrene )
3 , 4-Benzof luoranthene ( Benzo ( B ) Fluoranthene )
11 , 12-Benzof luoranthene ( Benzo ( K ) Fluoranthene )
Chrysene
Acenaphthylene
Anthracene
1 , 12-Benzoperylene ( Benzo ( (KI ) -Perylene )
Fluorene
Phenanthrene
1,2, 5, 6-Dibenzathracene(Dibenzo(A,H)Anthracene)
Indeno (1,2, 3-CC ) Pyrene ( 2 , 3-o-PhenylenePyrene )
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Vinyl Chloride (Chloroethylene)
Aldrin
Dieldrin
VII-24
-------
TABLE 7-6 Con't
91. Chlordane(TechnicalMixtureandMetabolites) 112.
92. 4,4'-DOT 113.
93. 4,4I-DDE(P,P'-DDX) TOXIC
94. 4,4'-DDD(P1FP'-TDE) 114.
95. Alpha-Endosulfan 115.
96. Beta-Endosulfan 117.
97. Endosulfan Sulfate 118.
98. Endrin 119.
99. Endrin Aldehyde 120.
100. Heptachlor 121.
101. HeptachlorEpoxide(BHC-Hexachlorocyclo- 122.
hexane) 123.
102. Alpha-BHC 124.
103. Beta-BHC 125.
104. Gamma-BHC(LIndane) 126.
105. Delta-BHC(PCB-Polychlorinated Biphenyls) 127.
106. PCB-1242(Arochlor 1242) 128.
107. PCB-1254(Arochlor 1254)
108. PCB-1221(Arochlor 1221)
109. PCB-1332(Arochlor 1232)
110. PCB-1248(Arochlor 1248)
111. PCB-1260(Arochlor 1260)
129. 2,3,7,8-Tetrachlorcdibenzo-P-Dioxin (TCDD)
PCB-1016(Arochlor 1016)
Toxaphene
METALS
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
NON-TOXIC METALS
Calcium
Magnesium
Aluminum
Manganese
/Vanadium
Boron
Barium
Molybdenum
Tin
Yttrium
Gobalt
Iron
Titanium
OTHER POLLUTANTS
Oil & Grease
Total Organic Carbon
Biological Oxygen Demand
Total Suspended solids
Phenols
Fluoride
Xylenes
Alkyl Epoxides
VII-25
-------
TABLE 7-7
OIL FILLED TRANSFORMER PROCESS WATER
(PLANT I.D. NO. 19563) -
Strean I.D. No.
Flow Rate (Liters/Hr)
Duration (Hrs/Day)
Sample Number
TOXIC ORGANICS
11 1,1,1-Trichloroethane
22 Parachloroaeta Cresol
23 Chloroform (Trichloromethane)
24 2-Chlorophenol
39 Fluoranthene
44 Methylene Chloride (Dichloromethane)
55 Naphthalene
65 Phenol
66 Bis(2-ethylhexyl)Phthalate
67 Butyl Benzyl Phthalate
68 Di-N-Butyl Phthalate
70 Diethyl Phthalate
78 Anthracene/Phenanthrene
80 Fluorene
84 Pyrene
86 Toluene
107 PCB-1254 (Atochlor 1254)
Total Toxic Organics
TOXIC METALS
114 Antimony
115 Arsenic
117 Berylliuffl
118 Cadmium
119 ChroBiua
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Seleniuo
126 Silver
127 Thallium
128 Zinc
Total Toxic Metals
NON-TOXIC METALS
Calcium*
Aluminua
Vanadium
Barium
Tin
Cobalt
Titanium
Magnesium*
Manganese
Boron
Molybdenum
Yttrium
Iron
Sodium*
Total Non-Toxic Metals
OTHER POLLUTANTS
pH
121 Cyanide
Oil & Grease
Total Organic Carbon
Biochemical Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
I-(Interference Present)
tng/1
400
Skinner No. 1
Effluent
152977
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3947
0.048
0.800
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0.660
0.01
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
0.014
1.532
<0.005
<0.005
<0.005
0.005
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0.01
<0.04
<0.001
<0.04
<0.004
<0.005
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0.169
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32.23
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89894
24
3948
0.062
<0.010
0.570
<0.010
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1.200
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TABLE 7-12
MICA PAPER MANUFACTURING RAW AND TREATED WASTEWATER
PLANT ID #43055
Streaa Identification
Flow Rate, Liters/Hr.
Duration, Hrs/Day
TOXIC ORGANICS
04 Benzene
07 Chlorobenzene
11 1,1,1-trichloroethane
23 Chloroform
38 Ethylbenzene
44 -Methylene Chloride
66 Bis(2-ethylhexyl)Phthalate
67 Butyl Benzyl Phthalate
68 Di-n-butyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
Total Toxic Organics
TOXIC METALS
114 Antimony
115 Arsenic
117 Beryllium
118 Cadmium
119 Chromium
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127. Thallium
128 Zinc
Total Toxic Metals
NON-TOXIC METALS
Aluminum
Barium
Boron
Calcium*
Cobalt
Iron
Magnesium*
Manganese
Molybdenum
Sodium*
Tin
Titanium
Vanadium
Yttrium
Total Non-Toxic Metals
OTHER POLLUTANTS
PH
Temperature, C
121 Cyanide, Total
Oil & Grease
Total Organic Carbon
Biochemical Oxygen DeraanJ
Total Suspended Solids
Phenols
mjs/1
03653
Raw Waste
146037
24
<0.010
<0.010
0.180
<0.010
<0.01
0.029
<0.010
<0.010
<0.010
<0.010
<0.010
<0.010
0.209
<0.005
<0.003
<0.001
0.001
0.004
0.011
0.013
<0.001
0.023
<0.003
<0.003
<0.025
0.017
0.055
0.260
0.013
0.052
9.693*
<0.001
0.107
3.270*
0.004
0.002
1.613*
0.027
0.002
0.028
<0.001
0.495
kg/day
24
.63088
.10164
mg/1 kg/
03654
Treated Waste
146037
24 24
.73252
0.0035
0.014
0.038
0.046
0.081
0.060
0.192
0.911
0.046
0.182
0.368
0.014
0.007
0.095
0.007
0.098
1.728
7.0
13
0
0.4
1.9
2.0
103
0.008
1.402
6.659
7.0
361.0
0.028
NOT
ANALYZED
<0.005
<0.003
<0.001
0.001
0.004
0.010
0.016
<0.001
0.039
<0.003
<0.003
<0.025
0.016
0.086
0.110
0.009
0.044
9.639*
<0.001
0.039
3.257*
0.002
0.001
1.521*
0.034
0.001
0.024
0.003
0.2653
6.9
13
0
1.0
1.7
1.2
7.2
0.006
0.0035
0.014
0.035
0.056
0.137
0.056
0.302
0.386
0.032
0.154
0.137
0.007
0.0035
0.119
0.0035
0.084
0.011
0.937
3.505
5.958
4.206
25.235
0.021
*Not Included in Totals
VII-32
-------
Sample Blanks - Blank samples of organic-free distilled
water were placed adjacent to sampling points to detect
airborne contamination of water samples. These sample
blank data are not subtracted from the analysis results,
but, rather, are shown as a (B) next to the pollutant
found in both the sample and the blank. The tables show
figures for total toxic organics, total toxic and
non-toxic metals, and other pollutants.
Oil Filled Transformers - Four oil filled transformer plants were
visited, one of which was sampled. Table 7-7 presents the analyses
of the effluent streams from oil/water separators. Raw wastewater
samples were not collected at this facility.
Oil Filled Capacitors - Tables 7-8 through 7-11 present data from a
plant manufacturing oil filled capacitors and utilizing water to clean
the outside of the capacitors subsequent to filling with dielectric
fluid. The plant was sampled on two separate occasions. On one
occasion, four sample points were taken - the wastewater lagoon ef-
fluent (total plant composite raw process waste), the multimedia
filter effluent, the carbon filter effluent and the final waste
treatment effluent (following the second carbon filter and diato-
maceous earth filter). Tables 7-8 through 7-10 trace the progres-
sion of concentration changes through the waste treatment system
components for three days of operation and sampling.
Table 7-11 presents data from the same plant sampled at an earlier
date and includes additional sample points (supply water, deter-
gent wash of filled capacitors, and rinse following detergent wash).
This table also traces the progression of concentration changes
through the waste treatment system components. The data are
given for two days of operation.
Mica Paper Dielectric - Table 7-12 presents data from a plant pro-
ducing mica paper. The data were taken before and after two settling
ponds in series used to settle out mica flakes in the plant effluent.
The samples were collected over a 24 hour period.
Summary of Raw Wastewater Stream Data
Table 7-13 summarizes pollutant concentration data for the process
wastewater streams sampled in the dielectric materials subcategory.
Minimum, maximum, mean, and flow-weighted mean concentrations
have been determined for the raw waste streams sampled. The flow
weighted mean concentration was calculated by dividing the total mass
rates (mg/day) by the total flow (liters/day) for all appropriate
sampled data for each parameter. Trace level concentrations were
not used in these calculations. Table 7-13 also summarized mean
pollutant concentration data for mica paper dielectric manufactur-
ing. Only one stream at Plant ID 43055 was sampled.
Pollutant parameters listed in Table 7-13 were selected based upon
their occurrence and concentration in the sampled streams. Those
parameters not detected in the sampled streams were excluded from
this table. The information presented in Table 7-13 is based on
VII-33
-------
TABLE 7-13
DIELECTRIC MATERIALS SUBCATEGORY
SUMMARY OF DIELECTRIC RAW WASTE STREAM DATA*
(EXCLUDES MICA PAPER MANUFACTURING)
Minimum Maximum Mean Flow Weighted
Concentration Concentration Concentration Mean Concentration
(mg/1) (mg/1) (mg/1) (mg/1)
TOXIC ORGANICS
6 Carbon tetrachloride
8 1,2,3-trichlorobenzene
11 1,1,1-trichloroethane
29 1,1 dichloroethylene
30 1,2 trans-dichloroethylene
44 Methylene chloride
66 Bis(2-ethylhexyl)phthalate
68 Di-n-butyl phthalate
70 Diethyl phthalate
86 Toluene
87 Trichlorothylene
107 PCB-1254
TOXIC METALS
118 Cadmium
119 Chromium
120 Copper
122 Lead
124 Nickel
126 Silver
128 Zinc
OTHER POLLUTANTS
121 Cyanide
Oil & Grease
Total Organic Carbon
Total Suspended Solids
Biological Oxygen Demand
Phenols
0
0.02
0.045
0.02
0.01
1.2
2
0.06
3.22
0.02
0.01
0.017
ND**
0.0023
<0.01
0.03
0.025
<0.025
<0.01
0.415
0.54
0.2,
0.28
0.03
3.8
0.48
0.06
3.22
0.02
0.015
0.20
ND
0.585
0.041
1.7
1.45
0.05
0.02
0.555
0.28
0.123
0.12
0.02
2.5
0.34
0.06
3.22
0.02
0.013
0.109
ND
0.21
0.02
0.617
0.548
0.033
0.013
0.5
<0.004
8.2
50.
16.
12.
0.12
0.079
780,000.
8140.
9900.
2810.
0.18
0.041
156053.
2747 .
3373.
983.
0.14
2.
0.
0.
0.273
0.049
0.037
0.02
.45
.339
.06
3.22
0.02
0.015
0.193
ND
0.03
0.025
0.854
0.119
0.037
0.015
0.261
0.041
17.05
53.36
70
5
21
15
0.12
*Non-Toxic Metals Were Not Analyzed
**Not Detected
VII-34
-------
TABLE 7-13 CON'T
MICA PAPER MANUFACTURING
SUMMARY OF RAW WASTE DATA
11 lr1/1 Trichloroethane
44 Methylene Chloride
118 Cadmium
119 Chromium
120 Copper
122 Lead
124 Nickel
128 Zinc
Aluminum
Barium
Boron
Iron
Manganese
Molybdenum
Tin
Titanium
Vanadium
Total Organic Carbon
Total Suspended Solids
Phenols
Oil & Grease
Mean Concentration*
0.18
0.029
0.001
0.004
0.011
0.013
0.023
0.017
0.26
0.013
0.052
0.107
0.004
0.002
0.027
0.002
0.028
1.9
103
0.008
0.4
Flow (liters/day) 3,504,888
*Only one sample stream, Plant ID 43055 (See Table 7-12)
VII-35
-------
data in Tables 7-11 (detergent wash stream, detergent wash rinse
stream, and lagoon influent). For mica paper manufacturing, Table
7-12 (raw waste stream) was used. The concentration data in Table
7-13 must be used with care, because the detergent wash stream has
an extremely low average flow rate (it is a batch dump) and the raw
waste stream has an extremely high flow rate. Thus, many of the
maximum concentrations are associated with a very low flow rate, and
many of the mean concentrations are strongly influenced by this
same stream. The flow-weighted mean concentrations are essentially
equal to the concentrations of the high flow rate (raw waste) stream.
Treatment In Place
The following subsections describe treatment in place for wastewater
from oil filled transformers, oil filled capacitors, and mica paper
dielectric production.
PCS Dielectric Fluids - Plants which used PCS as a dielectric fluid
are faced with the problem of decontaminating equipment used for im-
pregnating or filling the final product. In some cases, this neces-
sitates the removal of equipment and piping systems. As a minimum,
PCS storage containers, piping, and other equipment has to be drained
of fluid and flushed with an organic solvent until all but trace
amounts of PCB are removed.
PCB's and solvent used for flushing such equipment is the liability
of the company performing the operation and has to be disposed of
or stored in an approved manner. Residual amounts of PCB are not
readily degraded in the environment.
The decontamination of plant land area has also been necessary in
some cases owing to accidental oil spills. A successful system was
sampled for removing oils from a land area bordering on a river.
It is shown schematically in Figure 7-4. The observed system
operates in a manner similar to a leaching field working in
reverse. Water and oil are collected from an oil contaminant land
area through pipes buried under the surface. The oil-water mixture
goes to a well and is pumped to an oil-water separator. The oil is
analyzed for the concentration level of PCB. If the concentration
is over 50 mg/1 but less than 500 mg/1 the oil is stored as a PCB
contaminated waste oil. If the concentration exceeds 500 mg/1, the
oil is stored as PCB waste fluid. If the concentration is less than
50 mg/1, the oil is treated as an ordinary waste oil and is disposed
of accordingly.
4
At present, there are no EPA approved incinerators which can be used
for PCB disposal. Two companies, Rollins Environmental Services of
Wilmington, Delaware and ENSCO of Eldorado, Arkansas have applied
VII-36
-------
I
r-
w
a
is
a
a
E-i
§
CJ
s
o
VII-37
-------
for approval. Rollins has two incinerators which are currently
under consideration. One, in Houston, Texas is presently being
tested. The second plant in Bridgeport, N.J. is still involved in
a local legal conflict preceding the planned "test burn". Rollins
estimates that the cost of disposing of PCB will be Ilff to 14jz? per
kilogram. The ENSCO plant in Arkansas has been put through a test
burn. A decision on approval has not yet been made.
Oil Filled Transformers - Manufacturers within the oil filled trans-
former industry that discharge wastewater typically treat their waste
with one or more of the following operations:
Filtration
Solids settling in tank or pond
Oil separation
Skimming and hauling or storage of oil
Figure 7-5 depicts the treatment system observed at Plant ID 19563,
the oil filled transformer plant that was sampled. This system
consisted of an oil skimming device only.
Oil Filled Capacitors - Plant 30082 is one of the largest oil filled
capacitor manufacturers in the U.S. The pliant uses very few water
producing operations, but the discharge from the capacitor manufac-
ture is substantial (approximately 187,200 liters per day). The
waste treatment system at this facility, shown schematically in
Figure 7-6, was designed to handle oil and grease, total and dis-
solved solids and metals, and sanitary and run-off wastes. The
settling lagoon is continuously skimmed and the skimmed oil is
drummed and contractor removed for disposal.
The discharge from the lagoon is sent to two mixed media filters
connected in parallel. After filtration these flows combine and pass
through carbon absorption and a diatomaceous earth filter. Each
of the multimedia filters in the waste treatment system is back-
washed on a regular basis. After sludge thickening, the decant water
is put back into the lagoon. The final treatment system discharge
rate is between 20-27 1pm (80-100 gpm). For such a large throughput,
only one or two 55 gallon drums of solids are removed each year.
Mica Paper Dielectric - Plant 43055 is a large mica paper dielectric
manufacturing facility using nearly 3.785 million liters per day (one
million gallons per day) of process water. The raw wastewater dis-
charged from the manufacturing process has high amounts of suspended
mica which are inert mineral particles. This facility utilizes three
settling lagoons or ponds to allow the heavy mica particles to settle
out of suspension. The retention time in each of the ponds is approxi-
mately 8-1/2 hours. During normal operation, only two of the ponds
are used in series while the third is allowed to dry. After drying
the pond is dredged, and the sludge is contractor hauled. The waste
treatment system for this plant is depicted in Figure 7-7. The
effluent analysis data for this facility are presented in Table 7-12.
VII-38
-------
OIL SKIMMING
RAW WASTE DISCHARGE
I
OIL DRUMMED
(IF PCB LEVEL IS >5*0 PPM,
'OTHERWISE INCINERATED)
FIGURE 7-5
DIELECTRIC MATERIALS SUBCATEGORY
OIL-WATER SEPARATOR
PLANT ID 19563
RECOMMENDED LEVEL 1 TREATMENT
VII-39
-------
Waste Water
i
Lagoon
(Oil Separation
And Skimming)
Multimedia
Filter
Multimedia
Filter
{ Backwash
. I i n ».i—. \m
Backwash
Holding
Tank
Decant
Activated
Carbon
Adsorber
Sludge
Settling
Tank
I
Sludge (Haul)
Activated
Carbon
Adsorber
Arrows Indicate
Wastewater Discharge
Oiatomaceous
Earth Filter
Discharge To River
FIGURE 7-6
DIELECTRIC MATERIALS SUBCATEGORY
WASTEWATER TREATMENT SYSTEM
PLANT ID 30082
RECOMMENDED LEVEL 2 TREATMENT
VII-40
-------
SETTLING
POND
SETTLING
POND
SETTLING
POND
DISCHARGE
'TO STREAM
* Raw Waste To Alternating Ponds
FIGURE 7-7
DIELECTRIC MATERIALS SUBCATEGORY
MICA PAPER DIELECTRIC MANUFACTURE
WASTEWATER TREATMENT SYSTEM
PLANT ID 43055
RECOMMENDED LEVEL 1 ^TREATMENT
VII-41
-------
POTENTIAL SELECTED POLLUTANT PARAMETERS
Selected pollutants in the.dielectric materials subcategory (exclud-
ing Mica Paper Manufacture) are:
6 Carbon tetrachloride
30 1,2 Trans-dichloroethylene
44 Methylene Chloride
68 Di-n-butyl phthalate
87 Trichloroethylene
107 PCB - 1254*
120 Copper
122 Lead
128 Zinc
Total Suspended Solids
Oil and Grease
Total Organic Carbon
These parameters were selected based upon their occurrence in the
process wastewater and upon the treatability of each at the levels
found. It should be noted that data on non-toxic metals was un-
available.
Table 7-14 lists pollutants other than the potential pollutant
parameters listed above that were analyzed in the raw waste streams
sampled for the dielectric materials subcategory. Each pollutant is
listed in the appropriate grouping as being not detected, detected
at trace levels, or detected at levels too low to be effectively
treated prior to discharge.
The selected pollutant in the mica paper manufacturing industry is:
Total Suspended Solids
Table 7-15 lists pollutants other than the potential pollu-
tant parameter listed above that was analyzed in the raw waste
streams sampled for the mica paper manufacturing industry. Each
pollutant is listed in the appropriate grouping as being hot
detected, detected at trace levels, or detected at levels too
low to be effectively treated prior to discharge.
APPLICABLE TREATMENT TECHNOLOGIES
The treatment systems selected for the dielectric materials
subcategory are those defined earlier in this section in Figures
7-5, 7-6, and 7-7. The systems are designated as Level 1 or Level
2. The Level 1 system shown in Figure 7-5 consists of oil skim-
ming and applies to wet transformers and oil-filled capacitor
manufacture. The Level 2 system shown in Figure 7-6 applies to
the same industry segments but provides improved performance. It
consists of oil skimming, multimedia filtration, carbon adsorption,
and diatomaceous earth filtration. The Level 1 system shown in
Figure 7-7 applies to the mica paper dielectric segment. It con-
sists of two stages of sedimentation.
*PCB-1254, See Appendix A
VII-42
-------
The following subsections will present performance and cost data
for these treatment technologies for the dielectric subcategory.
Treatment systems for oil filled capacitors, oil filled transformers^
and mica paper dielectric wastewater are discussed in these subsections,
For oil filled capacitors, it is possible to eliminate the need for
process water use by substituting solvent cleaning for detergent
washes and rinses. A moderately large plant (Plant, I.D. No. 19103)
manufacturing capacitors employs solvent cleaning of finished capa-
citors. The solvent is distilled and reused. The still bottoms are
contractor hauled and incinerated.
Although the use of solvents in cleaning oil filled capacitors will
diminish or replace the need for process water, the solvents used
must be collected and disposed of properly. Discharge of solvents
to the environment would be more harmful than discharge of detergent
washes and rinses.
Substituting other dielectric fluids for PCB is required by law.
There are several fire resistant fluids which are proposed as sub-
stitutes for PCB. Table 7-2 presented a summary of PCB substitute
dielectric fluids currently used or proposed for use in oil filled
capacitors and oil filled transformers. Di-n-octyl phthalate is
widely used in fluid filled capacitors although it is a priority
pollutant. Silicone oils are probably the most popular PCB substi-
tute for dielectric fluids.
VII-43
-------
TABLE 7-14
DIELECTRIC MATERIALS SUBCATEQORY
(EXCLUDES MICA EAPER MANUFACTURING)
POLLUTANT PARAMETERS
NOT DETECTED IN RAW WASTE STREAMS
TOXIC ORGRNICS
1. Acenaphthene 46.
2. Acrolein • 47.
3. Acrylonitrile 48.
4. Benzene 49.
5. Benzidine 50.
7. Chlorobenzene 51.
8. 1,2,4-Trichlorobenzene 52.
9. Hexachlorbenzene 53.
10. 1,2-Dichlorethane 54.
11. 1,1/1-Trichloroethene 55.
12. Hexachloroethane 56.
13. 1,1-Dichloroethane 57.
14. 1,1,2-tfrichloroethane 58.
15. 1,1,2,2-Tetrachloroethane 59.
16. Chloroethane 60.
17. Bis(Oiloromethyl)Ether 61.
18. Bis(2-chloroethyl)Ether 62.
19. 2-Chloroethyl Vinyl Ether(Mixed) 63.
20. 2-Chloronaphthalene 64.
21. 2,4,6-Trichlorophenol 65.
22. Parachlorometa Cresol 67.
23. Chloroform(Trichlorcmethane) 68.
24. 2-chlorophenol 69.
25. 1,2-Dichlorobenzene . 70.
26. 1,3-Dichlorobenzene 71.
27. 1,4-Dichlorobenzene 72.
28. 3/3-Dichlorobenzidine 73.
31. 2,4-Dichlorophenol • 74.
32. 1,2-Dichloropropane 75.
33. l,2-Dichloropropylene(l,3HDichloropropene) 76.
34. 2,4HDimethylphenol 77.
35. 2,4-Dinitrotoluene 78.
36. 2,6-Dinitrotoluene 79.
37. 1,2-^iphenylhydrazine 80.
38. Ethylbenzene 81.
39. Pluoranthene 82.
40. 4-chlorophenylPhynyl Ether 83.
41. 4HBromophenylPhenyl Ether 84.
42, Bis (2-chloroisopropyl) Ether
43. Bis (2-chloroethO3cy) Methane
44. Jfethyl Chloride(Chlororaethane)
Methylbrcmide (Brononethane)
Bromoform (Tribromomethane)
Dichlorobroroctnethane
Trichlorofluorcmethane
Dichlorodifliioromethane
Chlorodibrxxnorte thane
Hexachlorobutadiene
Hexachlorocyclcpentadiene
Isophorone
Naphthalene
Nitrobenzene
2-Nitrophenol
4-«itrophenol
2,4-Dinitrophenol
4,6-Dinitro-o-cresol
N-*Iitrosodimethylami.ne
KH«itrosodiphenylamine
N-Nitrosodi-*I-Propylamine-
Pentachlorophenol
Phenol
Butyl Benzyl Phthalate
Dins-Butyl Phthalate
Di-N-Octyl Phthalate
Diethyl Phthalate
Dimethyl Phthalate
1,2-Benznathracene (Benzo (A) Anthracene)
Benzo(A)Pyrene (3,4-fienzo-Pyrene)
3,4-Benzofluoranthrene(Benzo(B)Pluoranthene)
11,12-Benzofluoranthene(Benzo(K)Fluoranthene)
Chrysene
Acenaphthylene
Anthracene
1,12-Benzoperylene(Benzo(GHI)-Perylene)
Fluorene
Phenanthrene
1,2,5,6HDibenzathracene(Dibenzo (A,H)Anthracene
Indeno(1,2,3-DC)Pyrene(2,3-o-PhenylenePyrene)
Pyrene
VEI-44
-------
TABLE 7-14 (Continued)
85. Ttetrachloroethylene 100.
88. Vinyl Chloride (Chloroethylene) 101.
89. Aldrin 103.
90. Dieldrin 104.
91. ailon3ane(TechnicaWixtureandMetabolitEs) 105.
92. 4,4'HDOT 106.
93. 4,4'HDDE (P,P'-DDX) 107.
94. 4f4'-DDD (P,P'-TDE) 108.
95. Alpha-Endosulfan 109.
96. Beta-Endusulfan 110.
97. Endosulfan Sulfate 111.
98. Endrin 112.
99. Endrin Aldehyde 113.
129.
Xylenes
Alkyl Epoxides
Heptachlor
Hepthachlor Epoxide(BHC-Hexachlorocyclohexane)
Beta-*HC
Gamma-BHC (Lindane)
Delta-BHC (PCB-Polychlorinated Biphenyls)
PCB-1242 (Arochlor 1242)
(Arochlor 1254)
(Arochlor 1221)
(Arochlor 1332)
(Arochlor 1248)
(Arochlor 1260)
(Arochlor 1016)
PCB-1254
PCB-1221
PCB-1332
PCB-1248
PCB-1260
PCB-1016
Itoxaphene
2,3,7,8-Tetrachlorodibenzo-P-Dioxin
(TCDD)
VII-45
-------
TABLE 7-14 (Continued)
DETECTED AT TRACE LEVELS IN RAW WASTE STREAMS
114. Antimony
115. Arsenic
117. Beryllium
123. Mercury
125. Selenium
127. Thallium
VII-46
-------
TABLE 7-14 (Continued)
DETECTED AT LEVELS TOO LOW TO REQUIRE TREATMENT*
8 1,2,3 Trichlorobenzene
11 1,1,1 Trichloroethane
118 Cadmium
119 Chromium
124 Nickel
126 Silver
121 Cyanide
Phenols
Biochemical Ojcygen Demand
Mean Concentration (mg/1)
0.123
0.12
0.21
0.02
0.033
0.013
0.041
0.14
983.
Flow Weighted
Mean Concentraiton (mg/1)
0.049
0.037
0.03
0.025
0.037
0.015
0.041
0.12
15.5
These parameters do not require treatment because (1) the raw waste concentration
is less than the daily maximum figure (See Table 7-17) or (2) no performance data is
available for treatment of these parameters.
VII-47
-------
TABLE 7-15
MICA PAPER MATERIALS SUBCATEGQRY
POLLUTANT PARAMETERS
NOT DETECTED IN RAW WASTE STREAMS
TOXIC CRGANICS
1. Acenaphthene 46.
2. Acrolein 47.
3. Acrylonitrile 48.
5. Benzidine 49.
6. Carbon Tetrachloride (Tetrachloromethane) 50.
8. 1,2,4-Trichlorobenzene 51.
9. Hexachlorobenzene 52.
10. 1,2-Dichloroethane 53.
12. Hexachloroethane 54.
13. 1,1-Dichloroethane 55.
14. 1,1,2-JTrichloroe thane 56.
15. 1,1,2,2-Tetrachloroethane 57.
16. Chloroethane 58.
17. Bis(Chloromethyl)Ether 59.
18. Bis(2-Chloroethyl)Ether 60.
19. 2-Chloroethyl Vinyl Ether (Mixed) 61.
20. 2-Chloronaphthalene 62.
21. 2,4,6-^ichlorophenyl 63.
22. Parachlorometa Cresol 64.
24. 2-Chlorophenol 65.
25. 1,2-Dichlorobenzene 69.
26. 1,3-Dichlorobenzene 70.
27. 1,4-Oichlorobenzene 71.
28. S/S'-Dichlorofaenzidine 72.
29. 1,1-Dichloroethylene 73.
30. 1,1-Trans-Dichloroethylene 74.
31. 2,4-Dichlorophenol 75.
32. 1,2-Dichloropropane 76.
33. l,2-Dichloropropylene(l,3^)ichlorc3prcpene) 77.
34. 2,4-Dimethylphenol 78.
35. 2,4-Dinitrotoluene 79.
36. 2,6-Dinitrotoluene 80.
37. 1,2-Diphenylhydrazine 81.
39. Fluoranthene 82.
40. 4-Chlorophenyl Phenyl Ether 83.
41. 4-Bronophenyl Phenyl Ether 84.
43. Bis(2-<3iloroethoxy)Methane 88.
45. Methyl Chloride (Chloromethane) 89.
90.
Methylbronu.de (Bromomethane)
Bromoform (Tribrornomethane)
Dichlorobrononethane
Trichlorofluoromethane
Dichlorodifluoromethane
Chlorodibromomethane
Hexachlorocyclopentadiene
Hexachlorocyclopentadiene
Isophorone
Napthalene
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
2,4-Dinitrophenol
4,6-Dini tro-o-cresol
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitrosodi-N-Propylamine
Pentachlorophenol
Phenol
Di-n-octyl Phthalate
Diethyl Phthalate
Dimethyl Phthalate
1,2-Benzanthracene(Benzo(A)Anthracene)
Benzo(AJPyrene(3,4-Benzo-Pyrene)
3,4-Benzofluoranthrene(Benzo(B)Fluoranthene)
11,12-Benzofluoranthene(Benzo(K)Fluoranthene
Chrysene
Acenaphthylene
Anthracene
1,12-Benzoperylene(Benzo(GHI)-Perylene)
Fluorene
Phenanthrene
l,2,5,6-Dibenzathracene(Dibenzo(A,H)Anthrace
Indeno(1,2,3-DC)Pyrene(2,3-o-PhenylenePyrene
Pyrene
Vinyl Chloride (Chloroethylene)
Aldrin
Dieldrin
VII-48
-------
TABLE 7-15 (Continued)
91. Chlordane (Technical Mixture and 103.
Metabolites) 104
92. 4,4'-Dnr io5.
93. 4,4'-DDB (P,P'-DEK) 106.
94. 4,4'-DDD (P,P'yTDE) 108.
95. Alpha-Endosulfan 109.
96. Beta-Endusulfan HO.
97. Endosulfan Sulfate 111
98. Endrin . 112.
99. Endrin Aldehyde 113]
100. Heptachlor 129.
101. Heptachlor Epoxide (BHC-Hexachlorocyclc-
hexane)
Beta-BHC
Gamma-BBC (Lindane)
Delta-BHC (PCB-Polychlorinated Biphenyls)
PCB-1242 (Arochlor 1242)
PCB-1221 {Arochlor 1221)
PCB-1332 (Arochlor 1332)
PCB-1248 (Arochlor 1248)
PCB-1260 (Arochlor 1260)
PCB-1016 (Arochlor 1016)
Toxaphene
2,3,7,8-Ttetrachlorodibenzo-P-Dioxin (TCDD)
Xylenes
Alkyl Epoxides
VII-49
-------
TABLE 7-15 (Continued)
DETECTED AT TRACE LEVELS IN PAW WASTE STREAMS
4. Benzene
7. Chlorobenzene
23. Chloroform
38. Ethylbenzene
66. Bis(2H3thylhexyl)Phthalate
67. Butyl Benzyl Phthalate
68. Di-n-butyl Phthalate
85. Tetrachloroethylene
86. Toluene
87. Trichloroethylene
114. Antimony
115. Arsenic
117. Beryllium
123. Mercury
125. Selenium
126. Silver
127. Thallium
Cobalt
Yttrium
VII-50
-------
TABLE 7-15 (Continued)
DETECTED AT LEVELS TOO IOW TO REQUIRE TREATMENT*
Parameter
11. 1,1,1-^Trichloroethylene
44. Methylene Chloride
118. Cadmium
119. Chromium
120. Copper
122. Lead
124. Nickel
128. Zinc
Aluminum
Barium
Boron
Iron
Manganese
Molybdenum
Tin
Titanium
Vanadium
Total Organic Carbon
Mean Concentration (mg/1)**
0.18
0.029
0.001
0.004
0.011
0.013
0.023
0.017
0.26
0.013
0.052
0.107
0.004
0.002
0.027
0.002
0.028
1.9
* = These parameters do not require treatment because 1) the raw waste
concentration is less than the daily maximum figure (See Table 7-17. )-, or
2) no performance data is available for treatment of these parameters.
** =
Only one sampled stream, Plant ID 43055
Vli-51
-------
Performance of Observed Treatment Systems
The actual performance of Level 1 and Level 2 treatment systems
that have been sampled for the dielectric materials subcategory
is presented in Table 7-16. Data from individual effluent streams
utilized in the development of this table are presented in Tables
7-9 through 7-13.
Performance of Recommended Treatment Systems
Performance of the recommended treatment systems is shown in Table
7-17. These performance figures are based upon data from treatment
component performance transferred from the metal finishing industry.
This performance data can be transferred to the dielectric materials
industry because of the similarity of the raw wastes. Section XII
describes the treatment components and the performance levels
achievable by each component. A comparison of observed versus
recommended treatment performance is presented in Table 7-18.
Estimated Cost of Recommended Treatment Systems
The determination of estimated costs for recommended treatment sys-
tem components is discussed in Section XIII of this report. Tables
7-19 through 7-24 show estimated costs for each of the recommended
treatment systems for treatment of dielectric fluid materials waste-
waters that were discussed previously. Table 7-25 shows estimated
costs for a Level 1 treatment system for the treatment of mica
paper dielectric manufacturing. Flow rate input for treatment
costs characterize small, medium, and large facilities in the dielec-
tric materials subcategory.
VI1-52
-------
TABLE 7-16
PERFORMANCE OF OBSERVED TREATMENT SYSTEMS
Dielectric Subcategory (Excluding Mica Paper) - mg/1
Parameter
6. Carbon Teta
30. l,2-Trans-<
44. Methlene Cl
87. Trichloroel
107. PCB 1254
120. Copper
122. Lead
128. Zinc
Total Susp«
Oil and Grease
Level 1*
achloride ND**
ichlorethylene ND
loride 0.93
hylene ND
<0.01
0.1
<0.04
0.104
nded Solids 11.
ase 3.5
ic Carbon 16.5
Level 2**
ND
0.046
0.0113
0.0052
ND
0.01
0.048
0.70
47^ ****
3 g****
g 5****
Mica Paper Dielectric Manufacture
Parameter
Total Suspended Solids
Level l*****
7.2
ND**
***
*****
Mean of two sampled streams, Plant ID 19563
Not Detected
Flow Weighted Mean Concentration, Final Effluent (Plant ID 30082, Stream 03553,
03557, 03549, and M22-10)
Mean Concentration, Plant ID 30082, Stream M22-10
Plant ID 43055, mean concentration
VII-53
-------
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VII-54
-------
TABLE 7-18
COMPARISON OF OBSERVED VS. RECOMMENDED
TREATMENT SYSTEMS
Dielectric Materials Subcategory - Effluent Concentration (rag/1)
(Excludes Mica Paper Manufacturing)
Parameter
6. Carbon Tetrachloride
30. 1,2-Trans-dichloroethylene
44. Methylene Chloride
87. Trichloroethylene
107. PCB 1254
Total Toxic Organics
120. Copper
122. Lead
128. Zinc
Total Suspended Solids
Oil & Grease
Total Organic Carbon
Observed
Level 1*
Treatment
ND**
ND
0.93
ND
<0.01
0.93
0.1
<0.04
0.104
11.
3.5
16.5
Recommended
Level 1
Treatment
NA***
NA
NA
NA
NA
0.940
0.814
0.005
0.551
17.8
11.9
NA
Observed Recommended
Level 2**** Level 2
Treatment Treatment
ND
0.046
0.0113
0.0052
ND
0.063
0.01
0.048
0.70
47t *****
3ag*****
8]§*****
NA
NA
NA
NA
NA
0.04
0.368
0.034
0.247
12.7
7.1
NA
Total Suspended Solids
Mica Paper Manufacturing
7.2***** 17.8
*
ND**
NA***
****
*****
Mean of two sampled streams, Plant ID 19563
Not Detected
Not Available
Flow weighted mean concentration, Plant ID 30082, (Samples # 03553, 03557,
03549, and M22-10)
Single stream value, See Table 7-16.
VII-55
-------
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BENEFIT ANALYSIS
The following is an analysis of the industry-wide benefit esti-
mated to result from applying the levels of treatment previously
discussed in this section to the total process wastewater generated
by the dielectric materials subcategory. This analysis estimates
the total amount of pollutants that would not be discharged to the
environment if each of the levels of treatment were applied on a
subcategory-wide basis. An analysis of the benefit versus estimated
subcategory-wide cost for each of the treatment levels will also be
provided.
Industry-wide Costs
By multiplying the investment and annual costs of each level of
treatment at various flow rates by the number of plants in each flow
regime in the industry, a subcategory-wide cost figure is estimated
(Table 7-26). This figure represents the cost of each treatment
level for the entire dielectric materials subcategory. This calcu-
lation does not make any allowance for waste treatment that is
currently in-place at dielectric materials facilities.
Industry-wide Cost and Benefit
Table 7-27 presents the estimate of total cost to the dielectric
materials subcategory to reduce pollutant discharge. The calcu-
lations of industry-wide cost we're determined by multiplying
the investment and annual costs for each level of treatment by the
number of plants discharging wastewater or potentially discharging
wastewater in the case of dielectric fluid use. This table also
presents the benefit of reduced pollutant discharge for the dielec-
tric materials subcategory resulting from the application of the two
levels of recommended treatment. Benefit was calculated by multiply-
ing the estimated number of liters discharged annually by the sub-
category times the performance attainable by each of the recommended
treatment systems as shown in Table 7-17. Table 7-16 presents the
performance attained by observed treatment of mica paper wastewaters.
Values are presented for each of the selected subcategory pollu-
tant parameters.
The column "Raw Waste" shows the total amount of pollutants that
would be discharged annually to the environment if no treatment
was employed by any facility,in the industry. The columns "Levels
1 and 2 treatment" show the amount of pollutants that would be
discharged if any one of these two levels of treatment were applied
to the total wastewater estimated to be discharged by the dielectric
materials subcategory.
VEI-63
-------
INVESTMENT***
Annual Costs
Capital Costs
Depreciation
Operation & Maint.
Energy and Power
Total Annual Costs
TABLE 7-26
DIELECTRIC MATERIALS SUBCATEGORY
INDUSTRY-WIDE COST
Dielectric Fluid Use
Level 1 Treatment
$10,317,046.
$ 869,885.6
$ 2,063,409.1
$ 1,763,425.8
0
$ 4,696,720.0
Level 2 Treatment
$114,700,000
$ 9,670,840.9
$ 22,939,586.
$ 18,437,510.0
1,172,767.7
$ 52,220,704
***COST ESTIMATES BASED UPON AN ESTIMATE OP 70 PLANTS CURRENTLY USING DIELECTRIC FLUID
Mica Paper Dielectric Manufacturing
INVESTMENT*
Annual Costs
Capital Costs
Depreciation
Operation & Maint.
Energy and Power
Total Annual Cost
$444,312**
$ 37,455.5
$ 88,862.4
$216,000.0
$ 0
$342,317.9
* DOES NOT INCLUDE COST OF IAND OR LINING (IF NEEDED)
** COST ESTIMATE BASED ON 18 PLANTS CURRENTLY MANUFACTURING MICA PAPER DIELECTRICS
VII-64
-------
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-------
-------
SECTION VIII
ELECTRIC LAMP SUBCATEGORY DISCUSSION
INTRODUCTION
This discussion of the electric lamp industry consists of the
following major sections:
Products
Size of the Industry
Manufacturing Processes
Materials
Water Usage
Production Normalizing Parameter
Waste Characterization & Treatment In Place
Potential Pollutant Parameters
Applicable Treatment Technologies
Benefit Analysis
Data contained in this section were obtained from several sources.
Engineering visits were made to ten plants within the subcategory.
Wastewater samples were collected from five of these ten
facilities. A total of thirty-seven electric lamp manufacturing
plants were contacted by telephone. A literature survey was
also conducted to ascertain differences between types of electric
lamp products, process chemicals used, and typical manufacturing
processes.
PRODUCTS
The electric lamp subcategory includes the manufacture of incan-
descent, fluorescent, and electric discharge (other than fluores-
cent) lamps, as well as the manufacture of tungsten filaments for
use in incandescent and fluorescent lamps. The major lamp product
areas are described in accordance with the manner in which they
produce radiant energy within the visible light spectrum. Because
of the diversity in artificial lighting requirements, lamps use
a variety of raw materials for specific applications. Lamps
are used for general lighting and display, photography and
projection, transportation lighting, photochemical and photo-
biological processes, as sources of infrared and ultraviolet
electromagnetic radiation, and as circuit components in electronic
circuitry.
VIII-1
-------
There are two basic types of artificial light production: incandes-
cence and luminescence. The four primary lamp manufacturing pro-
duct areas fall into these two basic types of artificial light pro-
duction. These product areas are: (1) tungsten filament lamps
(incandescent), (2) electric discharge lamps other than fluores-
cent lamps (luminescent), (3) fluorescent lamps (luminsecent), and
(4) filament manufacture (incandescent and luminescent).
Incandescent tungsten filament lamps operate on the principle of pas-
sing an electric current through a conductor, resulting in the pro-
duction of heat. Light is emitted if enough electrical energy is
supplied to raise the temperature above approximately 500°C.
There are two types of lamps that produce luminescence: fluores-
cent and electric discharge other than fluorescent. Electric
discharge lamps produce mainly radiant energy. A gas discharge
light source is produced by providing a voltage between a cathode
and an anode. Electrons emitted from the cathode surface are
accelerated by the electric field and collide with gas atoms,
elevating valence electrons to higher energy states. After a
period of time, the electrons drop to lower energy states, emit-
ting photons of light. The wavelength of these photons is determined
by the difference between levels occupied by the electrons.
Fluorescent lamps are electric discharge lamps that utilize a low
pressure mercury arc in argon. Through this process, the lowest
excited state of mercury efficiently produces short wave ultra-
violet radiation at 2537 angstroms. Phosphor materials commonly
used such as calcium halophosphate and magnesium tungstate absorb
the ultraviolet photons iftto their crystalline structure from which
they are re-emitted as visible white light.
Based on the manner in which they produce radiant energy within
the visible light spectrum, the primary lamp numufacturing product
areas are as follows:
Incandescent lamps for use as a light, heat, or
infrared radiation source.
Fluorescent lamps which are specific applications of
electric discharge lamps for use as a source of light.
Electrical discharge lamps other than fluorescent lamps
for use as a light, heat, infrared, or ultraviolet
radiation source.
. Coiled tungsten filaments for use in incandescent and
hot cathode fluorescent lamp manufacture.
The .electric lamp subcategory involves products comprising the
entire SIC 3641, Electric Lamps, and also includes portions of
SIC 3699, Electrical Equipment and Supplies, Not Elsewhere Clas-
sified, for plants that only manufacture coiled tungsten fila-
ments. The major products of the electric lamp subcategory are
VIII-2
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as follows:
Photographic Incandescent Lamps
- Photoflash
- Projection
- Photo-Enlarger
- Photoflood
Large Incandescent Lamps
- General Lighting
- Reflector
- Infrared
- Traffic and Street
- Decorative
Miniature Incandescent Lamps
- Automotive
- Flashlight
- Panel
Electric Discharge Other than Fluorescent
- Photochemical
- Photo-biological
- Indicator Glow
- Circuit Components
- Sunlamps
- High Intensity General Lighting
Fluorescent
- Hot Cathode
- Cold Cathode
Christmas Tree Lamps
Coiled Tungsten Filaments
SIZE OF THE INDUSTRY
The size of the industry is defined by the number of plants and
the number of production employees for plants engaged in the manu-
facture of electric lamps, SIC 3641, and tungsten filaments, SIC 3699
Number of Plants
It is estimated that there are between 125 and 168 plants engaged
VIII-3
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in the manufacture of electric lamp products in SIC 3641.
In addition, a number of these plants also manufacture tungsten
filaments. To avoid double counting, plants manufacturing both
lamps and filaments are counted in SIC 3641. The number of
plants is based on the following two sources:
Department of Commerce 1977 Census of Manufactures
(Preliminary Statistics). It is estimated from this
data base that 168 plants are engaged in the manufacture
of electric lamp products.
The 1977 Dun and Bradstreet listing of companies
whose primary products area is in SIC 3641. After
removal of known non-manufacturers of electric lamp
products, 125 plants are estimated to be involved in
the manufacture of electric lamp products.
It is estimated that 9 plants are engaged in the manufacture of
tungsten filaments as applicable to the electric lamp subcategory
and included in SIC 3699. These estimates are based on the
following 2 sources:
. Department ;of Commerce 1977 Census of Manufactures
(Preliminary Statistics). It is estimated from this
data base that 9 plants are engaged in the manufacture
of electric lamp components. Included in this sub-
classification are the manufacture of lead-in wires,
supports, electrodes, and tungsten filaments.
Under this current study, a review of both actual
plant visits and plant telephone contacts has led
to an estimate of 9 plants involved in the manu-
facture of electric lamp components. These com-
ponents include; filaments, filament supports, elec-
trodes, and lead-in wires.
Number of Employees
It is estimated that 25,300 production employees are engaged in
the manufacture of electric lamps as described under SIC 3641.
This estimate is based on information from the Department of
Commerce 1977 Census of Manufactures (Preliminary Statistics).
Plants that have been visited during this study have from 70 to
400 production employees each. These plants could be described as
medium to large size facilities.
VIII-4
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It is estimated that 1917 production employees are engaged in
the manufacture of tungsten filaments as described under SIC
3699. This estimate is derived from two facilities contacted
during this study employing 125 and 300 production workers re-
spectively. These plants are medium to large size facilities.
From the estimate of 9 plants engaged in the manufacture of tung-
sten filaments, together with an average of 213 production em-
ployees for those two plants contacted, it is estimated that 1917
employees are engaged in tungsten filament manufacture.
Production Rate
Production information encompassing nearly all types of electric
lamps and electric lamp components is presented in Table 8-1.
This information was obtained from the Department of Commerce
1977 Census of Manufactures (Preliminary Statistics).
MANUFACTURING PROCESSES
There are two common characteristics of all electric light sour-
ces: finite lamp life and diminishing luminosity with lamp age.
Manufacture of all lamp types seeks to optimize the.generation
of light, the efficiency of illumination, and the reliability (or
lamp-life). The following description of manufacturing processes
for the electric lamp products area includes both electric lamp and
electric lamp component manufacture.
Discussion of electric lamp manufacturing is based on the
primary lamp types: incandescent, electric discharge other than
fluorescent, and fluorescent. Electric lamp component manufacturing
is restricted to filament manufacturing only. Other electric
lamp components involve electroplating and other processes not ap-
plicable to this study. However, a brief discussion is included
on lamp base manufacture (part of the Metal Finishing- Category)
because of its importance as an electric lamp component.
Incandescent Lamp Manufacture
Most lamp-making operations are performed by highly automated
machines generally consisting of a mount machine, a seal and
exhaust machine/ and a finish machine. Incandescent lamp manu-
facturing is a dry process requiring"no process water. A typical
incandescent lamp manufacturing process is described below and
depicted in Figure 8-1.
The mount machine assembles a glass flare, an exhaust tube, lead-
in wires, and molybdenum filament supports. Tjtie lead-in wires are
heat pressed into the glass and the components are mechanically
constructed forming a stem assembly. The coiled filament is
attached to the lead-in wires and support wires where applicable.
The filament is then coated with a getter solution which is an
absorption medium for impurities. When the lamp is eventually
flashed, the getter solution is activated, absorbing impurities
and moisture from the atmosphere of the lamp. This entire
unit becomes a mount assembly.
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TABLE 8-1
PRODUCTS AND PRODUCT CLASSES, QUANTITY
AND VALUE OP SHIPMENTS BY ALL PRODUCERS
OF ELECTRIC LAMP PRODUCTS
Millions
of Lamps
Per Year (1977)
Value
in Millions
of Dollars (1977)
SIC 3641
Photographic Incandescent
Lamps
Large Incandescent Lamps
Miniature Incandescent
Lamps
Electric Discharge Lamps
General Electric Discharge
Hot Cathode Fluorescent
Cold Cathode Fluorescent
Christmas Tree Lamps
Other Lamp Products Not
Elsewhere Classified
SIC 3699
Electric Lamp Components- -
Supports, Filaments,
Electrodes, Lead-in Wires
2198.4
1720.0
1147.1
181.6
295.7
N/A
N/A
N/A
N/A
307.1
585.7
285.9
123.5
324.4
53.8*
N/A
N/A
173.8
N/A * Not Available ;
* s This value .denotes cold cathode fluorescent and other lamp
products not elsewhere classified. These categories were
^combined to avoid disclosure of individual companies.
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Glass Bulb
*
Glass Bulb Coat
Fuse Mount
To Bulb
Glass Tube
i
Glass Flare
Manufacture
1
Mount Assembly
1
Filament Coat
Lead Wires, Filament,
& Filament Support
Anneal
I
Exaust &
Gas Fill
I
Seal Lamp
Solder Lead Wire
To Base
Base Attachment
1
Age & Test
f
Ship
FIGURE 8-1
INCANDESCENT LAMP MANUFACTURE
VIII-7
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A glass bulb is electrostatically coated with silica and the
bulb and mount are connected at the exhaust and seal machine.
The glass bulb is lowered over the mount. The flared rim of
the mount is then sealed to the neck of the bulb with a natural
gas flame.
The bulb assembly is annealed, exhausted, filled with an inert
gas, and sealed with a natural gas flame. The inert gas is
usually a combination of argon and nitrogen, which reduces tung-
sten evaporation and hence "bulb blackening". In addition, the
gases allow higher filament temperature and higher efficiencies
without sacrificing lamp life.
The finishing machine solders the lead wires to the metallic base
which is then attached by a phenolic resin cement or by a mech-
anical crimping operation.
The finished lamp is aged and tested by illuminating it with
excess current for a period of time to stabilize its electrical
characteristics. In addition, this process activates the getter
material to absorb atmospheric impurities within the glass en-
velope. This is the last.step in the production process.
Electric Discharge (Other Than Fluorescent) Lamp Manufacture
The wavelength spectrum of light from an electric discharge lamp
differs considerably from that of an incandescent filament lamp.
Discharge lamps concentrate radiation at particular wavelengths
which are not continuous. Incandescent filament lamps produce
light over a wide, continuous spectrum of wavelengths.
Electric discharge lamps emit different colors of light depending
on the kind of gas used and its applied pressure. Gases generally
used include argon, neon, xenon, krypton, and vapors of sodium
and mercury. Pressures applied may vary from a few microns to hun-
dreds of atmospheres. Electrode material usage varies according
to lamp type, with the most common being nickel, tungsten, and iron.
The efficiency of a cathode may be improved markedly by the use
of an emissive coating. This coating reduces the breakdown vol-
tage and consequently the ionization time necessary to produce
a discharge between the electrodes, which in turn is required to
make the lamp glow. Glass encapsulation can be a simple glass
envelope, an arc tube supported inside a glass enclosure control-
ling the internal thermal condition, or a quartz tube where high
temperatures and pressures can be maintained.
VIII 8
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Electric discharge lamps consist of a glass envelope or tube filled
with an inert gas and contain a set of electrodes between which
an arc discharge occurs. In addition to the gas atmosphere, a
metallic vapor or halogen gas may be added to some discharge lamps.
In general, the manufacture of these lamps are dry in their process-
ing operations as they apply to the E&EC Category. However, the
manufacture of quartz mercury vapor lamps employs a wet process
at the conclusion of the manufacturing sequence. A low volume
of process wastewater is produced from a hydrofluoric acid clean-
ing bath and a subsequent water rinse. Wastewater produced contains
primarily fluorides and silica. This wet process is performed on
the exterior of the quartz enclosure. Because mercury is confined
to within the finished lamp, it is detected in the wastewater at
a very low concentration. i
The manufacture of a miniature neon glow discharge lamp is des- '
cribed below and depicted in Figure 8-2. This manufacturing
process is representative of most other electric discharge lamps
(other than fluorescent) with one exception. Instead of a con-
ventional lamp base, the lead wires extend beyond the lamp and
are attached directly to a power source.
Copper-clad steel lead wires are coated with an emissive mixture of
barium and strontium carbonate. The lead wires are placed within
a thin glass tube and the glass is heated and pressed around the
leads.
The glass envelope is annealed at approximately 1000 °C, removing any
moisture present in the envelope. Radio frequency waves bombard the
unit, break down the emissive coating, and leave barium oxide on the
electrode surface.
The final operations consist of exhausting the glass
filling it with a neon-argon mixture before tipping
tube. This is done .by heating the end of the tube,
away, and producing a pointed tip to the top of the
electroplated lead wires are cleaned in an ammonium
hydrochloric acid solution followed by water rinsing
process removes the copper oxide remnant on the lead
sulting from the annealing operation. The lamps are
in an oven, aged, tested, and shipped.
envelope and
off the glass
drawing it
lamp. The
chloride-
This
wires re-
then dryed
Production of a neon glow discharge lamp is highly automated and
totally dry in its processing operations that are part of the
E & EC Category. Water usage is restricted to electroplated lead
wire cleaning and subsequent water rinsing which is part of the
Metal Finishing Category and as such will not be discussed further
in the E & EC Category.
VIII-9
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Glass Tube Copper-Clad Steel
Denotes Water
Flow Path
Ba-Sr-Carbonate
Coating
Glass &
Lead Hire
Press Assembly
Bake 1050°C
RF Wave
Bombardment
Air Exhaust
and Gas Pill
Radioactive
Dopant
Addition
Lamp Cleaning
Acid Dump
Cold ELO Rinse
Aerated H20 Rinse
Aerated H_0 Rinse
Aerated H20 Rinse
Oven Dry
Age and lest
r
Ship
FIGURE 8-2
ELECTRIC DISCHARGE LAMP MANUFACTORE
VIII-10
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Other electric discharge lamps such as quartz mercury vapor lamps
are manufactured by a similar process. However, annealing pro-
duces an aesthetically undesirable silica deposit on the surface
of the quartz tube. This deposit is removed by a strong hydro-
fluoric acid etching process, which is followed by a rinsing step.
However, the volume of wastewater is estimated to be very low
from this process.
\
Fluorescent Lamp Manufacture
These lamps are electric discharge lamps used to produce light.
They are usually in a long tubular form with an internal coating
of phosphor material. The discharge passing through the gas
atmosphere generates ultraviolet radiation of approximately 2537
angstroms. This radiation is used to excite the'phosphor materials
to emit visible light.
Although the manufacturing processes are similar, there are two
types of fluorescent lamps based on differences in cathode design.
These two types are hot cathode and cold cathode. The manufacturing
of a hot cathode fluorescent lamp is described below and depicted
in Figure 8-3. Hot cathode fluorescent lamps, which operate at 115
volts, utilise a coiled coil or triple coil tungsten filament. The
cathode usually receives an electron emissive coating -of barium,
strontium, and calcium carbonates. During operation, the cathode
is preheated by passing electric current through a starting device.
The hot cathode emits electrons which flow to the anode thus passing
through the mercury vapor. Cold cathode fluorescent lamps, which
operate at high voltages, utilize a cylindrical electrode which
may or may not be coated with an emissive coating material. The
iron cathode normally operates at 150°C which is "cold" compared
to the small hot spot on a hot cathode type lamp, which is at about
900°C. The cold cathode lamp starts instantly without a starter,
uses low current, is of small diameter, and usually is greater than
4 feet in length. These lamps normally outlive hot cathode lamps,
because flashing, dimming, and the number of starts do not affect
cold cathode lamp life as they do hot cathode lamps. Because the
cold cathode manufacture is primarily an electroplating operation
performed at a plant other than that which manufactures electric
lamps, its manufacture is not part of this study but is included
in the Metal Finishing Category. In both hot and cold cathode
fluorescent lamps, there is an inherent negative resistance as
in all electric discharge lamps. For this reason, ballasts are
used to control and regulate electric current.
VIII-11
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Glass Tube
*
SnCl4 Coat
Phosphor
Application
Glass Tube Dry
Brush Scrub
or
Sponge Wipe
Bake
Glass Tube
Assemble & Seal
Air Exhaust &
Gas Pill
Base Attachment
Silicone Coat
Age and Test
t
Ship
Fumes
Glass Tube
Glass Flare
Manufacture
Mount Assembly
Denotes Water
Flow Path
FIGURE 8-3
FLUORESCENT LAMP MANUFACTURE
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Hot cathode fluorescent lamp manufacturing is a highly automated
process. Glass tubing is received and rinsed with deionized water.
This removes any remnant dust or silica material from the surface
of the tubing. Some of the glass tubes receive a tin chloride
coating for energy saving-low wattage lamps, while others bypass
this process and proceed directly to phosphor application. The
phosphor coating solution is a combination of phosphors, an organ-
ic binder such as xylol, and often a lacquer. The coating solu-
tions can be water based or solvent based depending on the par-
ticular plant operation. The coating solutions are gravity fed
through the tubing and subsequently dried. The ends of the tubing
are cleaned by a mechanical brush scrub or sponge wipe. This
process may or may not require process water usage. The glass
tubing is then baked at approximately 600°C.
Coiled tungsten filaments receive an emissive coating. They are
then assembled together with lead wires, an exhaust tube, a glass
flare, and a starting device to produce a mount assembly. The
mount assemblies are heat pressed to the two ends of the glass
tubing. The glass tubes are exhausted, filled with an inert gas,
usually argon, and a drop of mercury is added. The lead wires
are soldered to the base, and the base is attached to the tube
ends, usually with a phenolic resin cement.
The finished lamp receives a silicone coating solution to prevent
the lamp' from arcing. The silicone coating solution may or
may not be discharged depending on the particular plant opera-
tion. The lamp is then aged and tested, before shipment.
Filament Manufacture
The filament is the most important component of all incandescent
lamps. It is also an integral component of hot cathode fluorescent
lamps. Tungsten is the preferred material for filament usage
because it combines a very high melting point of 3380°C with a
relatively slow and consistent rate of evaporation. Filament.de-
sign is a balance between light output and filament life.. The
higher the filament temperature, the more light is emitted and
the shorter the filament life.
Pure tungsten metal is prepared in powder form, pressed--into ingot
bars, strengthened in an electric furnace, and sintered. The bars
of tungsten are then swaged and drawn to wire as small as 0.00114
centimeters in diameter. Tungsten filaments have a tensile strength
several times that of steel. Tungsten filament manufacture is
described below and depicted in Figure 8-4. - a
Filament manufacture begins with inspection of the tungsten wire. 4
The wire is then wound on mandrels of molybdenum, steel, or copper-
clad steel. Coiled filaments wound on molybdenum are of the:, high-
est quality. These filaments are usually used in hot cathode
VIII-13
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Tungsten Wire
Filament Coil
Anneal
Re-Coil
Re-Anneal
T
Molybdenum Mandrel
Dissolution
Copper-Clad Steel Mandrel
t
Steel Mandrel
HN03-H2S04
Dissolution
HCL
Dissolution
Rinse
Rinse
Rinse
Neutralization
HCL Dissolution
Neutralization
Rinse
Rinse
Rinse
Acid Clean
Neutralization
Acid Clean
Rinse
Rinse
Rinse
Alcohol Dip
Acid Clean
Dry
Dry
Rinse
'Dry
Denotes Water
Flow Path
FIGURE 8-4
TUNGSTEN FILAMENT MANUFACTURE
VIII-14
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fluorescent lamps and in automated, high speed, incandescent lamp
manufacturing. Filaments wound on copper-clad steel mandrels are
required when the filament cannot tolerate iron poisoning. These
filaments are most commonly found in incandescent lamps. Fila-
ments for lower quality applications are wound on plain steel man-
drels and are usually used in incandescent lamps as well.
The coiled filaments are annealed, re-coiled, re-annealed, and
sent to mandrel dissolution. Coiling of filaments improves effi-
ciency by improving heat concentration. In addition, coiling of
filaments reduces the linear length requirement compared to un-
coiled filaments, permitting use of fewer filament supports which
conduct heat from the filament.
In all cases, molybdenum mandrels are dissolved in nitric acid-
sulfuric acid solutions and water rinsed. Most plants follow this
mandrel dissolution with a neutralization in sodium hydroxide. At
one of the visited plants, an ammonia-water solution was used in
place of sodium hydroxide. Neutralization removes any excess acid
remaining on the coiled filaments and prevents further etching of
the tungsten. Another plant eliminated neutralization by extensive
centrifugal water rinsing.
The coiled filaments then receive a nitric acid or nitric acid-
sulfuric acid cleaning followed by an alcohol dip in methanol
or isopropanol. The same plant not only eliminated neutralization
but also eliminated the alcohol dip by using a high speed, centrifugal
drying process. Prevention of water spotting on the filaments is
always important.
Steel and copper-clad steel mandrel dissolution processes are very
similar. Copper-clad steel mandrels, however, receive a prelimin-
ary nitric acid-sulfuric acid mandrel dissolution to dissolve the
copper plated material that would otherwise require a substantial
length of time in a hydrochloric acid solution. In addition, this
step reduces tungsten removal which occurs with protracted exposure
to hydrochloric acid.
Both steel and copper-clad steel mandrels are dissolved in
hydrochloric acid followed by sodium hydroxide or, in one in-
stance, trisodium phosphate neutralization. The coils then
generally receive an acid cleaning in hydrochloric acid and are
dried centrifugally or under hot lamps. One plant used sulfuric
acid-chromic acid cleaning followed by a methanol dip and finally
hot lamp drying. With the exception of the alcohol dip, water
rinsing follows each of the mandrel dissolution, neutralization,
and cleaning processes. The completed coiled filaments are then
sent to incandescent and fluorescent lamp manufacturing.
VIII-15
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Lamp Base Manufacture
Lamp bases are pressed from sheet metal using a lubricant oil.
Materials commonly used include brass, stainless steel, aluminum,
and nickel-iron alloys. The lamp bases then receive a detergent
cleaning to remove the lubricant oil. The bases are bright dipped,
dried•, and sent to lamp manufacturing facilities to become part of
the final lamp product. Lamp base manufacture is covered by the
Metal Finishing Category.
MATERIALS
Materials used in the manufacture of lamps can be classified as
raw materials and process materials. Raw materials include:
encapsulating materials, light emitting materials, mount materials,
filling gases, glass coatings, and lamp bases. Process materials
include mandrels for filament manufacturing and cleaning solutions
for lamp manufacturing.
Encapsulating Materials
These materials are used to enclose the lamp components and provide
an environment in which to create light.
Lime-Soda Glass - A soft glass used for the bulbs
of almost all incandescent lamps and for general use
in electric discharge and fluorescent lamps.
. Borosilicate Glass - A hard glass used for lamps that
produce high temperatures, such as projection lamps.
The low thermal expansion of this glass makes it
suitable for use in lamps that receive changing
temperatures as well, such as sealed beam lamps.
. Fused Silica - At extreme temperatures and pressures
such as 1000°C and 10 atmospheres, fused silica (quartz)
is the best material for lamp construction because
of its structural strength. Arc tubes of high pres-
sure mercury and sodium lamps necessitate the use
of quartz enclosures.
Glass Tubes - Primarily a type of lime-soda glass
used in fluorescent, miniature, incandescent, and
electric discharge lamps.
Light Emitting Materials
These materials vary considerably and are important because the
lamp characteristics are determined by the light emitting materials.
VIII-16
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Filaments - Used in incandescent and hot cathode
fluorescent lamps. Materials include: platinum,
osmium, tantalum, tungsten, and carbon. Tungsten
filaments are the most commonly used because they
can be operated at higher temperatures than the
others, while still giving long life without ex-
cessive blackening of the bulb or tube.
Electrodes - Structures that provide a continual supply
of electrons to the gas atmosphere of electric dis-
charge and cold cathode fluorescent lamps. Tungsten,
thoriated tungsten, and nickel are used in electric
discharge lamps. Cold cathode fluorescent lamps
employ a cylindrical electrode of iron.
Emissive Coatings - These materials are usually alka-
line earth oxides, such as barium, strontium, and cal-
cium carbonates. Often getters of pure barium or zir-
conium are included. The emissive coatings allow
cathodes to operate at muchvlower temperatures, thus
increasing their efficiency. Getters are used ,to re-
move atmospheric contaminants within the environment
of the encapsulator. In particular, emissive coated
cathodes are very susceptible to contaminants, and
getter solutions very often are used in lamps with
emissive coated cathodes.
Phosphors - These are solid luminescent materials
used in fluorescent lamps and mercury lamps.
Visible light is produced by excitation of the
phosphor materials by ultraviolet radiation from
mercury vapor. Phosphor materials most commonly
used include: calcium halophosphates, cadmium and
zinc sulfides, fluorides, silicates, borates, tungstates
and aluminates of the alkaline earth metals such as
barium, strontium, calcium, magnesium, and beryllium.
In addition, activator ions and organic binders are
necessary in combination with the phosphor materials.
The common activator ions include: manganese, tin,
lead, copper, and antimony. A common organic binder
is xylol.
Mount Materials
These consist of a stem press containing the lead wires and
electrodes for* electric gas discharge lamps and the lead wires,
filaments, and filament supports in hot cathode fluorescent and
incandescent lamps.
VIII-17
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. Lead Oxide Glass - Glass containing approximately
30% lead oxide is used as the stem press assembly. This
glass contains the lead wires and is used because of
its high electrical resistivity.
Lead Wires - These deliver the electric current to
the light emitting source. A typical lead wire from
an incandescent lamp consists of the following: a
nickel section that supports the filament, a dumet
(dual-metal) section of a copper-clad, nickel-iron
alloy formed in the stem press and matching the
thermal expansion of glass, a nickel fuse hermetically
sealed within, the glass, and finally the copper lead
which is soldered to the contacts of the lamp base.
. Filament Support - A molybdenum section supporting the
tungsten filament to the lead wires and preventing
excess vibration, which prolongs the life of the filament,
. Starting Devices - These are control mechanisms neces-
sary to heat the cathodes and provide voltage to start
a discharge in hot cathode fluorescent lamps. A set of
metallic electrodes is commonly used in conjunction with
a ballast that limits the current through the lamp.
Filling Gases
The type of gas and its applied pressure determine the spectral
emission of the radiant energy generated.
. Inert Gases - Gases of argon, neon, nitrogen, helium,
krypton, and xenon are most commonly used. Gases are
used in incandescent lamps to suppress tungsten filament
evaporation. Gas is used in an electric discharge lamp
to reduce the starting voltage necessary to establish
a discharge.
. Metallic Vapors - Many electric discharge lamps use
inert gases to reduce the starting voltage. These
trigger the metallic vapors such as mercury and sodium
that actually sustain this arc.
Glass Coatings
These materials enhance the quality of light from a lamp.
. Silica and Titania (titanium dioxide) - Fine particu-
late coatings are often used in incandescent lamps to
"frost" the glass. This coating reduces glare and
increases the diffusion of light.
VIII-18
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no * -.TransParent coatings on the inside and
outside of the lamps that produce light of various colors
Reflector Coatings - Found usually in incandescent lamps
such as the parabolic reflector lamps. Coatings of
aluminum and silver are frequently used.
Ceramic Coating - Pigments fused into the glass. These
provide permanence to the coated material.
Tin Chloride - Used in low wattage-energy saving lamps.
The metallic coating enhances electrical conductivity.
Silicone Coat - An external coating to a finished lamp
which prevents arcing from occurring in the presence
of high humidity.
Lamp Bases
These are essential in securing a lamp to a lighting fixture and
as an aid in transferring electric current from a power source
to the electrodes within the lamp. Lamp bases are commonly made
of tin, brass, or plastic materials.
Phenolic Resin Cement - Most lamps employ this
material to attach the base to the lamp.
Mechanical Crimp - Some lamps of extremely high
temperatures use this technique to insure that the
lamp base stays securely fastened to the lamp.
Mandrels
Tungsten wire is wound on mandrels of molybdenum, steel, and
copper-clad steel. The mandrels are then removed by strong
solutions of hydrochloric acid, nitric acid, and sulfuric acid.
Cleaning Solutions
Ammonium chloride and hydrochloric acid are used to remove
copper oxide from the lead wires on miniature glow lamps. Quartz
lamps often have silica deposits on the lamp surface from an
annealing operation. Hydrofluoric acid is commonly employed to
remove this aesthetically undesirable material.
WATER USAGE
From the Department of Commerce 1972 Census of Manufactures,
gross water usage is estimated to be 13.6 billion liters/day for
the electric lamp products industry as described under SIC 3641.
VIII-19
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Process water is approximately 6 percent of the gross or 816
million liters/day. It is also estimated that 42 percent or 5.7
billion liters/day of the gross water usage is discharged. No
estimates could be found of water usage within the tungsten
filament manufacturing industry as described under SIC 3699.
Observation of process operations at plants manufacturing electric
lamps and tungsten filaments revealed large differences in water
usage rates from plant to plant.
Of the 5.7 billion liters/day of discharged water from electric
lamp manufacturing, it is estimated that 7 percent or 400 million
liters/day of the total discharged water is treated. Treatment
technologies observed' at visited plants manufacturing electric
lamps, SIC 3641, and tungsten filaments, SIC 3699, are summarized
in Table 8-2.
PRODUCTION NORMALIZING PARAMETERS
Production normalizing parameters are used to relate the pollu-
tant mass discharge to the production level of a plant. Regu-
lations expressed in terms of this production normalizing parameter
are multiplied by the value of this parameter at each plant to
determine the allowable pollutant mass that can be discharged.
However, the following problems arise in defining meaningful
production normalizing parameters for electric lamps:
Size, complexity and other product attributes affect
the amount of pollution generated during manufacture
of a unit.
Differences in manufacturing processes for the same
product result in differing amounts of pollution.
Lack of applicable production records may impede
determination of production rates in terms of de-
sired normalizing parameters.
Several broad strategies have been developed to analyze applicable
production normalizing parameters. They are as follows:
The process approach - In this approach, the pro-
duction normalizing parameter is a direct measure of
the production rate for each wastewater producing
manufacturing operation. These parameters may be
expressed as sq. m. processed per hour, kg. of pro-
duct processed per hour, etc. This approach requires
knowledge of all the wet processes used by a plant
because the allowable pollutant discharge rates for
each process are added to determine the allowable
pollutant discharge rate for the plant. Regulations
based on the production normalizing parameter are
multiplied by the value of the parameter for each
process to determine allowable discharge rates from
each wastewater producing process.
VIII-20
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Concentration limit/flow guidance - This strategy
limits effluent concentration. It can be applied
to an entire plant or to individual processes. To
avoid compliance by dilution, concentration limits
are accompanied by flow guidelines. The flow guide-
lines, in turn, are expressed in terms of the pro-
duction normalizing parameter to relate flow dis-
charge to the production rate at the plant.
The electric lamp subcategory will be subdivided into two areas
for discussion of production normalizing parameters: electric
lamp manufacture and filament manufacture. Because the manufac-
ture of these products differs considerably, each product has
its own production normalizing parameter.
Electric Lamp Manufacture
Fluorescent lamps and, to a limited extent, other electric dis-
charge lamps use wet manufacturing processes requiring an ef-
fluent mass discharge limitation. Potential candidates for pro-
duction normalizing parameters include: surface area of product
processed, number of lamps processed, and amount of raw materials
consumed. It has been determined that surface area of product
processed is more closely associated with pollutant discharge than
are the other potential parameters.
Area Processed - There is a direct relationship between the sur-
face area processed and pollutant load generated. Wet processes
consisting of glass tube rinse, tin chloride coat, phosphor appli-
cation and silicone coat are all directly applied to the glass
tube surface. Thus, there is a correlation between the surface
area processed and the pollutant discharge from wet processes.
Fluorescent lamp surface area is easily calculated knowing the
number of each glass tube size processed. Most fluorescent lamps
are produced in standard sizes for which length and diameter are
known. The number of lamps of each type produced is readily avail-
able from production records. Thus the pollutant load generated
can be related directly to the total calculated surface area pro-
cessed.
Some electric discharge lamps, namely mercury lamps with quartz
envelopes which were manufactured at one plant that was visited,
use a wet process that is directly related to surface area pro-
cessed. Finished lamps are given a hydrofluoric acid etch to
remove surface silica deposits on the lamp. The entire lamp is
submerged in the acid bath. Lamp surface area is a known con-
stant for each product type. Knowing the surface area per lamp
type and the production rate in terms of the number of each type
of lamp produced yields total surface area processed.
VIII-22
-------
Number of Lamps Processed - This is the most readily available
Rn? So-" param*Jer obtainaKBB**rom lamf* manufacturing facilities.
But, because of the variety of lamp sizes manufactured! the num-
ber of lamps produced cannot stand alone as a production related
?S£Jme!:e!:*i However' in conjuction with the size of each lamp
SoduoMon pr°C*ssed area is easily obtained and is a meaningful
production normalizing parameter.
f!^"5.^ RtW "aterials Consumed - All fluorescent lamp manu-
facturing planes contacted and" isited use similar raw materials
a?di-?f°£:SS ch®mi?als- Differences in lamp manufacturing varies
little from a basic sequence of process operations. The unique
feature of each plant's manufacturing processes is the phosphor
sofuMon f°Hmulation' tin chloride coating, and silicone coating
solution. Since most plants maintain that these formulations,
particularly phosphor coatings, are proprietary, information
regarding their composition and consumption is unobtainable
Hence, raw material and process chemical usage is unavailable
for use as a basis for effluent discharge limitations.
Filament Manufacture
Potential candidates for filament manufacturing production nor-
malizing parameters include: weight of mandrel dissolved? num-
ber of filaments processed, weight of filaments processed, and
amount of process chemicals consumed. The weight of mandrel
dissolved is the best production related parameter because of
its close association with the mass of discharged pollutants.
Weight of Mandrel Dissolved - Coiled tungsten filaments are wound
on particular types of mandrels in accordance with their specific
use in incandescent and fluorescent lamps. Filaments for differ-
ent applications are wound on mandrels made of molybdenum, steel
??i f™PP?r~Clad "fteel. Coiled, coiled-coil, and triple coil tungsten
filaments are all wound initially on primary mandrels that are
eventually dissolved in strong acid. After initial coiling, fila-
ments to become coiled-coil and triple coil filaments are re-
wound on secondary mandrels that do not accompany the filament to
iSllJ w?i££1Uti;n;i Inst*ad' these secondary mandrels are mechan-
ically withdrawn following an annealing process.
There is a de terminable length of primary mandrel per unit lenqth
Sf^i16*3!.?"198^11 filament- In addition, each filament type
dictates the mandrel material needed, and the diameter of the man-
ArS dljta^e? fche size of coiling. The length, diameter, and man-
drel material used result in a mandrel weight per filament type.
Since pollution from filament manufacture results directly from
mandrel dissolution, the weight of mandrel dissolved becomes the
parameter for Determining effluent
VIII-23
-------
Number of Filaments Processed - Because filament types vary with
mandrel material and diameter, there is no direct relationship
between number of filaments produced and the pollutant mass dis-
charged. The number of coiled filaments of each type can be
used, however, in calculating the total number of mandrels used.
This can be used to calculate the total weight of mandrel dis-
solved per number of coiled filaments produced. However, the
weight of mandrel material used can be obtained more directly
from purchasing records.
Weight of Filament Processed - This production parameter is not
applicable becausedifferent coiled filament types may have a
different number of coiled turns per length of mandrel used.
This results in filament weights that are independent of mandrel
size and weight. Thus, there can be varying filament weights for
the same size and type of mandrel and varying filament weights for
the same pollutant mass discharge. Therefore, there is a
characteristic pollutant discharge relative to the type and
diameter of mandrel material that is not related to the weight
of filament processed.
Amounts of Process CheriFicals Consumed - Different mandrel materials
require dissolution processes that employ various types of acids
at varying concentrations and consumption rates. This results
in a non-uniform pollutant discharge characteristic which
discounts this parameter as a basis for effluent discharge
limitations.
Summary of Production Normalizing Parameters^
In summary, the production normalizing.parameters for the elec-
tric lamp subcategory are as follows:
Product
Fluorescent Lamps
Quartz envelope
mercury discharge
lamps
Filament Manufac-
ture
Production Normalizing
Parameter
glass tube surface area
envelope surface area
weight of mandrel dis-
solved
Units
of Mass
Discharge
mg/sq m
mg/sq m
mg/kg
WASTE CHARACTERIZATION AND TREATMENT IN PLACE
This section presents the sources of waste in the electric
lamp subcategory and sampling results for this wastewater. The
in-place waste treatment systems are discussed and treated
effluent sample data from these systems presented.
VIII-24
-------
Process Descriptions and Water Use
There are eight wet processes used by the electric lamp industry.
These wet processes are:
Glass Tube Rinse
Tin Chloride Scrubber
Sulfur Dioxide Scrubber
Glass Tube Brush Scrub or Sponge Wipe
Silicone Coating
Quartz Envelope Cleaning and Subsequent Water Rinsing
. Mandrel Dissolution, Filament Neutralization, Acid Cleaning,
and Subsequent Water Rinsing
Lead Wire Cleaning
Of these wet processes, only seven are unique to the electric
lamp industry, because lead wire cleaning is covered in the Metal
Finishing Category.
Wastewater producing processes depend upon product type, pro-
duction rate, and size of facility, as well as on the variation
in technological advancement and degree of automation. The
electric lamp manufacturing processes that use water in their
operations are described below..
There are four electric lamp product areas. Three of the product
areas consist of electric lamp types and include: incandescent,
electric discharge other than fluorescent, and fluorescent lamps.
The fourth product area is tungsten filament manufacture. In-
candescent lamp manufacture is a dry process. In general, elec-
tric discharge lamp manufacture of other than fluorescent lamps
also requires no process water usage. However, there are a few
low volume cleaning operations of quartz envelopes that encapsu-
late mercury vapor lamps. Fluorescent lamp manufacture utilizes
wet processes which include: glass tube rinse, tin chloride
scrubber, sulfur dioxide scrubber, glass tube brush scrubbing,
and silicone coating. Tungsten filament manufacture uses process
water for rinsing after mandrel dissolution, filament neutralization,
and acid cleaning, in addition to wet air scrubbing.
Table 8-3 presents product type, wastewater producing processes,
volume of water used, and number of production employees for those
plants visited within the industry. Process descriptions for
each of those manufacturing operations requiring water usage are
presented in the following subsections.
Glass Tube Rinse - This process is associated with fluorescent
lamp manufacturing. Glass tubing in straight length and circu-
lar forms is rinsed to remove any excess dust or silica impuri-
ties from the surface of the glass. These impurities may weaken
the bond of phosphors to the wall of the glass tube.
VIII-25
-------
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The visited plants use hot deionized water spray rinses. Glass
tubing is held in a vertical position by a spring-clip mechanism
and sent through an automated spray rinse. The rinse water is
sprayed down through the tubing and collected in a holding basin
below. At Plant 33189, all rinse water is deionized and returned
to the spray rinse at a flow rate of 36,336 I/day (9,600 gpd).
At Plant 28126 rinse water is discharged to a storm sewer which
flows to a nearby creek at a flow rate of 3,789 I/day (1,000 gpd).
Plant 19121 employs a similar automated hot water spray rinse.
The glass tubing, however, is held in a vertical position by a
rack assembly from above and below. In the subsequent phosphor
application process, phosphor coating solution is gravity fed
through the tubing and collected in a holding basin below.
As a result, the lower rack also receives the water-based phosphor
coating. This coating is removed from the rack when the rack
returns to the glass tube rinsing process. The rinse water is
sprayed down through the glass tubing, cleaning the glass of
dust and silica and the racks of phosphor coating material. The
rinse water flows to a 2,044 liter (540 gallon) settling tank,
the phosphors are recovered, and the remaining wastewater flows
to the sanitary sewer at a rate of 93,141 I/day (24,608 gpd).
Plant 19121 uses much more water than the other two plants pre-
viously discussed because a larger volume of rinse water is re-
quired to remove and recover phosphor materials from the racks
that contain the glass tubes.
Tin Chloride Wet Scrubber - Energy saving fluorescent lamps re-
ceive a tin chloride coating prior to phosphor application and
after glass tube rinsing. The tin chloride solution is applied
as a spray coating and is continually recirculated through a
holding basin. At Plant 19121, the tin chloride vapors are ex-
hausted through a wet air scrubber. Scrubber water is sent to
pH adjustment at a flow rate of 29,069 I/day (7,680 gpd) before
being discharged to the sanitary sewer.
Plant 33189, using a similar coating process, has very little
process water discharge. Wastewater from the wet air scrubber
is sent to a pH adjustment tank at a flow rate of 163,512 I/day
(43,200 gpd). The pH is adjusted with sodium hydroxide to a
level of 10-12, precipitating tin hydroxide out of solution. The
decant is recirculated back to the wet air scrubber, and the
settled material is contractor removed weekly. In addition,
weekly maintenance of this system discharges approximately 379
liters (100 gallons) or less of wastewater to a municipal treat-
ment system.
VIII-27
-------
Sulfur Dioxide Scrubber - Sulfur dioxide is used as a lubricant
in the automated process of glass flare manufacturing. A glass
flare seals the mount assembly to the inner rim of the glass
tubing. A small diameter glass tube is heated with a natural
gas flame and lubricated with small quantities of sulfur dioxide
introduced in the gas flame. The tube is then slowly forced
over a die, forming a funnel-shaped glass flare. Two visited
plants use such a small amount of sulfur dioxide that no wet
air scrubber is required.
However, a third facility, Plant 19121, uses sulfur dioxide in
quantities necessitating a wet air scrubber. The sulfur dioxide
fumes are exhausted through the scrubber and the wastewater flows
to a pH adjustment tank before being discharged to a municipal
treatment system. Approximately 36,336 I/day (9,600 gpd) of
water are used by this facility in the manufacturing of glass
flares. Because this fume scrubbing process of .glass flare
manufacturing is believed to occur only at this plant, no
effluent discharge limitation is recommended for this process.
Glass Tube Brush Scrub and Sponge Wipe - All plants that were
visited during this study that manufacture fluorescent lamps
employ a highly automated phosphor application process in which
the phosphor materials are prepared as solvent-based or water-
based solutions. Both types of phosphor coating solutions are
gravity fed through glass tubes held in a vertical position. As
the coating materials drip off the lower end of the tube, phos-
phors accumulate around the inner and outer rim of the tube.
After the phosphors are dried, but prior to baking, the lower ends
of the glass tubes are brush scrubbed or sponge wiped to remove
the excess phosphor material. One plant applies a solvent
based phosphor coating and uses a dry mechanical brush scrub.
Because of its solvent base, the dried phosphor is very hard and
can be removed only by an abrasive brush scrub. As the material
is removed, the hardened pieces fall into a series of pans. The
removed phosphors are dissolved in a solvent and sent to the
phosphor application area for reuse.
Two plants were visited in which water based phosphor coatings
are applied. At Plant 19121, the phosphor material is removed
by a dry mechanical brush scrub as a fine dust, which is removed
by a vacuum exhaust dust collector. The other facility, Plant
33189, utilizes a water based phosphor application and employs
a mechanical sponge wipe accompanied by a water spray rinse.
The rinse dissolves the phosphors, which drop into a settling
tank, below. The phosphors are recovered by gravitational settling,
and the water is recycled. This plant has achieved zero discharge.
All water is recirculated at a rate of 1817 I/day (480 gpd).
VIII-28
-------
Process operations for glass tube brush scrubbing or sponge
wiping are either dry or use a low water rinse flow rate. At
the plant using a wet process, zero discharge has been achieved
through settling and total recycle.
Silicone Coat - All fluorescent lamps receive a final silicone
coating prior to being aged and tested. This coating is applied
to the outer surface of the finished lamp as a dip coat or as a
roll coat. At two of the visited plants the silicone coating
solution is never discharged. Solution is added to make up
the amount consumed in the coating operation.
Plant 33189 discharges 76 I/month of silicone coating solution
from roll coating. This is done to clean the coating solution
trough of any particulate matter that may have fallen into the
solution or been dragged in by the lamp itself.
Plant 19121 employs a dip coating operation in which the lamp
travels along a conveyor and through the coating solution. In
this process the coating solution is continually added to the
coating basin and overflows at a rate of 242 I/day (64 gpd).
Quartz Envelope Lamp Cleaning - Cleaning of quartz envelope
mercury discharge lamps was observed at only one facility,
Plant 28086. During an annealing process, silica deposits
develop on the surface of the quartz tube. The lamps are dipped
into a 70% hydrofluoric acid bath to remove the undesirable de-
posits. Several rinses follow the acid bath.
This is a relatively low volume operation in which the rinse
wastewater contains primarily silica and fluorides at a flow
rate of 1817 I/day (480 gpd). At this particular facility, the
process water flow rate is independent of production rate be-
cause the rinses continually overflow regardless of the number
of lamps cleaned. Rinse water flow rates can be controlled
and reduced significantly by not allowing the rinses to con-
tinuously overflow during periods of lamp cleaning inactivity.
Mandrel Dissolution - Coiled tungsten filaments, wound on mandrels
of molybdenum, steel, and copper-clad steel, are dissolved in
very strong solutions of sulfuric-nitric acid or hydrochloric
acid. Mandrel dissolution is usually a manual operation which
commonly occurs in small (57-76 liter) tanks or in 2 liter bea-
kers. Frequently, mandrel dissolution is followed by a canister
dip to insure no further acid etching of the tungsten filament.
In addition, one plant, 28086, uses a centrifuge for molybdenum
mandrel dissolution processes. All filament manufacturing
employs wet mandrel dissolution processes. Most process water
is used for rinsing after dissolution, filament neutralization,
cleaning processes, and for wet air scrubbing of acid fumes.
With the exception of one plant employing metal recovery, all
plants pH adjusted their raw wastewater before discharging to a
municipal treatment system.
VIII-29
-------
Total process water usage for rinsing and wet air scrubbing at
visited plants ranges from 11,567 I/day (3,056 gpd) to 127,055
I/day (33,568 gpd), depending mainly upon the number of scrubbers
per plant, the efficiency of each scrubber, and the size of the
mandrel dissolution process. Plant 33202 uses the most process
water. It employs an automated system, has a high production
rate, and has several wet air scrubbers discharging water.
Plant 28077 uses the least process water, employs a manual
operation, has a lower production rate, and has one wet air
scrubber discharging water.
Wastewater Analysis Data
Wet processes from electric lamp manufacturing processes were
sampled at five facilities. Samples were analyzed for parameters
identified on the list of 129 toxic pollutants, non-toxic pol-
lutant metals, and other pollutant parameters presented in
Table 8-4.
Tables 8-5 through 8-9 present analysis data of process waste-
waters and final discharged effluents for those plants sampled
within the electric lamp subcategory. This table presents pollu-
tant parameters, concentrations, and mass loadings of the processes
sampled. Pollutant parameters are grouped according to toxic
pollutant organics, toxic pollutant metals, non-toxic pollutant
metals, and other pollutant parameters. Summation of pollutant
concentrations greater than the minimum detectable limit is pre-
sented as well as mass loadings of those pollutant parameters
whose concentrations were measurable. Mass loadings were derived
by multiplying concentration by the flow rate and the hours per
day that a particular process is operated. Some entries were
left blank for one of the following reasons: the parameter was
not detected; the concentration used for the kg/day calculation
is less than the lower quantifiable limits or not quantifiable.
The kg/day is not included in totals for calcium, magnesium, and
sodium.' The kg/day is not applicable to pH. Totals do not in-
clude values preceded by "less than".
Toxic pollutant organics, toxic pollutant metals, and non-toxic
pollutant metals were detected at measurable levels as well as
at levels below the quantitative limit. Other pollutant para-
meters are all reported in measurable quantities. The following
conventions were followed in presenting the data.
Trace Levels - Pollutants detected at levels too low to
be quantitatively measured are reported as the value
preceded by a less than sign (<). All other pollutants
are reported as the measured value.
VHI-30
-------
TABLE 8-4
POLLUTANT PARAMETERS ANALYZED
TOXIC POLLUTANT ORGANICS
1. Acenaphthene 46.
2. Acrolein 47.
3. Acrylonitrile 48.
4. Benzene 49.
5. Benzidine 50.
6. Carton Tetrachloride(Tetrachloromethane) 51.
7. Chlorobenzene 52.
8. 1,2,4-Trichlorobenzene 53.
9. Hexachlorobenzene 54.
10. 1,2-Dichlorethane 55.
11. 1,1,1-Trichloroethene 56.
12. Hexachloroethane 57.
13. 1,1-Dichloroethane 58.
14. 1,1,2-Trichloroethane 59.
15. 1,1,2,2-Tetrachloroethane 60.
16. Chloroethane 61.
17. Bis(Chloromethyl)Ether 62.
18. Bis(2-Oiloroethyl)Ether 63.
19. 2-Chloroethyl Vinyl Ether(Mixed) 64.
20. 2-Chloronaphthalene 65.
21. 2,4,6-Trichlorophenol 66.
22. Parachlorometa Cresol 67.
23. Ghloroform(Trichloromethane) 68.
24. 2-Chlorophenol 69.
25. 1,2-Dichlorobenzene 70.
26. 1,3-Dichlorobenzene 71.
27. 1,4-Dichlorobenzene 72.
28. 3,3'-Dichlorobenzidine 73.
29. 1,1-Dichloroethylene 74.
30. 1,2-Trans-Dichloroethylene 75.
31. 2.4-Dichlorophenol 76.
32. 1,2-Dichloropropane 77.
33. l,2-Dichloropropylene(l,3-Dichloropropene) 78.
34. 2,4-Dimethylphenol 79.
35. 2,4-Dinitrotoluene 80.
36. 2,6-Dinitrotoluene 81.
37. 1,2-Diphenylhyclrazine 82.
38. Ethylbenzene 83.
39. Fluoranthene 84.
40. 4-Chlorophenyl Phenyl Ether 85.
41. 4-Bromophenyl Phenyl Ether 86.
42. Bis(2-Chloroisopropyl)Ether 87.
43. Bis(2-Chloroethoxy)Methane 88.
44. Methylene Chloride(Dichloromethane) 89.
45. Methyl Chloride(Chloromethane) 90.
Methylbromide (Bromonethane)
Bromoform (Tribrpmcmethane)
Dichlorobromomethane
Trichlorofluoromethane
Dichlorodifluoronethane
Chlorodibromcxnethane
Hexachlorobutadiene
Hexachlorocyclopentadiene
Isophorone
Naphthalene
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
2,4-Dinitrophenol
4,6-Dinitro-o-cresol
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitrosod i-N-Propylamine
Pentachlorophenol
Phenol
Bis(2-Ethylhexyl)Phthalate
Butyl Benzyl Phthalate
Di-N-Butyl Phthalate
Di-N-Cctyl Phthalate
Diethyl Phthalate
Dimethyl Phthalate
1,2-Benzanthracene(Benzo(A) Anthracene)
Benzo(A)Pyrene (3,4-Benzo-Pyrene)
3,4-Benzofluoranthene(Benzo (B)Fluoranthene)
11,12-Benzofluoranthene(Benzo(K)Fluoranthene)
Chrysene
Acenaphthylene
Anthracene
1,12-Benzoperylene(Benzo(C3JI)-Perylene)
Fluorene ,
Phenanthrene
1,2,5,6-Dibenzanthracene(Dibenzo(A ,H)Anthracene
Indeno(1,2,3-CD)Pyrene(2,3-o-PhenyleneFyrene)
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Vinyl Chloride (Chloroethylene)
Aldrin
Dieldrin
VIII-31
-------
TABLE 8-4 Con't
91. Chlordane(TechnicalMixtureandMetabolites)
92. 4,4'-DDT
93. 4,4I-DDE(P,P'-DDX)
94. 4,4I-DDD(P,P'-TOE)
95. Alpha-Endosulfan
96. Beta-Endosulfan
97. Endosulfan Sulfate
98. Endrin
99. Endrin Aldehyde
100. Heptachlor
101. IfeptachlorEpoxide(B!K-Hexachlorocyclo-
hexane)
102. Alpha-BHC
103. Beta-BHC
104. Ganma-BHC(Lindane)
105. Delta-BHC(PCB-Polychlorinated Biphenyls)
106. PCB-1242(Arochlor 1242)
107. PCB-1254(ftrochlor 1254)
108. PCB-1221(Arochlor 1221)
109. PCB-1332(Arochlor 1232)
110. PCB-1248(Arochlor 1248)
111. PCB-1260(Arochlor 1260)
112. PCB-1016(Arochlor 1016)
113. Toxaphene
114. Antimony
115. Arsenic
117. Beryllium
118. Cadmium
119. Chromium
120. Copper
121. Cyanide
122. Lead
123. Marcury
124. Nickel
125. Selenium
126. Silver
127. Thallium
128. Zinc
129. 2,3,7,8-Ttetrachlorodibenzo-P-Dioxin(TCDD)
NON TOXIC POLLUTANT METALS
Calcium
Magnesium
Aluminum
Manganese
Vanadium
Boron
Barium
Molybdenum
Tin
Yttrium
Cobalt
Iron
Titanium
Potassium
Gallium
Uranium
OTHER POLLUTANTS
Oil & Grease
Total Organic Carbon
Biochemical Oxygen Demand
Total Suspended solids
Phenols
Fluoride
Xylenes
Alkyl Epoxides
Germanium
Rubidium
Strontium
Zirconium
Niobium
Palladium
Indium
Tellurium
Cesium
Tantalum
Tungsten
Osmium
Platinum
Gold
Bismuth
VIII-32
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Mass Load - Total daily discharge in kilograms/day of a
particular pollutant is termed the mass load. This figure
is computed by multiplying the measured concentration (mg/1)
by the water discharge rate expressed in liters, per day.
Sample Blanks - Blank samples of organic-free distilled
water were placed adjacent to sampling points to detect
airborne contamination of water samples. These sample
blank data are not subtracted from the analysis results,
but, rather, are shown as a (B) next !to the pollutant
found in both the sample and the blank.
The manufacture of electric lamps occurs alt ten visited plants,
five of which were sampled. Raw waste stream samples were taken
of process wastewaters including five of the eight wet processes
listed in Table 8-3.
Tungsten Filaments - Four plants manufacturing tungsten fila-
ments were visited and sampled. Tables 8-5 through 8-8 present
the analyses of raw waste and effluent discharge streams for
process water usage associated with filament mandrel dissolution.
Quartz Mercury Vapor Lamps - In addition to filament manufacture,
Table 8-8 presents a raw waste sample of hydrofluoric acid clean-
ing of quartz mercury vapor lamps.
Fluorescent Lamps - Three plants manufacturing fluorescent lamps
were visited of which one was sampled. Table 8-9 presents the
analyses of raw waste and effluent discharge streams for process
water usage associated with fluorescent lamp manufacturing.
Summary of Raw Waste Stream Data
Tables 8-10 and 8-11 summarize measurable pollutant concentration
data of raw waste streams sampled for the electric lamp subcategory,
Minimum, maximum, mean, and flow weighted mean concentrations
have been determined for the summarized raw waste streams. The
flow weighted mean concentration was calculated by dividing the
total mass rates (mg/day) by the total flow rate (I/day) for '
all sampled data for each parameter. Pollutant' parameters
listed in Tables 8-10 and 8-11 were selected based upon their
occurrence and concentration in the sampled streams. Those
parameters either not detected or detected at trace levels in
all sampled streams were excluded from these tables.
VIII-45
-------
TABLE 8-10
Summary of Raw Waste Data For
Tungsten Filament Manufacturing
Toxic Organics
23 Chloroform
44 Methylene Chloride
48 Dichlorobroroomethane
Toxic Metals
135 Arsenic
117 Beryllium
118 Cadmium
119 Chromium
120 Copper
122 Lead
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
NorHIbxic Metals
Aluminum
Manganese
Vanadium
Boron
Barium
Molybdenum
Tin
Yttrium
Cobalt
Iron
Titanium
Strontium
Zirconium
Niobium
Palladium
Indium
Tungsten
Gold*
Uranium
Minimum Maximum Mean
Concentration Concentration Concentration
mg/1 mg/1 mg/1
0.012
0.021
NO
<0.005
<0.001
0.012
<0.031
0.208
<0.070
<0.103
<0.003
0.014
0.065
<0.010
0.621
0.270
0.067
0.234
0.007
21.661
0.051
0.026
0.061
13.421
0.005
0.082
<0.020
0.040
<0.016
1.64
0.66
0.400
0.03
0.040
0.063
0.010
<0.040
<0.010
0.090
11.030
3.600
0.290
0.500
0.110
<0.130
0.170
0.160
2.230
0.426
1.040
0.809
0.040
678.
<0.515
0.072
<1.030
127.
<0.041
0.350
0.400
1.70
0.300
2.73
7.00
0.400
<0.300
0.029
0.035
0.003
0.022
0.004
0.044
3.712
1.347
0.175
0.302
0.039
0.068
0.102
0.077
1.550
0.354
0.396
0.474
0.019
258.5
0.215
0.043
0.397
66.45
0.019
0.198
0.157
0.61
0.125
2.07
4.32
0.400
0.133
Flow Weighted
Mean Concentration
mg/1
0.024
0.048
0.003
0.032
0.007
0.058
0.714
0.420
0.110
0.184
0.075
0.097
0.073
0.032
1.764
0.373
0.714
0.620
0.010
462.6
0.362
0.055
0.709
91.77
0.028
0.263
0.270
1.15
0.202
2.42
5.17
0.400
0.214
V1II-46
-------
TABLE 8-10 CON'T
Summary of Raw Waste Data For
Tungsten Filament: Manufacturing
Other Pollutants
121 Cyanide, Total NO
Total Organic Carbon 13
Biochemical Oxygen Demand 30**
Total Suspended Solids 1.0
Phenols 0.008
Fluoride ND
Minimum Maximum Mean Flow tfeighted
Concentration Concentration Concentration Mean Concentration
mg/1 mg/1 mg/1
0.010
188
30**
660
0.025
0.540
0.005
101
30**
301
0.017
0.270
0.002
156
30**
110
0.017
0.095
* 3 Single Stream Sample Value.
** = Toxic Response. Value May Be As High As That Which is Indicated.
ND = Mot Detected
VJII-47
-------
TABLE 8-11
Summary of Raw Waste Data
Fluorescent Lamp Manufacturing
Stream Identification
Sample Number
Plow Rate - Liter/Day
SO, Scrubber,
SnCl Scrubber, and
Sllicone Coat
03749-85310
65648
Developed
SnCl. Scrubber
29069
Glass Tube &
Rack Rinse
03750-85308
93136
Developed
Summary Process
Waste
122205
Toxic Organics
44 Methlene chloride
86 Tbluene
Toxic Metals
114 antimony
118 Cadmium
119 Chromium
120 Copper
122 Lead
126 Silver
128 Zinc
Non-Toxic Metals
Aluminum
Manganese
Vanadium
Boron
Barium
Tin
Yttrium
Cobalt
Iron
Concentration*
rag/1
0.063
0.011
<0.005
0.005
0.009
0.112
0.022
0.005
0.113
0.143
0.012
0.035
0.278
0.025
40.859
0.010
0.055
0.200
Flow Weighted**
Mean
Concentration Concentration*
mg/1 mg/1
NC
NC
0.011
0.020
0.253
0.050
0.011
0.255
0.323
0.027
0.079
0.628
0.058
92.273
0.023
0.011
0.452
NA
NA
0.597
0.399
<0.008
0.148
0.022
<0.005
0.146
0.619
0.445
0.009
0.064
0.121
0.033
0.033
0.003
0.193
Flow Weighted***
Mean
Concentration
NC
NC
0.458
0.307
0.011
0.173
0.029
0.006
0.172
0.549
0.346
0.026
0.198
0.106
21.974
0.031
0.005
0.255
VIII-48
-------
TABLE 8-11 (Continued)
Summary of Raw Waste Data
Fluorescent Lamp Manufacturing
Concentration*
Other Pollutants
Oil and Grease
Total Organic Carbon
Biochemical Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
Flow Weighted**
Mean
Concentration Concentration*
mg/1 mg/l
5
159
540
194
0.018
5.2
NC
NC
NC
434
NC
11.7
NA
NA
NA
52
NA
0.170
Flow Weighted***
Mean
Concentration
mg/1
NC
NC
NC
143
NC
2.9
*
**
***
NA
! Single Stream Sample Value
! Developed Process Waste From Sample Stream 03749-85310.
• Summary Waste Includes Developed SnCl Waste And Glass Tube And Rack Rinse Waste.
It Does Not Include Equipment And FloSr Washdowns.
Not Analyzed
NC = Not Considered For Developed Streams
VIII-49
-------
Table 8-10 summarizes mandrel dissolution raw waste streams
sampled at the following plants manufacturing tungsten filaments:
19082, 28077, and 33202. Plant 28086 also manufactures tungsten
filaments. However, data from this plant are not included in the
summarization because a total raw waste sample was not obtained.
Table 8-11 presents raw waste pollutant concentration data of
two samples taken at Plant 19121. Sample 03749-85310 includes
process wastewater from tin chloride and sulfur dioxide wet air-
scrubbers as well as wastewater from a silicone coating operation.
Raw waste characteristics are developed for the tin chloride coat-
ing wet air scrubber from the existing sampled stream, sample
number 03749-85310. Not all parameters summarized in Table 8-11
for this sampled stream are transferable to the developed tin
chloride scrubber stream. The organic pollutants detected are
thought to originate from sampling equipment cleaning and pre-
paration. Phenols and oil and grease may originate in the silicone
coating solution. Total organic carbon and biochemical oxygen
demand are not readily equated to any one of the three process
wastes comprising the sampled stream. The remaining pollutant
parameters as presented in Table 8-11 for the sampled stream,
03749-85310, are flow weighted for the developed tin chloride
scrubber stream. These parameters include toxic and non-toxic
metals as well as total suspended solids and fluorides. It is
expected that these pollutants result from the tin chloride coating
process.
Sample 03750-85308 is also presented in Table 8-11. This sample
includes wastewater from glass tube and rack rinsing, but does
not include wastewater from equipment and floor washdowns. This
process waste stream is flow weighted together with the developed
tin chloride scrubber waste stream, producing a developed summary
process waste stream. Pollutant parameters and wastewater flow
rates attributed to the sulfur dioxide wet air scrubber and the
silicone coating process are not used in calculating the sum-
mary process waste for fluorescent lamp manufacturing. The
sulfur dioxide scrubber is known only to exist at this sampled
facility. Wastewater from this process consists of sulfurous
and sulfuric acid. In-place waste treatment utilizes sodium
hydroxide pH adjustment of these acids. Because of its limited
use and proper in-place treatment, no further consideration is
given to characterizing sulfur dioxide scrubber wastes as they
relate to fluorescent lamp manufacturing. Silicone coating
wastes will also not receive further consideration in character-
izing fluorescent lamp manufacturing for several reasons. Si-
licone coating of fluorescent lamps was observed at three
facilities. Plant 19082 never discharges their coating solution.
Plant 33189 discharges approximately 76 liters/month and Plant
19121 discharges approximately 242 liters/day. It is expected
that the volume of silicone coating wastes is relatively low
throughout the industry. In addition, there are only a limited
number of plants manufacturing fluorescent lamps. It is known
that at least one plant employs solvents in their silicone
coating solution. Therefore, recommended treatment for silicone
coating process wastes is solution collection and removal.
VIII-50
-------
Process wastewater from fluorescent lamp manufacturing was
sampled at one facility, Plant 19121. In-place treatment tech-
nologies include pH adjustment and gravitational settling as
shown in Figure 8-5. Table 8-12 presents performance for gravi-
tational settling of wastewater containing phosphor materials.
In addition to process wastewater from glass tube and rack rinsing,
equipment and floor washdowns from the phosphor preparation area
flow to the settling tank. A flow could not be determined for
this process because of its irregular occurrence. The raw waste
sample contained only wastewater from the glass tube and rack
rinse. The effluent sample contained treated wastewater from the
washdowns from the phosphor preparation area as well as that
from glass tube and rack rinsing. Although settling did occur,
the pollutant concentrations in the effluent were higher for
most parameters than those of the sampled raw waste. This
occurred because of the additional raw waste source not contained
in the raw waste as sampled.
Treatment-In-Place
The following is a plant-by-plant discussion of raw waste and
final effluent process wastewaters sampled at plants manu-
facturing electric lamps. A discussion of waste treatment
technologies presently in existence at these sampled plants
is also presented. The treatment systems at several plants
visited but not sampled are also discussed. Table 8-13
summarizes treatment in-place and effluent discharge destina-
tions of ten plants visited during this study.
Plant 28086 produces incandescent lamps, quartz mercury vapor
lamps and coiled tungsten filaments for use in incandescent and
fluorescent lamp manufacturing. Process wastewaters produced from
the manufacturing of quartz mercury vapor lamps and coiled tung-
sten filaments were sampled and analytical results were presented
in Table 8-8. Figure 8-5 depicts sampling locations and wastewater
treatment. A grab sample was taken of the hydrofluoric acid
bath used in cleaning quartz envelope mercury vapor lamps. The
rinse after acid cleaning was of low volume discharging directly
to the municipal treatment system and was not sampled. With the
exception of spent acid used for molybdenum mandrel dissolution,
all other mandrel dissolution process wastewaters from filament
neutralization, cleaning, and rinsing flow to a pH adjustment
tank. The spent acid used for molybdenum mandrel dissolution is
sent to a holding tank from which a grab sample was taken. To
this 303 liters (80 gallons) of acid, 1211 liters (320 gallons)
of water is added. TJie solution is pH adjusted to a level of
2.5 with the use of ammonia, and precipitation of ammonium
molybdate occurs. After a 12 hour settling period, the decant
is sent to pH adjustment. A grab sample was taken of this
decant. At this point, a cold water rinse of approximately 1136
liters (300 gallons) is added to the remaining ammonium molybdate
VTII-51
-------
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TABLE 8-12
Performance of In-Place Treatment Technologies
Plant 19121
Stream Identification
Sample Number
Parameters
Toxic Organics
44 Methylene chloride
86 Toluene
Toxic Metals
114 Antimony
118 Cadmium
119 Chromium
120 Copper
122 Lead
126 Silver
128 Zinc
Non-Toxic Metals
Aluminum
Manganese
Vanadium
Boron
Barium
Tin
Yttrium
Cobalt
Iron
Other Pollutants
Glass Tube and Rack
Rinse Pre-Settle
03750-85308
Concentration (mg/1)
NA
NA
0.597
0.399
<0.008
0.148
0.022
<0.005
0.146
0.619
0.445
0.009
0.064
0.121
0.033
0.033
0.003
0.193
Oil and Grease NA
Total Organic Carbon NA
Biochemical Oxygen Demand NA
Total Suspended Solids 52
Phenols NA
Fluoride 0.170
Glass Tube, Rack Rinse, and
Washdown Post-Settle
03751-85309
Concentration (mg/1)
<0.010
ND
0.893
0.668
<0.008
0.186
0.054
<0.005
0.172
1.217
0.774
0.021
0.132
0.350
0.056
0.148
0.002
0.463
0
17
60*
82
0.023
0.150
NA = Not Analyzed
ND * Not Detected
* = Toxic Response.
Value May Be As High As That Which Is Reported.
VIII-53
-------
TABLE 8-13
Electric Lamp Manufacture
Summary Of Wastewater Treatment At Visited Plants
Plant ID No.
19121
33189
19082
28077
33202
28086
28120
34044
28126
28127
Treatment In-Place
pH adjust, settling
Chemical precipitation,
pH adjust, settling,
contractor removal,•
recycle (99.8%)
pH adjust
pH adjust
pH adjust
Chemical precipitation, settling,
vacuum filtration, pH adjust,
contractor removal
None
None
Contractor removal (solvents)
No water usage
Discharge
I
I
D
I
I
I
I
I
D
NA
I 3 Indirect
D » Direct
NA » Not Applicable
VIII-54
-------
precipitate. The mixture is stirred, settled, decanted and the
procedure repeated. However, during the sampling visit, proper
settling did not occur. As a result,-this 1136 liter (300
gallon) mixture rather than the usual settled material was sent
through the vacuum filtration unit. The filtrate flows to
pH adjustment and the sludge is contractor removed.
Together with wastewater from the molybdenum recovery process,
other mandrel dissolution wastewater flows to a pH adjustment
tank. The wastewater is pH adjusted with ammonia and flows
to a second pH adjustment unit where it is mixed with the 303
liter (80 gallon) batch discharge from a wet air scrubber. A
final pH adjustment with ammonia to a pH of 8.9 occurs prior
to discharge to the sanitary sewer.
Plant 19121 manufactures fluorescent lamps. Table 8-9 pre-
sented analytical results for those wet processes sampled.
Figure 8-5 depicts sampling locations and wastewater treatment
at this plant. Glass tube rinse, doubling as a rack rinse,
sends process wastewater to a 2044 liter (540 gallon) settling
tank. The settling tank is baffled twice. Wastewater under-
flows the first baffle, overflows the second, and is discharged
from the settling tank to the municipal treatment system. The
settled phosphors are recovered by gravitational settling and
returned to phosphor preparation.
Wastewater from a wet air scrubber associated with tin chloride
coating flows to a pH adjustment tank. The pH is adjusted to
approximately 7-8 with sodium hydroxide, and the wastewater is
stirred continuously so as to prevent settling of a tin hydrox-
ide precipitate. The wastewater is discharged to the municipal
treatment system.
A wet air scrubber associated with sulfur dioxide glass flare
manufacturing sends wastewater to a pH adjustment tank. The
pH is adjusted to approximately 8-9 before final discharge to
the municipal treatment system.
The silicone coating solution continually overflows its coating
basin and flows directly to the municipal treatment system.
A flow proportioned composite sample was taken of wastewater
produced from the two wet air scrubbers and the silicone
coating overflow.
At Plant 19082 a total raw waste sample was taken of waste-
water generated from the mandrel dissolution process, and the
analysis results were presented in Table 8-5. There is no for-
mal waste treatment system at this plant. All process waste-
water from the manufacturing of coiled tungsten filaments flows
VIII-55
-------
to a dry well containing a 45,420 liter (12,000 gallon) tank
of calcium carbonate marble chips. The pH adjusted wastewater
subsequently percolates into the ground. Figure 8-6 depicts
sampling locations and wastewater treatment at this facility.
Plant 28077 manufactures incandescent lamps, mercury vapor
lamps, and coiled tungsten filaments for use, in incandescent
and fluorescent lamp manufacturing. The only wet process at
this facility is filament mandrel dissolution. Filaments
wound on molybdenum mandrels are used in fluorescent lamp
manufacturing, and filaments wound on steel and copper-clad
steel mandrels are used in incandescent lamp manufacturing.
An attempt was made to segregate the two different mandrel dis-
solution processes. However, because of the variability in
number and size of the solution dumps, not all bath dumps could
be sampled proportionally. Therefore, the two raw waste samples
are not truly representative of the individual dissolution pro-
cesses. Analysis of these raw waste streams was presented in
Table 8-6, and sampling locations and wastewater treatment are
depicted in Figure 8-6.
All mandrel dissolution wastewater flows to a twice baffled
3,482 liter (920 gallon') pH adjustment tank. The wastewater
underflows the first baffle and overflows the second baffle
before discharge to the muninipal treatment system. Because the
mandrel dissolution wastewater is generally very acidic, pH
adjustment employs sodium hydroxide addition only. The caustic
addition is automatically controlled, and the wastewater is
continually mixed. During the sampling visit the pH control
monitoring device was malfunctioning. A pH of 8-9 is normally
maintained, but a level of 11.6 was recorded for the 8-hour
sampling period. An 8-hour continuous composite sample of the
final effluent was taken, and analysis results were presented in
Table 8-6.
Plant 33202 manufactures coiled tungsten filaments and employs
a wet mandrel dissolution process. All process wastewater flows
to a pH adjustment tank prior to discharge to the municipal
treatment system. Process wastewater at a pH of 2.0-2.5 is pH
adjusted to a level of 8-9. Analytical results of the final
effluent were presented in Table 8-7, and Figure 8-6 depicts
sampling locations and wastewater treatment.
Plant 33189 manufactures fluorescent lamps. This plant was
visited but not sampled. Wastewater treatment in-place is
depicted in Figure 8-7. Process wastewater from a wet air
scrubber associated with tin chloride coating is sent to a
2082 liter (550 gallon) settling tank in which chemical pre-
cipitation occurs. Sodium hydroxide is added to precipitate
VIII-56
-------
c
o
CM
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SB*
in
o
4J
m
c
o
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3
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O
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m
u
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0)
0
03
s
3
•H
•a
o
CO
CN
00
O
cn
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3
J
CU
c
o
-l-l
Q
I
o
M CO
3 CU
IW 13 -U
VH -H CO
3 O (0
co
-------
Tin
Chloride
Scrubber
Waste
Return
To
Process
±
Chemical
Precipitation
& Settling
I
Settling
1
Settling
t
Contract Haul
Municipal
' Treatment
System
Municipal
•Treatment
System
Return
To
Process
Glass Tube
Sponge Wipe -w
Waste
Settling
t
Phosphors Reprocessed
Return
To
Process
Glass Tube .^
Rinse Waste.
Deionization
PLANT 33189
FIGURE 8-7
IN PLACE WASTE TREATMENT'
VIII-58
-------
tin hydroxide and the treated wastewater is returned to process.
Once a week the settled sludge is pumped to another settling
tank and settled for three days. The decant is sent to the muni-
cipal treatment system, and the settling procedure is repeated.
The sludge is then contractor removed. At the time of contractor
removal of sludge/ a total of 379 liters (100 gallons) or less
of wastewater has been discharged to the municipal treatment system.
Process wastewater from glass tube sponge wiping flows to a
189 liter (50 gallon) settling tank. The phosphors are re-
covered and reprocessed, and the treated wastewater is returned
to process. Process wastewater from deionized glass tube rinsing
is sent to a holding tank, deionized, and returned to process.
POTENTIAL POLLUTANT PARAMETERS
Potential pollutant parameters for the electric lamp subcategory
were selected from the list of pollutant parameters analyzed for
as presented in Table 8-4. Rationale for selection as a potential
pollutant parameter was based on the followingj
Presence of toxic pollutants, non-toxic
metals, and other pollutants
Occurrence of pollutant as a raw material or process
chemical in electric lamp manufacturing processes
. Treatability of pollutants at reported concen-
tration levels
Toxicity of pollutants at reported concentration
levels
Table 8-14 presents the potential pollutant parameters for the
electric lamp subcategory.
Tables 8-15 and 8-16 list pollutants other than those selected
as potential parameters that were analyzed in the process raw
waste streams sampled for the electric lamp subcategory. Pol-
lutants are presented according to the following criteria:
not detected, detected at trace levels, or detected at levels
too low to be effectively treated prior to discharge. Pollutant
concentrations are determined too low to be effectively treated
for any or all of the following reasons:
Levels of treatability for many non-toxic
parameters are unknown.
VIII-59
-------
TABLE 8-14
POTENTIAL POLLUTANT PARAMETERS
Toxic Metals
114 Antimony
118 Cadmium
119 Chromium
120 Copper
122 Lead
126 Selenium
Non-Toxic Metals
Molybdenum
Tin
Iron
Tungsten
Other Pollutants
Total Suspended Solids
Fluorescent Lamps
X
X
Tungsten Filaments
X
X
X
X
X
X
X
X
X - Potential Parameters
VIII-60
-------
TABLE 8-15
POTENTIAL POLLUTANT PARAMETERS NOT SELECTED FOR
FILAMENT MANUFACTURE
NOT DETECTED IN RAW WASTE STREAMS
Toxic Organics
1. Acenaphthene 46.
2. Acrolein 47.
4. Benzene 49.
5. Benzidine 50.
6. Carbon Tetrachloride(Tetrachlororaethane) 52.
7. Chlorobenzene 53.
- 8. 1,2,4-Trichlorobenzene 54.
9. Hexachlorobenzene 56.
10. 1,2-Dichlorethane 57.
12. Hexachloroethane 59.
13. 1,1-Dichloroethane 60.
14. 1,1,2-Trichloroethane 61.
15. 1,1,2,2-Tetrachloroethane 62.
16. Chloroethane 63.
17. Bis(Chloronethyl)Ether 64.
18. Bis(2-Chloroethyl)Ether 67.
19. 2-Chloroethyl Vinyl Ether (Mixed) 69.
20. 2-Chloronaphthalene 71.
21. 2,4,6-Trichlorophenol 72.
22. Parachlorometci Cresol 73.
24. 2-Chlorophenol 74.
25. 1,2-Dichlorobenzene 75.
26. 1,3-Dichlorobenzene 76.
27. 1,4-Dichlorobenzene 77.
28. 3,3'-Dichlorobenzidine 79.
29. 1,1-Dichloroethylene 80.
30. 1,2-Trans-Dichloroethylene 82.
31. 2.4-Dichlorophenol 83.
32. 1,2-Dichloropropane 84.
33. 1,2-Dichloropropylene(1,3-Dichloropropene).85.
34. 2,4HDimethylphenol 87.
35. 2,4-Dinitrotoluene 88.
36. 2,6-Dinitrotoluene 89.
37. 1,2-Diphenylhydrazine 90.
38. Ethylbenzene 91.
39. Fluoranthene 92.
40. 4-Chlorophenyl Phenyl Ether 93.
41. 4-Bromophenyl Phenyl Ether 94.
42. Bis(2-Chloroisopropyl)Ether 95.
43. Bis(2-Chloroethoxy)Methane 96.
45. Methyl Chloride(Chloromethane) 97.
Methylbromide (Bronomethane)
Brcsnoform (Tribrcairanethane)
Trichlorofluoronethane
Dichlorodifluorcsnethane
Hexachlorobutadiene
Hexachlorocyclc^entadiene
Nitrobenzene
2-Nitrophenol
2, 4H3initrophenol
4, 6-Dinitro-o-Cresol
N-Nitrosodimethylamine
N-«itrosodiphenylamine
N-^Iitrosodi-N-Propylamine
Pentachlorophenol
Butyl Benzyl Phthalate
Di-W-Octyl Phthalate
Dimethyl Phthalate
1,2-Benzanthracene (Benzo(A)Anthracene)
Benzo (A) Pyrene (3,4-Benzo-Pyrene)
3, 4^enzofluoranthene (Benzo(B)Fluoranthene)
11 , 12-fienzof luoranthene (Benzo ( K ) Fluoranthene )
Chrysene
Acenaphthylene
1, 12-Benzoperylene (Benzo (GHI ) -Perylene )
Fluorene
1, 2, 5, 6-€>ibenzathracene(Dibenzo(A,H)Anthracene)
Indeno (1,2, 3-CD ) Pyrene ( 2 , 3-0-Phenylene Pyrene )
Pyrene
Tetrachloroethylene
_ Trichloroethylene
"vinyl Chloride (Chloroethylene)
Aldrin
Dieldrin
Chlordane (Technical Mixture and Metabolites)
4, 4 '-DDT
4,4'-DDE (P,P'-DDX)
4, 4 '-ODD (P,P-JTDE)
Alpha-Endosulfan
Beta-Endosulfan
Endosulfan Sulfate
VIII-61
-------
TABLE 8-15 CON'T
POTENTIAL POLLUTANT PARAMETERS NOT SELECTED FOR
FILAMENT MANUFACTURE
NOT DETECTED IN RAW WASTE STREAMS
98. Endrin 106.
99. Endrin Aldehyde 107.
100. Heptachlor 108.
101. Heptachlor Epoxide (BHC= Hexachloro- 109.
cyclohexane)
102. Alpha-BHC 110.
103. Beta-BHC 111.
104. Gamma-BBC (Lindane) 112.
105. Delta-BHC (PCB-Polychlorinated Biphenyls) 113.
129.
OTHER POLLUTANTS
Oil and Grease
Xylenes
Alkyl Epoxides
PCB-1242 (Aroclor 1242)
PCB-1254 (Aroclor 1254)
PCB-1221 (Aroclor 1221)
PCB-1232 (Aroclor 1232)
PCB-1248
PCB-1260
(Aroclor 1248)
(Aroclor 1260)
PCB-1016 (Aroclor 1016)
Toxaphene
2,3,7,8-Tetrachlordibenzo-P-Dioxin (TCDD)
DETECTED AT TRACE LEVELS
TOXIC ORGANICS
3. Acrylonitrile
11. 1,1,1-Trichloroethane
51. Chlorcdibrcmomethane
55. Naphthalene
58. 4-Nitrophenol
65. Phenol
66. Bis(2-Ethylhexyl) Phthalate
68. DiHfl-Butyl Phthalate
70. Diethyl Phthalate
78. Anthracene
81. Phenanthrene
86. Toluene
TOXIC METALS
114. Antimony
123. Mercury
KOHTOXIC METALS
Potassium
Gallium
Germanium
Rubidium
Tellurium
Osmium
Platinum
Bismuth
VIII-62
-------
TABLE 8-15 (Continued)
DETECTED AT LEVELS NOT REQUIRING TREATMENT
TOXIC ORGANICS
23. Chloroform
44. Methylene Chloride
48. Dichlorobronome thane
TOXIC METALS
115.
117.
124.
126.
127.
128.
Arsenic
Beryllium
Nickel
Silver
Thallium
Zinc
NON-TOXIC METALS
Aluminum
Manganese
Vanadium
Boron
Barium
Tin
Yttrium
Cobalt
Titanium
Strontium
Zirconium
Niobium
Palladium
Indium
Gold
Uranium
OTHER POLLUTANTS
121. Cyanide Total
Total Organic Carbon
Biochemical Oxygen Demand
Phenols
Fluoride
Mean Concentration
mgA
0.039
0.035
0.007
0.022
0.004
0.302
0.068*
0.102
0.077
1.550
0.354
0.396
0.474
0.019
0.215*
0.043
0.397*
0.019*
0.198
0.157
0.61
0.125
2.07
0.400**
0.133*
0.005
101
30
0.017
0.270
* = Does Not Require Treatment As Maximum Value Is At A Trace Level,
** = Single Stream Sample Value.
VIII-63
-------
TABLE 8-16
POTENTIAL POLLUTANT PARAMETERS NOT SELECTED FOR
FLUORESCENT LAMP MANUFACTURE
NOT DETECTED IN RAW WASTE STREAMS
TOXIC ORGflNICS
1. Acenaphthene . 46.
2. Acrolein 47.
3. Acrylonitrile 49.
5. Benzidine 50.
6. Carbon Tetrachloride(Tetrachlorcjnethane) 51.
7. Chlorobenzene 52.
8. 1,2,4-Trichlorobenzene 53.
9. Hexachlorobenzene 54.
10. 1,2-Dichlorethane 55.
12. Hexachloroethane 56.
13. 1,1-Dichloroethane 57.
14. 1,1,2-Trichloroethane 58.
15. 1,1,2,2-Tetrachloroethane 59.
16. Chloroethane 60.
17. Bis(Chloromethyl)Et±er 61.
18. Bis(2-Chloroethyl)Ether 62.
19. 2-Chloroethyl Vinyl Ether (Mixed) 63.
20. 2-Chloronaphthalene 64.
21. 2,4,6-Trichlorophenol 67.
22. Parachlorometa Cresol 69.
24. 2-Chlorophenol 72.
25. 1,2-Dichlorobenzene 73.
26. 1,3-Dichlorobenzene 74.
27. 1,4-Dichlorobenzene 75.
28. 3,3'-Dichlorobenzidine 76.
29. 1,1-Dichloroethylene 77.
30. 1,2-Trans-Dichloroethylene 79.
31. 2.4-Dichlorophenol 80.
32. 1,2-Dichloropropane 82.
33. l,2-Di<±loroprcpylene(l,3-Dichloropropene) 83.
34. 2,4-Diroethylphenol 84.
35. 2,4-Dinitrotoluene 85.
36. 2,6-Dinitrotoluene 87.
37. 1,2-Diphenylhydrazine 88.
38. Ethylbenzene 89.
39. Pluoranthene 90.
40. 4-Chlorophenyl Phenyl Ether 91.
41. 4-Brcmophenyl Phenyl Ether 92.
42. Bis(2-Chloroisopropyl)Ether 93.
43. Bis(2-Chloroethoxy)Methane 94.
45. Mathyl Chloride(Chlororaethane) 95.
Methylbromide (Bromoraethane)
Bromoform (Tribromoraethane)
Trichlorofluoronethane
Dichlorodifluoromethane
Chlorodibromcxnethane
Hexaohlorobutadiene
Hexachlorocyclopentadiene
Isophorone
Naphthalene
Nitrobenzene
2-Nitrophenol
4-^Iitrophenol
2,4-Dinitrophenol
4,6-Dinitro-o-cresol
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitrosodi-N-Propylamine
Pentachlorophenol
Butyl Benzyl Phthalate
Di-«-Octyl Phthalate
l,2HBenzanthracene (Benzo(A)Anthracene)
Benzo (A) Pyrene (3,4-Benzo-Pyrene)
3,4-Benzofluoranthene (Benzo(B)Floranthene)
ll,12^enzofluoranthene(Benzo(K)Fluoranthene)
Crysene
Acenaphthylene
1,12-Benzoperylene(Benzo(GHI)-Perylene)
Fluorene
1,2,5,6-Dibenzathracene(Dibenzo(A,H)Anthracene)
Indeno(1,2,3-CD)Pyrene(2,3-0-Phenylene Pyrene)
Pyrene
Tetrachloroethylene
Trichloroethylene
Vinyl Chloride (Chloroethylene)
Aldrin
Dieldrin
Chlordane (Technical Mixture and Metabolites)
4,4'-DDT
4,4'-DDE (P,P'-DDX)
4,4'-ODD (P,P-TDE)
Alpha-Endosulfan
VIII-64
-------
TABLE 8-16 CON'T
POTENTIAL POLLUTANT PARAMETERS NOT SELECTED FOR
FLUORESCENT LAMP MANUFACTURE
NOT DETECTED IN RAW WASTE STREAMS
95. Alpha-Endosulfan
96. Beta-Endosulfan
97. Endosulfan Sulfate
98. Endrin
99. Endrin Aldehyde
100. Heptachlor
101. Heptachlor Epoxide (BHC=Hexachloro-
cyclohexane)
102. Alpha-^HC
103. Beta-BHC
104. Gamma-BHC (Lindane)
105. Delta-BHC (PCB-Polychlorinated Biphenyls)
106. PCB-1242 (Aroclor 1242)
107. PCB-1254 (Aroclor 1254)
108. PCB-1221 (Aroclor 1221)
109. PCB-1232 (Aroclor 1232)
110. PCB-1248 (Aroclor 1248)
111. PCB-1260 (Aroclor 1260)
112. PCB-1016 (Aroclor 1016)
113. Toxaphene
129. 2,3,7,8-Tetrachlorodibenzo-P-Dioxin (TCDD)
OTHER POLLUTANTS
121 Cyanide, total
Xylenes
Alkyl Epoxides
DETECTED AT TRACE LEVELS
TOXIC ORGANICS
4. Benzene
11. 1,1,1-Trichloroethane
23. Chloroform
48. Dichlorobromomethane
65. Phenol
66. Bis(2-Ethylhexyl) Phthalate
68. Di-N-butyl Phthalate
70. Diethyl Phthalate
71. Dimethyl Phthalate
78. Anthracene
81. Phenanthrene
TOXIC METALS
115. Arsenic
123. Mercury
124. Nickel
127. Thallium
117. Beryllium
125. Selenium
NON-TOXIC METALS
Molybdenum
Titanium
VIII-65
-------
TABLE 8-16 CON'T
DETECTED AT LEVELS NOT REQUIRING TREATMENT
TOXIC ORGANICS
44. Methylene Chloride
86. Toluene
TOXIC METALS
119. Chromium
120. Copper
126. Silver
128. Zinc
NON-TOXIC METALS
Aluminum
Manganese
Vanadium
Boron
Barium
Yttrium
Cobalt
OTHER POLUJEANTS
Oil and Grease
Total Organic Carbon
Biochemical Oxygen Demand
Phenols
Fluoride
Developed
Plow Weighted*
Mean Concentration
(mg/1)
0.063**
0.011**
0.011
0.173
0.006
0.172
0.549
0.036
0.026
0.198
0.106
0.031
0.005
5 **
159 **
540 **
0.018**
2.9
**
Single Stream Sample Value
Parameters Do Not Require Treatment Based On Single Stream Sample Values.
VIII-66
-------
Pollutants are not selected if raw waste
=" concentrations are less than the long terra
average concentrations established for the
levels of recommended treatment.
Aluminum, silver, tin, cobalt, titanium, and manganese have not
been selected as potential pollutant parameters for filament
manufacture because the three recommended levels of treatment
will effectively reduce their.concentrations while precipitat-
ing other potential pollutant metals. Additionally silver,
tin, cobalt, and titanium, as well as uranium, have not been
selected because the maximum concentrations reported for
these metals are at nonquantifiable levels* Therefore, when
these nonquantifiable levels are used in calculating the mean
concentrations and the flow weighted mean concentrations, they
increase these calculated values to concentration levels that
are potentially controllable.
An example of this situation exists for tin. Table 8-10
presents minimum, maximum, mean, and flow weighted mean con-
centrations for filament mandrel dissolution as sampled at
three facilities. Tin concentrations for the three sampled
streams include: 0.051 mg/1, 0.080 mg/1, and <0.515 mg/1.
If only measurable concentrations, 0..051 mg/1 and 0.080 mg/1,
are used in determining mean and flow weighted mean concentra-
tions, then resultant concentration levels are 0.060 mg/1
and 0.056 mg/1 respectively. These levels are less than that
which is achievable by the levels of recommended treatment.
However, if all three streams are utilized in determining the
mean and flow weighted mean concentrations,increased concentra-
tion levels occur as presented in Table 8-10. These concentra-
tions are indeed attainable by the levels of recommended treat-
ment. Because they were determined using a nonquantifiable value
which is also the maximum reported value, this parameter is pre-
sented in Table 8-14 at a concentration not requiring treatment.
Wastewater analysis for gold was performed at one of three plants
considered in summarizing raw waste data for Table 8-10. The
sample for which gold was analyzed contains 7.0 mg/1 of tungsten.
Gold and tungsten have been observed on several occasions to
appear together on emission spectra. Therefore, it As possible
that an analytical interference occurs between gold and tungsten.
This would explain the presence of gold in samples known to
contain tungsten and which should not contain gold.
APPLICABLE TREATMENT TECHNOLOGIES
Based on the potential pollutant parameters selected and actual
treatment technologies observed within the electric lamp industry,
the following treatment technologies are recommended for pollu-
tant control within this subcategory:
Chemical precipitation and sedimentation
VIII-67
-------
Settling
Reverse osmosis
Sludge dewatering
Final pH adjustment
Multimedia filtration
Pressure filtration
Contract removal
These technologies are discussed in detail in Section XI1 of this
report.
Recommended Treatment Systems
Alternative waste treatment technologies are presented for the
electric lamp subcategory. Treatment technologies are defined
for process wastes from the manufacture of fluorescent lamps,
tungsten filaments, and quartz mercury vapor lamps. The following
discussion presents 2 levels of waste treatment for fluorescent
lamp manufacture, 3 levels of waste treatment for filament manufac-
ture, and 1 level of waste treatment for quartz mercury vapor
lamp manufacture.
Fluorescent Lamps - Level 1 - Treatment of process wastewater
for fluorescent lamp manufacture requires only two levels of
treatment to achieve total recycle. The recommended Level 1
treatment system is shown in Figure 8-8. Level 1 treatment
consists of the following:
Settling of phosphor wastes
Chemical precipitation and sedimentation in a
clarifier of wet air scrubber wastes using lime,
a coagulant aid, and a polyelectrolyte
. Sludge dewatering
. Final pH adjustment
. Collection and removal of silicone coating
wastes
Level 2 - Recommended treatment includes the system described
for Level 1 with two additions. Level 2 treatment is shown
in Figure 8-8 and the additions are as follows:
Total recycle of treated wastes for the wet
air scrubber associated with tin chloride coating.
. Total recycle of treated wastewater for glass
tube brush scrub or sponge wipe, and rack cleaning.
Tungsten Filaments - Level 1 - Recommended treatment for fila-
ment mandrel dissolution is shown in Figure 8-9. The Level 1
treatment system includes:
Chemical precipitation and sedimentation in a
clarifier with the use of lime, ferric sulfate, a
coagulant aid, and a polyelectrolyte
VIIl-68
-------
LEVEL 1
* Lime
Wet Air
Waste , i
Sponge Wipe "" ' '*"""
Brush Scrub &
Hack Clean " "
Phosphor a
Reprocessing
LEVEL 2
Wet Air ,,._,'
Waste i
Chemical
Precipitation
i '
Vacuum Filter
1 '
Contract Haul
Lime
Chemical
Precipitation
Return to
Process!
Sponge Wipe """ "" 1
or . •. Settling — »
Brush Scrub &
Hack Clean "•'"
Phosphor _
Reprocessing
Vacuum Filter
i
Contract Haul
Return to Process
"I
FIGURE 8-8
FLUORESCENT LAMP WASTE TREATMENT
VIII-69
-------
LEVEL 1
Mandrel
Dissolution-
Haste
Ferric Sulfate
&
Lime
t
Chemical
Precipitation
Vacuum Filter
Contract Haul
pH Adjustment
LEVEL 2
Ferric Sulfate
&
Lime
Mandrel
Dissolution-
Haste
Chemical
Precipitation
Vacuum Filter
Contract
Haul
LEVEL 3
Mandrel
Dissolution-
Haste
Return to
Holding
Tank
1
EH
Adjustment
NoOH
to
pH 5
Process
Reverse
Osmosis
i
I
Pressure
Filtration
1
1
Contract Haul
1
Ferric Sulfate
S
Lime
Chemical
Precipitation
i
Vacuum Filter
i
Contract Haul
Multimedia . ..
Filtration
FIGURE 8-9
FILflHIMT MANUFACTURE HASTE TREATMENT
vm-70
-------
Sludge dewatering
Final pH adjustment
Level 2 - Recommended treatment consists of Level 1 treatment with
the addition of multimedia filtration to reduce the concentration
of suspended solids. Multimedia filtration for effluent polishing
is used in many industries as well as in municipal treatment appli-
cations, and the technology is readily transferable. Level 2
treatment is also shown schematically in Figure 8-9.
Level 3 - Recommended treatment consists of Level 2 treatment with
two additional processes. The additions are shown in Figure 8-9
and comprise;
pH adjustment with sodium hydroxide to precipitate iron
Pressure filtration to remove iron oxide precipitate
prior to reverse osmosis
Reverse osmosis to concentrate the wastes.
Recycle of the permeate from the reverse osmosis to
the process.
Quartz Mercury Vapor Lamps - Level 1 - Recommended treatment for
the acid cleaning of quartz mercury vapor lamps is presented in
Figure 8-10. This low volume wet process was observed at only
one facility, Plant 28086. It is not known if there are other
lamp manufacturing facilities employing a similar process. There-
fore, only Level 1 treatment is recommended for quartz mercury
vapor lamp manufacture and includes wastewater collection and
contract removal.
Performance of In-Place Treatment Systems
The performance of treatment .components that have been sampled
as in-place technology for the electric lamp subcategc-ry is
presented in Tables 8-12 and 8-17. Filament mandrel dissolution
was observed and sampled at four facilities. Plants 19082,
28077, and 33202 employed pH adjustment of the final effluent
as their only wastewater treatment process. The fourth plant,
28086, had some additional treatment processes as well. These
processes are shown in Figure 8-5 and performance of the treatment
components is presented in Table 8-17. None of the three levels of
treatment recommended for filament manufacture has been observed
as in-place treatment systems within the industry. Performance of
in-place treatment for fluorescent lamp manufacturing was observed
and sampled at one facility, Plant 19121. Discussion and performance
of treatment technologies is presented under the "Summary of Raw
Waste Stream Data" section and in Table 8-12, respectively.
VIII-71
-------
LEVEL 1
Quartz
Lamp fc
Cleaning
tfoeji-ia
Holding
Tank
Contract
Haul
FIGURE 8-10
Quartz Mercury Vapor Lamp Manufacture
Waste Treatment
VUI-72
-------
la a
r-.
in
00
m
o
o\ *r vo 'a4 m
o>) in ro in o
O in rHrH O
• • • « •
o o oo o
oao
oo oo
on
• •
00 OJ t~ O
O iH iH m O
ro
crt
OJ4J
\o
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VO
OO
01
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VIII-73
-------
Performance of Recommended Treatment Systems
<•
Performance of the two levels of recommended treatment for fluor-
escent lamp manufacture is presented in Table 8-18. Performance
of the three levels of recommended treatment for tungsten filament
manufacture is presented in Table 8-19. Performance is based on
sampling data obtained from visited plants in the E&EC Category as
well as data from plants from other industries with similar wastes
and treatment. Because of similarity in raw waste characteristics
to other industries, the performance of treatment technologies
in other industries is applicable to the E&EC Category. Performance
of the individual treatment components is presented in Section XII.
A Level 1 treatment system for fluorescent lamp manufacture was
not observed in-place at any of the visited plants and thus per-
formance of the recommended treatment system is transferred from
other industries. However, phosphor settling of glass tube and
rack rinse wastes was observed and sampled at Plant 19121. Sampl-
ing data for gravitational settling of phosphors was presented in
Table 8-12. The raw waste sample and flow rate does not include
equipment and floor wasdowns which were not obtained during the
sampling effort. The effluent does contain all wastewater sent
through the settling tank. Therefore, true performance of this
treatment technology is not complete. In addition, retention time
for the gravitational settling of phosphors was at most twenty
minutes if based only on the known flow rate entering the settling
tank. The additional unknown flow rate from equipment and floor
washdowns will reduce the retention time below twenty minutes.
Level 2 treatment for fluorescent lamp manufacturing does not
include any treatment technology additional to the recommended
Level 1 treatment system. Pollutant discharge is eliminated by
total recycle of treated wastes. Level 2 treatment for fluorescent
lamp manufacture was observed but not sampled at Plant 33189. This
treatment system is.known to exist as in-place treatment at two
other fluorescent lamp manufacturing facilities.
None of the three levels of recommended treatment for tungsten
filament manufacture have been observed as in-place treatment
and performance of the recommended treatment systems is trans-
ferred from other industries. This performance is presented in
Table 8-19. Levels 2 and 3 treatment for tungsten filament manu-
facture employ the addition of a multimedia filter to the Level
1 treatment system. This improves metals removal while lowering
the total suspended solids level. This occurs because some of
the metal hydroxide precipitates will be further removed by the
multimedia filter. In addition, Level 3 utilizes reverse osmosis
to concentrate wastes and produce a treated permeate for process
reuse. It is estimated that 85 percent of the treated wastewatef
will be returned to process.
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VIII-76
-------
Recommended treatment for quartz mercury vapor lamp manufacturing
was not observed in-place. However, recommended treatment is based
on a low volume lamp cleaning process which occurs at Plant 28086.
Estimated Cost of Recommended Treatment Systems
The determination of estimated costs for recommended treatment
system components is discussed in Section XIII of this report.
Tables 8-20 through 8-28 show the estimated costs for each of
the recommended treatment systems discussed previously for the
electric lamp subcategory. Costs have been estimated for Levels
1, 2, and 3 recommended treatment for filament manufacture and
Levels 1 and 2 for fluorescent lamp manufacture. The variations
in system costs resulting from changes in system flow rate are re-
presented by using three flow rates for filament manufacture and
two flow rates for fluorescent lamp manufacture. The three fila-
ment manufacturer flow rates represent small, medium, and large
size facilities. The two fluorescent lamp manufacturer flow rates
represent medium size facilities. These treatment system costs
reflect complete installation of the recommended treatment systems
and do not account for treatment in-place at electric lamp faci-
lities. Quartz mercury vapor lamp manufacture was observed at
one facility, Plant 28086. Cost of treatment is presented for a
flow rate of 606 I/day (160 gpd). Because the flow rates and
number of facilities manufacturing quartz mercury vapor lamps
are expected to be small, further costs for benefit analysis are
not presented.
BENEFIT ANALYSIS
This section presents an analysis of the industry-wide benefit
estimated to result from applying the three levels of treatment
previously discussed in this section to the total process waste-
water generated by the electric lamp subcategory. This analysis
estimates the amount of pollutants that would not be discharged
to the environment if each of the three levels of treatment were
applied on a subcategory-wide basis. An analysis of the benefit
versus estimated subcategory-wide cost for each of the treatment
levels will also be provided.
Industry-wide Costs
By multiplying the annual and investment costs of each level of
treatment at various flow rates by the number of plants in each
flow regime in the industry, subcategory-wide annual and invest-
ment cost figures are estimated (Tables 8-29 and 8-30). These
figures represent the cost of each treatment level for fluorescent
lamp and tungsten filament manufacture contained within the electric
lamp subcategory. This calculation does not make any allowance for
waste treatment that is currently in-rplace at electric lamp
facilities.
VIII-77
-------
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-------
TABLE 8-29
Industry-Wide Cost Analysis
Fluorescent Lamps
Level 1 Level 2
Investment (Thousands of Dollars) 2463.831 2156.814
Annual Costs (Thousands of Dollars)
Capital Costs 207.739 181.851
Depreciation 492.766 431.363
Operation and Maintenance 193.167 179.531
Energy and Power 14.856 10.567
Total Annual Cost (Thousands of 908.528 623.781
Dollars)
Discharge Flow (million I/year) 251.597 0
VIII-87
-------
TABLE 8-30
Industry-Wide Cost Analysis
Tungsten Filaments
Investment (Thousands
of Dollars)
Annual Costs (Thousands
of Dollars)
Level 1
3860.397
Level 2
4537.570
Level 3
5982.878
Capital Costs 325.491
Depreciation 772.079
Operation and 286.747
Maintenance
Energy and Power 23.175
Total Annual Cost (Thou-
sands of Dollars) 1407.792
Discharge Plow
(million I/year)
557.531
382.588
907.514
356.553
26.177
1672.832
557.531
504.447
1196.575
1187.971
73.825
2962.818
83.630
VIII-88
-------
Industry-wide Cost and Benefit
Tables 8-31 and 8-32 present the estimate of total annual cost
to the electric lamp subcategory to reduce pollutant discharge.
This table also presents the benefit of reduced pollutant discharge
for the electric lamp subcategory resulting from the application
of the three levels of recommended treatment. Benefit was
calculated by multiplying the estimated number of gallons discharged
by the subcategory times the performance attainable by each of
the recommended treatment systems as shown in Table 8-18.
Values are presented for each of the selected subcategory pollutant
parameters.
The column "Raw Waste" shows the total amount of pollutants that
would be discharged to the environment if no treatment were employed
by any facility in the industry. The columns "Levels 1,2, and 3
treated effluent" show the amount of pollutants that would be dis-
charged if any one of these three levels of treatment were applied
to the total wastewater estimated to be discharged by the electric
lamp subcategory.
The total amount of wastewater discharged from each level of
treatment is also presented in this table to indicate the amount
of process wastewater to be recycled by each of the three levels
of treatment. Process wastewater recycle is a major step toward
water conservation and reduction in pollutant discharge.
VIII-89
-------
Parameter
Flew (million I/year)
114. Antimony
118. Cadmium
122. Lead
Tin
Total Suspended Solids
Total Annual Cost (thou-,
sand dollars) ,
TABLE 8-31
Cost and Benefit
Fluorescent Lamps
Raw Waste
(kg/year)
251.597
Level 1 Treated
Effluent
(kg/year)
251.597
115.231
77.403
34.180
5528.592
35978.371
12.580
3.019
12.580
31.701
4478.427
908.528
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(kg/year)
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0
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* =* Level 2 Pollutant Discharge Eliminated With 100% Reuse Of Treated
Process Wastewater
VIII- 90
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SECTION IX
ELECTRON TUBE SUBCATEGORY DISCUSSION
INTRODUCTION
This discussion of the electron tube industry consists of the
following major sections:
Products
Size of the Industry
Manufacturing Processes
Materials
Water Usage
Production Normalizing Parameter
Waste Characterization and Treatment in Place
Potential Pollutant Parameters
Applicable Treatment Technologies
Benefit Analysis
Data contained in this section were obtained from several sources.
Engineering visits were made to five plants within the subcategory.
Wastewater samples were collected from three of these five facili-
ties. A total of thirty-six electron tube manufacturing plants
were contacted by telephone. A literature survey was also conducted
to ascertain differences between types of electron tube products, pro-
cess chemicals used, and typical manufacturing processes.
PRODUCTS
Electron tubes are devices in which electrons or ions are con-
ducted between electrodes through a vacuum or ionized gas within
a gas tight envelope which may be glass, quartz, ceramic, or
metal. Electron tubes depend upon two basic phenomena for their
operation. The first is the emission of electrons by certain
elements and compounds when the energy of the surface atoms is
raised by the addition of heat, light photons, kinetic energy of
bombarding particles, or potential energy. The second phenomenon
is the control of the movement of these electrons by the force
exerted upon them by electric and magnetic fields. The three
types of electron tubes which are to be discussed in this section
are:
Receiving type electron tubes
Television picture tubes
. Transmitting type electron tubes
Receiving type electron tubes (Reference Figure 9-1) are noted
for their low voltage and low power applications. They are used
in radio and television receivers, computers, and sensitive
IX-1
-------
exhaust tip
getter
screen grid
suppressor grid
glass-metal seal
base pin
FIGURE 9-1
RECEIVING TUBE
IX-2
-------
control and measuring equipment. Structurally, electron tubes
are classified according to the number of electrodes they contain.
The electrodes are usually made of nickel mounted on a base
penetrated by electrical connections and are encapsulated in a
glass or metal envelope which is evacuated. The tube is evacu-
ated to 10 mm of mercury and the electrodes and/or the envelope
is heated to remove absorbed gases. The passage between the
tube and pumping system is sealed off. A getter material (usually
magnesium, calcium, sodium, or phosphorus) previously introduced
in the evacuated envelope is flashed. Flashing occurs by applying
an electric current to the electrodes of the tube for several
seconds. The getter material condenses on the inside surface
and absorbs any gas molecules. The result is that the vacuum
within the tube becomes progressively stronger until an equili-
brium value of 10 mm is reached.
Television picture tubes function by modification of a horizontal
scanning of high velocity electrons striking a luminescent
surface. The number of electrons in the stream at any instant
of time is varied by electrical impulses corresponding to the
transmitted signal. A typical color television tube is shown in
Figure 9-2.
The tube is a large glass envelope. A special composition of
glass is used to minimize optical defects and to provide electri-
cal insulation for high voltages. The structural design of the
glass bulb is made to withstand 3-6 times the force of atmos-
pheric pressure. The light-emitting screen is made up of small
elemental areas, each capable of emitting light in one of the
three primary colors (red, green, blue). An electron gun for
each color produces a stream of high velocity electrons which is
aimed and focused by static and dynamic convergence mechanisms
and an electro-magnetic deflection yoke. An aperture mask
behind the face of the screen allows phosphor excitation according
to incident beam direction. Commercially available aperture
mask tubes are manufactured in a number of sizes.
Transmitting type electron tubes are characterized by the use
of electrostatic and electromagnetic fields applied externally
to a stream of electrons. There are several different types of
transmitting tubes. They generally are high powered devices
operating over a wide frequency range, are larger and struc-
turally more rugged than receiving tubes, and are completely
evacuated. Figure 9-3 is a diagram of a klystron tube, which is
typical of a transmitting type tube. In a klystron tube, a
stream of electrons from a concave thermionic cathode is focused
into a smaller cylindrical beam by the converging electrostatic
fields between the anode, cathode, and focusing electrode. The
beam passes through a hole in the anode and enters a magnetic
field parallel to the beam axis. The magnetic field holds the
beam together, overcoming the electrostatic repulsion between
electrons. The electron beam goes through the cavities of the
klystron, emerges from the magnetic field, spreads out and is
IX-3
-------
mask
three
electron
beams
special
glass bulb
static and dynamic
convergence
of three
electron beams
(magnetic)
base
/•onnections
three
electron
guns
electromagnetic
deflection yoke
high-voltage contact
fluorescent light-emitting
three-color screen
(with aluminum
mirror backing)
FIGURE 9-2
COLOR TELEVISION PICTURE TUBE
IX-4
-------
collector
fully bunched
electrons
input
coaxial
transmission
line
high
voltage
supply
spreading
electron beam
magnetic polepiece
output catcher
^s cavity
output
waveguide
output
coupling ins
antibunch
electron bunch
forming
intermediate
cascade cavity
iron magnet
shell
electromagnet
solenoid coil
input buncher
cavity
anode
converging
electron beam
focus electrode
insulating bushing
thermionic cathode
heater filament
heater leads
FIGURE 9-3
TRANSMITTING TUBE
IX-5
-------
stopped in a hollow collector where the remaining kinetic energy
pf the electrons is dissipated as heat.
The electron tube subcategory includes products which were
classified under SIC 3671, Electron Tubes, Receiving Type; SIC
3672, Cathode Ray Picture Tubes; and SIC 3673, Electron Tubes,
Transmitting Type. These industries have been included under
SIC 3671 by the Department of Commerce for their Census of
Manufactures for the year 1977. The three SIC groups have been
classified together because of the declining size of the industry,
The major products of the electron tube subcategory are as
follows:
. Receiving Type Electron Tubes
Television Picture Tubes
- Color Picture Tubes
- Black and White Picture Tubes
- Rebuilt Picture Tubes
. Transmitting Type Electron Tubes
- Power and Special Tubes
Vacuum Tubes
Gas and Vapor Tubes
Klystrons
Magnetrons
Traveling Wave Tubes
- Light Sensing Tubes
Camera Tubes, Photoemissive and
Photoconductive
Image Intensifiers and Converters
Photomultipliers
- Light Emitting Devices
Storage Tubes
Cathode-Ray Tubes, Industrial and
Military
SIZE OF INDUSTRY
This discussion estimates the number of plants and the number of
employees for plants engaged in the manufacture of electron
tubes, SIC 3671.
Number of Plants
It is estimated that 143 plants are engaged in the manufacture of
electron tubes. This estimate is from the Department of Commerce
1977 Census of Manufactures (Preliminary Statistics).
IX-6
-------
Number of Employees
It is estimated that 27,200 production employees are engaged in the
manufacture of electron tubes. This estimate is from the Department
of Commerce 1977 Census of Manufactures (Preliminary Statistics).
Production Rate
The total number of electron tubes produced is not available. How-
ever, partial information was obtained from the Department of Commerce
1977 Census of Manufactures. This information is summarized in,Table
9-1.
MANUFACTURING PROCESSES
Discussion of electron tube manufacturing is arranged by the primary
electron tube types: Receiving, Television Picture, and Transmitting.
Receiving Tube Manufacture
The manufacture of a receiving tube is similar to that of a transmit-
ting tube and is depicted schematically in Figure 9-4. Raw materials
required for receiving tube manufacture include glass envelopes,
kovar and other specialty metals, tungsten wire, and copper wire.
The metal parts are punched and formed, chemically cleaned, and
electroplated with copper, nickel, chromium, gold, or silver. The
iron or nickel cathode is coated with a getter solution. The metal
pacts are hand assembled into a tube mount assembly. Glass parts for
the tube base are cut and heat treated. Copper lead wires are sealed
in the "glass mount" machine. The glass mount piece is then heat
treated by baking in an oven. The metal tube mount assembly is then
hand welded to the glass mount piece. The upper glass bulb is rinsed.
On a "sealex" machine, the bulb is evacuated, sealed, and the glass
extensions are cut off. The glass exterior is rinsed and the com-
pleted tube is aged, tested, and packaged.
Television Picture Tube Manufacture
The manufacture of a television picture tube is a highly complex,
automated process as depicted in Figure .9-5. Television picture
tubes comprise four major components: the glass panel, steel aper-
ture mask, glass funnel, and the electron gun mount assembly. The
glass panel is the front of the picture tube through which the picture
is viewed. The steel aperture mask is used to direct the electron
beam to the phosphor coated glass panel. The glass funnel is the
casing which extends back from the glass panel and is the largest
component of the picture tube. The mount assembly is attached to
the funnel and contains the electron gun and the electrical base
connections. Most manufacturing operations utilizing a chemical
process will be accompanied by one or several water rinses.
Manufacture of a television picture tube begins with a steel aperture
mask degrease. Steel aperture masks are produced at other facilities,
received by the picture tube manufacturer, formed to size, solvent
degreased, and oxidized. The steel aperture masks are inserted
within the glass panel which is commonly referred to as a panel-mask
"mate". The panel-mask mate is annealed and the mask is removed.
IX-7
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TABLE 9-1
PRODUCTS AND PRODUCT CLASSES, QUANTITY
AND VALUE OF SHIPMENTS BY ALL PRODUCERS
0? ELECTRON TUBE PRODUCTS
SIC
3671
Receiving Tubes, All
Types (except Cathode-
Ray Tubes)
Receiving Tubes, Not
Specified by Kind
Millions of Tubes
Per Year (1977)
90.4
N/A
Television Picture Tubes
Color, New 7.7
Color, Rebuilt; Black and
White, New; Black and
White, Rebuilt 5.6
Television Picture Tubes,
Not Specified by Kind N/A
Transmitting Tubes
Power and Special Tubes
Vacuum Tubes 2151.3
Gas and Vapor Tubes 8223.0
Klystrons 51.9
Magnetrons 138.2*
Traveling Wave Tubes 37.8
Light Sensing Tubes
Camera Tubes, Photoemissive
and Photoconductive 273.6
Image Intensifiers and
Converters 45.8
Photomultipliers 310.7
Light Emitting Devices
Storage. Tubes 42.3
Cathode Ray Tubes,
Industrial and Military 717.0
Other Special Purpose Tubes X
Value in
Millions of Dollars
(1977)
92.3
13.6
513.9
77.1
1.4
74.7
33.7
48.1
56.1
90.3
34.9
30.8
20.3
18.3
61.2
76.1
N/A
X
Not Available
This number does not include pulsed, fixed, and tunable
magnetrons.
Data Not Collected
IX-8
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Metal Components
Glass Tubes
J
Metal
Form
ad
res
1
' m.
Glass
Cut
t
Anneal
t
Glass
Mount
Machine
Catl
1
aet
Co
a
iod
f
ter
at
'
e
--*-
Parts
Clean
t
Electroplate
t
Tube Mount
Assembly
Weld
Components
Glass Tube
Rinse
Exhaust &
Seal
Glass Tube j_
Rinse . I
I
Age &
Test
Ship
T
'•—**"= Denotes Water
Plow Path
Figure 9-4
RECEIVING TUBE MANUFACTURE
IX-9
-------
PANEL HASH
Glass Panels
Aperture Masks
J
Mask
Degrease
Panel and
Mask Mace
Rejected.
Panels
PHOTORESIST APPLIGYTICN
—
—
Anneal
1
Panel
i
Mash
1
1 Photoresist
Application
i
Panel
Mask
and
Hate
Mask
—
!
PICTURE TUBE RECLAIM
Spent
Picture Tubes
Eanel-FunneJl
Defrit I
HIOSHOR APPLICATION
Rejected"
Panels
—
Light
Exposure
1 Phosphor-
Application
f
Panel and
Mask Mate
—
Mask
Mask
'
Panel
Clean
Panel-Mask
Separation
*
_J
—El
Mask |_
Clean |
inel
can
Return to
Picture Tube Manufacture
.». Electron Gun
Figure 9-5
TELEVISION PICTURE TUBE MRNUFACTURE
-------
The glass panels proceed to panel wash. Panel wash includes several
hydrofluoric-sulfuric acid glass washes and subsequent water rinses.
The panels are then sent to photoresist application. The glass
panels are coated with a photoresist and the masks are mated to the
panel. The panel is then exposed to light through the mask. The
mask is removed, and the panel is developed. The panel is graphite
coated and cleaned in a hydrofluoric-sulfuric acid solution. The
panel at this point has surrounding clear dots onto which the
phosphors will be deposited. The panels then proceed to phosphor
application. The panels undergo another photoresist application.
Phosphors are then deposited onto the panels applying each of the
three phosphor colors to their respective clear dots on the panel
matrix. The panel and mask are mated and the panel is exposed to
light. The mask and panel are separated, and the panel is developed,
lacquer coated to seal the phosphors, aluminum is vacuum-deposited
to enhance reflection, the mask is mated with the panel, and the
panel is cleaned.
Glass funnels are cleaned and coated with graphite. Electron shields
are degreased arid attached to the panel. Panel-mask assemblies
and glass funnels are then joined together using a heat-fused lead
frit, followed by annealing. The electron gun mount is cleaned,
aged, and heat sealed to the base of the funnel. At this stage the
assembled panel, funnel, and mount are termed a "bulb." The bulb is
exhausted, sealed, and aged by applying current to the cathode.
The tube is tested, an external graphite coating is applied, and an
implosion band is secured to the tube. The tube is retested before
shipment to facilities that assemble television sets.
Panels may be rejected upon inspection at many points along the
manufacturing process. If completely rejected, panels may be sent
back to the panel wash at the beginning of the manufacturing sequence.
If panels need only to be "rescreened", they are returned to the
phosphor application process.
In addition, there may or may not be a picture tube salvage area to
reclaim spent picture tubes. Wet processes include a panel-funnel
acid defrit, acid cleaning of panels and funnels, and cleaning of
aperture masks. These reclaimed components are returned to process
for reuse.
Transmitting Tube Manufacture
The manufacture of a typical transmitting tube presented schematically
in Figure 9-6 is typified by a magnetron. Intricately shaped and
machined copper and steel parts are cleaned and rinsed. Some of
these parts are then electroplated using materials such as copper,
gold, and silver. Assembly of the electron tube is generally a
manual operation. The electron tube components consist of the metal
parts, a tungsten filament, a glass window, and a glass tube. The
components undergo a number of soldering, brazing, welding, heat
treating, and polishing operations. A significant energy user is
the heat treating area with associated non-contact cooling water.
The assembled electron tube undergoes an extensive series of elec-
trical and mechanical testing procedures and an aging process before
final shipment. There are specialized types of transmitting type
IX-11
-------
Metal Components
Metal
Form
Parts
Clean
Glass
Tube
Glass Filament
Window
ube window I
I I I
i
Electroplate
I
Solder
Braze
Weld
Anneal
I
Evacuate
& Seal
Polish
Age &
Test
I
Ship
t
Denotes Water
Flow Path
Figure 9-6
TRANSMITTING TUBE MANUFACTURE
IX-12
-------
electron tubes, such as image intensifiers, that are produced in a
manner similar to that of a magnetron. However, there are two
wet processes utilized in addition to those depicted in Figure 9-6.
These additional wet processes include alkaline cleaning-rinsing
and alcohol dipping-rinsing of ceramic or glass envelopes brazed
to metal; and acid cleaning of glass tube bodies. Because these
processes are known to exist at only one facility, they are not
included in Figure 9-6 as processes common to most transmitting
type electron tube manufacture.
MATERIALS
The materials used to manufacture all types of electron tubes
(SIC 3671) are classified as raw materials and process materials.
The raw materials are conductors, wire leads, encapsulating mater-
ials, inert gases, glass funnels and panels, masks, photosensitive
materials, phosphors, and various solders and pastes. Raw materials
and process materials consist of the following:
Conductors - Copper and steel basis materials with
various plated surfaces such as copper, nickel, gold,
silver, and chromium are used extensively in electron
tube manufacture. These materials are used because
they are good conductors and/or supporting mediums,
are easily shaped and formed, and are most cost
effective.
Leads - Copper and nickel are the most common material
for electron tube leads. Often the leads are a simple
extension of one of the conducting electrodes.
Encapsulating materials - Glass, ceramics, and various
metals such as steel are used for electron tube 'encap-
sulating materials. These materials provide overall
structural strength and assure integrity of the applied
vacuum or gas filling.
. Inert gases - Electron tubes may either be filled with
special inert gases such as neon, argon, and krypton
or completely evacuated. Either method provides a
dielectric medium of a predetermined resistance to the
flow of electrons.
! • ' •
Glass funnels and panels - Special glass is used to
enhance optical and electrical characteristics while
maintaining reasonable strength with minimum weight in
television picture tubes.
Mask - The steel aperture mask is placed behind the
panel and is used to allow electron beams to strike
the phosphors selectively on the panel in a color
television picture tube.
IX-13
-------
Photosensitive materials - These materials are used to
prepare the glass surface for phosphor application.
The solution commonly contains dichromate, an alcohol,
and other proprietary substances. Developer solutions
often are composed of hydrogen peroxide and/or deion-
ized water.
Phosphors - Phosphors are the heart of color tele-
vision picture tube performance. Common phosphor
materials include cadmium sulfide, zinc sulfide,
yttrium oxide, and europium oxide. Many proprietary
processes have been observed in applying these mate-
rials as red, green, and blue phosphors to the glass
panel. Application of the phosphors themselves and
many of the associated operations produce wastewater
discharges containing priority and other pollutants.
Protective Coatings - Toluene based lacquer and silicate
coatings are commonly applied over the phosphor coatings
in picture tubes. These processes seal the phosphors
in place protecting them from damage.
Graphite coatings - These materials are applied to
inner surfaces of the panel and funnel to prevent
reflection within the picture tube.
Solders - The assembly of the picture tube is a highly
mechanized process whereby the four basic parts of the
picture tube are held together with various solders.
The most prominent solder used in picture tube manu-
facture contains lead oxide and is used to fuse the
glass panel and funnel together.
Process materials - Acids, plating solutions and
various types of solvents are used in the manufacture
of all types of electron tubes. Acids, such as
hydrofluoric, hydrochloric, sulfuric, and nitric, are
used primarily in cleaning and conditioning of metal
parts and glass encapsulating materials. A number of
these metal parts are electroplated with a variety of
highly conductive metals such as gold, silver, copper,
nickel, and chromium. Solvents such as methylene
chloride and trichloroethylene are used in a number of
clean-up operations for receiving and transmitting
tubes. Color picture tubes use solvents, such as
methylene chloride, trichloroethylene, methanol,
isopropanol, acetone, and polyvinyl alcohol. These
solvents are used primarily in cleaning processes such
as aperture mask degreasing as well as phosphor appli-
cation and development steps.
IX-14
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WATER USAGE
Process water is used in solutions and rinses associated with
electroplating of anodes/ cathodes, and grids. Water is also
used to wash glass and ceramic tube bodies both before and after
seating to the base, or at the conclusion of the manufacturing
process.
Receiving and transmitting electron tube manufacturing processes
produce wastewater discharges primarily through metal finishing
operations which are covered under the Metal Finishing Category.
A number of ancillary operations such as deionized water back-
wash, cooling tower blowdown, and boiler blpwdown contribute
sizeable discharge rates compared to metal finishing operations.
*
In addition, there are some isolated instances of plants manu-
facturing specialized transmitting type electron tubes such as
image intensifiers and photomultipliers that require process water.
Alkaline cleaning and acid etching of glass-metal and ceramic tube
components discharge process wastewater as a result of alkaline
and acid bath dumps and their associated water rinses. These wet
processes are similar to several found in television picture tube
manufacture. There is also a glass tube rinse or rinses which
conclude the manufacture of receiving tubes. These are intended to
remove surface particutates and dust deposited on the tube body
during the manufacturing process.
Wastewater producing operations for manufacture of television picture
tubes and other types of cathode ray tubes are unique and sizeable.
Process wastewater sources include both bath dumps and subsequent rin-
sing associated with: glass panel wash, aperture mask degrease,
photoresist application, phosphor application, glass funnel and
mount cleaning, and tube salvage. In addition, there is process
wastewater at those facilities manufacturing aperture masks by a
chemical etching process which is also followed by rinsing.
Segregation of process wastewater to obtain flow rates and dispo-
sition is very difficult because of the proprietary nature and large
size of picture tube manufacturing facilities.
PRODUCTION NORMALIZING PARAMETERS
Production normalizing parameters are used.to relate the pollutant
mass discharge to the production level of a plant. Regulations
expressed in terms of this production normalizing parameter are
multiplied by the value of this parameter at each pla'nt to deter-
mine the allowable pollutant mass that can be discharged. However,
the following problems arise in defining meaningful production nor-
malizing parameters for electron tubes:
Size, complexity and other product attributes affect
the amount of pollution generated during manufacture
of a unit.
IX-15
-------
. Differences in manufacturing processes for the same
product result in differing amounts of pollution.
. Lack of applicable production records may impede
determination of production rates in terms of desired
normalizing parameters.
Several broad strategies have been developed to analyze applicable
production normalizing parameters. They are as follows:
. The process approach - In this approach, the production
normalizing parameter is a direct measure of the produc-
tion rate for each wastewater producing manufacturing
operation. These parameters may be expressed as sg.m.
processed per hour, kg of product processed per hour, etc.
This approach requires knowledge of all the wet processes
used by a plant because the allowable pollutant discharge
rates for each process are added to determine the allowable
pollutant discharge rate for the plant. Regulations based
on the production normalizing parameter are multiplied by
the value of the parameter for each process to determine
allowable discharge rates from each wastewater producing
process.
Concentration limit/flow guidance - This strategy limits
effluent concentration. It can be applied to an entire
plant or to individual processes. To avoid compliance
by dilution, concentration limits are accompanied by
flow guidelines, in turn, are expressed in terms of the
production normalizing parameters to relate flow discharge
to the production rate at the plant.
Discussion of production normalizing parameters for the electron
tube subcategory will be restricted to television picture tubes.
Other types of cathode ray tubes and electron tubes have wet
processes other than meta finishing operations. These wet
processes are also common to those found in television picture
tube manufacture. However, they do not have manufacturing
operations that are as diverse or require as much process water
as those involved in television picture tube manufacture.
Therefore, a discussion of television picture tubes will encom-
pass wet processes common to other electron tube manufacture.
Potential candidates for production normalizing parameters for
television picture tube manufacturing include surface area of
product processed, number of picture tubes processed, and amount
of process chemicals consumed. Surface area processed has been
determined to be the best production normalizing parameter for
picture tube manufacturing.
Area Processed
Three picture tube components use wet manufacturing processes:
glass panels, glass funnels, and steel aperture masks. There are
three wet processes directly involved with glass panels: panel wash,
photoresist application, and phosphor application. All of these wet
IX-16
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processes have associated rinses. The pollutant discharge from each
of these three wet processes is directly related to the surface area
of the glass panel.
Aperture masks, used in conjunction with the panel to produce a
visual image, are manufactured by a chemical etching and rinsing pro-
cess, commonly employing ferric chloride. The aperture masks are
subsequently detergent degreased and rinsed at the tube assembly plant.
Every glass panel processed has an accompanying aperture mask
which has the same surface area as the panel. Thus, the mass of
wastewater pollutants resulting from aperture mask manufacture
is proportional to the panel area.
Pollutant discharge from the glass funnel washes and rinses do not
directly reflect the surface area of the glass panel. However,
there is a specific funnel for every panel size, so that the sur-
face areas of the panels and funnels are in direct proportion to
each other.
Tube salvage is an additional operation observed at two picture
tube plants. Tube salvage uses wet processes that have pollut-
ant mass discharges that reflect the surface area of the glass
panels. Expended picture tubes are separated into panel and
funnel by a nitric acid defritting and rinsing process. This
process breaks the bond holding the funnel to the panel. This
bonded area is a function of the circumference of the glass panel,
and is thus in proportion to its surface area as well. Other tube
salvage wet processes are: stripping the funnel and panel surface
coatings in a sodium hydroxide solution; glass panel and funnel
hydrofluoric acid cleaning and aluminum oxide or iron oxide buf-
fing; and aperture mask cleaning in a morpholine solution. All
of these processes have associated water rinses. The amount of
material removed, and thus the pollutant mass discharged, is in
direct proportion to the surface area of the panel.
The manufacture of transmitting electron tubes such as image inten-
sifiers and photomultipliers use wet processes that discharge waste-
water pollutants at a rate that is directly related to surface area.
The inner glass or ceramic envelope is alkaline cleaned, water rinsed,
alcohol dipped, and water rinsed. The outer glass tube body is acid
cleaned and rinsed. In both cases, the entire surface area of the
component is processed. Surface area of each electron tube processed
together with a production rate yields a total surface area
processed.
Number of Picture Tubes Processed
As in lamp manufacturing, the number of units produced cannot stand
alone as a production normalizing parameter because of varying pro-
duct sizes and types which affect the pollutant mass discharged.
However, when the number of units produced is used in conjunction
with the processed area for each picture tube type* a total processed
area is easily determined for use in calculating allowable mass
discharge.
IX-17
-------
Amounts of Process Matecials and Chemicals Consumed
Process chemical usage varies considerably for picture tube manufacture,
In particular, photoresist and phosphor applications have formulations
for process materials and chemicals in accordance with individual
plant specifications and types of tubes produced. One example of
process chemical variation is the different phosphors used for green
cathode-ray tubes, black and white picture tubes, and color picture
tubes. In addition, both the composition and consumption of both
photoresist and phosphors is considered proprietary. Thus, no direct
correlation can be made between pollutants discharged and process
materials and chemicals used, which eliminates process materials
and chemicals as a production normalizing parameter.
WASTE CHARACTERIZATION AND TREATMENT IN PLACE
This section will present the sources of waste in the electron tube
subcategory and sampling results of this wastewater. The in-place
waste treatment systems will also be discussed and effluent sample
data from these systems will be presented.
Process Descriptions and Water Use
There are ten wet processes used by the electron tube industry.
Seven of the wet processes are characteristic of television
picture tube and other types of cathode ray tube manufacture.
Other cathode ray tube manufacture employs many but not all of
those wet processes found in television picture tube manufacture.
Therefore, discussion of wet processes for these two product
types will be limited to television picture tube manufacture.
Two of the three remaining wet processes are known to exist for
transmitting type electron tube manufacture. The third remaining
wet process is known to exist for receiving type electron tube
manufacture. The wet processes are:
Television Picture Tubes
Panel Wash and Rinses
. Aperture Mask Degrease and
Rinses
. Photoresist Application and
Rinses
Phosphor Application and Rinses
Funnel and Mount Cleaning and Rinses
Tube Salvage and Rinses
Aperture Mask Formation and Rinses
Transmitting Electron Tubes
Acid Etch and Rinses
Alkaline Clean and
Rinses
Receiving Electron Tubes
Glass Tube Rinse
The electron tube manufacturing processes that employ water in
their operations are described below. Wastewater generation
depends upon product type, production rate, size of facility,.
aad degree of automation. Table 9-2 presents product type, wasfce-
vater producing manufacturing processes, volume of water used, and
number'of employees for those plants contacted within the electron
tube industry.
IX-18
-------
M ^>4 **4 I
a-
(N
I
I £
(3 -i
-i o
CM
OI
IX-19
-------
Television Picture Tube Processes - Picture tube manufacturing is
a highly automated operation involving .many water consuming processes.
Picture tubes consist of four major components: the glass panel,
steel aperture mask, glass funnel, and cathode ray tube mount assembly,
The manufacture of television picture tubes is a highly complex pro-
cess. Discrete wet process water flow rates at picture tube
facilities were unobtainable. However, water usage for the produc-
tion of aperture masks was obtained. The following process descrip-
tions discuss wet operations involved in the manufacture of picture
tubes as observed at two plants, Plant 30172 and Plant 11114. The
manufacture of aperture masks which was observed at a third plant,
Plant 36146, is also discussed.
Panel Wash - Glass panels are the front glass section of a pic-
ture tube through which the picture is viewed. The panels are
cleaned in a hydrofluoric acid-sulfuric acid solution. This
prepares the glass for photoresist application. Process water
is used for rinsing after each acid cleaning step. High concen-
trations of acids and fluorides result from this process.
During the manufacture of television picture tubes, the panels are
inspected at various points along the process sequence. A percen-
tage of panels are rejected and returned to the initial panel wash
to be reprocessed. Therefore, pollutants generated at panel wash
also include pollutants typically found in wastewater from subse-
quent photoresist and phosphor applications.
Aperture Mask Degrease - Steel aperture masks are used in direc-
ting the electron beam from the cathode to the panel for use
both in photoresist development and eventually for phosphor
excitation. The masks are vapor degreased in trichloroethylene
prior to other processing operations. A low volume of waste-
water is produced by a carbon adsorption solvent recovery system.
The wastewater results from condensing steam used to regenerate
the carbon bed. Wastewater produced by the solvent recovery
system has a moderate concentration of trichloroethylene.
Photoresist Application - A chromium bearing photoresist solution
is applied to the panel to prepare the surface for selective
phosphor application. The photoresist solution is applied, the
mask is placed over the panel, the panel is exposed to light,
developed, graphite coated, re-developed, and cleaned in several
hydrofluoric-sulfuric acid solutions. The photoresist application
process results in a graphite coated panel surface with a multi-
tude of uncoated dots. These dots are then coated with phosphors
during phosphor application. Wastewater from spent ac.id, photo-
resist, developer solutions and rinses contain high concentrations
of hexavalent chromium, strong acids, fluorides, graphite, and
proprietary chemicals included in the photoresist solutions.
Phosphor Application - This process is commonly referred to as
screening. A photoresist solution is coated over the panel sur-
face followed by a red, blue, and green phosphor coating. The
IX-20
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Acid Clean - The glass tube body is fused to a metal base, hydro-
chloric acid etched to remove metal oxides from the glass surface,
and rinsed twice. The tube body is polished with a wet hone using
glass beads and then rinsed.
The phosphor coated fiber optic window is inserted into the tube
body, fused to the base of the glass tube, evacuated, sealed, aged,
and tested. Combined process water usage for alkaline cleaning and
acid etching is estimated to be 18168-22710 liters/hr at this one
facility contacted.
Plant 19102 produces a variety of specialized electron tube pro-
ducts which include: magnetrons, klystrons, cross field amplifiers,
modulators and electron tube sub-assemblies. Water usage is limited
to electroplating of tube parts, which is included in the Metal
Finishing Category. No process water is used in the assembly of
electron tube products at this facility.
Receiving Type Electron Tube Processes - Plant 23337 produces power
amplifiers and microwave tubes. The majority of process water
usage is for electroplating of tube parts, which,is included in the
Metal Finishing Category. In addition, there are two glass tube body
rinses that require no chemical cleaning processes and, therefore,
produce no pollutants in their effluent discharge. These
wet processes will not receive any further consideration. These
rinses are intended to remove dust and particulate matter from the
surface of the glass tube.
Wastewater Analysis Data
Wet processes from television picture tube manufacturing were
sampled at two facilities. Samples were analyzed for parameters
identified on the list of 129 toxic pollutants, non-toxic pol-
lutant metals, and other pollutant parameters presented in Table 9-3.
Tables 9-4 through 9-6 present analysis data of process wastewaters
and final effluents for those picture tube plants sampled within the
electron tube subcategory. This table presents pollutant parameters,
concentrations, and mass loadings of the processes sampled. Pollu-
tant parameters are grouped according to toxic pollutant organics,
toxic pollutant metals, non-toxic pollutant metals, and other
pollutant parameters. Summation of pollutant concentrations greater
than the minimum detectable limit are presented as well as mass
loadings of those pollutant parameters whose concentrations were
measurable. Mass loadings were derived by multiplying concentration
by the flow rate and the hours per day that a particular process is
operated. Some entries were left blank for one of the following
reasons: the parameter was not detected; the concentration used for
the kg/day calculation is less than the lower quantifiable limits or
not quantifiable. The kg/day is not included in totals for calcium,
magnesium, and sodium, The kg/day is not applicable to pH. Totals
do not include values preceded by "less than".
Toxic pollutant organics, toxic pollutant metals and non-toxic
pollutant metals were detected at measurable levels as well as
at levels below the quantitative limit. Other pollutant parameters
are all reported in measurable quantities. The following conventions
were followed in presenting the data:
IX-21
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panel is exposed to light, developed, precoated, lacquer coated,
and aluminized. After the mask and panel are mated for the final
time, the panel face and edge are cleaned. The phosphor materials
adhere to the uncoated dots on the glass panel surface and are the
elements of the finished tube that produce a colored visual image.
Wastewater from phosphor coating solutions, developer solutions,
aluminizing, panel face and edge cleaning, and rinses contain high
levels of phosphor materials such as cadmium sulfide, zinc sulfide,
yttrium, and europium. In addition, there are moderate levels of
proprietary photoresists.
Funnel and Mount Cleaning - Glass funnels are the casing extended
back from the panel and are the largest component of a picture
tube. The funnel is alkaline cleaned, rinsed, and graphite coated.
Electron shields are solvent degreased and attached to the panel-
mask assembly. The panel is fused to the funnel with a lead
frit. Lastly, the mount assembly is cleaned, aged, inserted
into the neck of the glass funnel, and the entire unit becomes
a picture tube. The tube is aged, receives an external coat-
ing, and is tested prior to shipment. Wastewater'from the
funnel cleaning rinse contains lov; level of silicates. Waste-
water from mount cleaning contains oily materials from mount
manufacture.
Tube Salvage - Expended picture tubes are received and disas-
sembled to recover the panel, funnel, and mask. The unit is de-
fritted in a strong acid solution, the mount assembly is discar-
ded, and the remaining components are cleaned and reprocessed to
become part of a new picture tube. Levels of nitric and hydro-
fluoric acids, lead., and fluoride pollutants are high. Pollutant
levels of aluminum and iron resulting from rinsing after abrasive
oxide cleaning of the masks are moderate.
Aperture Mask Formation - Steel aperture masks, which line the.
inner face of the glass panel, are produced at facilities other
than those manufacturing the television picture tubes. At Plant
36146 sheet steel is cleaned, flow coated with photosensitive
material, covered with a perforated pattern, and exposed to light.
A developer is then applied and air dried. Holes in the aperture
mask are etched with ferric chloride and rinsed. Pollutants
include iron, chromium, zinc, trichloroethylene, total suspended
solids, oil and grease, and photochemicals.
Transmitting Type Electron Tube Processes - The following process
description discusses the wet operations involved in the manufacture
of a light sensing image intensifier. These wet processes existed
at one contacted plant, Plant 41122.
Alkaline Clean - A ceramic or glass envelope is brazed to several
metal components. This unit is then alkaline cleaned, rinsed,
alcohol dipped, rinsed, and the metal portion of the unit is
phosphor coated. This phosphor coated component is the fiber
optic window used to portray the light image in the assembled
product.
IX-22
-------
TABLE 9-3
POLLOTANT PARAMETERS ANALYZED
TOXIC POLLOTANT OBGANICS
1. Acenaphthene 47.
2. Acrolein 48.
3. Acrylonitrile 49.
4. Benzene 50.
5. Benzidine 51.
6. Carbon Tetrachloride 52.
(Tetrachloromethane) 53.
7. Chlorobenzene 54.
8. 1,2,4-Trichlorobenzene 55.
9. Hexachlorobenzene 56.
10. 1,2-Dichloroethane 57.
11. 1,1,1-Trichloroethane 58.
12. Hexachloroethane 59.
13. 1,1-Dichloroethane 60.
14. 1,1,2-Trichloroethane 61.
15. 1,1,2,2,-Tetrachloroethane 62.
16. Chloroethane 63.
17. Bis (Chlorornethyl) Ether 64.
18. Bis(2-Chloroethyl)Ether 65.
19. 2-Chloroethyl Vinyl Ether (Mixed) 66.
20. 2-Chloronaphthalene 67.
21. 2,4,6-Trichlorophenol 68.
22. Parachlorometa Cresol 69.
23. Chloroform (Trichlorpmethane) 70.
24. 2-Chlorophenol 71.
25. 1,2-Dichlorobenzene 72.
26. 1,3-Dichlorobenzene 73.
27. 1,4-Dichlorobenzene 74.
28. 3,3'-Dichlorobenzidine
29. lfl-Dichloroethylene 75.
30. 1,2-Trans-Dichlorethylene
31. 2,4-Dichlorophenol 76.
32. 1,2-Dichloropropane 77.
33. 1,2-Dichloropropyiene 78.
(1,3-Dichloropropene) 79.
34. 2,4-Dimethylphenol 80.
35. 2,4-Dinitrotoluene 81.
36. 2,6-Dinitrotoluene 82.
37. 1,2-Diphenylhydrazine
38. Ethylbenzene 83.
39. Fluorantfrene
40. 4~Chlorophenyl Phenyl Ether 84.
41. 4-Bromaphenyl Phenyl Ether 85.
42. Bis(2-Chloro.isopropyl) Ether 86.
43. Bis(2-Chloroethoxy)Methane 87.
44. Methylene Chloride 88.
45. Methyl Chloride (Chloromethane) 90.
46. Methyl Bromide (Bromomethane) 91.
92.
Bromoform (Tribrcanomethane)
Dichlorobromomethane
Trichlorofluoromethane
Dichlorodifluoromethane
Chlorodibromomethane
Hexachlorobutadiene
Hexachlorcx^clopentadiene
Isophorone
Naphthalene
Nitrobenzene
2-Nitrophenol
4HSlitrophenol
2,4HDinitrophenol
4,6-Dinitro-O-Cresol
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Wi trosod i-N-Propylamine
Pentachlorophenol
Phenol
Bis(2-ethylhexyl) Phthalate
Butyl Benzyl Phthalate
Di-N-Butyl Phthalate
Di-^-Octyl Phthalate
Diethyl Phthalate
Dimethyl Phthalate
1r2-Benzanthracene (Benzo(A)Anthracene)
Benzo (A) Pyrene (3,4-Benzo-Pyrene)
3,4-^enzofluoranthene (Benzo(B)
(Fluoranthene)
11,12-Benzofluoranthene (Benzo(K)
Fluoranthene)
Chrysene
Acenaphthylene
Anthracene
1,12-Benzoperylene(Benzo(GHI)-Perylene)
Fluorene
Phenanthrene
1,2,5,6-Dibenzathracene(Dibenzo(A,H)
Anthracene)
Idenb(l,2,3-CD)Pyrene(2,3-0-Phenylene
Pyrene)
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Vinyl Chloride (Chloroethylene)
Dieldrin
ChlordaneCltechnical Mixture and
Metabolites)
4,4'-DDT
IX-23
-------
TABLE 9-3 CONTINUED
93. 4f4'-DDE (P,P'-DDX) 113.
94. 4,4'-DDD (P,P-TDE) 114.
95. Alpha-Endosulfan 115.
96. Beta-Endosulfan 117.
97. Endosulfan Sulfate 118.
98. Endrin 119.
99. Endrin Aldehyde 120.
100. Heptachlor 121.
101. Heptachlor Epoxide (BHC~Hexachloro- 122.
cyclophexane) 123.
102. Alpha-BHC 124.
103. Beta-BHC 125.
104. Gamma-BHC (Lindane) 126.
105. Delta-BHC (PCB-Polychlorinated 127.
Biphenyls ) 128 .
106. PCB-1242 (Arochlor 1242) 129.
107. PCB-1254 (Arochlor 1254)
108. PCB-1221 (Arochlor 1221)
109. PCB-1232 (Arochlor 1232)
110. PCB-1248 (Arochlor 1248)
111. PCB-1260 (Arochlor 1260)
112. PCB-1016 (Arochlor 1016)
NON-TOXIC POLLUTANT MSIALS
Calcium Germanium
Magnesium Rubidium
Sodium Strontium
Aluminum Zirconium
Manganese Niobium
Vanadium Palladium
Boron Indium
Barium Tellurium
Molybdenum Cesium
Tin Tantalum
Yttrium Tungsten
Cobalt Osmium
Iron Platinum
Titanium Gold
Potassium Bismuth
Gallium Uranium
OTHER POLLUTANT
Oil and Grease
Total Organic Carbon
Biological Oxygen Demand ,
Total Suspended Solids
Phenols
Fluoride
Xylenes
Alkyl Epoxides
Toxaphene
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
2,3,4,8-Tetrachlorodibenzo-P-
Dioxin (TCDD)
IX-24
-------
Stream Identification
Sample Number
Flow Pate Liters/Hr-Gallons/Hr
Duration Hours/Day
TOXIC ORGANICS
1 Acenapthene
4 Benzene
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
23 Chloroform
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene
39 Pluoranthene
44 Methylene chloride
48 Dichlorcbronoraethane
51 Chlorodibrcroomethane
55 Napthalene
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-N-butyl phthalate
70 Diethyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
86 Toluene
87 Trichloroethylene
95 Alpha-Endosulfan
102 Alpha-BHC
105 Delta-BHC
Total Toxic Organics
TOXIC ^ETALS
114 Antimony
115 Arsenic
117 Beryllium
118 Cadmium
119 Chrcciium
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
Total Toxic Metals
TABLE 9-4A
PICTURE TUBE PROCESS WASTES
(PLANT ID# 30172)
mg/1 kg/day
Chromium Treatment
Influent
03661
491 - 130
24
< 0.010
0.058(B) .0.0007
(B)
< 0.010
0.490(B) 0.006
< 0.010
0.460
0.010
0.005
0.0001
< 0.010
< 0.010
< 0.010
0.029 0.0003
O.OIO(B) 0.0001
1.057
0.122
0.003
< 0.004*
0.001
< 0.002
86.800
0.028
< 0.040
< 0.001
0.009
0.004
<- 0.001
< 0.001
< 0.001
0.00004
0.00001
1.02
0.0003
0.0001
0.00005
rag/1 kg/day
Lead Treatment
Influent
85125
45 - 12
24
Nbt
Analyzed
rag/1 . kg/day
Total Raw Waste Into
Primary Treatment
85127
13028 - 3442
24
Nbt
Analyzed
86.845 1.0205
0.092
0.250
0.004
1.070
4.670
< 0.050
891.000
0.001
18.500
< 0.020
0.060
0.002
1510.000
2425.649
0.0001
0.0003
0.000004
0.001
0.005
0.962
0.000001
0.02
0.00006
0.000002
1.631
2.619467
0*188
0.100
< 0.001
0.215
2.470
0.093
20.700
< 0.001
0.062
< 0.004
0.001
< 0.001
6.770
30.599
0.059
0.031
0.067
0.772
0.029
6.47
0.019
0.0003
2.117
9.5643
Interference Present
IX-25
-------
TABLE 9-4A (COOT.)
PICTURE TUBE PROCESS WASTES
(PLANT ID# 30172)
NOB-TOXIC METALS
Calcium *
Magnesium *
Sodium *
Aluninun
Manganese
Vanadium
Boron
Barium
Molybdenum
Tin
Yttrium
Cobalt
Iron
Titanium
Potassium
Gallium
Germanium
Rubidium
Strontium
Zirconium
Niobium
Palladium
Indium
Tellurium
Tungsten
Osniun
Platinum
Gold
Bianuth
Uranium
Total Hoasureable Non-Toxic Metals
4.960 0.058
1.220 0.014
11.200 0.132
0.034 0.0004
0.008 0.00009
0.016 0.0002
< 0.002
0.027 0.0003
0.180 0.002
0.111 0.001
0.013 0.0002
< 0.050
0.173 0.002
0.006 0.00007
Not
Analyzed
< 0.003
Not Analyzed
< 0.003
Not Analyzed
0.006 0.00007
< 0.002
Not Analyzed
0.574 0.00633
87.800 0.095
30.900 0.033
640.000 0.691
12.000 0.013
5.860 0.006
0.161 0.0002
346.000 0.374
205.000 0.221
1.600 0.002
3.010 0.003
16.800 0.018
2.650 0.003
1940.000 2.095
0.314 0.0003
Not
Analyzed
0.318 0.0003
Nbt Analyzed
0.029 0.00003
Not Analyzed
0.090 0.0001
< 0.004**
Not Analyzer!
2533.832 2.73593
88.600 27.702
7.970 2.492
173.000 54.
3.250 1.016
0.040 0.013
0.010 0.003
9.170 2.867
1.100 0.344
< 0.035
0.119 0.037
2.290 0.716
< 0.050
7.720 2.414
0.222 0.069
Not
Analyzed
< 0.003
Not Analyzed
0.003 0.0009
Not Analyzed
< 0.005
< 0.002
Not Analyzed
23.924 7.4799
OTHER EOUOTANTS
o
Temperature C
121 Cyanide, Total
Oil & Grease
Total Organic Carbon
Biochemical Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
5.3
21
<0.005
66
1000
2
2
0.01
0.82
0.78
11.78
0.02
0.02
0.0001
0.010
< 2.0
19
<0.005
11
< 1.0
< 1.0
190
0.01
160
0.012
0.205
0.00001
0.173
2.7
21
<0.005
14
47
< 1.0
130
0.01
260
4.4
14.70
40.6
0.003
81.3
* Metals Not Included In Total
** Interference Present
IX-26
-------
Stream Identification
Sample Number
Flow Rate Liters/Hr
Duration Hours/Day-
TOXIC ORGANICS
1 Acenapthene
3 Acrylonitrile
4 Benzene
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
23 Chloroform
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene'
39 Fluoranthene
44 Methylene chloride
48 Didilorobrcmomethane
51 Chlorodibrcmoroethane
55 Napthalene
58 4-Nitrophenol
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-N-butyl phthalate
70 Diethyl phthalate
71 Dimethyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
95 Alpha-Endosulfan
102 Alpha BHC
105 Delta BHC
Total Toxic Organics
TOXIC METALS
114 Antimony
115 Arsenic
117 Beryllium
118 Cadmium
119 Chrotiium
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
Total Toxic Metals
TABLE 9-4A
PICTURE TUBE PROCESS WASTES
(PLANT ID# 30172)
(CONT)
mg/1 kg/day
Chromium Treatment
Effluent
85124
491 - 130
24
Not
Analyzed
0.005
0.044
< 0.001
< 0.002
76.400
0.027
0.106
< 0.001
< 0.005
0.013
< 0.001
< 0.001
0.038
76.633
0.00006
0.0005
0.900
0.0003
0.001
0.0002
0.0004
0.90246
mg/1 kg/day
.Lead Treatment
Effluent
85126
157 - 42
7
Not
analyzed
< 0.015
0.010
< 0.001
< 0.005
0.027
0.048
1.900
< 0.001
0.641
< 0.004
< 0.002
< 0.010*
11.400
14.026
0.00001
0.00003
0.00005
0.002
0.0007
0.013
0.01579
mg/1 kg/day
Primary Treatment
Clarifier Effluent
85128
13028 - 3442
24
NOt
Analyzed
0.146
0.008
0.001
0.002
0.292
0.015
0.273
0.001
0.010
0.005
0.001
0.001
0.112
0.862
0.046
0.003
0.091
0.005
0.085
0.003
0.002
0.0003
0.035
0.2703
*Interference Present
IX-27
-------
NOJ-TOXIC 1«TALS
Calcium *
Magnesiuri * ,
Sodium *
Aluminum
Manganese
Vanadium
Boron
Barium
Molybdenum
Tin
Yttrium
Cobalt
Iron
Titanium
Potassium
Gallium
Germanium
Rubidium
Strontium
Zirconium
Niobium
Palladium
Indium
Tellurium
Tungsten
Osmium
Platinum
Gold
Bi smith
Uranium
Total Non-Toxic Metals
OTHER POLLUTANTS
Temperature C
121 Cyanide, Total
Oil & Grease
Total Organic Carbon
Biochemical Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
TABLE 9-4A (COMT.)
PICTURE TUBE PROCESS WASTES
(PLANT ID# 30172)
5.400
1.220
62.300
0.054
0.039
0.011
0.239
0.037
0.106
0.102
0.023
< 0.050
5.220
0.003
wot
Analyzed
0.064
0.014
0.734
0.0006
0.0005
0.0001
0.003
0.0004
0.001
0.001
0.0003
0.062
0.00004
< 0.010**
Not Analyzed
0.020 0.0002
< 0.005
< 0.002
Hot Analyzed
5.854 0.06914
< 2.0
22
<0.005
10
880
< 1.0
2
0.02
0.40
0.118
10.4
0.024
0.0002
0.005
28.800
18.500
13400.000
0.679
0.546
0.024
395.000
12.400
0.171
0.392
< 0.008
< 0.119
0.378
0.043
Not
Analyzed
0.032
0.020
14.7
0.0007
0.0006
0.00003
0.434
0.014
0.0002
0.0004
0.0004
0.00005
< 0.003
Not Analyzed
0.013 0.00001
0.020 0.00002
< 0.050**
Not Analyzed
409.666 0.45041
7.3
19
<0.005
14
160
< 1.0
17
0.08
76
0.015
0.176
0.019
0.00009
0.084
334.000 104.4
7.950
126.000
, 0.309
0.006
0.004
1.880
0.182
< 0.035
0.119
0.006
< 0.050
0.197
< 0.002
Mot
Analyzed
2.49
39.4
0.097
0.002
0.001
0.588
0.057
0.037
0.002
0.062
< 0.003
Not Analyzed
0.004 0.001
< 0.005
< 0.002
Not Analyzed
2.707
0.847
8.5
19
<0.005
10
49
5
2
0.03
6.5
3.1
15.3
1.56
0.625
0.009
2.0
* Metals Not Incluccc In Total
** Interference Present
IX-28
-------
TABLE 9-4A
PICTURE TUBE PROCESS WASTES
(PLSNT ID# 30172)
(CONT)
Stream Identification
Sample Number
Plow Rate Liters/Hr
Duration Hours/Day
TOXIC &ETALS
1 Acenapthene
3 Acrylonitrile
4 Benzene
11 l,lfl-Trichloroethane
13 1,1-Dichloroethane
23 Chloroform
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene
39 Fluoranthene
44 Methylene chloride
48 Dichlorobrcmomethane
51 Chlorodibromomethane
55 Napthalene
58 4-Nitrophenol
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-N-butyl phthalate
70 Diethyl phthalate
71 Dimethyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
95 Alpha-Endosulfan
102 Alpha-BHC •
105 Delta-BHC
Total Toxic Organics
TOXIC METALS
114 Antimony
115 Arsenic
117 Beryllium
118 Cadmium
119 Chromium ,
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
Total Toxic Metals
mg/1 kg/day
Primary Treatment
Sand Filter Effluent
03662
13028 - 3442
24
< 0.010
< 0.010
< 0.010
< O.OIO(B)
0.400(B)
< 0.010
< 0.010
<.0.010
< 0.010
< 0.010
< 0.010
< 0.010
< 0.010
<0.010
<0.010
<0.010
<0.010
0..400
0.117
0.010
<0.001
<0.002
0.247
0.017
0.152
< 0.001
0.012
< 0.004
0.001
< 0.001
0.055
0.611
0.125
0.125
0.037
0.003
0.077
0.005
0.048
0.004
0.0003
0.017
0.1913
IX-29
-------
NOtMXJXIC METALS
Calcium *
Magnesium *
Sodium «
Aluminum
Manganese
Vanadium
Boron
Barium
Molybdenum
Tin
Yttriura
Cobalt
Iron
Titanium
Potassium
Gallium
Germanium
Rubidium
Strontium
Zirconium
Niobium
Palladium
Indium
Tellurium
Tungsten
OsraLum
Platinum
Gold
Bismuth
Uranium
Total Non-Toxic Metals
OTHER POIIOTANTS
Temperature C
121 Cyanide, Total
Oil & Grease
Total Organic Carbon
Biochemical Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
TABLE 9-4A (GOUT.)
PICTURE TUBE PROCESS WASTES
(PLANT ID# 30172)
345.000
8.230
123.000
0.239
0.005
0.002
1.530
0.155
< 0.035
0.117
< 0.003
< 0.050
0.048
0.002
108
2.573
38.5
0.075
0.002
0.0006
0.478
0.049
0.037
0.015
Not
Analyzed
< 0.005*
Not Analyzed
< 0.004
Not Analyzed
< 0.005
< 0.002
Not Analyzed
2.096
0.6566
8.5
19
<0.01
5
40
4
1.4
0.02
10
1.6
12.5
1.3
0.44
0.006
3.1
*Metals Not Included In Totals
**Interferences Present
IX-30
-------
TABLE 9-4B
PICTURE TUBE PROCESS WRSTES
(PLANT H3# 30172)
Stream Identification
Sample Number
Flew Rate Liters/Hr
Duration Hours/Day
TOXIC ORGANICS
1 Acenapthene
3 Acrylonitrile
4 Benzene
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
23 Chloroform
29 l,l-Bic±iloroethylene
30 1,2-Trans-diciiloroethylene
38 Ethylbenzene
39 Pluoranthene
44 Methylene chloride
48 Dichlorobromoniethane
51 Chlorodibrcmoinethane
55 Napthalene
58 4-Nitrophenol
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-N-butyl phthalate
70 Diethyl phthalate
71 Dimethyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
95 Alpha-Endosulfan
102 Alpha-BHC
105 Delta-BHC
Total Toxic Organics
TOXIC NETALS
114 Antimony
115 Arsenic
117 Beryllium
118 Cadmium
119 Chromium
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
Total Toxic Metals
mg/1 kg/day
Chromium Treatment
Influent
85129
377 - 100
24
Not
Analyzed
< 0.003
0.006
0.001
<0.002
100.000
0.012
0.295
< 0.001
< 0.005
< 0.004
< 0.001
< 0.001
0.038
100.352
0.00005
0.000009
0.905
0.0001
0.003
0.0003
0.908459
mg/1 kg/day
Total Raw Waste
Primary Treatment
85138
13716 - 3624
24
Not
Analyzed
0.126
0.102
< 0.001
0.135
3.150
0.052
11.200
< 0.001
0.070
< 0.004
0.002
< 0.001
5.120
19.957
0.041
0.034
0.044
1.037
0.017
3.687
0.023
0.0007
1.685
6.5687
mg/1 kg/day
Chromium Treatment
Effluent
85131
377 - 100
24
Not
Analyzed
0.003
0.004
< 0.001
< 0.002
74.200
0.011
< 0.040
< 0.001
< 0.005
< 0.004
< 0.001
< 0.001
< 0.001
0.00003
0.00004
0.671
0.0001
74.218 0.67117
IX-31
-------
TABLE 9-4B (CUNT.)
PICTURE TUBE PROCESS WASTES
(PLANT ID# 30172)
NCN-TOKIC M3TALS
Calcium *
Magnesium *
Sodium *
Aluminum
Manganese
Vanadium
Boron
Barium
Molybdenum
Tin
Yttrium
Cobalt
Iron
Titanium
Potassium
Gallium
Germanium
Rubidium
Strontium
Zirconium
Niobium
Palladium
Indium
Tellurium
Tungsten
Oanium
Platinum
Gold
Bismuth
Uranium
Total Non-Toxic Metals
OTHER POUiOTANTS
pH
Temperature °C
121 Cyanide, Total
Oil & Grease
Total Organic Carbon
Biochemical Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
2.230
0.474
6.200
0.066
0.005
0.017
0.196
0.044
0.089
0.127
0.102
0.050
0.094
0.007
0.020
0.004
0.056
0.0006
0.00005
0.0002
0.002
0.0004
0.0008
0.001
0.0009
0.0009
0.00006
Not
Analyzed
0.747
0.00691
68.900
8.640
114.000
4.060
0.043
0.003
9.520
0.586
0.059
0.025
1.290
0.050
8.640
0.002
22.68
2.84
37.5
1.336
0.014
0.001
3.134
0.193
0.019
0.425
2.844
Not
Analyzed
24.201
7.966
4.7
23
<0.005
10
170
2
0.8
0.02
0.90
0.091
1.5
0.002
0.007
0.0002
0.008
2.1
21
<0.005
11
58
< 1.0
88
< 0.01
270
3.6
19.09
29
88.9
4.830
1.170
111.000
0.053
0.014
0.004
0.079
0.022
0.156
0.082
0.011
< 0.050
1.130
< 0.002
0.044
0.011
1.004
0.0005
0.0001
0.00004
0.0007
0.0002
0.001
0.0007
0.0001
0.010
Not
Analyzed
1.551
0.01334
1.9
23
•C0.005
330
490
50
0.6
0.01
0.30
2.99
4.43
0.45
0.005
0.00009
0.003
*Metals Not Included In Totals
IX-32
-------
TABLE 9-4B
PICUTRE TUBE PROCESS WASTES
(PLANT ID# 30172)
(CONT)
Stream Identification
Sample Hunter
Plow Rate Liters/a?
Duration Hours/Day
TOXIC ORGANICS
1 Acenapthene
3 Acrylonitrile
4 Benzene
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
23 Chloroform
29 1,1-Dichloroethylene
. 30 1,2-Trans-dichloroethylene
38 Ethylbenzene
39 Pluoranthene
44 Methylene chloride
48 Dichlorobronamethane
51 (Morodibranomethane
55 Napthalene
58 4-Nitrophenol
65 Phenol
66 Bis(2-ethylhex/l)phthalate
67 Butyl benzyl phthalate
68 Di-N-butyl phthalate
70 Diethyl phthalate
71 Dimethyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
95 Alpha-endosulfan
102 Alpha-BHC
105 Delta-BHC
Total Toxic Organics
TOXIC ^ETAIlS
114 Antimony
115 Arsenic
117 Beryllium
118 Cadmium
119 Chromium
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
Total Toxic Metals
mg/1 kg/day
Primary Treatment
Clarifier Effluent
85132
13716 - 3624
24
mg/1 kg/day
Primary Treatment
Sand Filter Effluent
85130
13716 - 3624
24
Sample
Lost
Not
Analyzed
Sample
Lost
0.136
0.008
< 0.001
< 0.002
0.250
0.009
0.228
< 0.001
0.006
< 0.004
0.001
< 0.001
0.110
0.748
0.045
0.003
0.082
0.003
0.075
0.002
0.0003
0.036
0.2463
IX-33
-------
TABLE 9-4B (CONT.)
PICTURE TUBE PROCESS WASTES
(PLANT ID# 30172)
NON-TOXIC ^£TALS
Calcium *
Magnesium *
Sodium *
Aluminum
Manganese
Vanadium
Boron
Barium
ttolybdenum
Tin
Yttrium
Cobalt
Iron
Titanium
Potassium
Gallium
Germanium
Rubidium
Strontium
Zirconium
Niobium
Palladium
Indium
Tellurium
Tungsten
Osmium
Platinum
Gold
Bismuth
Uranium
Total Non-Toxic Metals
OTHER POLLUTANTS
o
Terjerature C
121 Cyanide, Total
Oil & Grease
Total Organic Caitoon
Biochemical Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
Sample
Lost
7.1
19
<0.005
52
Sanyle
Lost
17.12
273.000
9.040
172.00
0.237
0.009
< 0.001
2.450
0.142
< 0.035
0.068
< 0.003
< 0.050
0.227
< 0.002
Not
Analyzed
< 0.01
Saraple Lost
3.133
6.9
18
•C0.005
37
40
10
7
0.02
8.2
89.9
2.976
56.6
0.078
0.003
0.807
0.047
0.022
0.075
1.032
12.18
13.17
3.29
2.3
0.007
2.7
*Metals Not Included In Totals
IX-34
-------
TABLE 9-4C
PICTURE TUBE PROCESS WASTES
(PLANT IDf 30172)
Stream Identification
Sample Number
Flow Rate Liters/Hr
Duration Hours/Day
TOXIC ORGANICS
1 Acenapthene
3 Acrylonitrile
4 Benzene
11 1,1,1-Tridiloroethane
13 1,1-Dichloroethane
23 Chloroform .
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene
39 Pluoranthene
44 Methylene chloride
48 Didhlorcbrcrnomethane
51 Chlorodibronomethiane
55 Napthalene
58 4-Nitrophenol
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-N-butyl phthalate
70 Diethyl phthalate
71 Diitiethyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
95 Alpha-Endosulfan
102 Alpha-BHC
105 Delta-BHC
Total Toxic Organics
.TOXIC NETALS
114 Antimony
115 Arsenic
117 Beryllium
118 Cadmium
119 Chromium
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
Total Toxic Metals
mg/1 kg/day
Chromium Treatment
Influent
85133
454 - 120
24
Not
Analyzed
0.004
0.006
0.001
< 0.002
80.400
0.017
< 0.040
< 0.001
< 0.005
0.004
0.001
0.050
< 0.001
80.483
0.00004
0.00007
0.00001
0.876
0.0002
0.00004
0.00001
0.0005
0.87687
mg/1 kg/day
Total Raw Waste Into
Primary Treatment
85137
11972 - 3163
24
Not
Analyzed
0.146
0.160
C 0.001
0.163
2.980
0.052
10.600
< 0.001
0.089
< 0.004
0.001
< 0.001
6.340
20.531
0.042
0.046
0.047
0.856
0.015
3.046
0.026
0.0003
1.822
5.9003
mg/1- . kg/day
Chromium Treatment
Effluent
85135
454 - 120
24
Not
Analyzed
0.003
0.004
< 0.001
< 0.002
69.400
0.008
< 0.040
< 0.001
< 0.005
0.016
< 0.001
< 0.001
0.023
69.454
0.00003
0.00004
0.756
0.00009
0.0002
0.0003
0.75666
IX-35
-------
NON-TOXIC
Calcium »
Magnesium *
Sodium *
Aluminum
Manganese
Vanadium
Boron
Barium
Molybdenum
Tin
Yttrium
Cobalt
Iron
Titanium
Potassium
Gallium
Germanium
Rubidium
Strontium
Zirconium
Niobium
Palladium
Indium
Tellurium
Tungsten
Osmium
Platinum
Gold
Bismuth
Uranium
Total Non-Toxic Metals
OTHER POLLUTANTS
o
Temperature C
121 Cyanide, Total
Oil & Grease
Total Organic Carbon
Biochemical Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
TABLE 9-4C (CONT.)
tTCTURE TUBE PROCESS WASTES
(PLANT ID# 30172)
1.260
0.398
7.010
0.011
0.005
0.008
0.167
0.019
0.128
0.064
0.010
0.073
0.049
0.002
0.0137
0.004
0.0764
0.0001
0.00005
0.00009
0.002
0.0002
0.001
0.0007
0.0001
0.0008
0.0005
91.300
8.340
149.000
4.190
0.050
0.005
7.080
0.626
0.098
< 0.025
1.470
0.050
9.320
< 0.002
26.2
2.396
42.8
1.204
0.014
0.001
2.034
0.180
0.028
0.422
2.678
Not
analyzed
0.534 0.00554
5.4
24
•C0.005
24
950
20
< 1.0
0.01
1.8
0.262
10.4
0.218
0.0001
0.020
Not
Analyzed
22.839
1.7
22
<0.005
12
43
< 1.0
50
< 0.01
490
6.561
3.45
12.4
14.4
141
7.230
1.590
66.100
0.112
0.040
0.002
0.115
0.059
0.113
0.088
0.033
C 0.050
5.260
0.002
Not
Analyzed
5.822
< 2.0
25
<0.005
36
860
30
3
0.02
0.60
0.079
0.017
0.720
0.001
0.0004
0.00002
0.001
0.0006
0.001
0.001
0.0004
0.057
0.06242
0.392
9.37
0.327
0.033
0.0002
0.007
*Metals Not Included In Totals
IX-36
-------
Stream Identification
Sample Number
Flow Pate Liters/Hr
Duration Hours/Day
TOXIC ORGANICS
1 Acenapthene
3 Acrylonitrile
4 Benzene
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
23 Chloroform
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene
39 Fluoranthene
44 Methylene chloride
48 Dichlorobranonethane
51 Chlorodibrctnottiethane
55 Napthalene
58 4-Nitrophenol
65 Phenol
66 Bis(2-ethylhex^l)phthalate
67 Butyl benzyl phthalate
68 Di-N-butyl phthalate
70 Diethyl phthalate
71 Dimethyl phthalate
78 anthracene
81 Phenanthrene
84 Pyrene
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
95 Alpha-Endosulfan
102 ftlpha-BHC
105 Delta-BHC
Total Toxic Organics
TOXIC METALS
114 Antimony
115 Arsenic
117 Beryllium
118 Cadmium
119 Chromium
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
Total Toxic Metals
TABLE 9-4C
PICTURE TUBE PROCESS WASTES
(PLANT ID# 30172)
(COOT)
mg/1 kg/day
Lead Treatment
Effluent
85139
97 - 26
8
Not
Analyzed
0.123
0.008
< 0.001
< 0.004
0.017
0.035
0.479
< 0.001
1.180
0.008
< 0.001
0.002
26.000
27.852
0.0001
0.000006
0.00001
0.00003
0.0004
0.0009
0.000006
0.000002
0.020
0.021454
mg/1 kg/day
Primary Treatment
Clarifier Effluent
85136
11972 - 3163
24
Not
Analyzed
0.119
0.010
< 0.001
< 0.002
0.195
0.014
0.233
< 0.001
0.016
< 0.004
< 0.001
< 0.001
0.150
0.737
0.034
0.003
0.056
0.004
0.067
0.005
0.043
0.212
mg/1 kg/day
Primary Treatment
Sand Filter Effluent
85134
11972 - 3163
24
Not
Analyzed
0.106
0.010
< 0.001
< 0.002
0.128
0.016
0.109
< 0.001
0.026
< 0.004
< 0.001
< 0.001
0.059
0.454
0.030
0.003
0.037
0.005
0.031
0.007
0.017
0.130
IX-37
-------
NON-TOXIC t-ETALS
Calcium *
Magnesium *
Sodium *
Aluminum
Manganese
Vanadium
Boron
Barium
Molybdenum
Tin
Yttrium
Cobalt
Iron
Titanium
Potassium
Gallium
Germanium
Rubidium
Strontium
Zirconium
Niobium
Palladium
Indium
Tellurium
Tungsten
Osmium
Platinum
Gold
Bismuth
Uranium
Total Non-Toxic Metals
OTHER POLLUTANTS
TABLE 9-4C (CONT.)
PICTURE TUBE PROCESS WASTES
(PLANT ID# 30172)
30.400
16.100
10500.
0.577
0.634
0.010
250.
8.140
0.256
0.105
0.012
0.496
0.080
0.021
0.024
0.012
8.148
0.0004
0.0005
0.000008
0.194
0.006
0.0002
0.00008
0.000009
0.0004
0.00006
0.00002
309.
6.150
139.
0.485
0.008
< 0.001
2.060
0.150
0.043
< 0.025
0.005
< 0.050
0.262
< 0.002
88.8
1.767
39.9
0.139
0.002
0.592
0.043
0.012
0.001
0.075
NOt
analyzed
260.331
0.201677
Not
Analyzed
3.013
0.864
301.
6.160
140.
0.427
0.007
< 0.001
2.090
0.135
0.037
< 0.025
< 0.003
< 0.050
0.071
< 0.002
86.5
1.770
40.2
0.123
0.002
0.601
0.039
0.011
0.020
Not
Analyzed
2.767
0.796
o
Teraperataire C
121 Cyanide, Total
Oil & Grease
Total Organic Carbon
Biochemical Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
6.4
19
<0.005
8
19
< 1.0
5
0.01
81
0.006
0.015
0.004
0.000008
0.063
8.1
20
<0.005
830
22
< 1.0
3
0.02
7.7
238.5
6.3
0.86
0.006
2.2
7.8
20
<0.005
20
39
2
1
0.03
15
5.75
11.2
0.575
0.287
0.009
4.31
*Metals Not Included In Totals
IX-38
-------
TABLE 9-5A
PICTURE TUBE PROCESS WASTES
(PLANT ID! 11114)
Treatment System I
-------
NON-TOXIC METALS
Calcium *
Magnesium *
Sodium *
Aluminum
Manganese
Vanadium
Boron
Barium
tfolybdenum
Tin
Xttrium
Cobalt
Iron
Titanium
Potassium
Gallium
Germanium
Rubidium
Strontium
Zirconium
Niobium
Palladium
Indium
Tellurian
Tungsten
Osnium
Platinum
Gold
Bismuth
Uranium
Total Non-Toxic Metals
TABLE 9-5A (COOT.)
PICTURE TUBE PROCESS WASTES
(PLANT IDf 11114)
TREATMENT SYSTEM I
8.260
8.300
1170.
7.070
0.023
< 0.002
21.20
0.289
< 0.036
< 0.026
0.358
< 0.051
1.600
0.037
2.210
2.22
313.
1.891
0.006
5.672
0.077
0.096
0.428
0.010
Not
Analyzed
4.420
6.800
1180.
6.790
0.024
< 0.001
18.00
0.163
< 0.035
<, 0.025
0.053
< 0.050
1.120
0.032
1.182
1.819
315.7
1.817
0.006
4.8
0.044
0.014
0.300
0.009
Not
Analyzed
19.60
4.850
35.70
9.150
0.012
0.005
11.50
0.397
< 0.035
< 0.025
0.590
< 0.050
1.280
0.127
5.235
1.295
9.534
2.444
0.003
0.001
3.071
0.106
0.158
0.342
0.034
Not
Analyzed
30.577
8.180
26.182
6.970
23.061
6.159
i/'ta
OTHER POIIOTANTS
pH ' 6.2 6.0 2.7
Temperature °C 26 27 24
121 Cyanide, Total 0.011 0.003 0.185 0.049 0.009 0.002
Oil & Grease 20 5.35 20 5.35 1 0.3
Total Organic Carbon 7 l'.9 4 1.07 139 37.1
Biochemical Oxygen Demand 12 3.2 22 5.6 0 0
Total Suspended Solids 39 10.43 22 5.89 185 49.4
Phenols 00 00 0.027 0.007
Fluoride 910 243.5 1070 286.3 1925 514.1
* Metals Not Included In Totals
IX-42
-------
. TABLE 9-5A
PICTORB TUBE PROCESS WASTES
(PUNT IDf 11114)
Treatment System I
(COOT)
Stream Identification
Sample Number
Flow Rate: liters/Hr-Gallons/Hr
Duration Hours/Day
TOXIC ORGANICS
1 Acenapthene
3 Acrylonitrile
4 Benzene
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
23 Chloroform
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene
39 Fluoranthene
44 Methylene chloride
48 Dichlorobrcraomethane
51 Chlorodibromomethane
55 Napthalene
58 4-Nitrophenol
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-N-butyl phthalate
70 Diethyl phthalate
71 Dimethyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrene
85 Tetraehloroethylene
86 Toluene
87 Trichloroetnylene
95 Alpha-Endosulfan
102 Alpha-BHC
105 Delta-BHC
Total Toxic Organics
TOXIC MET.M.S
114 Antimony
115 Arsenic
117 Beryllium
118 Cadmium
119 Chromium
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
Total Toxic Metals
rng/1 kg/day
Final Effluent
85270
22275 - 5885 .
24
NOt
Analyzed
0.061
0.064
( 0.005
0.370
0.305
0.030
13.800
< 0.001
0.111
< 0.002
0.002
< 0.001
32.800
47.543
0.033
0.034
0.198
0.163
0.016
7.377
0.059
•0.001
17.535
25.416
IX-43
-------
NON-TOXIC ^ETALS
Calcium*
Magnesium *
Sodium*
Aluminum
Manganese
Vanadium
Boron
Barium
Molybdenum
Tin
Yttrium
Cobalt
Iron
Titanium
Potassium
Gallium
Germanium
Rubidium
Strontium
Zirconium
Niobium
Palladium
, Indium
Tellurium
Tungsten
Osmium
Platinum
Gold
Bismuth
Uranium
Total Non-Toxic Metals
OTHER POUOTANTS
Tsjperature C
121 Cyanide, Total
on & Grease
Total Organic Carbon
Biochemical Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
TABLE 9-5A (COOT.)
PICTURE TUBE PB3CESS WASTES
(PLANT ID* 11114)
TREATMENT SYSTEM I
8.310
7.730
1200.
7.610
0.048
< 0.001
19.40
0.503
< 0.035
< 0.025
0.049
< 0.050
2.040
0.122
4.443
4.132
641.5
4.068
0.026
10.4
0.269
0.026
1.091
0.065
Not
Analyzed
•29.772 15.919
6.1
24
0.525
51
89
0
80
0.034
1140
0.281
27.26
47.58
0
42.77
0.018
609.4
*Metals Not Included In Totals
IX-44
-------
Stream Identification
Sample Niinber
Plow Rat« Liters/Hr-Gallons/Hr
Duration Hours/Day
TOXIC ORC3ANICS
1 Acen.jpthene
3 Acrylonitrile
4 Benzcine
11 1,1,1-Trichloroethane
13 1,1-Oichloroethane
23 Chloroform
29 1,1-Dichloroethylene.
30 1,2-lScans-dichloroethylene
38 Ethy].benzene
39 Fluoranthene
44 Msthylene chloride
48 Di<^iorobramomethane
51 Gilorodibromomethane
55 Naptlialene
58 4-Nilaxphenol
65 Phenol
66 Bis(;>^thylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-N--butyl phthalate
70 Diethyl phthalate
71 DiroeWiyl phthalate
78 Anthracene
81 Phencinthrene
84 Pyrerie
85 Tetrachloroethylene
86 Tolucoie
•87 Trichloroethylene
95 AlphEi-Endosulfan
102 Alphct-BHC
105 Deltci-BHC
Total Tosdc Organics
TOXIC MEl'KLS
114 flntinony
115 Arsenic
117 Beryllium
118 Cadmium
119 Chrcniiian
120 CcKJeir
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silveir
127 Thallium
128 Zinc
Total Tcoiic Metals
TABLE 9-5B
PICTURE TUBE PROCESS WASTES
(PLANT ID# 11114)
Treatment System II
tng/1 kg/day
HP Etch
Post Settle
03686
20439 - 5400
16
Not
Analyzed
mg/1 kg/day
Other Process
Raw Waste
03680
17033 - 4500
24
< 0.010
< 0.010
< 0.010
0.020 0.008
Not
Analyzed
0.010
< 0.010
0.004
< 0.010
0.030
0.060
0.012
0.024
0.003
0.005
< 0.005
< 0.005
5.580
0.127
< 0.050
< 0.001
0.144
< 0.010 *
0.001
< 0.001
0.194
6.054
0.001
0.002
2.737
0.062
0.071
0.0005
0.095
2.9685
0.440
0.266
< 0.005
0.076
0.025
0.013
2.570
< 0.001
0.014
< 0.002
< 0.001
< 0.001
2.130
5.534
0.180
0.109
0.031
0.010
0.005
1.051
0.006
0.871
2.263
mg/1
kg/day
Post Filtration
03684
17033 - 4500
24
Not
Analyzed
0.440
0.191
< 0.005
0.018
0.015
0.016
0.883
< 0.001
< 0.013
0.004
0.002
< 0.001
0.605
2.174
0.180
0.078
0.007
0.006
0.007
0.361
0.002
0.0008
0.247
0.8888
"Interference Present
IX-45
-------
NON-TOXIC METALS
Calcium *
Magnesium *
Sodium *
Aluminum
Manganese
Vanadium
Boron
Barium
ftolybdenura
Tin
Yttrium
Cobalt
Iron
Titanium
Potassium
Gallium
Germanium
Rubidium
Strontium
Zirconium
Niobium
Palladium
Indium
Tellurium
Tungsten
Osniura
Platinum
Gold
Bismuth
Uranium
Total Non-Toxic Metals
OTHER POLLUTANTS
Temperature C
121 Cyanide, Total
Oil & Grease
Total Organic Carbon
Biochemical Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
TABLE 9-5B (CONT.)
PICTURE TUBE PROCESS WASTES
(PLANT ID# 11114)
TREATMENT SYSTEM II
19.7Q
7.080
786.
0.121
0.296
< 0.001
0.770
0.034
< 0.035
< 0.025
0.042
< 0.050
80.
< 0.002
9.66
3.47
385.6
0.060
0.145
0.378
0.017
0.021
39.24
Not
Analyzed
81.263 39.86
26.20
8.270
637.
9.830
0.007
0.002
17.700
1.900
0.074
< 0.025
0.681
< 0.050
1.220
0.453
10.71
3.381
260.4
4.018
0.003
0.0008
7.236
0.777
0'.030
0.278
0.499
0.185
6.090
3.340
1810.
9.410
0.003
0.003
17.800
0.616
< 0.036
< 0.025
0.152
< 0.051
0.636
0.313
2.490
1.365
739.9
3.847
0.001
0.001
7.276
0.252
0.062
0.260
0.128
Not
Analyzed
31.867 13.0268
Not
Analyzed
28.933 11.827
7.7
27
0.002
18
5
16
178
0
15
0.001
8.83
2.45
7.85
87.32
0
7.36
2.3
36
0.009
14
8
0
137
0
1800
0.004
5.72
3.27
0
56
0
735.8
6.6
36
0
18
10
11
16
0
4000
0
7.4
4.1
4.5
6.5
0
1635.2
"Metals Not Included In Totals
IX-46
-------
Stream Identification
Sample Number
Plow Rate Liters/Hr-Gallons/Hr
Duration Hours/Day
TOXIC ORGiiNICS
1 Acenapthene
3 flcrylonitrile
4 Benzene
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
23 Chlorofoim
29 1,1-Dichloroethylehe
30 l,2-ri:ans-dichloroethylene
38 Ethyllsenzene
39 FluoKjnthene
44 tfethylene chloride
48 Dichlorcbrcrnonethane
51 ChlorcxiLbranomethane
55 Naptheilene
58 4-Nitaxphenol
65 Phenol;
66 Bis(2"etnylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-N-*»utyl phthalate
70 Diethyl phthalate
71 Dimethyl phthalate
78 Anthracene
81 Phenanthrene
84 Pyrena
85 Tetra<4iloroethylene
86 Toluene
87 Trichloroethylene
95 Alpha-Endosulfan
102 Alpha-BHC
105 Delta-BHC
Total Tosd-c Organics
TOXIC
114 Antimony
115 Arsend.c
117 Beryllium
118 Cadmium
119 Chromum
120 Coppeir
122 Lead
123 Mercuiy
124 Nickel
125 Selenium
126 Silver
127 Thalli.um
128 Zinc
Total Toxic Metals
TABLE 9-5B
PICTURE TUBE PROCESS WASTES
(PLANT ID# 11114)
Treatment System II
(CONT)
mg/1 kg/day
Final Effluent
03685
30659 - 8100
24
mg/1 kg/day
HP Dump
85268
17033 - 4500
Batch
Not
Analyzed
Nat
Analyzed
0.079
0.062
< 0.005
0.006
•3.750
0.100
0.315
< 0.001
0.097
< 0.010 *
< 0,001
< 0.001
0.318
4.727
0.058
0.046
0.004
2.759
0.074
0.232
0.071
0.234
3.478
mg/1 kg/day
Final Effluent
03681
20439 - 5000
Batch
< 0.010
< 0.010
< 0.010
< 0.010
< 0.010
27.000
9.000
< 0.010
0.975
1.500
0.074
6.820
0.002
0.420
< 0.300 *
0.001
< 0.025 *
10.300
56.092
0.092
0.031
0.003
0.005
0.0003
0.023
0.000007
0.001
0.000003
0.035
0.19031
3.200
1.570
< 0.005
0.031
0.020
0.020
3.190
< 0.001
< 0.013
< 0.025 *
0.004
< 0.010 *
1.080
9.115
0.013
0.006
0.0001
0.00008
0.00008
0.013
0.00002
0.004
0.03628
"Interference Present
IX-47
-------
NON-TOXIC M3TALS
Calcium *
Magnesiun *
Sodium *
Aluminum
Manganese
Vanadium
Boron
Barium
Molybdenum
Tin
yttrium
Cobalt
Iron
Titanium
Potassium
Gallium
Germanium
Rubidium
Strontium
Zirconium
Niobium
Palladium
Indium
Tellurium
Tungsten
Osmium
Platinum
Gold
Bismuth
Uranium
Total Non-Toxic Metals
Temperature C
121 Cyanide, Total
Oil & Grease
Total Organic Carbon
Biochemical Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
TABLE 9-5B (CONT.)
PICTURE TUBE PROCESS WASTES
(PLANT IDS 11114)
TREATMENT SYSTEM II
15.10
5.700
1050.
5.060
0.196
0.002
11.00
0.229
0.037
< 0.025
0.081
< 0.050
56.70
0.112
11.11
4.194
772.6
3.723
0.144
0.001
8.09
0.169
0.027
0.060
41.72
0.082
6.220
2.920
5250.
311.
0.540
0.326
862.
5.110
1.840
0.311
0.047
< 0.100
22.20
15.20
0.021
0.010
17.88
1.059
0.002
0.001
2.936
0.017
0.006
0.001
0.0002
0.076
0.052
3.310
1.190
10800.
62.600
< 0.001
0.045
193.
1.630
0.087
0.089
0.025
0.548
1.050
0.412
0.014
0.005
44.148
0.256
0.0002
0.789
0.007
0.0004
0.0004
0.0001
0.002
0.004
0.002
Not
Analyzed
73.417 54.016
7.5
36
0.520
10
8
0
135
0
700
0.383
7.36
5.89
0
99.34
0
515.1
Not
Analyzed
1218.574
4.1522
Not
Analyzed
259.486
1.0611
0.011
17
24
0
3350
0.008
8400
0.00004
0.058
0.082
0
11.412
0.00003
28.615
0.007
17
472
0
38
0.008
4500
0.00003
0.069
1.929
0
0.155
0.00003
18.39
*Metals Not Included In Totals
IX-48
-------
TABLE 9-5C
PICTURE TUBE PROCESS WASTES
(PUNT IDf 11114)
Treatment System III
(CONT)
Stream Identification
Sample Numtxjr
Flew Rate L±ters/Hr-Gallons/Hr
Duration Hours/Day
TOXIC ORGBNICS
1 Acenaptliene
3 AcrylonJLtrile
4 Benzene
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
, 23 Chloroform
29 1,1-Dichloroethylene
30 l,2y£raiis~dichloroetnylene
38 Ethylbenzene
39 Fluorantliene
: 44 Methylene chloride
48 Dichlorobranctnethane
51 Chlorodjiaranoniathane
55 Naptnalesne
58 4-Nitropnenol
65 Phenol
66 Bis(2-et:hylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-N-butyl phthalate
70 Diethyl phthalate
71 Diraethyl phthalate
78 Anthracene
, 81 Phenant±irene
84 Pyrene
85 Tetrachloroethylene
86 Toluene
87 Trichloxoethylene
95 Alpha-Endosulfan
102 Alpha-BBC
105 Delta-BBC
Total Toxic Organics
TOXIC MJTALS
114 Antimony
115 Arsenic
117 Beryllium
118 Cadmium
119 Chromium
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
Total Toxic Metals
mg/1 kg/day
Total Phosphor
Effluent
03682
5110 - 1350
24
< 0.010
< 0.010
< 0.010
< 0.010
< 0.010
0.020
Not
Analyzed
< 0.010
< 0.010
0.002
0.030 0.004
< 0.010
0.050 0.006
Not
Analyzed
mg/1 kg/day
Green Phosphor
Effluent
85276
1703 - 450
24
Not
Analyzed
0.004
< 0.002
< 0.005
11.600
2.380
0.013
0.050
0.001
0.013
0.002
0.001
( 0.001
19.100
33.085
0.0002
0.474
0.097
0.00004
0.781
1.35224
mg/1 kg/day
Blue Phosphor
Effluent
85275
1703 - 450
24
Not
Analyzed
< 0.001
< 0.002
< 0.005
0.020
/3.750
0.013
0.050
0.001
0.013
0.002
0.008
< 0.001
31.500
35.278
0.0008
0.153
0.0003
1.29
1.4441
IX-49
-------
NON-TOXIC ^ETALS
Calcivn *
Magnesium *
Sodium *
Aluminum
Manganese
Vanadium
Boron
Barium
l-blybdenura
Tin
Yttriun
Cobalt
Iron
Titanium
Potassium
Gallium
Germanium
Rubidium
Strontium
Zirconium
Niobium
Palladium
indium
Tellurium
Tungsten
Osnium
Platinum
Gold
Bismuth
Oraniun
Total Non-Toxic Metals
TABLE 9-5C (GOMT.)
PICTURE TUBE PROCESS WASTES
(PLANT ID# 11114)
TREATMENT SYSTEM II
0.257
< 0.025
18.300
0.021
< 0.001
< 0.001
0.094
0.538
< 0.035
< 0.025
0.037
0.212
Not 0.004
Analyzed < 0.002
Teraperature C
Rl Cyanide, Total
Oil 6 Grease
Total Organic Carbon
Biochemical Oxygon Demand
' Total Suspended Solids
Phenols
Fluoride
0
505
J30
48
1030
0
45
0
61.9
15.9
5.9
132.5
0
5.5
0.011
0.748
0.0009
0.004
0.022
0.002
0.009
0.0002
Not
Analyzed
0.906 0.0381
4.8
28 1.14
Not Analyzed
35 1.43
Not Analyzed
1.110
0.187
20.200
0.158
0.001
0.001
0.137
0.552
: 0.035
: 0.025
0.142
0.193
0.009
: 0.002
0.045
0.008
0.826
0.006
0.006
0.023
0.006
0.008
0.0004
Not
Analyzed
1.191 0.0494
5.0
28 1.14
Not Analyzed
36 1.47
Not Analyzed
*Metals Not Included In Totals
IX-50
-------
Stream identification
Sample number
Plow Rate Liters/Hr - Gallons/Hr
Duration Hours/Day
TOXIC OIX3ANICS
TABLE 9-SC
PICTURE TUBE PROCESS HASTES
(PLANT ID* 11114)
Treatment System III
mg/1 kg/day
Green Phosphor
Raw Waste
85273
1703 - 450
24
mg/1 kg/day
Blue Phospher
Raw Waste
85272 *
1703 - 450
24
mg/1 kg/day
Red Phosphor
Raw Waste
85271
1703 - 450
24
1 Acenapthene
3 Acrylonitrile.
4 Benxene
11 1,1,.1-Trichloroethane
13 l,l--Dichloroethane
23 Chloroform
29 1,1-Dichloroethylene
30 l,2"Trans-dichloroethylene
38 Ethylbenzene
39 Fluoranthene
44 tfethylene chloride
48 Dichlorobrgmomethane .
51 Chlorodibranotnethane
55 Napliialene
58 4-Nitrophenol
65 Phenol
66 Bis(2-ethylhexyl)phtnalate
67 Butyl benzyl phthalate
68 Di-N-butyl phthalate
70 Dielihyl phthalate
71 Dimeithyl phthalate
78 Anttiracene
81 Pheiianthrene
84 Pyrtsne
85 Tetrachloroethylene
86 Toluene
87 Tricjhloroethylene
95 Alpha-Endosulfan
102 Alpha-BHC
105 Dslta-BHC
Total TcscLc Organics
TOXIC MITALS
114 AntJjnony
115 Arscsnic
117 Berjrllium
118 Cadmium
119 Chrttnium
120 Copjier
122 Leafl
123 ffercwry
124 Nid-el
125 Selenium
126 Silver
127 Thallium
128 Zinc:
Total Toxic Metals
Not
Analyzed
Not
Analyzed
< 0.001
0.006
< 0.005
184.
4.970
0.240
< 0.
<0.
.050
.001
< 0.013
< 0.010*
0.005
< 0.001
1540
1729.221
0.0002
7.52
0.203
0.010
0.0002
62.94
70.6735
0.001
0.002
< 0.005
0.756
4.480
< 0.013
< 0.050
< 0.001
< 0.013
< 0.010 *
0.360
< 0.001
1910.
1915.599
0.00004
0.00008
0.031
0.183
0.015
78.07
78.29912
?•»*•' *i
sfes'
Not
Analyzed
< 0.001
0.008
< 0.005
0.120
3.710
< 0.013
< 0.050
< 0.001
< 0.013 ,
< 0.010*
0.004
< 0.001
2.860
6.702
0.0003
0.005
0.152
-,
0.0002
0.117
0.2745
* Interference Present
IX-51
-------
NON-TOXIC MSTALS
Calcium *
Magnesiur *
Sodium *
Aluminum
Manganese
Vanadium
Boron
Barium
Molybdenum
Tin
Yttrium
Cobalt
Iron
Titanium
Potassium
Gallium
Germanium
Rubidium
Strontium
Zirconium
Niobium
Palladium
Indium
Tellurium
Tungsten
Osraiun
Platinum
Gold
Bisnuth
Uranium
Total Non-Toxic Metals
OTHER POLLOTANTS
Temperature C
121 Cyanide, Total
Oil & Grease
Total Organic Carbon
Biochemical Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
TABLE 9-5C (OOMf.)
PICTURE TUBE PROCESS WASTES
(PIAWT ID# 11114)
TREATMENT SYSTEM II
0.481
< 0.049
787.
0.426
< 0.001
< 0.003
2.390
0.825
< 0.069
0.123
0.411
0.293
0.093
< 0.004
0.020
32.2
0.017
0.098
0.034
0.005
0.017
0.012
0.004
5.120
0.794
1280.
1.010
< 0.001
< 0.001
< 0.002
0.151
< 0.035
0.111
8.160
< 0.050
0.024
< 0.002
0.209
0.032
52.3
0.041
0.006
0.005
0.334
0.001
Not
Analyzed
4.561 0.187
4.9
31
NOt
Analyzed
2450
Not
Analyzed
100.1
Not
Analyzed
0.271
0.496
149.
0.188
< 0.001
0.172
0.721
0.012
0.133
0.591
1300.
4.730
< 0.001
0.038
0.011
0.020
6.09
0.008
0.007
0.030
0.0005
0.005
0.024
53.13
0.193
0.002
Not
Analyzed
9.456
4.9 sr
28 |p
Not '
Analyzed
2560
Not
Analyzed
0.387
1306.586 53.3995
5.0
35
Not
Analyzed
104.6
1840
Not
Analyzed
75.20
*Matals Not Included In Totals
IX-52
-------
TABLE 9-5C (OONT)
PICTURE TUBE PROCESS WASTES
(PLANT IDS H114)
Treatment System III
Stream Mortification
Sample Nuritoer
Flow Rate Liters/Hr-Gallons/Hr
Duration Hours/Day
TOXIC ORQiNICS
1 Acenapthene
4 Benzene
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
23 Chloroform
29 1,1-Dichloroethylene
30 1,2-tirans-dichloroethylene
38 Ethyltenzene
39 Fluorcinthene
44 Methylene chloride
48 Dicftlorcbrcrrtcmethane
51 Chlorodibrancmethane
55 Napthsilene
58 4-Nitrophenol
65 Phenol
66 Bis(2-ethylhexyl)phthalate
67 Butyl benzyl phthalate
68 Di-N-biutyl phthalate
70 Diethyl phthalate
71 Dimethyl phtnalate
78 Anthracene
81 Phenanthrene
84 Pyrenei
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
95 Alpha-Endosulfan
102 Alpha-BHC
105 Delta-BHC
Total Toxic Organics
TOXIC ^ETACS
114 Antimony
115 Arsenic
117 Beryllium
118 Cadmium
119 Chromium
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
Total Toxio Metals
•s?
mg/1 kg/day
Red Phosphor
Effluent
85274
1703 - 450
24
Not
Analyzed
0.001
0.002
0.005
0.065
2.620
0.013
0.050
0.001
0.013
0.020
0.001
0.001
0.718
3.423
0.003
0.107
0.0008
0.029
0.1398
mg/1 kg/day
Total Plant
Effluent
03683
283875 - 75000
24
O.OIO(B)
0.050
0.010
(B)
O.OIO(B)
0.010
0.010
0.341
0.060
< 0.010
< 0.010
0.010
0.090
0.030
0.005
0.005
0.230
0.052
0.037
: 0.005
1.310
1.230
0.045
1.960
O'.OOl
0.047
0.002
: 0.001
: o.ooi
7.310
11.993
0.409
0.613
0.204
1.567
0.354
0.252
8.925
8.380
0.307
13.353
0.320
0.014
49.80
81.706
IX-53
-------
NON-TOXIC METALS
Calcium *
Magnesium * •
Sodium *
Aluminum
Manganese
Vanadium
Boron
Barium
Molybdenum
Tin
Yttrium
Cobalt
Iron
Titanium
Potassium
Gallium
Germanium
Rubidium
Strontium
Zirconium
Niobium
Palladium
Indium
.Tellurium
Tungsten
Osmium
Platinum
Gold
Bismuth
Oranium
Total Non-Toxic Metals
OTHER POLLUTANTS
Temperature C
121 Cyanide, Total
Oil & Grease
Total Organic Carbon
Biochemical Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
TABLE 9-5C (COOT.)
PICTURE TUBE PROCESS WftSTES
(PLANT IDS 11114)
•TREATMENT SYSTEM II
0.157
< 0.025
9.930
2.400
< 0.001
< 0.001
0.383
0.005
< 0.035
< 0.025
2.460
0.186
0.031
0.007
0.006
0.406
0.098
0.016
0.0002
0.101
0.008
0.001
0.0003
23.200
8.380
454.
4.100
0.037
0.002
9.420
0.186
< 0.035
< 0.025
0.237
< 0.050
9.930
0.045
158.1
57.09
3093.
27.9
0.252
0.014
64.18
1.267
1.615
67.65
0.307
NOt
Analyzed
5.472 0.2245
5.0
32
Not Analyzed
8
0.327
Not
Analyzed
23.957 163.185
7.2
0.002 0.014
49
101
71
63
334
688.1
484
429
0.046
0.313
Not Analyzed
480
3270
*Metals Not Included In Totals
IX-54
-------
•CABLE 9-6
APERTURE MASK PROCESS WASTES
(PLANT ID# 36146)
Stream Identification
Sample Numljer
Flow Rate I,iters/Hr-Gallons/Hr
Duration Hours/Day
TOXIC ORGAMICS
1 Acenaptftene
3 Acryloriitrile
4 Benzene!
11 1,1,1-Irichloroethane
13 1,1-Dichloroethane
23 Chloroform
29 1,1-Dichloroethylene
; 30 1,2-Trans-dichloroethylene
38 Ethylbenzene
39 Fluoranthene
44 Metnylene chloride
48 Dichlorobrcmomethane
51 Chlorodibrcitcraethane
55 Napthalene .
58 4-Nitrophenol
65 Phenol
66 Bis(2-ethylhe3{yl)phthalate
67 Butyl bsnzyl phthalate
68 Di-N-butyl phthalate
70 Diethyl phthalate
71 Dimethyl phthalate
78 Anthraoane
81 Phenantlirene
, 84 Pyrene
85 Tetxadiloroethylene
86 Toluene
87 Trichlojcoethylene
95 Alpha-Eildosulfan
102 Alpha-BHC
105 Delta-HIC
Total Toxic Qrganics
PRIORITY MKi!ALS
114 Antimony
115 Arsenic
117 Beryllium
118 Cadmium
119 Chronium
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
Total Toxic Metals
mg/1 kg/day
Aperture Mask
Etch Waste
M17-1-1
39515 - 10440
24
0.060(B) 0.057
0.060
0.0005
0.005
0.005
0.0002
3.480
0.570
0.009
0.001
0.025
0.005
0.015
0.0005
0.193
4.2522
0.057
0.0002
3.300
0.541
0.009
0.183
4.0332
IX-55
-------
TABLE 9-6 (COOT.)
APERTURE MASK PROCESS WASTES
(PLANT IDf 36146)
NON-TOXIC METALS
Calcium *
Magnesium *
Sodium *
Aluminum
Manganese
Vanadium
Boron
Barium
tfelybdenum
Tin
Yttrium
Cobalt
Iron
Titanium
Potassium
Gallium
Germanium
Rubidium
Strontium
Zirconium
Niobium
Palladium
Indium
Tellurium
Tungsten
Osmium
Platinum
Gold
Bismuth
Uranium
Total Non-Toxic Metals
OTHER POLLOTANTS
Temperature C
121 Cyanide, Total
Oil & Grease
Total Organic Carbon
Biochemical Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
Not
Analyzed
3.1
23
2.1
8.4
4.0
18
52
< 0.002
Not Analyzed
1.992
7.966
3.793
17.07
49.315
*Matals Not Included In Totals
IX-56
-------
Trace Levels - Pollutants detected at levels too low
to be measured quantitatively are reported as the value
preceded by a less tlmn sign U-^. All other pollu-
tants are reported as^ihe' measured value.
. : Mass Load - Total daily discharge in kilograms/day of
a particular pollutant is termed the mass load. This
{ figure is computed by multiplying the measured concen-
! tration (mg/1) by the water discharge rate expressed
in liters per day.
Sample Blanks - Blank samples of organic-free, distilled
water were placed adjacent to sampling points to
detect airborne contamination of water samples. These
sample blank data are not subtracted from the analysis
; results,, but, rather, are shown as a (B) next to the
pollutant found in both the sample and the blank.
Television picture tube manufacture was sampled at two plants.
Manufacture of steel aperture masks, used in subsequent picture
tube manufacturing, was sampled at one plant. Because of the
complexity of picture tube manufacturing, segregation of the wet
processes for wastewater sampling was impractical, and discrete
process samples were not obtained. Many samples taken include
wastewater from more than one of the wet processes listed in
Table 9--2.
Television Picture Tubes - Two plants manufacturing television pic-
ture tubes were visited and sampled. Tables 9-4 and 9-5 present the
analysis of raw waste and treated effluent discharge streams for
process water usage associated with television picture tube manu-
facture,,
Aperture Mask Manufacture - One plant manufacturing aperture masks
was visa.ted and sampled. Table 9-6 presents analysis of a raw waste
sample for process water usage associated with aperture mask manu-
facture.
Summary of Raw Waste Stream Data
Tables 9-7 and 9-8 summarize pollutant concentration data for
the raw waste streams sampled for the electron tube subcategory.
Minimum, maximum, mean, and flow weighted mean concentrations have
been determined for the summarized raw waste streams. The flow
weighted! mean concentration was calculated by dividing the total
mass rates (mg/day) by the total flow rate (liters/day) for all
sampled data for each parameter. Pollutant parameters listed in
Tables 9-7 and 9-8 were selected based upon their occurrence and
concentration in the sampled streams. Those parameters either not
detected or detected at trace levels in all sampled streams were
excluded from these tables.
IX-57
-------
S:
Si
(*i *o m co o
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s
5
O
ooooioinoor-
ro o o co o o o ^o g
S
r«j F-I VD o o ^« o\ o'o r* m
r*mor»op*
fHiHrH^O^OOOiH
ooooaoooom
ti o »r**3
II ti
o 0) 5
•H to o o
? Jl S5-H
'li'SSg J|
^H 4J t-« -^ g3 E
'H'SSSH o
(n *v4
-<«;
-------
TABLE 9-8
Summary of Raw Waste Data for
Aperture Mask Manufacture
Plant 36146
Toxic Organics
Methylene chloride
Toxic Metals
118 Cadmium
119 Chromium
120 Copper
122 Lead
128 Zinc
Other Pollutants
121 Cyanide, Total
Oil and Grease
Total Organic Carbon
Biochemical Oxygen Demand
Total Suspended Solids
Concentration*
(mg/D
0.060
0.0002
3.480
0.570
0.009
0.193
2.1
8.4
4.0
18
52
Single Stream Sample Value
IX-59
-------
The manufacture of television picture tubes and of steel aperture
masks for use in television picture tubes were ' the only electron
tube product areas sampled. The other two major electron tube
product types, transmitting and receiving, utilize process water
primarily for electroplating which is included iin the Metal Fini-
shing Category. |
Plants having wet processes other than electroplating are limited
in number and in most instances limited in process water usage.
These plants consist of those manufacturing cathode-ray tubes
other than television picture tubes and plants manufacturing
particular types of transmitting tubes. These!plants have wet
processes similar to many found within television picture tube
manufacture. i
Table 9-7 summarizes raw waste streams sampled|at two plants manu-
facturing television picture tubes, Plants 301?2 and 11114. Plant
30172 was composite sampled for three 24-hour periods, and Plant
11114 was composite sampled for one 24-hour period. Obtaining total
raw waste samples at both plants was impractical. Therefore,
individual process raw waste samples are summarized to produce a
combined raw waste stream for each plant. The total raw waste stream
developed for Plant 30172 includes all process wastes that, receive
wastewater treatment, but does not include untreated process- wastes
discharged directly. The total raw waste stream developed for Plant
11114 includes all process wastes that receive wastewater treatment
as well as those process wastes that do not receive treatment. The
untreated process wastewater flows are significant .and constitute 48
and 78 percent of the total process wastewater;at Plants 30172 and
11114, respectively. These untreated process wastewaters predomi-
nantly include dilute rinse waters associated with wet process opera-
tions. In addition, both facilities have raw pastes that are not
included in the summary raw wastes and are discussed below.
At Plant 30172 phosphor coating raw waste samples could not be
obtained prior to treatment because of the proprietary nature of
the process. Phosphor coating raw wastes were|obtained at Plant
11114 and account for much of the differences between several
metals concentrations for the two plants. These metals include
cadmium, zinc, and yttrium, all of which are prime constituents
of phosphor coating materials. !
At Plant 11114, eight of nine raw waste streams were sampled and
proportioned together as a total raw waste. Tl^e ninth raw waste
stream was a hydrofluoric acid etch waste that;was discontinued
the week following the sampling visit. 'Therefore, this raw
waste stream was not included as a component o£ the summary raw
waste for this facility.
Table 9-8 presents raw waste concentration data for one sample
taken at Plant 36146. This sample represents all process waste-
water from the manufacture of aperture masks by chemical etching.
IX-60
-------
In addition, an organics analysis of total raw waste was not obtained
at the two facilities manufacturing picture tubes. However, indivi-
dual process wastes were sampled and analyzed for organic pollutants
if organic pollutants were known to be used in a particular manufac-
turing process. Therefore, organic analysis is not available for
all sampled raw waste streams. However, organic analysis is pre-
sented for the raw waste stream developed on a pollutant mass balance
on the sampled streams at Plant 11114. Organic analysis is presented
in Table 9-8 for Plant 36146 which manufactures steel aperture masks.
Treatment In-Place
The following is a plant-by-plant discuss ton-of raw waste and final
effluent process ^astewatecs sampled for this study at plants manu-
facturing television picture tubes and aperture masks for use in
television picture tubes. A discussion of waste treatment techno-
logies presently in use at these same plants is also presented.
Table 9-9 summarizes treatment in-place and effluent discharge des-
tinations of plants visited during this study.
Plant 30172 produces color television picture tubes. Figure 9-7 de-
picts sampling locations and wastewater treatment at Plant 30172.
Sampling locations were selected on two bases. First, wastewater from
many of the wet processes was sent to «H fire cent treatment systems
because of the different pollutant characteristics of each process
waste stream, Second, accessibility to process operations was
restricted during the sampling visit. Analytical results were
presented in Tables 9-4A, 9-4B, an'd 9-4C.
Wastewaters produced from red, green, and blue phosphor applica-
tions flow to separate settling tanks* Wastewater from the red
phosphor settling tank is subsequently sent through a paper
filtration unit. The phosphors are recovered by gravitational
settling and returned to phosphor preparation. The wastewater
is sent to a final holding lagoon.
Process wastes from the tube salvage operation are sent to lead
treatment. The wastes flow to a 6613 liter (1800 gallon) treat-
ment tank where sodium carbonate is added. The partially treated
wastes are sent through a sludge dewatering unit. Approximately fifty
208 liter (55 gallon) drums per year of carbonate sludge are sent to
a toxic chemical landfill and the filtrate is sent to primary
treatment. Samples were taken before and after lead treatment.
The photoresist solution and the deionized water developer
solution are sent to chromium treatment. The chromium bearing
wastewater is reduced'from the hexavalent to the trivalent state
using sulfuric acid and sodium bisulfite. The partially treated
wastes then flow to primary treatment. Wastewater samples were
taken before and after chromium treatment.
IX-61
-------
TABLE 9-9
ELECTRON TUBE MANUFACTURE
SUMMARY OF WASTEWATER TREATMENT AT VISITED PLANTS
Plant ID No.
30172
11114
36146
41122
19102
23337
I « Indirect
D * Direct
NA s Not Applicable
Treatment In-Place Discharge
Chemical precipitation and clari- D
fication, multimedia filtration,
sludge dewatering, chromium reduc-
tion, phosphor settling, sludge
drying lagoon, solvent collection
and incineration, holding lagoon
Chemical precipitation and sedi- I
mentation, pH adjustment, phosphor
settling
pH adjustment, settling D
pH adjustment I
No Wet Processes For Electron NA
Tube Manufacture !
No Wet Processes For Electron NA
Tube Manufacture
IX-62
-------
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r* r-f 4 i
in V *
e *
3'*
'O *"
Q
03 .", '
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CO 0\ rH
in in (*i^
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c
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44 '*•*
at **
si!
u a s
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fi o W
u o «
o us
cu
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-------
Process wastewaters from the following operations receive no
chemical waste treatment and flow directly to the final holding
lagoon: final deionized water rinses after photoresist applica-
tion; phosphor settling associated with screening; an ultrasonic
cleaning rinse associated with mount assembly; ai funnel deter-
gent clean rinse; the rinse that concludes paneli cleaning from
the tube salvage process; and wastewater from a trichloroethylene
carbon adsorption recovery system.
All Bother process wastewatecs aot associated with phosphor appli-
cation, which include rinses from many oE the wejt processes, to-
i/efchec with the partially treated wastes (from chromium d'ul l«d«l
bceafcment, flow to a primary fluoride treatment system. Primary
fluoride waste treatment is intended to reduce pollutant levels of
metals, solids, and fluorides, as well as to adjust the wastewater
pH. The wastes are sent to one of two holding tanks and then to a
flash mix tank where sodium bisulfite, calcium chloride, and lime are
added. A polyelectrolyte is added prior to sedimentation in a 113,550
liter (30,000 gallon) clarifier. The settled sludge is sent through
a rotary vacuum filtration unit and then to a sludge drying bed.
Recently, 570,909 kg (628 tons) of dried sludge collected over an 8
year period was sent to a toxic materials landfill. The filtrate
from the sludge dewatering unit is returned to trie clarifier. The
effluent from the clarifier flows through a series of dual-media
sand/carbon filters and a holding lagoon before peing discharged to
a river. All organic solvents from cleaning and!coating operations
are collected from their respective processes an<3 incinerated.
Sampling within primary fluoride treatment occurred at the
following locations: prior to rapid mixing; after the clarifier,
and after sand/carbon filtration. j
Plant 11114 produces color television picture tubes. Because of
the size of the plant, process wastewater is sent: to one of
three treatment systems according to the locatioft of the waste-
water source within the facility. Wastewater treatment consists
of pH adjustment, settling, and filtration. In all cases, pH
adjustment is accomplished with sodium carbonate!and settling
occurs in 18,925 liter (5,000 gallon) tanks. All settled material
is contractor removed. Tables 9-5A, 9-5B, and 9^5C presented
analytical results, and Figure 9-8 presents waste treatment
technologies and sampling locations at Plant 11114.
i
One treatment system receives hydrofluoric acid (Containing
wastes from tube salvage. The wastewater is sent to a holding
tank for pH adjustment before entering a settling tank. A
sample was taken of these wastes prior to pH adjustment and
after the initial settling. Other wastewater from the tube
salvage process is pH adjusted and sent to another settling
tank, A sample was taken of these wastes prior to pH adjust-
ment. Wastewater from the two settling tanks flow together
through a series of three more settling tanks and a cartridge
filter. Samples were taken before and after the ; filtration unit.
IX-64
-------
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Wastewaters from aperture mask degreasing and panel wash are pH
adjusted and settled. This wastewater, together with waste-
water from the filtration unit, flows through three settling
tanks prior to final discharge to the municipal treatment system.
Samples were taken of aperture mask degreasing and panel wash
wastewater prior to pH adjustment. Samplesj were also taken of
the final treated effluent. I
i
The second treatment system receives wastewater from another
area of the facility containing aperture ma^k hydrofluoric acid
etching wastes. These wastes are first pH Adjusted and then flow
through three settling tanks. Wastewater was sampled after the
third settling tank. The process producing this wastewater was
discontinued the week following the sampling visit. Other pro-
cess wastewater is pH adjusted, settled twice, and sent through
a cartridge filter. This partially treated1 waste then flows to a
finalsettling tank together with the treated hydr9fluoric acid
containing wastes. Wastewater was sampled prior to pH adjustment,
after the filtration unit, and before discharge to the municipal
treatment system. j
j
There are some additional hydrofluoric acidj containing wastes
that are pH adjusted, settled, and sent to the municipal treat-
ment system. Wastewater was sampled before; and after this
treatment process.
The remaining treatment system recovers phosphor materials. There
are six subsystems, two each for red, greenl and blue phosphors.
In each subsystem, phosphor coating solution flows to a holding
tank, then through a settling tank and a ceiitrifugation filter
before being discharged to the municipal treatment system.
Samples were taken before and after settling. The filtration
units were not in operation during the sampling visit.
All treated process wastewater, untreated process wasteiwater,
and non-contact cooling water flow together;to the municipal
treatment system. A composite sample was taken of this final
plant effluent. j
Plant 36146 produces steel aperture masks foe use in color
television picture tubes. The masks are produced by a photo-
graphic etching process. A composite sample was taken of waste-
water from the etching process, including both dumps and rinses,
and analytical results were presented in Takle 9-6. Figure 9-9
depicts'the sampling location and wastewatei: treatment at this
plant. The etching wastewater is pH adjusted with lime and sent
to a settling pond before discharge to a riyer.
IX-66
-------
Lime
1
Aperture Mask
Formation Waste
M17-1-1
a
pH Adjustment
Settling
Pond
•River
FIGURE 9-9
SAMPLING LOCATION AND IN-PLACE WASTE TREATMENT
PLANT 36146
IX-67
-------
POTENTIAL POLLUTANT PARAMETERS i
Potential pollutant parameters for the electron tube subcategory
are based on the list of pollutants presented in Table 9-3.
Rationale for pollutant selection was based on information from
the following: ;
i
Presence of toxic pollutants, non-toxic metals,
and other pollutant parameters ;
Occurrence of pollutant as a raw material or process
chemical in television picture tube and aperture mask
manufacturing processes
Treatability of pollutants at repotted concentration
levels I
i
Toxicity of pollutants at reported\concentration
levels , |
Table 9-10 presents the potential pollutant parameters for the
manufacture of television picture tube products and steel aper-
ture masks. j
1
Tables 9-11 and 9-12 list pollutants not selected as potential
parameters that were analyzed in the raw wastle streams sampled
for television picture tube manufacture and aperture mask manu-
facture. Both Tables 9-11 and 9-12 present pollutants according
to the following classifications: not detected, detected at trace
levels or detected at levels too low to be effectively treated
prior to discharge. Pollutant concentration^ are determined to
be too low for effective treatment for any or all of the following
reasons: !
Levels of treatability for many non-toxic parameters
are unknown. I
i
i
Pollutants are not selected if raw jwaste concentrations
are less than the long term average! concentrations
established for the levels of recom'mended treatment.
Organic analysis was not obtained for total r|aw waste samples at
Plants 30172 and 11114, which manufacture television picture tubes.
Samples were obtained and organic analysis .pe'rformed for those
process wastes either known to discharge or suspected of dis-
charging organic pollutants. The remaining process wastes,
treated and untreated, should not contain organic pollutants.
Therefore, those organic pollutant parameters! found in individual
process wastes will become relatively insignificant when included
in the total process raw waste stream. For these reasons, organic
pollutants have been selected as potential parameters based upon
their known occurrence in the manufacturing processes and their pre-
sence in the sampled streams. ' !
IX-68
-------
TABLE 9-10
POTENTIAL POLLUTANT PARAMETERS
Television Picture Tubes
Aperture Masks
Toxic Org
-------
TABLE 9-11
POTENTIAL POLLOTANT PARAMETERS NOT
SELECTED FOR TELEVISION PICTURE TUBE MANUFACTURE
NOT DETECTED IN RAW WASTE STREAMS
TOXIC ORGANICS
2. Acrolein 47.
3. Acrylonitrile 49.
5. Benzidine 50.
6. Carbon Tetrachloride 52.
(Tetrachloromethane) 53.
7. Chlorobenzene 54.
8. 1,2,4-Trichlorobenzene 56.
9. Hexachlorobenzene 57.
10. 1,2-Dichloroethane 58.
12. Hexachloroethane 59.
14. 1,1,2-Trichloroethane 60.
15. l,l,2,2,-
-------
TABLE 9-11 CONTINUED
93.
94.
96.
97,
98.
99.
100.
101,
103.
104.
106.
107.
108.
109.
110,
111.
112.
i 4,4'-DDE (P,P'-DDX)
4,4'-DDD (P,P-TDE) 129,
Beta-Endosulfan
Endosulfan Sulfate
Endrin
Endrin Aldehyde
Heptachlor
Heptachlor Epoxide (BHC=Hexachloro-
cyclophexane)
Beta-BHC
Gamma-BHC (Lindane)
PCB-1242 (Arochlor 1242)
PCB-1254 (Arochlor 1254)
PCB-1221 (Arochlor 1221)
PCB-1232 (Arochlor 1232)
PCB-1248 (Arochlor 1248)
PCB-1260 (Arochlor 1260)
PCB-1016 s;(Arochlor 1016)
Toxaphene
2,3,7,8-Tetrachlorodibenzo-P-
Dioxin (TCDD)
OTHER POLLUTANTS
Biochemical Oxygen Demand
Xylenes
Alkyl Epoxides
IX-71
-------
TABLE 9-11 (CON'T)
DETECTED AT TRACE LEVELS
TOXIC ORGANICS
1. Acenaphthene
4. Benzene
13. 1,1-Dichloroethane
23. Chloroform (Trichloromethane)
29. lrl-Dichloroethylene
30. Ir2-Jrrans-Dichloroethylene
38. Ethylbenzene
39. Fluoranthene
44. Methylene Chloride (Dichloromethane)
48. DicW.orobromomethane
51. Chlorodibromome thane
55. Naphthalene
65. Phenol
66. Bis(2-ethylhexyl) Phthalate
67. Butyl Benzyl Phthalate
68. DiHSItButyl Phthalate
70. Diethyl Phthalate
78. Anthracene
81. Phenanthrene
84. Pyrene
95. Alpha-Endosulfan
102. Alpha-BHC
105. Delt?L-BHC (PCB-Polychlorinated
Biphenyls)
129. 2,3,7,,8-TeteachlorQdibenzo-P-
Dioxin (TCDD)
TOXIC METALS
117. Beryllium
123. Marcury
125. Selenium
127. Thallium
OTHER POLLOTftNTS
Phenols
IX-72
-------
TABLE 9-11 CONTINUED
DETECTED AT LEVELS NOT REQUIRING TREATMENT
TOXIC METALS
120. Copper
124. Nickel
126. Silver
NON-TOXIC METALS
Aluminum
Manganese
Vanadium
Molyix3enum
Tin
Cobalt
Titanium
OTHER POLLUTANTS
121. Cyanide, Total
Total Organic Carbon
Single Stream Sanple Value
Developed
Flow Weighted
Mean Concentration*
mg/1
0.059
0.076
0.004
6.055
0.019
0.005
0.050
0.039
0.101
0.089
0.002
134.6
IX-73
-------
TABLE 9-12
POTENTIAL IOLLUTANT PARAMETERS NOT SELECTED
FOR APERTURE MASK MANUFACTURE j
I
NOT DETECTED IN RAW WASTE STREAMS
TOXIC ORGANICS
1. Acenaphthene 47.
2. Acrolein 48.
3. Acrylonitrile 49.
4. Benzene 50.
5. Benzidine 51.
6. Carbon Tetrachloride 52.
(Tetrachloromethane) 53.
7. Chlorobenzene 54.
8. 1,2,4-Trichlorobenzene 55.
9. Hexachlorobenzene 56.
10. 1,2-Dichloroethane 57.
11. 1,1,1-Trichloroethane 58.
12. Hexachloroethane 59.
13. 1,1-Dichloroethane 60.
14. 1,1,2-Trichloroethane 61.
15. 1,1,2,2,-Tetrachloroethane 62.
16. Chloroethane 63.
17. Bis(Chloromethyl)Ether 64.
18. Bis(2-Chloroethyl)Ether 65.
19. 2-Chloroethyl Vinyl Ether (Mixed) 66.
20. 2-Chloronaphthalene 67.
21. 2,4,6-Trichlorophenol 68.
22. Parachlorometa Cresol 69.
23. Chloroform (Trichloromethane) 70.
24. 2-Chlorophenol 71.
25. 1,2-Dichlorobenzene 72.
26. 1,3-Dichlorobenzene 73.
27.> 1,4-Dichlorobenzene 74.
28.' 3,3'-Dichlorobenzidine
29. 1,1-Dichloroethylene 75.
30. 1,2-Trans-Dichlorethylene
31. 2,4-Dichloropropylene 76.
32. 1,2-Dichloropropane 77.
33. 1,2-Dichloropropylene 78.
(1,3-Dichloropropene) 79.
34. 2,4-Dimethylphenol 80.
35. 2,4-Dinitrotoluene 81.
36. 2,6-Dinitrotoluene 82.
37. 1,2-Diphenylhydrazine
38. Ethylbenzene 83.
39. Fluoranthene
40. 4-Chlorophenyl Phenyl Ether 84.
41. 4-BrornDphenyl Phenyl Ether 85.
42. Bis(2-Chloroisopropyl) Ether 86.
43. Bis(2-Chloroethoxy)Methane 88.
44. Methylene Chloride 89.
(Dichloromethane) 90.
45. Methyl Chloride (Chloromethane) 91.
46. Mathyl Bromide (Bromomethane)
92.
Bromoform (Tribromomethane)
Dichlorobromomethane
Trichlorofluoromethane
Dichlorodifluoromethane
Chlorodibroijnome thane
Hexachlorotnli t ad iene
Hexachlorocyclopentadiene
Isophorone i
Naphthalene i
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
2,4-Dinitrophenol
4,6-Dinitro~O-Cresol
NHSIitrosodinTethylamine
N-Nitrosodiphenylamine
NHdtrosodi-N-Propylamine
Pentachlorophenol
Phenol
Bis(2-ethylhexyl) Phthalate
Butyl Benzyl Phthalate
DiHfl-Butyl Phthalate
Di-N-Octyl i>hthalate
Diethyl Phthalate
Dimethyl Phii>alate
1,2-Benzant^iracene (Benzo(A)Anthracene)
Benzo (A) Pyrene (3,4-Benzo-Pyrene)
3,4-Benzofluoranthene (Benzo(B)
Fluoranthene)
11,12-Benzofluoranthene (Benzo(K)
Fluoranthen^)
Chrysene
Acenaphthylene
Anthracene \
1,12-^enzoperylene(Benzo(GHI)-Perylene)
Fluorene !
Phenanthrene
1,2,5,6-Dibenzathracene(Dibenzo (A,H)
Anthracene)i
Indeno(1,2,3-CD)Pyrene(2,3-0-Phenylene
Pyrene) ,
Pyrene !
Tetrachloro^thylene
Toluene i
Vinyl Chloride (Chloroethylene)
Aldrin !
Dieldrin I
Chlordane(Technical Mixture and
Metabolites)
4,4'-DDT i
IX-74
-------
TABLE 9-12 CONTINUED
93. 4,4'-DDE (P,P'-DDX)
S>4. 4,4'-DDD (P/P-TDE)
95. Alpha-Endosulfan
96. Beta-Endosulfan
97. Endosulfan Sulfate
98. Endrin
99. Endrin Aldehyde
100. Heptachlor
101. Heptachlor Epoxide (BHC=Hexachloro-
cyclophexane)
102. Alpha-BHC
103. Beta-BHC
104. Gamma-BHC (Lindane)
105. Delta-BHC (PCB-Polychlorinated
Biphenyls)
106. PCB-1242 (Arochlor 1242)
107. PCB-1254 (Arochlor 1254)
108. PCB-1221 (Arochlor 1221)
109. PCB-1232 (Arochlor 1232)
110. PCB-1248 (Arochlor 1248)
111. PCB-1260 (Arochlor 1260)
112. PCB-1016 (Arochlor 1016)
113. Tbxaphene
129. 2,3,7,8-Tetrachlorodibenzo-P-
Dioxin (TCDD)
OTHER POLLUTMCTS
Xylenes
Alkyl Epoxides
IX-75
-------
TABLE 9-12 OONT.
DEHiCTEDAT TRACE LEVELS
TOXIC METALS
114. Antimony
115* Arsenic
'117. Beryllium
123. Mercury
124. Nickel
125. Selenium
126. Silver
127. Thallium
OfflER FOmJTANTS
Phenols
AT LEVELS NOT REQUIRING -TREATMENT
TOXIC OSGftNICS
87. Trichloroethylene
TOXIC METALS
118. Cadmium
122. Lead
128. Zinc
OTHER POLLUTANTS
121. Cyanide, Total
Total Organic Carbon
Biological Oxygen Demand
Mean Concentration*
•Ong/1)
0.060
0.0002
0.0009
0.193
2.1
4.0
18
* 3 Single Stream Sample Value
IX-76
-------
Aluminum and titanium are presented in Table 9-11 as metals detected
at levels not requiring treatment. Although both metals are at •
treatable levels, they have not been selected as potential pollutant
parameters for two reasons. First, both metals in the elemental form
are not considered to be highly toxic. Secondly, both metals will
be treated incidentally by any of the three levels of recommended
treatment to acceptable concentration levels.
Table 9-12 presents potential pollutant parameters not selected
for aperture mask manufacture as sampled at one facility. Cyanide
is listed as a parameter detected at too low a level to require
treatment. Although the reported concentration level is treat-
able, cyanide is not used in the manufacture of aperture masks.
Cyanide is used in electroplating processes also found at this
facility, and it is believed that this is the origin of this
pollutant. Therefore, cyanide is not selected as a potential
pollutant parameter.
APPLICABLE TREATMENT TECHNOLOGIES
Based on the potential pollutant parameters selected and actual
treatment technologies observed within the electron tube industry,
the following treatment technologies are recommended for pollutant
control within this subcategory:
Chemical precipitation and sedimentation
Fluoride treatment
Chromium reduction
Settling
Sludge dewatering
Multimedia filtration
Final pH adjustment
Solvent collection and removal
These technologies are discussed in detail in Section XII of
this report.
Recommended Treatment Systems
Alternative waste treatment technologies are presented for the
electron tube subcategory. Treatment technologies are defined for
process wastes from the manufacture of television picture tubes and
steel aperture masks. The following discussion presents three levels
of waste treatment for television picture tube and steel aperture mask
manufacture.
IX-77
-------
Level 1 - Recommended treatment for each levelj requires three treat-
ment systems, two for picture tubes and one for aperture masks, to
control the great diversity of process wastes.' Level 1 treatment is
presented schematically in Figure 9-10 and combines the following
technologies into three separate treatment systems.
Solvent collection and removal ;
. Chemical precipitation and sedimentation for concen-
trated metal wastes employing chemical additions of
lime, sodium carbonate, a coagulant aid, and a polyelec-
trolyte ;
Fluoride treatment to precipitate caicium fluoride
with the use of lime and calcium chloride
Chromium reduction with the use of sjalfuric acid and
sodium bisulfite i
Settling and reclamation of phosphor; wastes
Sludge dewatering
Final pH adjustment \
Level 2 - Recommended treatment consists of Level 1 treatment with an
additional multimedia filtration step on all three treatment systems.
Level 2 treatment is depicted in Figure 9-11. j
Level 3 - Recommended treatment consists of Level 2 treatment
with the addition of water reuse where possible. Level 3 recommended
treatment for aperture mask manufacture reuses!100% of treated
process wastewater. Level 3 recommended treatment for television
picture tube and aperture mask manufacture reuses approximately
60% and 100% of treated process wastewater,respectively. Figure
9-12 presents Level 3 treatment for television;picture tube and
aperture mask manufacture. j
Performance of In-Place Treatment Systems
The performance of treatment technologies that!have been sampled
in-place for the electron tube subcategory is presented in Tables
9-13 through 9-18. The manufacture of television picture tubes was
observed and sampled at two facilities, Plants!30172 and 11114.
The manufacture of steel aperture masks was observed and sampled at
one facility, Plant 36146. Tables 9-13, 9-14,;and 9-15 present per-
formance of treatment technologies and systems!for Plant 30172.
Tables 9-16, 9-17, and 9-18 present performance of treatment tech-
nologies and systems for Plant 11114. No performance of in-place
treatment is available for Plant 36146 as only I a raw waste sample
was obtained. Sample numbers and stream identification as pre-
sented in Tables 9-13 through 9-18 correspond to sampling location
and sample numbers of in-place treatment presented previously in
Figures 9-7 and 9-8. Other types of electron tube manufacture
were observed but not sampled. However, process water usage at
IX-78
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TABLE 9-13
Parameter
Sairple Number
TOXIC METALS
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium
122 Lead
128 Zinc
NCKKEOXIC JffiTALS
Boron
Barium
Iron
Yttrium
OTHER EOLU7TANTS
OH and Grease
Total Suspended Solids
Fluoride
pH
PERFORMANCE OF IN-PLACE TREATMENT TECHNOLOGIES
Plant 30172 - Chemical Precipitation and Settling
]
Influent Concentration! Effluent Concentration
(mg/1) (mg/1)
85125
0.092
0.250
1.070
4.670
891.
1510.
346.
205.
1940.
16.80
11.
190.
160.
<2.0
85126
<0.015
0.010
<0.005
0.027
1.9
11.4
395.
12.4
0.378
<0.008
14.
17.
76.
7.3
IX-82
-------
TABLE 9-14
PERFORMANCE OF IN-PLACE TREATMENT TECHNOLOGIES
I
Plant 30172 - Chemical Precipitation and Sedimentation in a Clarifier
Parameter
Sample Numbers
Toxic Metals
114 Antimony
115 Arsenic
118 Cadmium
119 Chrcmium
122 Lead
128 Zinc
Non-Toxic Metals
i
Boron
Barium !
Iron j
Yttrium |
Other Pollutants
Oil and Grease
Total Suspended
Solids
Fluoride
pH ;
Influent Concentration
(ing/1)
Day 1
85127
0.188
0.100
0.215
2.470
20.700
6.770
9.170
1.100
7.720
2.290
Day 2
85138
0.126
0.102
0.135
3.150
11.200
5.120
9.520
0.586
8.640
1.290
Day 3
85137
0.146
0.160
0.163
2.980
10.600
6.340
7.080
0.626
9.320
1.470
14
130
260
2.7
11
88
270
2.1
12
50
490
1.7
Effluent Concentration
(mg/1)
Day 1
85128
0.146
0.008
<0.002
0.292
0.273
0.112
1.880
0.182
0.197
0.006
10
2
6.5
8.5
Day 2*
85132
Day 3
85136
0.119
0.010
<0.002
0.195
0.233
0.150
2.060
0.150
0.262
0.005
830
3
7.7
8.1
Sample Lost
IX-83
-------
TABLE 9-15
PERFORMANCE OF IN-PLACE TREATMENT TECHNOLOGIES
Plant 30172 - Dual-Media Filtrajtion
Parameter
Sample Numbers
TOXIC METALS
114 Antimony
115 Arsenic
118 Cadmium
119 Chromiisti
122 Lead
128 Zinc
NON-TOXIC METALS
Boron
Barium
Iron
Yttrium
OTHER POLLUTANTS
Oil and Grease
Total Suspended
Solids
Fluoride
PH
* 3 Sairple Lost
Influent Concentration
(rog/1)
Day 1
85128
0.146
0.008
<0.002
0.292
0.273
0.112
1.880
0.182
0.197
0.006
10
2
6.5
8.5
Day 2*
85132
Day 3
85136
0.119
0.010
<0.002
0.195
0.233
0.150
2.060
0.150
0.262
0.005
830
3
7.7
8.1
Effluent Concentration
(mg/1)
Day 1
03662
0.117
0.010
<0.002
0.247
0.152
0.055
'
1.530
0.155
0.048
<0.003
Day 2
85130
0.136
0.008
<0.002
0.250
0.228
0.110
2.450
0.142
0.227
<0.003
Day 3
85134
0.106
0.010
<0.002
0.128
0.109
0.059
2.090
0.135
0.071
<0.003
1.4
10
8.5
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7
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IX-84
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these facilities is predominantly from electroplating and is thus
part of the Metal Finishing Category and not presented in this
document. The remaining process water usage at these plants is
characteristically similar to that found at many picture tube
facilities. Therefore, treatment technologies are transferable from
plants manufacturing television picture tubes 'to those manufacturing
other types of electron tube products. i
i
Because of the size and complexity of television picture tube
manufacture/ process wastewaters are not treated as a single
total raw waste. Treatment technologies are employed in accor-
dance with industrial process raw waste characteristics as well
as the physical location within the facility, j
Collection and removal of sspent solvents, oil,! and photoresist
solutions were observed at Plants 30172 and 11J114. Both plants
have good organic solvent collection and disposal procedures.
Performance of treatment components and systems is presented for
Plants 30172 and 11114. A total raw waste sample only was
obtained at Plant 36146. Therefore, no performance of in-place
treatment is presented for this facility.
Performance of Recommended Treatment Systems
Performance of the three levels of recommended treatment for
television picture tube and aperture mask manufacture are pre-
sented in Tables 9-19 and 9-20,respectively. [Performance is based
on sampling data obtained from visited plants]in the E&EC category
as well as data from other industries. Because of similarity in
raw waste characteristics to other industries, performance of treat-
ment technologies is applicable to the E&EC category. Section XII
describes treatment components, systems, and performance achievable
by the recommended treatment technologies. !
1 i
None of the three levels of recommended treatment for aperture
mask manufacture were observed in-place at any of the visited plants.
Level 1 recommended treatment for television picture tube manufacture
as presented previously in Figure 9-10 was not observed in its en-
tirety at any visited facility. However, a close approximation in-
corporating all treatment components utilized!in the Level 1 system
was observed and sampled at Plant 30172. In addition, waste stream
location within the recommended treatment system is very similar to
that observed at Plant 30172. |
j
Level 2 treatment for television picture tubejmanufacture includes
the addition of multimedia filtration to the recommended Level 1
system. Level 2 treatment for television picture tube manufac-
ture improves metals- removal performance whil4 lowering the suspended
IX-88
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solids and oil and grease levels. This occurs because some of the
metal hydroxide precipitate formed during chemical precipitation
will be further removed by the addition of multimedia filtration
in the Level 2 treatment system. This additional treatment tech-
nology was observed and sampled at Plant 30172, and therefore,
approximates the Level 2 recommended treatment system.
Level 3 treatment for television picture tube manufacture does not
include any treatment technology additional to the recommended
Level 2 system. Pollutant discharge from television picture tube
manufacture is reduced significantly by reuse of treated wastes.
It is estimated that 60-70 percent of the treated wastes are
sufficiently purified for process reuse. Level 3 treatment was not
observed at any visited plants.
All levels of recommended treatment for television picture tube
manufacture include the collection and removal of organic solvents.
Concentration levels in the sampled effluents of Plants 30172
and 11114 for organic pollutants were detected at levels less
than that requiring treatment. However, because of their
acknowledged use in the manufacturing process, four toxic organic
pollutants have been selected as potential pollutant parameters
as have total organics. A total organic concentration level of
.290 mg/1 has been established for television picture tube
manufacture. This is based on a total organic concentration
level of a sampled effluent at Plant 11114. Collection and re-
moval of organic solvents is discussed in detail in Section XII.
Table 9-21 compares performance of observed and recommended treat-
ment for the electron tube subcategory. Performance of observed
treatment is based on data obtained from two television picture
tube manufacturers, Plants 30172 and 11114. No performance of
observed treatment is available from the one aperture mask manu-
facturer sampled, Plant 36146. This comparison supports the
transfer of performance data from the Metal Finishing Category
as evidenced by the relative similarity in effluent concentration
levels of these streams. Comparison of Level 3 treatment perform-
ance does not appear in Table 9-21 as it was not observed in-place
at any visited facilities.
Performance of Level 1 and 2 observed treatment as presented in
Table 9-21 for toxic metals, non-toxic metals, and other pollu-
tant parameters was obtained from Plant 30172. This performance
data was previously presented in Tables 9-14 and 9-15. Table
9-14 presented a Day 1 and Day 3 effluent oil and grease concen-
tration of 10 mg/1 and 830 mg/1, respectively. - The calculated
mean as presented in Table 9-21 is 420 mg/1. The Day 3 and the
calculated mean concentration levels do not coincide with histor-
ical plant performance data or with the concentration level
IX-91
-------
TABLE 9-21
ELECTRON TUBE SUBCATEGORY
COMPARISON OF OBSERVED AND RECOMMENDED TREATMENT SYSTEMS
Parameters
TOXIC ORGANICS
11 1,1,1-TricU.oroethane
44 Methylene chloride
86 Toluene
87 Trichlorpethylene
Total Toxic Organics
TOXIC METALS
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium
122 Laad
128 .Zinc
NON-TOXIC METALS
Boron
Barium
Iron
Yttrium
OTHER POLLOTANTS
Oil and Grease
Total Suspended Solids
Fluoride
Level 1"
Observed
Treatment
mg/1
*
*
*
0.290**
0.133
0.009
<.002
0.244
0.253
0.131
1.970
0.166
0.230
0.006
420
2.5
7.1
Level 1B
Recommended
Treatment
mg/1
*
*
0.290**
0.05
0.05
0.012
0.572
0.050
0.551
1.970
0.166
0.797
0.006
11.9
17.8
15.3
Level 2A
Observed
Treatment
mg/1
0.290**
0.112
0.010
<0.002
0.188
0.131
0.057
1.810
0.145
0.060
0.003
12.5
1.2
12.5
Level 2B
Recommended
Treatment
mg/1
*
*
*
0.290**
NA
NA
0.011
0.319
0.034
0.247
1.810
0.145
0.257
0.003
7.1
12.7
4.76
A s Mean Concentration Of Day 1 And Day 3 Sampled Stream^ As Presented In Tables
9-14 And 9-15. ;
B » Mean Concentration Obtained From Table .9-19. j
* » Included In Total Toxic Organics j
** * This Figure Is The Concentration Of The Sampled Effluent From Plant 11114.
IX-92
-------
detected for ,the.Day 1 sampled effluent. In addition, the three
days of sampled influent presented in Table 9-14 appear at much
lower and consistent concentration levels than the Day 3 sampled
effluent. It is for these reasons that the Day 3 concentration
level of 830 mg/1 has not been included in determining the perform-
ance of oil and grease removal by the recommended treatment systems,
Estimated Cost of Recommended Treatment Systems
The determination of estimated costs for recommended treatment
system components is discussed in Section XIII of this report.
Tables 9-22 through 9-28 show the estimated costs for each of
the recommended treatment systems discussed previously for the
electron tube subcategory. Costs have been estimated for Levels
1,2, and 3 recommended treatment for television picture tube
and aperture mask manufacture. The variation in system costs
resulting from changes in system flow rate are presented for two
flow raites associated with television picture tube manufacture
and one flow rate associated with aperture mask manufacture. The
two flow rates for television picture tube manufacture are char-
acteristic of medium and large size facilities. The one flow
rate presented for aperture mask manufacture is typical of all
known aperture mask manufacturers. These costs do not reflect
treatment already in-place in the electron tube subcategory that
are designed to treat electron tube manufacturing .wastes exclu-
sively.; Similarly, these costs may be misleading because they
do not account for mixing wastewaters from electron tube manu-r
facturing with wastewaters from other manufacturing 'processes
(such eis electroplating) for treatment in existing wastewater
treatment facilities.
BENEFIT ANALYSIS
This section presents an analysis of the industry-wide benefit
estimated to result from applying each of the three levels of
treatment previously discussed in this section to the total
process wastewater generated by the electron tube subcategory.
This analysis estimates the amount of pollutants that would not
be discharged to the environment if each of the three levels of
treatment were applied on a subcategory-wide basis. An analysis
of the benefit versus estimated subcategory-wide cost for each
of the treatment levels will also be provided.
Industry-wide Costs
By multiplying the annual and investment costs of each level of
treatmesnt at various flow rates by the number of plants in each
flow regime in the industry, subcategory-wide annual and invest-
IX-93
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merit cost figures are estimated (Tables 9-29 and 9-30).
These figures represent the cost of each treatment level for
the entire electron tube subcategory. This calculation does
not make any allowance for waste treatment that is currently
in-place at electron tube facilities.
Industry-wide Cost and Benefit
Tables 9-31 and 9-32 present the estimate of total annual cost
to the electron tube subcategory to reduce pollutant discharge.
This table also presents the benefit of reduced pollutant dis-
charge for the electron tube subcategory resulting from the
application of the three levels of recommended treatment. Bene- •
fit was calculated by multiplying the estimated number of gallons
by each of the recommended treatment systems as shown in Table
9-18. ; Values are presented for each of the selected subcategory
pollutant parameters.
The column "Raw Waste" shows the total amount of pollutants that
would be discharged to the environment if no treatment were em-
ployed by any facility in the industry. The columns "Levels 1,
2, and 3" treatment show the amount of pollutants that would be
discharged if any one of these three levels of treatment were
applied to the total wastewater estimated to be 'discharged by
the electron tube subcategory.
i
The total amount of wastewater discharged from each level of treat-
ment is also presented in this table to indicate the amount of pro-
cess wastewater to be recycled by each of the three levels of treat-
ment. Process wastewater recycle is a major step toward water con-
servation and reduction in pollutant discharge.
IX-101
-------
TABLE 9-29 l
INDUSTRY-WIDE COST ANALYSIS
TELEVISION PICTURE TUBES
Investment
(Thousands Of Dollars)
Annual Costs
(Thousands Of Dollars)
Capital Costs
Depreciation
Operation &
Maintenance
Energy & Power
Total Annual Costs
(Thousands Of Dollars)
Discharge Plow
(million I/year)
LEVEL 1
9732.318
820.590
1946.463
1510.138
117.063
4394.254
2554.875
LEVEL 2
11488.674
968.679
2297.735
1717.916
126.142
5il0.472
2554.875
LEVEL 3
11649.174
982.209
2329.835
1724.336
131.632
5168.012
1021.950
IX-102
-------
Annual
TABLE 9-30
INDUSTRY-WIDE COST ANALYSIS
APERTURE MASKS
Investment
(Thousands Of Dollars)
Costs
(Thousands Of Dollars)
Capital Costs
Depreciation
Operation &
Maintenance
Energy & Power
Total Annual Costs
(Thousands Of Dollars)
Discharge Flow
(million I/year)
LEVEL 1
1989.748
1178.611
LEVEL 2
2406.905
1178.611
LEVEL 3
2622.905
167.767
397.951
295.072
15.969
876.759
202.940
481.381
338.566
18.163
1041.050
221.148
524.581
347.206
50.163
1143.098
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SECTION X
SEMICONDUCTOR SUBCATEGORY DISCUSSION
INTRODUCTION
This discussion of the semiconductor industry consists of the
following major sections:
Products
Size of the Industry
; Manufacturing Processes
Materials .
Water Usage
. Production Normalizing Parameter
Waste Characterization and Treatment in Place
Potential Pollutant Parameters
Applicable Treatment Technologies
Benefit Analysis
Data contained in this section were obtained from several
sources. Engineering visits were made to twenty plants
within the subcategory. Of these twenty plants, wastewater
samples were collected from twelve of these facilities. A
total of fifty-two semiconductor manufacturing plants were con-
tacted by telephone. A literature survey was also conducted
to ascertain differences between types of semiconductor pro-
ducts, process chemicals used, and typical manufacturing
processes.
PRODUCTS
Semiconductors are solid state electrical devices which perform
a variety of functions. These functions include information
processing and display, power handling, and the conversion be-
tween light energy and electrical energy. The semiconductors
range from the simple diode, which may be turned on or off like
a light bulb, to the integrated circuit which may have the equi-
valent of 250,000 active switching components in a 0.635 cm
(1/4 inch) square.
Semiconductors are used throughout the electronics industry.
The major semiconductor products a^e:
Silicon based integrated circuits which include
bipolar, MOS (metal oxide silicon), and analog
devices.
X-l
-------
Gallium arsenide and gallium phbsphide wafers
for the production of light emitting diodes (LED's).
F
Silicon and germanium for diode and transistor
production. |
Glass wafer devices such as for liquid crystal
display (LCD) production. '
Semiconductors are included within the Sl (Standard Industrial
Classification) codes 3674 (Semiconductors and Related Devices)
and 3679 (Electronic Components, Not Elsewhere Classified).
The major product areas of SIC code 3674 are:
Hybrid Integrated Circuits - thick film, thin film and
multichip devices.
Bipolar Integrated Circuits ;
. Metal Oxide Semiconductor Devices
. Transistors j
Diodes and Rectifiers ;
. Selenium Rectifiers ;
. Light Sensitive and Light. Emitting Devices (solar
cells and light emitting diodes)
!
. Thyristors '
i
The major product areas of SIC code 3679 are:
. Magnetic Bubble Memories j
. Liquid Crystal Displays j
SIZE OF INDUSTRY !
i
The size of the semiconductor industry is [presented in the fol-
lowing paragraphs in terms of number of plants , number of pro-
duction employees, and production rate. Size estimates are
based upon data collected from visited facilities, telephone
surveys, and literature surveys.
X-2
-------
Number of Plants - It is estimated that approximately 257 plants
are involved in the production of semiconductors. This estimate
comes from an August 1979 list-ing of plant locations compiled by
the Semiconductor Industry Association.
Number of Production Employees - It is estimated that approximately
62,000 production employees are engaged in the manufacture of
semiconductor products. This estimate is from the U.S. Depart-
ment of Commerce 1977 Census of Manufactures (Preliminary Statis-
tics) .
Typical plants surveyed or visited during this study employ be-
tween 30 and 2500 production employees. The majority of plants
employ between 150 and 500 production employees. Only nine of
the 51 plants in the data base have more than 500 production
employees.
Production Rate - The total number of semiconductor products for
the year 1978 was obtained from the Semiconductor Industry Asso-
ciation. During that year, 8.844 billion units were produced
for a total revenue of $3.123 billion.
A typical medium-sized plant employing 350 production employees
produces an estimated 299 million units per year. This figure
is based upon an average output of 142,380 units per production
employee (total units produced divided by total production em-
ployees ) .
MANUFACTURING PROCESSES
The manufacturing processes for semiconductor production are
described in the following paragraphs. Each type of semicon-
ductor and associated manufacturing operations is discussed
separately because production processes differ depending on the
basis material.
Silicon-based integrated circuits - (Reference Figure 10-1) -
These circuits require high purity polycrystalline silicon as
a basis material. Most of the companies involved in silicon-based
integrated circuit production purchase ingots (cylindrical cry-
stals which can be sliced into wafers) or purchase slices or wafers
from outside sources rather than grow their own crystals.
When the ingot is received it is sliced into round wafers approxi-
mately 0.76mm (0.030 inches) thick. These slices are then lapped
or polished by means of a mechanical grinding machine or are chemi-
cally etched to provide a smooth surface. Wastewater results
from cooling the diamond tipped saws used for slicing and from
deionlzed (DI) water rinses following chemical etching and mil-
ling operations.
X-3
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SILICON INTEGRATED CIRCUIT PRODUCTION
X-4 '
-------
The next step in the manufacturing process is the- growth of an
oxide layer on the surface of the wafer. This oxide layer
is the! area where all of the subsequent processing occurs. The
,epitaxial layer is grown on the wafer in a furnace where the
wafer is heated in a silane gas atmosphere at appr&xtrifately
1000°C for several hours. ''."". ~
The wafer is then coated with a photoresist, a photosensitive
emulsion that hardens and clings to the wafer when exposed.
to light. The wafer is next exposed to ultraviolet.light using
glass photomasks that allow the light to strike .only selected
areas. After exposure to ultraviolet light, unexpos'ed resist
is removed from the wafer, usually in a DI water rinse. The wafer
is then visually inspected under a microscope and etched in a
solution containing hydrofluoric acid (HP). The etchant produces
depressions, called holes or Windows, where the diffusion of
dopants later occurs. Dopants are impurities such as boron,
phosphorus and other specific metals. These impurities eventually
form circuits through which electrical impulses can be transmitted,
The wafer is then rinsed in an acid or solvent solution to remove
the remainder of the hardened photoresist material.
Diffusion of dopants is an evaporative process in which the
dopant to be diffused is heated in a furnace, causing the do-
pant to reach a gaseous state. The atoms of the dopant bombard
the wafer and enter the silicon through the windows at controlled
depths to form the electrical pathways within the wafer. Then
a second oxide layer is grown on the wafer, and the process is
repeated. This photolithographic-etching-diffusion-oxide process
sequence may occur as many as 20 times depending upon the appli-
cation of the semiconductor.
During the photolithographic-etching-diffusion-oxide processes,
the wafer may be cleaned many times in mild acid or alkali solu-
tions followed by DI water rinses and solvent drying with ace-
tone or isopropyl alcohol. This is necessary to maintain wafer
cleanliness.
After the.diffusion processes are completed, a layer of metal is
deposited onto the surface of the wafer to provide contact points
for final assembly. One of the following three processes are
used to deposit this metal layer:
Sputtering - a process whereby a thin layer of metal
is deposited on a solid surface in a vacuum. In this
process, ions bombard a cathode which emits the metal
atom.
X-5
-------
Evaporation - palladium, titanium,! or aluminum is
evaporated onto the surface of the! wafer to provide
a surface for contact connections.!
i
Electroplating - gold, nickel, copper, chromium, tin,
or silver is electroplated onto thle surface of the
wafer. j
i
Finally, the wafer receives a protective oxi<3e layer (passivation)
coating before being back lapped to produce ja wafer of the
desired thickness. Then the individual chips are diced from
the wafer and are assembled in lead frames fior use. Many companies
involved in semiconductor production do not dice finished wafers
in the United States. Rather, the completed wafer is packed and
sent to overseas facilities where dicing and' assembly operations
are less costly. This cost effectiveness is the result of the
amount of hand labor necessary to inspect and assemble finished
products.
Gallium arsenide and gallium phosphide waferis - (Reference Figure
10-2) These wafers are purchased from crystal growers and upon
receipt are placed in a furnace where a silicon nitride layer
is grown on the wafer. The wafer then receives a thin layer of
photoresist, is exposed through a photomask,! and is developed
with a xylene-based developer. Following this, the wafer is
etched using hydrofluoric acid or a plasma-gaseous-etch process,
rinsed in DI water, and then stripped of resist. The wafer is
again rinsed in DI water before a dopant is diffused into the
surface of the wafer. A metal oxide covering is applied next,
and then a photoresist is applied. The wafer is then masked,
etched in a solution of aurostrip (a cyanide-containing chemical
commonly used in gold stripping), and rinsed;in DI water. The
desired thickness is produced by backlapping!and a layer of metal,
usually gold, is sputtered onto the back of the wafer to provide
electrical contacts. Testing and assembly complete the production
process. j
Silicon and germanium chips - (Reference Figure 10-3) 'These chips
are used in transistors and diodes. They are usually small chips
of the pure crystal placed between two or three contacts., These
devices, called discrete devices, are manufactured on a large
scale, and their use is mainly in older or less sophisticated
equipment designs, although discrete devices still play an im-
portant role in high power switching and amplification.
The crystal material is cleaned in an acid or alkali solution,
rinsed in DI water, and coated with 'a layer of photoresist. The
wafer is then exposed and etched in a hydrofluoric acid solution.
This is followed by rinsing in DI water, drying, and doping in
diffusion furnaces where boron, phosphorus, or gold are diffused
into the surface of the wafer. The wafers are then diced into
individual chips and sent to the assembly ar4a. In the assembly
area the chip is placed between contacts and;is sealed in rubber,
glass, plastic, or ceramic material. Wires are attached and the
device is inspected and prepared for shipment.
X-6
-------
GALLIUM
ARSENIDE:
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APPLY
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EXPOSURE
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FIGURE 10-2
LED PRODUCTION
X-7
-------
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SILICON, GERMANIUM DIODE PRODUCTION
X-8
-------
Liquid Crystal Display (LCD) Production - (Reference Figure
10-4)A typical LCD production line begins with optically flat
; glass that is cut into four inch squares. The squares are then
cleaned in a solution containing ammonium hydroxide, immersed
in a mild alkaline stripping solution, and rinsed, in deionized
water. The plates are spun dry and sent to the photolithography
area for further processing. , •-
In the photolithographic process a liquid mask is applied with a
roller, and the square is exposed and developed. This square
then goes through deionized water, rinses and is dried, inspected,
etched in an acid solution, and rinsed in deionized water. A
solvent drying step is followed by another alkaline stripping
;solutipn. The square then goes through DI water rinses, is spun
dry, and inspected.
The next step of the LCD production process is passivation. An
oxide jlayer is deposited on the glass by using liquid silicon
dioxide, or by using silicon and oxygen gas with phosphene gas
; as -a dopant. This layer is used to keep harmful sodium ions on
the glass away from the surface where they could alter the elec-
tronic characteristics of the device. Several production steps
may occur here if it is necessary to rework the piece. These
include immersion in an ammonium bifluoride bath to strip sili-
con oxide from a defective piece followed by deionized water
rinses and a spin dry step. The glass is then returned to the
passivation area for reprocessing.
After passivation, the glass is screen printed with devitrified
liquid glass in a matrix. Subsequent baking causes the devi-
trified glass to become vitrified, and the squares are cut into
the patterns outlined by the vitrified glass boundaries. The
saws used to cut the glass employ contact cooling water which
is filtered and discharged to the waste treatment system.
The glass is then cleaned in an alkaline solution and rinsed
in deionized water. Following inspection, a layer of silicon
oxide is evaporated onto the surface to provide alignment for
the liquid crystal.^ The two mirror-image pieces of glass are
aligned and heated in a furnace bonding the vitrified glass
and creating a space between the two pieces of glass. The glass
is placed in a vacuum chamber, air is evacuated, and the liquid
crystal (a biphenyl compound) is injected into the space between
the glass pieces. The glass is then sealed with epoxy, vapor
degreased in a solvent, shaped on a diamond wheel, inspected,
and sent to assembly.
MATERIALS
The materials required to manufacture semiconductors may be
classed as raw materials and process chemicals. Raw materials
include basis, dopant, and layer materials. Process chemicals
are used for unit operations such as etching, rinsing
and photolithography.
X-9
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LCD PRODUCTION
X-10
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. .
Basis Materials - Several different basis materials are used
depending upon the product to be manufactured.
Silicon - in its purest form, silicon acts as an
excellent insulating material, holds up under ele-
vated temperatures, and its thin oxide layers are
used in photolithographic etching steps. Approxi-
mately 90-96% of the semiconductor industry utilizes
silicon as a basis material.
Germanium - used primarily in the production of
discrete devices such as diodes. First manufactured"
in the early 1950's, it is still manufactured to -
supply and maintain existing equipment but has
been replaced by silicon in recent applications.
Gallium Arsenide and Gallium Phosphide - used in
the production of (LED's) light emitting diodes.
At one time, the LED was in great demand but
production has fallen off drastically in the last
4-5 years because of the LCD. However, production of
LED's is increasing again for applications where
high speed transmission is necessary. :
Glass - used for LCD (liquid crystal display) pro-
duction. This product type has increased in pro-
duction due to its desirability over LED's. The
LCD requires less energy than LED's and requires
little or no maintenance.
Dopants - A dopant is an impurity added to the structure of the
semiconductor to produce the electronic pathways. The following
dopants are diffused into the wafer in their gaseous or solid
form.
. Arsenic in the form of arsene gas
Phosphorus in the form of phosphene gas
Boron, gold, and antimony in their solid forms
Layer Materials - These are used to form working layers on the
wafer and to create the electrical pathways or circuitry within
the layer. Included are:
Silicon oxides and silicon nitride - used to grow
layers on the wafers. These materials are used prior
to each photolithographic process to provide
electrical layers, and also as a passivation
or protective oxide layer on the finished wafer.
X-ll
-------
. Metals - are sputtered or evaporated onto the surface
of the wafer to provide electrical contacts. These
metals include aluminum, gold, chromium, tin, palla-
dium, nickel, titanium, copper, and platinum. Also,
combinations of these metals such as titanium and
copper may be used. Some metals may be electroplated
onto the wafer's metal surface to^provide the external
contacts. These metals include gold, tin, copper,
silver, and chromium. i
Process Chemicals - The process chemicals are grouped below by
process step in which they are used. !
i
. Flammable solvents such as acetone, isopropyl .alcohol,
methanol, and propanol are used mainly to dry the
wafer after DI water rinses. •
Chlorinated solvents such as 1,1,1-trichloroethane,
trichloroethylene, and tetrachloroethylene are used
as solvent degreasers or as cleaning agents to pre-
pare the wafer for further processing.
Photoresists are photosensitive emulsions used in the
photolithographic process. They are either positive
or negative in their action on the wafer. The positive
photoresist forms a positive image of the mask and
after being exposed to ultraviolet light, may be re-
moved with a water based alkaline material, such as
potassium hydroxide, or with a solvent. The excess
resist may be removed from the wafer after etching
by using a strong solvent stripper. The negative
photoresist is developed in a xylene-based solution
after exposure to ultraviolet light. The negative
photoresist is removed from the w^fer after etching
the oxide layer with a solution of sulfuric and
nitric acid, or in a gaseous plasma step called
ashering. When the negative resist is used over
metals, however, a xylene-based resist stripper is
used. |
I
Acids such as sulfuric (H2SO.), nitric (HNO,), hydro-
fluoric (HP, NH. HP), hydfocnloric (HC1), afid combina-
tions of these such as aqua-regia (nitric and hydro-
chloric acids) and sulfuric peroxide (H2SO4 and f^O,,)
are used as cleaners in dilute forms ana as etchants
in more concentrated forms. Hydrofluoric acid is the
most frequently used acid. It is used to etch the
silicon and silicon oxide layers from the wafers.
This is the major contributor of fluoride in waste-
waters generated by semiconductor production.
X-12
-------
Other process chemicals used include mild alkaline
detergents for wafer and equipment cleaning, vinyl
coverings used to protect the surface of the wafer
during processing, wax and ceramic mountings used to
| hold the wafers during some processing steps, an
! acetic acid solution used to remove the wax mounts,
; epbxy used in the assembly processes to attach the
semiconductor to the lead frame, and several gases
such as argon and nitrogen which are used to pro-
vide inert atmospheres in the growing and diffusing
furnaces.
WATER USAGE
Contact water is used throughout the production of semiconductors.
Plant incoming water is first pretreated by deionization to pro-
vide ultrapure water for processing steps. This ultrapure water
or deionized (DI) water is used to formulate acids; to rinse
wafers after processing steps; to provide a medium for collecting
exhaust gases from diffusion furnaces, solvents, and acid baths;
and to clean equipment and materials used in semiconductor produc-
tion. Water also cools and lubricates the diamond saws and grind-
ing machines used to slice, lap, and dice wafers during processing,
From information gathered during plant visits and phone contacts,
process water usage for the entire semiconductor industry is esti-
mated to be 628 million liters (166 million gallons) per day.
(257 plants x average flow rate from Table 10-2.) All of
the thirteen larger plants visited or surveyed use between
0.67. million and 11.12 million liters (0.18 million gallons and
2.94 million gallons) of process water per day. (Reference
Table 10-2.) For these visited plants, process water recycle
and reuse ranged from no water recycle or reuse to 80 percent
process water recycle and reuse. Most of the plants involved
in semiconductor production do not recycle or reuse any process
water and the plants that do recycle or reuse process water
are generally only the larger plants.
Based upon observations from visited facilities, it is estimated
that 100% of all process water used (approximately 628 million
liters) is treated prior to discharge. Treatment techniques
very considerably throughout the industry and consist mainly of
pH adjustment only. Treatment techniques presently in place at
semiconductor facilities are listed in Table 10-1.
X-13
-------
TABLE 10-1 i
WASTKWATER TREATMENT TECHNIQUES
IN PLACE IN SEMICONDUCTOR MANUFACTURING FACILITIES
OPERATION
Slicing, Dicing, Lapping
Diffusion
Acid Etch, Acid Clean, DI
Regeneration (Concentrated
Acids and DI W&ter Rinses)
Photoresist Application,
Solvent Cleaning,
Photoresist Strippers,
Developers
Hydrofluoric Acid Etching
Buffered HF (NH4HF)
Etching
TREATMENT SYSTEMS OBSERVED
Discharg<2 through clarifier;
sludge dewatered and contrac-
tor removed
Wet air scrubbers to collect
gases, volatile organics, acid
fumes. Discharge to on-site
treatment facility.
Discharge to pH adjustment tank
(pH adjust with sodium hydroxide
or lime)!
I
Collected in barrels or tank
for contractor removal and
disposal;
Collected and sold for reclaim
(some solvents)
I
Treat with lime (Ca(OH)?) and
discharge to sludge dewatering
for solids removal
Fluoride, treatment and ammonia
treatment by mixing with cyanides
from electroplating then to
clarifier for solids removal
X-14
-------
PRODUCTION NORMALIZING PARAMETERS
Production normalizing parameters are used to relate the pollu-
tant mass discharge to the production level of a plant. Regu-
lations expressed in terms of this production normalizing parameter
are multiplied by the value of this parameter at each plant to
determine the allowable pollutant mass that can be discharged.
However,, the following problems arise in defining meaningful
production normalizing parameters for semiconductors:
Size, complexity and other product attributes affect
the amount of pollution generated during manufacture
of a unit.
. Differences in manufacturing processes for the same
; product result in differing amounts of pollution.
Lack of applicable production records may impede
determination of production rates in terms of de-
sired normalizing parameters.
Several broad strategies have been developed to analyze ap-
plicable production normalizing parameters. They are as
follows:
The process approach - In this approach, the pro-
duction normalizing parameter is a direct measure of
the production rate for each wastewater producing
manufacturing operation. These parameters may be
expressed as sq m processed per hour, kg of pro-
duct processed per hour, etc. This approach requires
knowledge of all the wet processes used by a plant
because the allowable pollutant discharge rates for
each process are added to determine the allowable
pollutant discharge rate for the plant. Regulations
based on the production normalizing parameter are
multiplied by the value of the parameter for each
I process to determine allowable discharge rates from
; each wastewater producing process.
Concentration limit/flow guidance - This strategy
limits effluent' concentration. It can be applied
to an entire plant or to individual processes. To
avoid compliance by dilution, concentration limits
; ; are accompanied by effluent flow guidelines.
.:,.. The flow guidelines, in turn, are expressed in
•', terms of the production normalizing parameter to
; relate flow discharge to the production rate at
the plant.
X-15
-------
The selected production normalizing parameter for the semi-
conductor industry is the total volume of ultrapure water pro-
duced by a facility. As the production rate varies, the use
of ultrapure water will also vary. Consequently, the production
of ultrapure water can be directly related to the plant pro-
duction rate. The amount of ultrapure water produced is also a
more readily available figure than the number or mass of product
exposed to water producing operations. Using the production
normalizing parameter, a regulation can be determined expressed
in concentration (mg/1) of a specific pollutant and million
liters of ultrapure water produced per day at a given facility.
WASTE CHARACTERIZATION AND TREATMENT IN PLACE
This section presents both the sources of waste in the semi-
conductor subcategory and process' wastewaterj sample data.
The in place waste treatment systems are also discussed,
and effluent sample data from these systems for the twelve
semiconductor plants sampled are presented, i
Process Descriptions and Water Use ;
The "front end" operations, those processes iwhich produce the cir-
cuitry within the wafer, may be classified by the six wet processes
used in the manufacture of semiconductors, namely:
i
. Wafer cleaning and subsequent water rinsing
. Photoresist developing and subsequent water rinsing
Silicon oxide etching and metal etching and subsequent
water rinsing
i
Epitaxial diffusion furnace and fume hood wet air scrub-
bing ',
. Photoresist stripping and subsequent waiter rinsing
. Wafer lapping and dicing I
These wet processes are used in varying degrees by individual
plants depending primarily upon the product being manufactured.
The discrete semiconductor (such as a diode)i requires only one
layer of diffused material, whereas the integrated circuit re-
quires an average of 12 diffused layers. Therefore, process
water use varies among plants relative to th'e product, tn*e pro-
duction rate, and other factors. Process water use a!|gSO"varies
depending upon the flow rate from the deionized (DI) water rin-
ses used. These rinses have a flow range of' 0.87 to 17.4 liters/
minute with an average continuous flow rate !of 7 liters/minute
at the sampled plants. Table 10-2 delineates available wet pro-
cess data. Also included are size information, product type,
and plant effluent flow rates. j
X-16
-------
TABLE 10-2
SEMICONDUCTOR AVAILABLE RAW WASTE DATA & EFFLUENT FLOW RATE
Plant ID No.
Size
Product"
02040
02347
04152
04213
04249 ;
04290
04291
04292
04294
04296
06143
19100
19101
30167
35035 ',
36133
36135
36136
41061
42044
Large
Medium
Medium
Medium
Medium
Large
Small
Small
Small
Medium
Medium
Small
Medium
Large
Medium
Medium
Large
Medium
Large
Medium
Silc
Silc
Silc
LED
Silc
Silc, LED
LED
YIG, LED
Silc
Silc
Silc
Silc, Ger Diodes
Silc
Silc
Silc, LCD
Silc
Silc, LED
Silc
Silc
Silc, LCD
Raw Waste Data
S
S
NA
NA
NA
NA
NA
NA
S
S
S
NA
NA
S
S
S
S
S
S
S
Averaqe Flow Rate -
Effluent Flow I/day
11,124,000
3,136,512
151,400
1,090,080
NA
2,509,200
4,704
130,680
150,552
1,254,600
1,080,000
190,800
669,120
4,530,528
169,584
6,720,000
3,120,000
1,392,000
10,560,000
894,960
2,443,936
Note 1:
NA - not available
S - sampled
Note 2:
Silc - Silicon Integrated Circuit
LED - Light Emitting Diode
YIG - Yttrium Iron Garnet crystals
Gar Dio3es - Germanium Diodes
LCD - Liquid Crystal Display
X-17
-------
Wafer Cleaning - This process is associated with all types of
semiconductor manufacture. The semiconductor material is fre-
quently cleaned in mild acid or alkaline solutions to minimize
the introduction of contaminants into the wafer or into the che-
mical baths. Typical cleaning solutions include mildly alkaline
detergent solutions and dilute nitric, sulfuric, and hydro-
fluoric acids. A typical discharge from the cleaning operation
at the visited plants includes a four to seven liter batch dis-
charge of concentrate and approximately seven liters per minute
of deionized (DI) rinsewater. This cleaning process may be
utilized either prior to every process step or infrequently,
depending upon the requirement of the operation and the elapsed
time between process steps.
Photoresist Developing - This process folloWs the application of
photosensitive emulsion on the wafer and exposure of the photo-
resist material through a glass mask. The yrafer is then immersed
in a developing solution which removes unex^osed resist from the
wafer. The exposed resist is quite hard and insoluble in the
developing solution. The positive type phojtoresist uses a water-
based developer, whereas the negative type photoresist requires
a xylene-based developer. After the xylener-based developer is
spent, it is collected and contractor removed. The water-based
developer is discharged to the waste treatment system along
with the subsequent DI water rinse. Typically, the DI water
rinse discharged at approximately seven liters per minute at
the visited plants. i
Silicon Oxide and Metal Etching - After the! wafer is masked with
photoresist, it is etched in an acid solution either to create
windows for diffusion (silicon oxide etching) or to create ex-
ternal contacts for electrical connections !(metal etching).
Hydrofluoric acid is used throughout the semiconductor industry as
a silicon oxide etchant and is discharged tb the on-site waste
treatment system when spent. The metal etchants include a gold
stripper; phosphoric acid to dissolve alumihum; a solution of
nitric and hydrochloric acids to dissolve platinum; and several
other less frequently used acids. All of the spent etchants are
discharged to the waste treatment system as> are the associated
DI water rinses. |
Epitaxial Diffusion Furnace and Fume Hood Wgt Air Scrubbers -
After the windows have been etched into thej wafer, the wafer is
placed in a furnace where dopants are deposited into the windows.
The furnaces are vented to wet air scrubberp to remove pollutants
from the air prior to discharge. These scrjubbers are used in all
of the twenty plants which were visited during this study. The
water from the wet air scrubbers recirculates but has an average
bleed-off rate of 35 liters per minute discharging to the waste
treatment facility. This bleed-off is necessary because the
water in the scrubber becomes very acidic and laden with .pollu-
tants, i
X-18
-------
Eighteen of the visited plants vented their fume hoods to the
wet air scrubber system also. In the other two plants, fumes
from acids and solvents were discharged with large amounts of
air to the atmosphere. These two plants conduct regular analysis
to meet clean air requirements.
Photoresist Stripping - After the dopant has been added to the
wafer, the protective photoresist material must be removed. The
hardened photoresist is stripped from the wafer with a phenolic
and xylene-based stripper on metal surfaces. An acid or alkaline
strippier is used on an oxide layer. The spent phenolic and xylene
stripper is collected and stored for contractor removal, while
the spent acidic or alkaline stripper (potassium hydroxide, sul-
furic-peroxide, sulfuric-nitric acid) is discharged to the waste
treatment system with the accompanying DI water rinses. The
DI water rinse flow averaged seven liters per minute in these
processes at the visited plants.
Wafer Lapping and Dicing - After the wafer has completed the photo-
lithographic cycle, it must be machined to the proper thickness,
and the individual chips or dice must be removed. The water used
for cooling and lubrication in the process of grinding or lapping
the wafer produces wastewater. This water forms a slurry with the
ground material (kerf) and is discharged to the treatment facili-
ty' \
The wafer is diced in a computer-controlled saw. After cutting,
the dice are removed and prepared for assembly. In some facili-
ties the dice are separated from the wafer by selectively etching
the perimeter of each die. This process involves the application
of a photoresist, exposure through a mask, developing, etching,
and resist stripping. Dicing a wafer by using the photolithogra-
phic process is not an industry-wide procedure but will become
more frequently used in the future because it will allow more de-
tailed etching than the cutting process.
Many of the semiconductor facilities contacted do not lap or dice
wafers in the United States. The wafers are shipped to assembly
plants outside the U.S. where the wafers are lapped, diced, and
assembled. Thus, sample analysis data are not available for finish
lapping and dicing operations at any of the facilities visited
during this study.
Wastewater Analysis Data
Table 10-3 is a list of the 129 toxic pollutants and 23 other
pollutants for which sample analyses in the semiconductor
subcategory were conducted. Of the 129 toxic pollutants 31
were found in measurable quantities or were found at trace
levels. All other toxic pollutants were not detected in the
sampled streams.
X-19
-------
TftBLE 10-3
POLLUTANT PARAMETERS ANALYZED
TOXIC POLLUEftNT
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
Acenaphthene
Acrolein
Acrylonitrile
Benzene
Benzidine
Carbon Tetrachloride(Tetrachlorcmethane)
Chlorobenzene
1,2,4-Trichlorobenzene
Hexachlorbenzene
1,2-Dichlorethane
Hexachlocoethane
1,1-Dichloroethane
1,1,2-Trichlroethane
Iflf2f2-Tetrachloroethane
Chloroethane
Bis(Chloronethyl)Ether
Bis(2-Chlow>2thyl)Ether
2-CW.oroethyl Vinyl Ether(Mixed)
2-Chloronaphthalene
2,4,6-Trichlorophenol
Parachloroneta Cresol
Chlorofonn(Trichloraiethane)
2-Chlorophenol
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'HDichlorobenzidine
1,1-Dichldroethylene
1,2-Trans-Dichloroethylene
2.4-Dichlorcphenol
1,2-Dichlorcprcpane
lf2-DichlorcECCpylene(l,3-DichloroEiropene)
2,4-Diroeti^lphenol
2,4~Dinitrotoluene
2,6-Dinitrotoluene
1,2-Diphenylhydrazine
Ethylbenzene
Pluoranthene
4-CM.ocophenylPhynyl Ether
4-^roraophenylPhenyl Ether
Bis (2-CWLoroisopropyl) Ether
Bis(2-Chlciroethoxy)Methane
Methylene Chloride(Dichloranethane)
^5ethyl Chloride (Chlcaxraethane)
46. Methylbromide (Bromonethane)
47. Bromoform (Tribromanethane)
48. Dichlorobromomethane
49. Trichlorofluoromethane
50. Dichlorodifluoromethane
51. Chlorodibromonethane
52. Hexachlorobutadiene
53. Hexachlorocyclopentadiene
54. Isophorone
55. Naphthalene ;
56. Nitrobenzene j
57. 2-Nitrophenol
58. 4-Nitrophenol
59. 2,4-Dinitrophenol
60. 4,6-Dinitro-o-cresol
61. N-Nitrosodimethylamine
62. N-Nitrosodiptienylamine
63. N-^Iitrosodi-N-Propylamine
64. Pentachlorophenol
65. Phenol I
66. Bis(2-Ethylhexyl)Phthalate
67. Butyl Benzyl Phthalate
68. Di-NHButyl Phthalate
69. Di-N-Octyl Phthalate
70. Diethyl Phthalate
71. Dimethyl Phthalate
72. 1,2-Benzanthracene(Benzo(A) Anthracene)
73. Benzo(A)Pyrerje (3,4-Benzo-Pyrene)
74. 3,4-^enzofluoranthene(Benzo (B)Fluoranthene)
75. ll,12-Benzofiuoranthene(Benzo(K)Fluoranthene)
76. Chrysene '
77. Acenaphthylene
78. Anthracene !
79. l,12H3enzoperylene(Benzo(GHI)-Perylene)
80. Fluorene ]
81. Phenanthrene:
82. l,2,5,6-Dibenzathracene(Dibenzo(A,H)Anthracene)
83. Indeno(1,2,3-^DC)Pyrene(2,3-o-PhenylenePyrene)
84. Pyrene !
85. Tetrachloroethylene
86. Toluene l
87. Trichloroethylene
88. Vinyl Chloride (Chloroethylene)
89.- Aldrin |
90. Dieldrin ;
X-20
-------
TABLE 10-3 Con't
91. Chlordane(TechnicalMixtureandMetabDlites) 112.
92. 4,4'-DDT 113.
93. 4,4'-DDB(P,P'-DDX) 114.
94. 4,4I-DDD(P,PI-TDE) 115.
95. Alpha-Endosulfan 117.
96. Beta-Endosulfan 118.
97. Endosulfan Sulfate 119.
98. Endrin , 120.
99. Endrin Aldehyde 121.
100. Heptachlor 122.
101. HeiptachlorEpoxide(BHC-Hexachlorocyclo- 123.
hexane)
102. Alpha-«HC 124.
103. Beita-BHC 125.
104. Gamna-BHC(LIndane) 126.
105. Deilta-BHC(PCB-Polychlorinated Biphenyls) 127.
106. PCB-1242(Arochlor 1242) 128.
107. PCB-1254(Arochlor 1254) 129.
108. PCB-1221(Arochlor 1221)
109. PCB-1332(Arochlor 1232)
110. PCB-1248(Arochlor 1248)
111. KB-1260(Arochlor 1260)
PCB-1016(Arochlor 1016)
Toxaphene
Antimony
Arsenic
Beryllium
Cadmium
Chronium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
2,3,7,8-^etrachlorcdibenzo-P-Dioxin(TCI»)
POSER KILLUEANTS
Calcium Platinum
Magnesium Palladium
Aluminum Gold
Manganesse Tellurium
Vanadium
Boron
Barium
Molybdenum
Tin
Yttrium
Cobalt
Iron
Titanium
Oil & Grease
Total Oiganic Carbon
BiochemJLcal Oxygen Demand
Total Suspended solids
Phenols
Fluoride
Xylenes
Alkyl E{X>xides
X-21
-------
Detailed laboratory analysis data for the twelve sampled plants
are presented by plant ID number in Tables 10-r4 through 10-15.
The tables are in plant ID numerical order. •
The following conventions were used in quantifying the levels de-
termined by analysis:
Trace Levels - Pollutants detected at levels too low to
be quantitatively measured are reported as the value
preceded by a "less than" (<) sign. All other pollutants
are reported as the measured value. i
1
|
Mass_Load - Total daily discharge in kilo;grams/day of a
particular pollutant is termed the mass ioad. This figure
is computed by multiplying the measured concentration (mg/1)
by the water discharge rate expressed in jliters per day.
Sample Blanks - Blank samples of organic-;free distilled
water were placed adjacent to sampling po;ints to detect
airborne contamination of water samples. ! These sample
blank data are not subtracted from the analysis results,
but, rather, are shown as a (B) next to the pollutant
found in both the sample and the blank. |rhe tables show
data for total toxic organics, toxic and non-toxic metals,
and other pollutants. I
Blank Entries - Some entries were left bljank for one of
the following reasons: the parameter was, not detected;
kg/day is not given when the concentration is lower than
the minimum detectable limit or not quantifiable; kg/day
is not given and not' included in totals for parameters
typically found in incoming water (calcium, magnesium,
and sodium); kg/day is not applicable to pH.
Analyses of the sampled semiconductor raw waste streams show
high concentrations of some metals such as chrbmium, copper, and
nickel. In addition, in one stream the arsenic concentration
was measured at 6.25 mg/1, whereas in the other eight streams
arsenic was found at very low or trace levels. The source of arsenic
in this case is arsene gas used as a dopant in!diffusion fur-
naces. ^In semiconductor facilities where arsenic is used in
the basis material, gallium arsenide, the arsenic concentration
may be as high as 100 mg/1. In three other streams non-toxic
metals such as calcium, magnesium, and sodium make up most of
the discharge. These pollutants are contained;in the incoming
water. The highest discharge concentrations of organics are for
chloroform, phthalates, and phenolic compounds. Organics are
present in solvents and other organic process chemicals. High
levels of fluoride are present in one wet air scrubber stream
and in five of the eight raw waste streams sampled. The fluoride
results from the use of hydrofluoric acid for etching.
X-22
-------
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Summary of Raw Waste Stream Data ;
Table 10-16 summarizes pollutant concentration data for the sampled
raw waste streams for the semiconductor subcategory. Minimum,
maximum, mean, and flow weighted mean concentrations have been
determined for sampled raw waste streams. ' The minimum and
maximum values are taken from Tables 10-4 through 10-15.
The mean values were determined by calculating the average
concentration for each parameter from the raw waste streams
sampled. The flow weighted mean concentration was calculated
by dividing the total mass rates (ing/day) by the total flow
rate (liters/day) for all sampled data for] each parameter.
Pollutant parameters listed in Table 10-16 were selected based
upon their occurrence and concentration in!the sampled streams.
Those parameters either not detected or detected at trace levels
in the sampled streams were excluded from this table.
Treatment In-Place
Wastewater treatment techniques currently used in the semiconduc-
tor industry include both in-process and end-of-pipe treatment.
In-process waste treatment is designed to rhinimize wastewater flow
and to minimize pollutant generation, and end-of-pipe waste treat-
ment is designed to remove pollutants from!contaminated manufac-
turing process wastewater prior to discharge. Specific in-process
treatment and end-of-pipe treatment currently in use at semicon-
ductor facilities are discussed in the following subsections.
In-Process Treatment - In-process treatment techniques commonly
used in the semiconductor subcategory include collection and
contractor removal of spent process chemicals, rinse control, and
good housekeeping. Each of these is discussed in detail in the
following paragraphs. j
Collection and Contractor Removal Of SpentjProcess Chemical - All
of the twenty semiconductor facilities visited or sampled collect
.their spent solvents, photoresist developers and strippers. The
collection systems include piped-in systems that have been added
after building construction, systems incorporated in the produc-
tion sequence during plant construction, and manual dumping
and collection. All of the twenty visited plants separated their
spent process chemicals by segregating flammable and chlorinated
solvents for contractor removal. Three of the visited plants are
being paid for segregated spent solvents that are resold for use
by other industries. As solvent prices rise, the resale of spent
solvents will increase, but only if the solvents can be properly
segregated.
X-78
-------
TABLE 10-16
SEMICONEUCTOR
SUMMARY OF RAW WASTE DMA
Parameter;
8 l,2,!4-trichlorobenzene
11 1,1,1-trlchloroethane
23 Chloroform
25 1,2-dichlorobenzene
26 1,3-dichlorobenzene
27 1,4-dichlorobenzene
29 1,1-dichloroethylene
31 2,4~dichlorophenol
38 Ethylbenzene
44 Methylene Chloride
55 Naphthalene
57 2-nitrophenol
58 4-nitrophenol
65 Phenol
69 Di-n-octyl Phthalate
85 Tetrachloroethylene
86 Toliiene
87 Trichloroethylene
TOTAL TOXIC ORGANICS
|
114 Antimony
115 Arsenic
117 Beryllium
118 Cadmium
119 Chromium
120 Copper
121 Cyanide
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
Fheriols
Oil & Grease
Totcil Suspended Solids
Totcil Organic Carbon
Biochemical Oxygen Demand
Fluoride
Min. Cone.
rog/1
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.014
<0.01
<0.01
<0.01
0.007
Max. Cone.
mg/1
27.1
7.7
0.05
186.0
14.8
14.8
0.071
0.017
0.107
2.4
1.504
0.039
0.18
3.5
0.01
0.80
0.14
3.5
Mean Cone
mg/1
4.643
1.395
0.015
15.972
1.450
1.341
0.029
0.012
0.021
0.244
0.214
0.024
0.061
0.519
0.01
0.122
0.018
0.322
0.092
245.272
<0.001
<0.003
<0.001
<0.001
<0.001
<0.005
<0.005
<0.04
<0.001
0.005
<0.002
<0.001
<0.001
0.001
<0.002
ND
ND
ND
9
ND
0.187
0.067
<0.015
0.008
1.150
2.588
0.01
1.459
0.051
4.964
0.045
0.013
0.012
0.289
6.1
20.8
203
80
202
330
16.248
0.021
0.018
0.002
0.003
0.129
0.570
0.005
0.145
0.004
0.502
0.021
0.005
0.015
0.093
0.630
5.058
31.61
55.676
52.768
62.0
Flow Weighted
Mean Cone.
mg/1
0.410
1.478
0.025
0.795
0.277
0.249
0.015
0.015
0.010
0.438
0.031
0.044
0.024
0.324
0.01
0.578
0.054
0.282
3.358
0.021
0.021
0.003
0.003
0.159
0.861
0.006
0.098
0.009
1.044
0.011
0.006
0.018
0.074
1.294
4.424
48.52
27.22
61.86
57.18
ND - not Idetected
X-79
-------
Figure 10-5 presents total toxic organic concentration and
order of occurrence („") for raw waste streams sampled in the
semiconductor subcategory. There is a definite breakpoint in
this graph at 2.06 mg/1 of total toxic organics. Those plants
which were observed to have good solvent collection and disposal
procedures had total organic discharge concentrations of 2 mg/1
or less. Some organic solvents and chemicals will be discharged
as dragout on the rinsed wafer; however, these dragout concen-
tration of organics are minimal as evidenced by the low con-
centrations of total toxic organics discharged when effective
collection and disposal is used. Those plants that were known
to have a less effective procedure for solvent collection and
disposal had total toxic organic concentrations of 4.5 mg/1
and greater. '
Table 10-17 presents data from individual process streams and
associated effluent streams sampled at several semiconductor
facilities. The process streams were selected at random to
characterize the pollutant parameters found!in each. Concentrations
of total toxic organics in these streams range from <0.01 mg/1
to 0.105 mg/1. The effluent streams sampled at the same plants
for the same sampling period have total toxic organic concentra-
tions ranging from 1.613 mg/1 to 245.272 mg/1. If total toxic
organic concentrations in the raw waste streams were caused by
dragout on the wafer and the carrier boat, the value for total
toxic organics in the individual rinses would be expected to be
much higher. Since this is not the case, toxic organics must be
entering the waste stream from other source? including direct
solvent and organic chemicals discharge into the waste stream.
Rinse Water Control - Since process rinse water comprises most of
the volume of discharge to the end-of-pipe Waste treatment system,
control techniques reduce process wastewater flow. Rinse water
control techniques include: . j
Countercurrent Rinsing - All of the twenty visited
semiconductor facilities utilized two to four stage
countercurrent rinses following process baths. The
countercurrent rinse is an overflowing rinse that
requires much less water than a single overflowing
rinse, yet provides equivalent removal of process
chemical dragout from the wafer. ;Many plants use
an initial quench rinse r a single overflowing rinse -
after all processes to remove the imajority of con-
taminants from the wafer prior to jthe countercurrent
rinse. The quench rinse removes high pollutant
concentrations, and the following irinses provide
additional cleaning. Although the use of a single
overflowing quench rinse requires !as much water as
the subsequent rinse, the combination of the two is
effective in providing adequate wafer rinsing.
X-80
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Order Of Occurrence %
FIGURE 10-5
TOTAL ORGANICS RAW WASTE CONCENTRATION
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Conductivity Controllers - The ultrapure water re-
quired by the semiconductor industry for process
use must be in the range of twelve to eighteen
megohms of resistance. This measurement of resistance
reflects the presence of ions in the water. As the
conductance of the water increases the controller
allows ultrapure water into the rinse until the de-
sired resistivity level of the water is reached. At
this point, the water flow stops until the conductivity
controller senses another increase in the conductance.
These conductivity controllers minimize the amount
of make-up water added and provide high purity water
for semiconductor wafer rinsing and were used at
every visited plant.
Flow Restrictors - Flow restrictors are mechanical de-
vices used in the incoming water line to deliver a con-
stant supply of rinse water regardless of pressure
drops. For example, a rinse that requires one liter of
water per minute will be regulated at that rate with
the flow restrictor. Flow restrictors were used
at two visited plants.
Rinse Water Recycle - Three of the plants sampled
return process rinse water to the ultrapure water pro-
duction area for reuse. As much as 50-80% of the total
process water used is reused in these plants. (Plant
06143 recycles approximately 47% (43,214 liters/hr),
plant 35035 recycles approximately 59% (6,865 liters/
hr), and plant 42044 recycles up to 85% (34,505 liters/
hr)). Plants 06143 and 35035 are using a process
wastewater reuse system that discharges only the quench
rinse to the waste treatment system and returns all of
the rinse water for reuse. Plant 42044 reuses the quench
rinse as well.. The pollutant parameters present in the
1 reused process wastewater are removed in the deionized
water production area. When the components of deionized
.; water production are backwashed and regenerated, the
pollutants from reused rinse water and from supply water
are sent to the waste treatment area for treatment
I prior to discharge. This reuse conserves water, con-
' centrates the pollutants, and decreases wastewater
discharge. All of these factors contribute to the
cost effectiveness of the end-of-pipe treatment process.
,1 • '
Good Housekeeping - Based upon observations made at visited faci-
lities where good housekeeping procedures were evident, good
housekeeping and maintenance reduces wastewater discharge to the
treatment system. Pumps, filters, and water pipes are periodically
X-83
-------
inspected to insure proper operation. Solvents, organic strippers,
and developers are disposed of properly to prevent discharge to the
waste treatment system. Disposal procedures have been developed
and closely supervised to insure employee adherence. Chemical
storage areas are kept clean, uncluttered, and well lit to con-
trol accidental spills and leaks. Good housekeeping practices
for chemical storage include collection and treatment for solvent
and acid spills. Good housekeeping procedures and solvent dis-
posal procedures were observed at visited facilities.
I
End-of-Pipe Treatment - All twenty of the visited plants adjust
the pH of process wastewater prior to discharge. Of the twenty
plants, six discharge the treated effluent to the surface and
fourteen discharge to municipal treatment facilities. Table 10-18
summarizes treatment in-place and discharge destination of the
twenty plants visited during this study. ;
All of the twelve sampled plants utilize a pH adjust system to
treat process wastewater prior to discharge. Lime is used most
frequently, and ammonia and sodium hydroxide are also used. This
pH adjustment is necessary since process wastewater from semi-
conductor manufacturing typically has a pH of 2-3. The follow-
ing plants perform only pH adjustment of the wastewater prior to
discharge: 02040, 02347, 04294, 04296, 061^3, 35035, 41061, 42044.
Analysis results from effluent streams sampjLed at these plants are
presented in Tables 10-4 through 10-15. |
Pour of the plants sampled use chemical precipitation and sedimen-
tation in a clarifier with flocculant addition to assist in set-
tling suspended solids. The four plants are 30167, 36133, 36135,
36136. Analysis data from these plants are:also presented in
Tables 10-4 through 10-15. !
Plants 30167 and 36133 also utilize a fluoride treatment system
to treat high concentrations of fluoride from hydrofluoric acid
etching. The fluoride wastes are adjusted with lime to a pH
of 11 causing free fluoride ions to bond with calcium and settle
out of solution. Sulfuric acid is then used to readjust the
pH to 7.5, and polyelectrolytic flocculant |s used to settle the
solids more rapidly. The decanted water is!discharged to the
waste treatment system for further treatment prior to discharge,
and the sludge is dewatered in a vacuum filtration unit and col-
lected for contractor removal. In Plant 36133 further treatment
of the decant is required, because ammonia from the buffered
hydrofluoric acid etchant is released after fluoride treat-
ment. This facility is pumping the treated fluoride decant
stream to its cyanide treatment tank for ammonia and cyanide des-
truction before further treatment. Cyanides in this facility
are from electroplating operations and are therefore covered
under the Metal Finishing Category. Effluent data of samples
collected from the fluoride raw waste and effluent streams from
plants 30167 and 36133 are listed in Table 10-19.
X-84
-------
TABLE 10-18
SEMICONOJCTOR SUBCATEQORY
SUMMARY OP WASTEWATER TREATMENT AT VISITED FACILITIES
DISCHARGE DESTINATION
PLANT I
02040
02347
04152
04213
04249
04290
04291
04292
04294
04296
06143
19100
19101
30167
35035
36133
36135
36136
41061
42044
D - Di]
I - In<
D NO. TREATMENT IN-PLACE
pH adjust
pH adjust
pH adjust
pH adjust, settling
pH adjust
pH adjust
pH adjust
pH adjust
pH adjust
pH adjust
pH adjust, recycle (47%)
pH adjust
Chemical precipitation,
recycle (66-75%)
Chemical precipitation,
fluoride treatment
pH adjust, recycle (59%)
Chemical precipitation,
fluoride treatment
Chemical precipitation
Chemical precipitation
pH adjust
pH adjust, recycle
(up to 85%)
:ectly to surface water
airectly to surface waters through municipal
X-85
(D-DIRECT; I-INDIRECT)
I
I
I
I
I
I
I
I
I
I
D
I
I
D
D
D
D
D
I
I
treatment
-------
TABLE 10-19 I
[
I
ACTUAL PERFORMANCE OF FLUORIDE TREATMENT SYSTEMS
Plant 36133 MaanJ
Cone, (mg/1)
Plant 30167^
Cone, (mg/1)
In
1049*
Parameter
Plow (1/hr)
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Total Suspended Solids 4150
Fluoride 38750
Out
1049*
In
22583
0.087
<0.003
217.16
2.41
00.075
0.0025
0.145
0.007
0.02
<0.03
0.11
0.042
<0.003
0.39
0.11
0.065
0.007
0.2
<0.005
0.018
<0.03
0.218
<0.01
0.004
22.8
2.2
5.35
<0.001
0.69
<0.005
0.024
0.005
<0.01
747.3
24.3
5.6
760.0
Out
22583
<0.01
<0.001
0.055
0.145
OiOOS
<0.001
0:06,5
0.005
X0.01
0.012
<0.01
7l.O
37.0
* This is total flow in liters/hour for 3 streams sampled.
i
"These values are means because these streams were sampled over
3 different sampling periods. (See Table 10-11) j
"These are single stream values. (See TafcjLe 10-9) |
Note: The "in" streams are not total raw waste streams and thus
cannot be compared with values in summary of raw waste data.
X-86
-------
Plant 36135 does not have specific treatment for fluoride-contain-
ing wastewater. This facility collects all of the spent hydro-
fluoric acid solutions for contractor removal. The fluoride
from rinsing operations is at very low concentrations and re-
quires no further treatment other than chemical precipitation
and sedimentation in a clarifier.
The effluent analysis results in Tables 10-4 through 10-15 show
decreased concentrations of fluoride, metals, and suspended solids
when fluoride treatment, chemical precipitation, and sedimenta-
tion are used as treatment techniques. Those plants that only
adjust the pH prior to discharge show higher concentrations
of fluoride, metals and suspended solids in the effluent stream
than similar effluent streams from clarifier treatment systems.
Concentrations of toxic organics are also high (>1.0 mg/1) in
the effluent of plants 04294 and 04296, which only pH adjust. Si-
milar organics are found at lower concentrations (<0.01 mg/1) at
other sampled plants where clarification is used.
POTENTIAL POLLUTANT PARAMETERS
There are twenty-three pollutants present in the wastewater pro-
duced by the semiconductor industry that are at concentrations
that might require treatment prior to discharge. The potential
pollutants are:
8 1,2,4-trichlorobenzene
11 1,1,1-trichloroethane
23 Chloroform
25 1,2-dichlorobenzene
26 1,3-dichlorobenzene
27 1,4-dichlorobenzene
44 Methylene Chloride
55 Naphthalene
58 4-nitrophenol
65 Phenol
69 Di-n-octyl Phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
115 Arsenic
119 Chromium
120 Copper
122 Lead
124 Nickel
128 Zinc
Oil & Grease
Total Suspended Solids
Fluorides
X-87
-------
Table 10-20 lists pollutants (other than the twenty-three potential
pollutant parameters listed above) that were analyzed for in the
raw waste streams sampled for the semiconductor subcategory.
Each pollutant is listed in the appropriate grouping as being not
detected, detected at trace levels, or detected at levels too low
to be effectively treated prior to discharge.
APPLICABLE TREATMENT TECHNOLOGIES i
Based on the potential pollutant parameters presented above and
treatment in-place in the semiconductor industry, the following
technologies are applicable for treatment of wastewaters from
this subcategory: \
Chemical precipitation and sedimentation in a dlarifier
Fluoride treatment !
Arsenic treatment •
Solvent collection j
Chemical precipitation and sedimentation in a clarifier is discussed
in detail in Section XII of this report. Fluoride and arsenic
treatment and solvent collection have been Discussed previously
in this section. i
i
Recommended Treatment Systems '<
Three levels of wastewater treatment are recommended for the semi-
conductor industry, each providing increased control of pollutant
discharge. The following paragraphs describe each of the three
levels of treatment.
Level 1 Treatment (Reference Figure 10-6) -, Level 1 treatment consits
of the following:
i
Solvent collection and contractor' removal
. Wet air scrubber water recycle, concentrated
wastes bleed-off to waste treatment
Fluoride treatment for concentrated fluoride
streams \
Arsenic treatment (if applicable);
Dilute acid waste treated by chemical precipita-
tion with lime, coagulant addition, sedimentation
in a clarifer •
Sludge dewatering I
I
Level 2 Treatment (Reference Figure 10-7) -; Level 2 treatment con-
sists of all of the components of Level 1 treatment including the
following additions or revisions: i
X-88
-------
TABLE 10-20
ANALYZED POLLUTANT PARAMETERS
NOT DETECTED IN RAW WASTE STREAMS
1. Acenaphthene
2. Acrolein
3. Acrylonitrile
5. Benzidine •[.
6. Carbon Tetrachloride(Tetrachloromethane)
9. Hexachlorbenzene
10. 1,2-Dichlorethane
12. Hexachloroethane
14. 1,12-Trichlroethane
15. 1,1,2,2-Tetrachloroethane
16. Chloroethanfe
17. Bis (Chloroirethyl) Ether
18. Bis(2-Chloroethyl)Ether
19. 2-Chloroethyl Vinyl Ether(Mixed)
20. 2-Chloronaphthalene
21. 2,4,6-Trichlorophenol
22. Parachloroneta Cresol
28. 3,3'-Dichlorobenzidine
30. 1,2-Trans-Dichloroethylene
32. 1,2-Dichloropropane
33. 1,2-Dichloropropylene(1,3-DichloroprOpene)
34. 2,4-Dimethylphenol
35. 2,4-Dinitrcitoluene
36. 2,6-Dinitrotoluene
40. 4-ChlorophenylPhynyl Ether
41. 4-BromophenylPhenyl Ether
42. Bis(2-Chloroisopropyl)Ether
43. Bis(2-Chlroethoxy)Methane
45. Methyl Chloride(Chloroinethane)
46. Methylbromi.de (Brononethane)
47. Bromoform (Tribrornomethane)
48. Dichlorobromomethane
49. Trichlorofluoromethane
50. Dichlorodifluoromethane
52. Hexachlorobutadiene
53. Hexachlorooyclopentadiene
54. Isophorone
56. Nitrobenzene
59. 2,4-Dinitrophenol
60. 4,6-Dinitro-o-cresol
61. N-Nitrosod:Lmethylamine
62. N-Nitrosodlphenylamine
63. N-Nitrosod:L-N-Propylamine
64.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
88.
89
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
106.
107.
108.
109.
110.
111.
112.
113.
129.
Pentachlorophenol
Dimethyl Phthalate
1,2-Benzanthracene(Benzo(A)Anthracene)
Benzo(A)Pyrene (3,4-Benzo-Pyrene)
3,4-Benzofluoranthene(Benzo(B)Fluoranthene)
11,12-Benzofluoranthene(Benzo(K)Fluoranthene)
Chrysene
Acenaphthylene
Anthracene
1,12-Benzoperylene (Benzo ((MI) -Perylene)
Fluorene
Phenanthrene
1,2,5,6-Dibenzathracene(Dibenzo(A,H)Anthracen
Indeno(1,2,3-DC)Pyrene(2,3-o-PhenylenePyrene)
Pyrene
Vinyl Chloride (Chloroethylene)
Aldrin
Dieldrin
Chlordane(Technical Mixture and Metabolites)
4,4'-DDT
4,4'-DDE(PPP'-DDX)
4,4'-DDD(PfP'-TDE)
Alpha-Endosulfan
Beta-Endosulfan
Endosulfan Sulfate
Endrin
Endrin Aldehyde
Heptachlor
HeptachlorEpoxice(BHC=Hexachlorocyclohexane)
Alpha-BHC
Beta-BHC
Gamma-BHC(Lindane)
Delta-BHC(PDB-Polychlorinated Biphenyls)
PCB-1241(Arochlor 1242)
PCB-1254(Arochlor 1254)
PCB-1221(Arochlor 1221)
PCB-1332(Arochlor 1232)
PCB-1248(Arochlor 1248)
PCB-1260(Arpchlor 1260)
PCB-1016(Arochlor 1016)
Toxaphene
2,,3,7,8-Tetrachlorodebenzo-P-Dioxin(TCDD)
Xylenes
Alkyl Epoxides
X-89
-------
10-20 CON'T ;
PARAMETERS DETECTED IN RAW WASTE STREAMS AT TRACE LEVELS
4 Benzene
7 Chlorobenzene
24 2-Chlorobenzene
37 1,2-Diphenylhydrazine
38 Pluoranthene
66 Bis (2-Ethyimexyl) Phthalate
67 Butylbenzyl Phthalate
68 Di-n-butyl Phthalate
70 Diethyl Phthalate
PARAMETERS DETECTED IN RAW WASTE STREAMS AT LEVELS'TOO LOW TO REQUIRE TREATMENT*
(REFERENCE TABLE 10-16)
Parameter
29 1,1-Dichloroethylene
31 2.4-Dichlorphenol
38 Ethylbenzene
57 2-Nitrophenol
114 Antimony
117 Beryllium
118 Cadmium
123 Mercury
125 Selenium
126 Silver
127 Thallium
121 Cyanide
TOG
BOD
Mean Concentration
1 0.029
| 0.012
i 0.021
! 0.024
! 0.021
0.002
; 0.003
! 0.004
i 0.021
i 0.005
0.015
0.005
! 55.676
: 52.768
* These parameters do not require treatment because 1) the raw waste concen-
tration is less than the daily maximum figures for applicable treatment or
2) no performance data is available for treatment of this parameter.
X-90
-------
COAGULANT
ADDITION
U1ME
D1UUTE ACID
; WASTE ~~
GOIMCE NT RATED
FLUORIDE WASTE
CONCENTRATED
ARSENIC WASTE
(IF APPLICABLE)
PH ADJUST
EFFLUENT
DISCHARGE
CLARIFY
CLARIFY
RETURN TO
PH ADJUST
CONTRACTOR
REMOVAL
SLUDGE
FLAMMABLE
|SOLVENTS
CHLORINATED
' SOLVENTS
SOLVENT
COLLECTION
SOLVENT
COLLECTION
CONTRACTOR
REMOVAL
SOLVENTS
FIGURE 10-6
SEMICONDUCTOR LEVEL ! TREATMENT
X-91
-------
DILUTE ACID
WASTE
RETURN TO pi WATER
' PRODUCTION AREA, FOR REUSE
CONCENTRATED
FLUORIDE WASTE
CONCENTRATED
ARSENIC WASTES
(IF APPLICABLE)
CHLORINATED
SOLVENTS
FLAMMABLE
SOLVENTS ~
SOLVENT
COLLECTION
SLUDGE
DEW ATE R
T
CONTRACTOR
"REMOVAL'
SLUDGE
FILTRATE'
"DISCHARGE
CONTRACTOR
REMOVAL
SOLVENT
FIGURE 10-7 I
SEMICONDUCTOR LEVEL 2 TREATMENT
X-92
-------
. ! Recycle of dilute acid wastewater to DI water production
. ! Solvent collection and segregation for reclaim and
| resale
Level 3 Treatment (Reference Figure 10-8) - Level 3 treatment con-
sists of all of the components of Level 2 treatment including the
following additions and revisions:
. I Carbon adsorption column to treat wastewater from
i the sludge dewatering unit prior to discharge
Solvents are completely segregated and reclaimed for resale or
reuse by other industries.
Performance of In-Place Treatment Systems
The actual performance of Level 1 treatment systems that have
been sampled for the semiconductor subcategory is presented in
Table 10-19 (shown previously) and Table 10-21. Table 10-19
presents mean concentrations from two sampled facilities uti-
lizing a concentrated fluoride/heavy metals treatment system
as described previously. Table 10-21 shows minimum, maximum,
and flow weighted mean concentrations of pollutants from those
semiconductor facilities utilizing chemical precipitation and
sedimentation as waste treatment technologies. Data from in-
dividual effluent streams utilized in the formation of these
tables were presented in Tables 10-4 through 10-15.
Performance of Recommended Treatment Systems
Performance of the recommended treatment systems is shown in
Table 10-22. These performance figures are based upon data from
• treatment performance observed both in the E & EC industry and in
other industries. Performance from other industries can be trans-
ferred to the semiconductor industry because of the similarity of
the raw wastes. Section XII describes the treatment and the per-
formance levels achievable by each component.
I
The Total Toxic Organic concentration shown in Table 10-22 is the
mean concentration of plants having TTO less than 2.06 mg/1 in the
raw waste streams sampled for the semiconductor subcategory. All
other performance data are transferred from the Metal Finishing
Category and other industries as discussed in Section XII.
Level i treatment is a basic treatment system whose components., ex-
cluding arsenic treatment, are presently in use and have been ob-
served" at sampled facilities.
X-93
-------
DILUTE
WASTE
RETURN TO Dl WATER
PRODUCTION AREA FOR REUSE
CONCENTRATED
FLUORI DE WASTE"
CLARIFY
CONCENTRATED
ARSENIC WASTE"
CLARIFY
CONTRACTOR
REMOVAL.
SLUDGE
CARBON
ADSORPTION
"DISCHARGE
CHLORINATED
SOLVENTS"™
SOLVENT
COLECTION
FLAMMABLE
SOLVENTS
SOLVENT
COLLECTION
CONTRACTOR
REMOVAL
SOLVENTS
FIGURE tO-8
SEMICONDUCTOR LEVEL 3 TREATMENT
X-94
-------
TABLE 10-21
ACTUAL PERFORMANCE OF CHEMICAL PRECIPITATION
AMD SEDIMENTATION
Parameter Min. Cone./ Max. Cone* Mean Cone.
mg/1 / mg/1 mg/1
8 1,2,4-Trichlorobenzene <0.01 <0.01 <0.01
11 1,1,1-Trichloroethane <0.01 .013 0.005
23 Chloroform <0.01 0.02 0.013
24 2-Chlorophenol <0.01 <0.01 <0.01
25 1,2-Dichlorobenzene <0.01 <0.01 <0.01
26 1,3-Dichlorobenzene <0.01 <0.01 <0.01
27 1,4-Dichlorobenzene <0.01 <0.01 <0.01
44 Methylene Chloride <0.01 0.049 0.03
55 Naphthalene <0.01 <0.01 <0.01
58 4-Mitrophenol <0.01 <0.01 <0.01
65 Ihenol <0.01 <0.01 <0.01
69 Di-n-octyl phthalate <0.01 <0.01 <0.01
85 Tetrachloroethylene <0.01 <0.01 <0.01
86 Toluene <0.01 <0.01 <0.01
87 Trichloroethylene <0.01 <0.052 0.024
Total Toxic Organics 0..058 0.231 0.106
115 Arsenic <0.003 0.005 0.004
119 Chromium 0.019 0.059 0.04
120 Copper 0.03 0.134 0.061
122 Lead 0.082 0.102 0.077
124 Nickel 0.520 0.844 0.541
128 Zinc 0-022 0.040 0.027
Oil & Grease 2.4 17.4 6.46
Total Suspended Solids <1.0 60.0 23.8
Fluoride 5.42 17.50 16.1
X-95
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Level 2 treatment technologies have been discussed previously in
this section. All of the technologies in Level 2 treatment are
presently in use and have been observed at sampled facilities.
The Level 3 treatment system is not currently in-place in any of
the semiconductor facilities contacted in this study. This system
is designed to increase the efficiency of the Level 2 system by
decreasing the amount of Total Toxic Organics being discharged.
Other parameters will remain largely unchanged.
Table 10-23 compares performance of observed and recommended treat-
ment for: the semiconductor subcategory. This comparison supports
the transfer of performance data as evidenced by the similarity
in effluent characteristics between these streams. Only Level 1
treatment performance is compared in Table 10-23 because Level 2
performance is the same as Level 1 with only a reduction in flow
rate, and Level 3 treatment is not in place at any of the semi-
conductor facilities sampled as stated above.
Estimated Cost of Recommended Treatment Systems
The cost estimation methodology of recommended treatment system
components is discussed in Section XIII of this report. Tables
10-24 through 10-32 show estimated costs for each of the recom-
mended treatment systems discussed previously* Costs have
been estimated for level 1 treatment and for level 2 and
3 treatment for three different flow rates to present the
variation in system costs resulting from changes in system flow
rates. The three flow rates are characteristic of small, medium,
and large semiconductor facilities.
These costs do not reflect treatment already in-place in the
semiconductor subcategory that are designed to treat semiconduc-
tor wastes exclusively. Similarly, these costs may be misleading
because they do not account for mixing wastewaters from semicon-
ductor manufacturing with wastewaters from other manufacturing
processes (such as electroplating) for treatment in existing
wastewater treatment facilities.
BENEFIT ANALYSIS
This section presents an analysis of the industry-wide benefit
estimated to result from applying the three levels of treatment
previously discussed in this section to the total process waste-
water generated by the semiconductor subcategory. This analysis
estimates the total amount of pollutants that would not be dis-
charged to the environment if each of the three levels of treat-
ment were applied on a subcategory-wide basis. An analysis of
the benefit versus estimated subcategory-wide cost for each of
the treatment levels is also provided.
X-97
-------
TABLE 10-23
SEMICONDUCTOR SUBCATEGORY
COMPARISON OP OBSERVED AND RECOMMENDED TREATMENT SYSTEMS
PARAMETER
8 1,2,4-Trichlorobenzene
11 1,1,1-Trichloroethane
23 Chloroform
25 1,2-Dichlorobenzene
26 1,3-Dichlorobenzene
27 1,4-Dichlorobenzene
44 Methylene Chloride
55 Napthalene
58 4-Nitrophenol
65 Phenol
69 Di-n-octyl Phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
TOTAL TOXIC ORGANICS
115 Arsenic
119 Chromium
120 Copper
122 Lead
124 Nickel
128 Zinc
Oil & Grease
Total Suspended Solids
Fluorides
OBSERVED TREATMENT1
__ mg/1
RECOMMENDED LEVEL 1 TREATMENT2
_ _ mg/1
*
*
*
0.815**
0.004
0.040
0.061
0.077
0.541
0.027
6.46
23.8
16.1
ference Table 10-21
Tteference Table 10-22
*Included in Total Toxic Organics figures
*
*
*
*
*
*
*
*
*
*
0.815**
0.021
0.159
0.814
0.050
0.942
0.074
4.424
17.8
15.3
concentration from plants having TTO less
than 2.06 mg/1 in raw waste streams.
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Industry-wide Costs '•
I
A subcategory-wide cost was estimated by multiplying the cost of
each level of treatment at various flow rates by the number of
plants in each flow regime in the industry, (Table 10-33). This
figure represents the cost of each treatment level for the entire
semiconductor subcategory. This calculation does not make any
allowance for waste treatment that is currently in-place at semi-
conductor facilities. ;
Industry-wide Cost and Benefit ;
Table 10-34 presents the estimate of total cost to the semiconductor
subcategory and the estimated pollutant reduction for each treat-
ment level. Benefit was calculated by multiplying the estimated
number of gallons discharged by the subcategory times the per-
formance (long-term average) attainable by each of the recommended
treatment systems as shown in Table 10-22. Values are presented
for each of the selected subcategory pollutant parameters.
The column "Raw Waste" shows the total amount: of pollutant that would
be discharged to the environment if no treatment was employed by
any facility in the industry. The columns "Levels 1, 2, and 3 treat-
ment" show the amount of pollutants that would be discharged if any
one of these three levels of treatment were applied to the total
wastewater estimated to be discharged by the !semiconductor subcate-
gory. ,
The total amount of wastewater discharged from each level of treat-
ment is also presented in this table to indicate the amount of
process wastewater to be recycled by each of the three levels of
treatment. Process wastewater reuse is a major step toward water
conservation and reduction in pollutant discharge. Reuse is also
important because treatment component size is directly affected
by the flow rate through the component. As the flow rate decreases/
the size (and therefore the cost) of the component decreases. Re-
cycle is therefore desired both to reduce the cost of treatment and
to reduce the amount of pollutants discharged!. Thus, the
cost of Level 2 and Level 3 treatment is less than Level 1
treatment. ;
X-108
-------
TABLE 10-33
INDUSTRY-WIDE COST ANALYSIS
(MILLIONS OF DOLLARS)
Investment
Annual Costs
Capital Costs
Depreciation
Operation and Maintenance
Energy and Power
Total Annual Cost
LEVEL 1
201.1
17.0
40.2
105.3
3.2
165.7
LEVEL 2
71.5
6.0
14.3
62.9
2.8
86.1
LEVEL 3
167.8
14.1
33.6
168.1
3.1
218.9
X-109
-------
TABLE 10-34 ;
SEMICONDUCTOR SUBCATEGORY
COST AND BENEFIT ANALYSIS
Plow (million liters)
year**
I&rameter
8 1,2,4-Trichlorobenzene
11 1,1,1-Trichloroethane
23 Chloroform
25 1,2-Dichlorobenzene
26 1,3-Dichlorobenzene
27 1,4-Dichlorobenzene
44 Methylene Chloride
55 Napthalene
58 4-Nitrophenol
65 Ehenol
69 Di-n-octyl Phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
TOTAL TOXIC ORGANICS
115 Arsenic
119 Chromium
120 Copper
122 Lead
124 Nickel
128 Zinc
Oil & Grease
Total Suspended Solids
Fluoride
(xlO6) Dollars
** Year is based on 350 days
Raw Waste
855.4
kg/year
350.7
1264.2
21.4
680.0
236.9
213.0
374.7
26.5
20.5
277.1
8.6
494.4
46.2
241.2
2872.4
18.0
136.0
736.5
83.8
893.0
63.3
3784.3
41504.0
48911.8
Level 1
Treatment
855.4 ;
kg/year
*
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697.2 ;
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805.8 |
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19759.7 I
17022.5 ;
165.7
Level 2
Treatment
213.9
kg/year
*
*
*
*
*
*
*
*
*
*
*
*
*
*
174.3
174.1
10.7
201.5
3807.5
3272.7
86.1
Level 3
Treatment
213.9
kg/year
*
*
*
*
*
*
*
*
*
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*
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8.56
78.7
7.3
117.6
2716.5
1018.2
218.9
ince is unchanged i
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1
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X-110
-------
SECTION XI
j CAPACITOR SUBCATEGORY DISCUSSION
I
INTRODUCTION
This discussion of the capacitor subcategory consists of the
following major sections:
i Products
| Size of the Industry
; Manufacturing Processes
Materials
i. Water Usage
j Production Normalizing Parameter
i Waste Characterization and Treatment-In-Place
; Potential Pollutant Parameters
I Applicable Treatment Technologies
I Benefit Analysis
Data contained in this section were obtained from several sources
of information. Engineering visits were made to eight plants with-
in the subcategory. Wastewater samples were collected from three
of these eight facilities. A total of 33 capacitor manufacturing
plants were contacted by telephone during this survey. A litera-
ture survey was also conducted to ascertain differences among
types of capacitors, process chemicals used, and typical manu-
facturing processes.
PRODUCTiS
The capacitor industry manufactures both variable and fixed capa-
citors. Variable capacitors are typically a number of movable
metal plates using an air dielectric (insulator). Production pro-
cesses requiring water use are limited to Metal Finishing Category
manufacturing processes for variable capacitor manufacture. Because
of production process inclusion in another point source category,
variable capacitors are not discussed further in this document.
Fixed capacitors are layered structures of conductive and dielectric
surfaces. The layering of fixed capacitors is either in the form
of rigid plates or in the form of thin sheets of flexible material
which are rolled. Fixed capacitor types are distinguished from each
other by type of conducting material, dielectric material, and en-
capsulating material. Only fixed capacitors were considered during
this stvidy and henceforth, in this report, will be referred to as
"capacitors." Typical capacitor applications are as follows:
XI-1
-------
Energy Storage Elements - Capacitors are used to accumu-
late electrical energy at one rate and to discharge the
energy at a faster rate. Typical examples would be motor
starting capacitors, fluorescent lamp ballasts, and auto-
motive ignition condensers. '•
. Protective Devices - Capacitors are used in combination
with resistors to reduce radio interference caused by
arcing. Electrical components, audio equipment, and
electrical instrumentation often incorporate these types
of protective circuits.
Filtering Devices - Capacitors are used in filter cir-
cuits to distinguish among currents! of different fre-
quencies. Television components, audio equipment, and
specialized instrumentation often incorporate these
types of circuits.
i
Bypass Devices - Capacitors are used to prevent the flow
of direct current without impeding the flow of alternating
current. Bypass capacitors attenuate low frequency cur-
rents while permitting higher frequency currents to pass.
Television components, audio equipment, and specialized
instrumentation often incorporate these types of circuits.
! >
The electrical and physical characteristics that determine ulti-
mate selection of capacitor type and size are capacitance, voltage
breakthrough, current carrying capability, and stability. Capaci-
tance is a measure of the quantity of electrical charge the capacitor
will hold per unit of potential between conductors. Capacitance is
independent of the potential impressed on the unit. Voltage break-
through limits the ultimate application of any capacitor. If cur-
rent passes through a capacitor continually in one direction because
of arcing between the conducting layers, the value of capacitance
drops to zero. Current carrying capability is the maximum current
that can be continuously carried without causing permanent damage
to the device. The current carrying capability varies widely be-
tween capacitors depending upon the application. Stability refers
to a capacitor's ability to maintain a fixed value of capacitance
over a specified temperature range and for a specific length of time.
The manufacture of capacitors includes part o'f SIC 3629 and all of
SIC 3675. SIC 3629 includes oil filled capacitors, discussed
elsewhere, and other non-capacitor type electrical apparatus. SIC
3675 includes all types of fixed and variable capacitors. Fixed
capacitors covered under SIC 3675 are listed according to conducting
and/or dielectric materials as follows:
XI-2
-------
Paper Dielectric Tantalum Wet Slug
Film Dielectric Aluminum Electrolytic
Metallized Dielectric Mica Dielectric
Dual Dielectric Ceramic
Tantalum Dry Slug & Glass Encapsulated
Wire
Tantalum Foil
SIZE OF INDUSTRY
[
The size of the capacitor industry is presented in the following para-
graphs in terms of number of plants, number of production employees,
and production rate. Each of these figures represents an estimate
based upon data collected from visited facilities, telephone surveys,
and literature surveys.
Number of Plants
It is estimated that approximately 118 plants (including oil-filled
.manufacturers) are engaged in the manufacture of capacitors. Of
these, 97 plants have more than 200 total employees. These esti-
mates are based upon the Department of Commerce 1977 Census of
Manufactures (Preliminary Statistics) for SIC 3675. This estimate
is high because it includes facilities which manufacture variable
capacitors.
i
Number of Employees
It is estimated that 28,000 total employees are engaged in the manu-
facture of capacitors. Of the 28,000 total employees, 23,300 are
production workers. This estimate is based upon Department of
Commerce 1977 Census of Manufactures (Preliminary Statistics) for
SIC 3675. This estimate .is high because it includes the total
number of employees engaged in the manufacture of variable capacitors
Production Rate
The total number of capacitors produced is not available. However,
partial information from the Department of Commerce, 1977 Census of
Manufactures (Preliminary Statistics) is presented in Table 11-1.
MANUFACTURING PROCESSES
Manufacturing processes used in the production of paper dielectric,
film dielectric, metallized dielectric, dual dielectric, and tanta-
lum wire dielectric capacitors do not require process water that is
unique to the E&EC industry. All manufacturing process water used
is covered under the Metal Finishing Category by unit operation
and will not be discussed further in this document.
XI-3
-------
TABLE 11-1
ANNUAL CAPACITOR PRODUCTION
7 Digit SIC #
36750 13
36750 16
36750 23
36750 35
36750 37
36750 60
36750 62
36750 65
36750 67
36750 69
36750 73
36750 75
36750 77
36750 78
36750 80
36750 81
36750 83
36750 85
36750 86
36750 87
36750 89
Capacitor Description
Paper dielectric, metal case
Paper dielectric, non-metal case
Film dielectric, metal and non-
metal case
Metalized dielectric, metal case
Metalized dielectric, non-metal
.case
Dual dielectric, metal and non-
metal case
Tantalum electrolytic, slug and
wire, solid dry, metal case
hermetic
Tantalum electrolytic, slug and
wire, solid dry, metal case,
non-hermetic
Tantalum electrolytic, slug and
wire, solid dry, non-metal case
Foil and wet slug electrolytic
Aluminum electrolytic, tubular
case, 5/8" diameter and up
Aluminum elelctrolytic, tubular
case, subminiature 5/8" diame-
ter and less)
All others
Mica dielectric, fixed
Ceramic, fixed tubular, disc,
plate, stand-off tubular and
disc, all two terminal
Ceramic monolithic chips
Ceramic monolithic leaded-radial
Ceramic monolithic leaded-axial
Other ceramics
All other fixed
Variable air dielectric, mica,
ceramic and glass dielectric
; 1977 f
I Quantity 10
! 89.1
I 3.1
j 327.3
| 2.6
| 11.3
I 59.1
; 202.1
I 45.8
| 350.4
! 18.3
! 31.2
i 115.8
39.4
662.5
411.5
250.1
702.8
253.6
132.7
225.3
57.9
1977 f
$ Value 10
69.3
1.1
44.1
6.0
7.9
35.2
56.3
9.0
79.3
29.5
45.4
26.7
47.6
36.4
26.9
22.7
92.6
40.2
9.0
20.2
27.4
XI-4
-------
The types of capacitors included in this discussion are:
. ; Tantalum Wet and- Dry Slug
Tantalum Foil
. ; Ceramic
. > Aluminum Electrolytic
. > Glass Encapsulated
Mica Dielectric
The manufacturing processes used in producing each of these capa-
citors are described in the following paragraphs. Each type of
capacitor and associated manufacturing operations are discussed
separately.
Tantalum Wet and Dry Slug Capacitors
Tantalum slug capacitors are used in a wide variety of electronic
applications. Tantalum slug capacitors are encapsulated within a
dry epbxy molding (dry slug) or in a metal can filled with an elec-
trolyte (wet slug). Figure 11-1 depicts the construction of the
tantalum wet slug and dry slug capacitors. The anode fabrication
steps are similar for both tantalum wet slug and tantalum dry slug
capacitors. Dry tantalum slug capacitors have a second oxide layer,
and an electrode soldered directly to the second layer. The entire
dry slug capacitor is encapsulated in a dry epoxy molding. The
following processes are performed in the manufacture of tantalum
slug capacitors:
Tantalum Anode Fabrication (for dry and wet slug)
- Tantalum power is combined with an organic binder
and pressed into a pellet on a tantalum lead wire.
The pellets are heated in a vacuum furnace to
produce a sintered tantalum slug.
Formation Reactions (for dry and wet slug) - The
sintered tantalum slugs are dipped into a dilute acid
solution to. form a thin tantalum oxide film. This
reaction proceeds rapidly and the sintered tantalum
slug is then rinsed with deionized water and air dried.
Deionized rinse water is then discharged as process
wastewater.
Assembly of Tantalum Wet Slugs - Tantalum slugs used
in the wet capacitor receive no further treatment.
The sintered tantalum slug with its oxide coating is
inserted into a silvered metal can (the cathode), filled
with an electrolyte, and sealed. The unit is then elec-
trically evaluated and shipped.
XI-5
-------
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Manganese Nitrate Dip , Reforming, and Carbon Slurry (dry
slug only) - Sintered tantalum oxide coated pellets are
dipped into a viscous solution of manganese nitrate and
then placed in a heated atmosphere with steam. A mangan-
ese oxide coating develops on the tantalum oxide coat-
ing. The anode is then dipped into a dilute acid
solution to eliminate any defects in the oxide coatings
and then is rinsed with deionized water. The anodes
are then dipped into a carbon slurry and are air dried.
The deionized rinse water is discharged as process waste-
water.
Cathode Preparation (dry slug only) - Dry tantalum slug .
capacitors do not contain an electrolyte or a silvered
metal container (which is the cathode for the tantalum
wet slug capacitor). The dry tantalum slug anodes are
coated with a special silver paint which becomes the
cathode. Another tantalum lead wire is soldered to the
coating to electrically complete the capacitor. The
capacitor is then dipped into a molten epoxy or pheno-
lic compound and air dried. The capacitor is then
electrically evaluated and shipped.
Tantalum Foil Capacitors
Tantalum foil capacitors are used in a wide variety of electronic
applications where high quality and electrical stability are re-
quired. Tantalum foil capacitors are wound capacitors. The manu-
facturing processes for a typical ,
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XI-8
-------
amounts of acid, and glycol. The capacitors are then
sealed, air dried, and electrically aged (application
of a D.C. potential). The electrical aging improves
the integrity of the oxide coating and establishes the
equilibrium capacitance of the caThe finished capacitors
are electrically evaluated and shipped.
Ceramic Capacitors
Ceramic capacitors are used in a wide variety of electronic applica-
tions where thermal stability and low cost are of prime importance.
Some ceramic capacitors consist of a single layer of ceramic with two
conducting surfaces while others consist of as many as forty layers
of cera,mic and conducting surfaces.
A typical ceramic capacitor production process sequence is shown in
Figure 11-3. These capacitors are often manufactured without leads
and are directly attached to circuit substrates. Ceramic capacitor
manufacturing processes vary according to ceramic capacitor type.
They also vary from manufacturer to manufacturer, even for similar
types of capacitors. The dielectric used in ceramic capacitors is
the ceramic substrate itself. The ceramic substrate consists of
barium titanate with trace amounts of other compounds. The fol-
lowing discussion highlights typical manufacturing processes:
. i Ball Milling - Ceramic powders are purchased from
vendors or made at the facility. The powders are
\ carefully weighed and introduced into a ball mill with
i water and occasionally a solvent to control the vis-
i cosity of the resulting slurry. Water cleanup of the
; ball mill results in a wastewater discharge.
i
. ! Multiple layer ceramic capacitor manufacture - This pro-
! cess mixes the ceramic slurry with organic binders
; similar to those used in latex paint, and the slurry is
! sheet cast onto a moving, heated, paper belt. At the end
I of the'heated chamber, the ceramic substrate is separated
'! from the paper belt and rolled. Subsequent operations
i unroll the ceramic sheet and cut it into squares. These
operations do not result in a wastewater discharge.
.! Ceramic Capacitors Assembly - For single layer ceramic
capacitors, the cured substrate is silver painted on both
i sides, leads are soldered on, and then the capacitor is
dipped in molten epoxy. The epoxy is air dried, and the
I capacitor is electrically evaluated and shipped. For
! single layer ceramic capacitors, the ceramic substrate
I is fired in a furnace to harden the material.
XI-9
-------
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-------
Multiple layer ceramic capacitor assembly - Assembly begins
with an automated printing operation on the ceramic sheets.
The printing operation usually uses precious metal ink.
One facility produces its own ink by dissolving ingots of
the precious metals followed by precipitation reactions.
A wastewater discharge is associated with ink manufac-
turing in the ceramic capacitor industry.
The printed layered ceramic sheets are treated with a
vacuum and heat to eliminate air voids and to harden the
ceramic enough to be cut. As many as forty layers of
ceramic with printing on each sheet have been observed.
The sheets are then diced into individual capacitors,
and the ceramic capacitor chips are baked at a high tem-
perature to fully develop the ceramic properties. The
ceramic capacitors are then silver coated on two surfaces,
the leads are attached, and the whole capacitor is epoxy
molded. All of the assembly operations for multiple layer
ceramic capacitors are dry except for lead cleaning. At.
one visited facility, the leads were cleaned producing a
wastewater discharge from bath dumps and subsequent water
rinsing. The cleaning solution used is a mild detergent
followed by a water rinse.
Aluminum Electrolytic Capacitors
Aluminum electrolytic capacitors provide the greatest capacitance
per cubic inch (except for tantalum electrolytes) and the lowest
cost per microfarad of all capacitors. This type of capacitor is
commonly used in communications networks. A general schematic of
the manufacturing process for an aluminum electrolytic capacitor
is shown in Figure 11-4. .The overall construction of an aluminum
electrolytic capacitor is similar to a tantalum foil capacitor as
presented in Figure 11-2.
Aluminum electrolytic capacitors are polar, semi-polar or non-polar.
The polarity of an aluminum electrolytic capacitor is determined by
the location of the oxide coating on the anode and cathode. The
non-polar capacitor has equal thicknesses of oxide coating on .both the
anode and the cathode. The polar capacitor has an oxide coating on
the anode only, while the semipolar capacitor is similar to the polar
capacitor but has an additional thinner oxide coating on the cathode.
Each of these types of electrolytic capacitors has a specific use:
the polar capacitor is used in circuits where the current flows
only in one direction, the semi-polar capacitor is used in circuits
where a current may flow in either direction for a specific length
of time only, and the non-^polar capacitor is used in circuits where
a current may flow in either direction for an extended length of time.
XI-H
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XI -12
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The unique characteristics of these capacitors allows them to be used
in a variety of end uses and applications. Figure 11-5 is a schematic
of a polar, a non-polar, and a semi-polar aluminum electrolytic capa-
citor. : Basically, all aluminum electrolytic capacitors are wound
capacitors of etched and electrochemically aged aluminum foil,
interwoven with a kraft paper spacer and filled with a liquid elec-
trolyte. The following process operations are performed:
Etching And Forming Reactions - High purity aluminum
foil is etched to increase the effective surface area.
This increases the capacitance per square foot of area.
The capacitor is etched by passing current through the
foil while submerging it in strong acids, similar to
anodizing. This operation produces substantial quanti-
ties of wastewater from .bath dumps and subsequent water
; rinsing. The forming reaction is an additional electro-
chemical operation where a direct current potential is
applied between the aluminum foil roll and the steel
reaction tank, which is filled with a dilute ammonium
pentaborate solution. The. aluminum foil is slowly un-
' wound and passed through the solution and then rewound.
: This causes an aluminum oxide film of a predetermined
thickness to form on the foil.
A
Aluminum Electrolytic Capacitor Assembly - The etched
and formed aluminum foil is cut and leads are attached.
The foil is interwoven with a kraft paper spacer, wound
and inserted into a metal container. The capacitors are
then placed under heavy vacuum and are heated. The vacuum
is released and the chamber is filled with an electrolyte
which fills the capacitors. The chamber is drained,
opened, and the fill holes on the capacitors are soldered
closed. The electrolyte is water with trace amounts of
ethylene glycol, phosphoric acid and/or ammonium borate«
These operations usually do not produce any wastewater
i discharges. The capacitors are electrically aged by ap-
plication of direct current. This heals voids in the
oxide coating and brings the capacitance to an equilibrium
| value. The finished capacitors are electrically evaluated
; and shipped.
Glass Encapsulated Capacitors
Glass encapsulated capacitors with glass dielectric plates are noted
for their ability to operate at extreme temperatures, pressures, and
voltages. They are relatively expensive per unit of capacitance and
are traditionally used in high technology areas where costs are *
secondary to performance. Typical applications are precision instru-
mentation and space hardware manufacturing. Figure 11-6 represents
XI-13
-------
Anode
Anode
Anode-
Oxide Coating
POLAR
-Cathode
Oxide Coating
Cathode
NON-POLAR
Oxide Coating
L
F
•Cathode
SEMI-POLAR
FIGURE 11-5
POLAR, NON-POLAR, AND SEMI-POLAR
ELECTROLYTIC CAPACITORS
XI-14
-------
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a schematic of a glass encapsulated capacitor,
facturing operations are performed:
The following manu-
Capacitor Assembly - Ultra-thin glass ribbon is
alternately stacked with high purity aluminum foil
(unetched and unformed). Leads are attached, a
glass cover is placed into position and the unit is
annealed. These operations are dry and do not produce
a wastewater discharge. •
Terminal Cleaning, Glass Cutting & Penetrant Inspection -
the terminals of the sealed glass capacitors are dipped
in sulfuric acid and rinsed in water. The capacitor
bars are placed in a device where spinning disks are
hydraulically lowered through the glass capacitor bar
to individual capacitors. Water is sprayed over the
capacitor bar to cool the bar and flush away the glass
particles. Finally, the capacitors are penetrant in-
spected, rinsed, electrically evaluated, and shipped.
These operations produce a wastewater discharge from
contact cooling, bath dumps, and subsequent water
rinsing. ;
Mica Capacitors •
Mica capacitors are similar to glass encapsulated capacitors in func-
tion and construction. They display exceptional tolerance to extreme
temperature, pressure, and voltage. Mica capacitors are often encap-
sulated with plastic. Typical-process operations for mica capacitor
production are discussed below: I
. Dielectric Fabrication - Pure mica is subjected to high
velocity water jets which shred the mica into thin, small
flakes. The flakes are passed over a moving vacuum belt
which dries the mica flakes and interlocks them into a
fragile mica sheet. The mica sheet is treated with
silicon resins to add strength. This process has a
wastewater discharge from the water used as a medium to
carry the mica flakes to the paper making process.
i
. Conducting Surface Application - Various inks and appli-
cation techniques are used to apply k conducting surface
to the mica dielectric. Printing type ink with substan-
tial percentages of precious metals is commonly used.
The assembly of the capacitor is similar to a layered
ceramic capacitor. These operations|rarely result in a
wastewater discharge. Because of the inclusion of mica
dielectric fabrication separately and because the con-
ducting surface application does not;result in a waste-
water discharge, mica capacitors will not be discussed fur-
ther in this section.
XI-16
-------
MATERIALS
The materials used to manufacture capacitors are raw materials and
process chemicals. The raw materials are conductors, dielectrics,
electrolytes, leads, and encapsulating materials. The raw materials
become; part of the final product. The process chemicals are acids,
bases, salts and organics. The process chemicals do not enter the
product per se, but are necessary to perform certain operations.
These materials are discussed in this section.
Raw Materials
Conductors - Aluminum foil is used extensively in several types
of capacitors. Aluminum is an excellent conductor and is relative-
ly inexpensive compared to other conductive materials. Tantalum
foil and tantalum sintered metals are also used extensively
throughout the capacitor industry. This material' is relatively
expensive, but because of its durability and elec.trical stability
is extensively used in miniature and subminiature capacitor appli-
cations. The amount of tantalum used does not represent a signi-
ficant portion of the total cost of the capacitor. Numerous types
of precious metal inks are also used as conductors in layered capa-
citors. These inks are very expensive and constitute a significant
portion of miniature and subminiature capacitor costs.
Dielectrics - Capacitor dielectrics are solids, liquids; and gases.
Often combinations of these are used to take advantage of various
electrical characteristics. Ceramic capacitors use solid ceramic
substrates for the dielectric. These display exceptional dielectric
and thermal properties which increase their durability and reliability,
and they are relatively inexpensive. Kraft paper and plastic film
are used as dry dielectrics and are relatively inexpensive but are
not useful in high voltage situations. Glass and mica are excellent
dielectric materials and are relatively inexpensive but require spe?-
cial skills and equipment to handle efficiently. -Electrochemicaliy
formed oxide coatings are used extensively as dielectrics in higher
quality aluminum electrolytic, tantalum foil and tantalum slug
capacitors. These coatings provide exceptional dielectric pro-
perties at a reasonable cost. .
Electrolytes - Electrolytic capacitors usually use a liquid electro-
lyte and an oxide film as the dielectric. The kraft paper also serves
as a spacer and an absorbing medium for the electrolyte. The elec-
trolyte is usually less than a one percent solution of strong acids,
glycols, and salts dissolved in deionized water.
Leads
citor
often
- Copper and tantalum are the most common materials for capa-
leads. Capacitors that are used on printed circuit boards
do not have leads but are attached directly to the board.
XI-17
-------
Encapsulating Materials - Steel and aluminum containers, phenolic
moldings, and epoxy moldings are the most common encapsulating
materials. Wax and various other plastics are used to seal the
metal case capacitor containers. Glass encapsulation is also used.
Process Chemicals
Acids (sulfuric
hydroxide), and
cohol) are used
slug capacitors
tors. Organic
cohol are used
citors and are
WATER USAGE
, nitric acid), bases (potassium, hydroxide, sodium
organic solvents (trichloroethylene, isopropyl al-
in the formation reactions for tan'talum dry and wet
, aluminum foil capacitors, and tantalum foil capaci-
solvents such as trichloroethylene and isopropyl al-
primarily in clean-up operations, of completed capa-
not discharged. :
Prom information gathered during plant visits and telephone contacts,
process water usage for the entire capacitor industry is estimated to
be 0.95 million liters (0.25 million gallons) per day. Water usage
of the plants visited and surveyed ranges from 454 liters (120 gal-
lons) per day to 18168 liters (4800 gallons) pejr day. The wide range
of water flow rates is caused by a variety of factors including pro-
duct type/ production rate, location, facility size, and other factors
Of the approximately 0.95 million liters (0.25 million gallons) of
process wastewater discharged per day, it is estimated that between
30 and 40 percent is treated prior to being discharged. Treatment
techniques vary considerably throughout the industry and consist
mainly of pH adjustment only. Table 11-2 presents capacitor process
wastewater sources, observed in in-place treatment systems, and the
disposition of process wastewater according to capacitor type.
PRODUCTION NORMALIZING PARAMETERS
Production normalizing parameters are used to relate the pollutant
mass discharge to the production level of a plant. Regulations
expressed in terms of these production normalizing parameters are
multiplied by the value of tliis parameter at each plant to determine
the allowable pollutant mass that can be discharged. Meaningful
production normalizing parameters for capacitors that have been
considered are: |
. Size, complexity and other product attributes that
affect the.amount of pollution generated during
manufacture of a unit. \
Manufacturing processes, but differences in processes
used in the manufacture of the same product result in
differing amounts of pollution.
XI-18
-------
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Production records, but lack of applicable data may
impede determination of production rates in terms of
desired normalizing parameters. |
Several other broad strategies that have been developed to determine
normalizing parameters are as follows: j
The process approach - In this approach, the production
normalizing parameter is a direct measure of the produc-
tion rate for each wastewater producing manufacturing
operation. These parameters may be expressed as sq.m.
processed per hour, kg of product processed per hour,
etc. This approach requires knowledge of all the wet
processes used by a-plant because the allowable pollu-
tant discharge rates for each process are added to de-
termine the allowable pollutant discharge rate for the
plant. Regulations based on the production normalizing
parameters are multiplied by the value of the parameter
for each process to determine allowable discharge rates
from each wastewater producing process.
Concentration limit/flow guidance -!' This strategy limits
effluent concentration. It can be applied to an entire
plant or to individual processes. :To avoid compliance
by dilution, concentration limits are accompanied by
flow guidelines. The flow guidelines, in turn, are ex-
pressed in terms of the production [normalizing parameter
to relate flow discharge to the production rate at the
plant.
Based upon the nature of capacitor manufacturing processes, it
was determined that the principal factors affecting the waste
characteristics for the capacitor types producing wastewater
discharges are as follows: \
Capacitor Type
Tantalum Slug
Tantalum Foil
Aluminum Electrolytic
Glass Encapsulated
Ceramic
Production Normalizing Parameter
Mass of tantalum processed
Area of tantalum foil processed
Area of aluminum foil processed
Number of capacitors processed
Mass of ceramic substrates ball
milled, and mass of ink pro-
duced (where applicable)
Basing limitations of mass on specific raw material processed re-
sults in a limitation expressed as mg of a specific pollutant dis-
charged per kilogram of specific raw material used in production.
Basing limitations on the area of specific raw materials results
in a limitation expressed as mg of a specific pollutant discharged
XI-20
-------
per sq !m of specific raw material used in production. Basing li-
mitations on number of units processed results in a limitation ex-
pressed as mg of a specific pollutant discharged per number of units
processed. The limitations are listed below according to capacitor
type arid are discussed in the following subsections.
Capacitor Type
Tcintalum Slug
Taintalum Foil
Aluminum Electrolytic
Glass Encapsulated
Ceramic
Tantalum Slug Capacitors
Limitation
mg/kilogram tantalum
mg/sq m of tantalum foil
mg/sq m of aluminum foil
mg/number of capacitors
mg/kilogram
The wastewater producing processes in tantalum slug manufacture in-
clude bath dumps and subsequent water rinsing from forming, reforming
and cathode preparation. The use of these water discharging processes
is not uniform from plant to plant; however, mass discharge of selec-
ted pollutant parameters can be directly related to the weight of
tantalum powder purchased and processed. Surface area was not chosen
as a production parameter because the sintering process causes the
entire tantalum slug to become microscopically perforated and deter-
mination of real surface area is very imprecise. The weight of tan-
talum processed is easily determined from purchasing records and thus
is a very reliable and appropriate parameter on which to base limita-
tions . ;
Tantalum Foil Capacitors
The primary water discharging process from tantalum foil capacitor
manufacturing facilities is the oxide formation reaction. The mass
discharge from this reaction is directly proportional to the surface
area of the foil processed. This foil is typically handled in indi-
vidual strips and/or rolls, and area is easily obtainable from pur-
chasing records.
Aluminum Electrolytic Capacitors
i
The number of water discharging operations varies from plant to plant
because! not all processes are used an- equal number of times at each
facility. Some facilities do not use the etching step. An area
based limitation for each operation (etching and forming) would be
equitable for facilities that perform only one or both operations.
The aluminum is usually processed from a continuous roll, and the
surface area of the roll is easily obtainable.
XI-21
-------
Glass Encapsulated Capacitors
There are three water discharging operations associated with glass
encapsulated capacitors: penetrant inspection, .glass cutting, and
lead wire cleaning. The penetrant pollutant mass discharge rate is
associated with the surface area and the numberiof capacitors. The
pollutant mass discharge from the glass cutting ioperation is related
to the surface area and the number,of the cuts. , The lead cleaning
process pollutant mass discharge is truly a function of the number
of leads cleaned rather than of surface area. However, the pollutant
mass discharge can be related to total number of capacitors produced
because there is not a large difference in surface area between the
smallest and largest glass encapsulated capacitors.
Ceramic Capacitors
Ball mill washdown, ink manufacturing, and lead cleaning are the wet
process discharges for this type of capacitor. iBall mill and lead
cleaning mass throughput is an appropriate mass limitation. The
pollutant mass discharge rate is a function of the number of times
per day the mill is washed down and the area of ;the cleaned surface.
This rate can be related to the total mass throughput of the ball
mill because washdown is required after every batch. A number of
facilities manufacture precious metal inks which are used as the
conducting surfaces of the capacitor. The pollujtant mass discharge
rate is a function of the mass of precious metals precipitated.
The weight and proportion of the precious metals to the total
weight of ink manufactured is easily obtainable. Therefore, mass
of ink is a realistic parameter on which to base the mass of pre-
cious metals, and thus is an effective production normalizing
parameter. j
WASTE CHARACTERIZATION AND TREATMENT IN-PLACE :
This section will present the sources of waste in the capacitor sub-
category and sampling results of this wastewater. The in-place waste
treatment systems will also be discussed and effluent sample data
from these systems will be presented. Table 11-2 summarized ob-
served treatment facilities for various capacitor types.
Process Descriptions and Water Use ;
i
Capacitor types are grouped according to distinct wet process opera-
tions because the product type determines the wet manufacturing pro-
cesses used. Table 11-3 presents capacitor type;, wastewater dischar-
ging operations, and flow rates. Total plant discharge rate is
affected by the product type and production rate. Product varia-
tions by size and plant condition also affect total wastewater
discharge rate. The following paragraphs briefly describe the
distinct operations presented in Table 11-3 resulting in wastewater
discharge in this subcategory.
XI-22
-------
TABLE 11-3
CAPACITOR SUBCATEGORY
WASTEWATER DISCHARGING PROCESSES
Capacitor Type
Glass Encapsulated
Wastewater
Discharging Operations
Terminal Cleaning
Glass Cutting
Penetrant Inspection
Volume Flow
Rate (1/hr)
330
678
481
Ceramic
Tantalum
(dry &
wet slug)
Tantalum Foil
Ball Mill Washdown
Ink Manufacturing
(Optional)
Lead Cleaning
(Optional)
Etching
Forming
Reforming
'Other (Bar Wash)
Formation Reactions
1,130
1,797
NA
38
19
38
114
115
Aluminum Electrolytic
Etching
Formation Reactions
380
190
NA = Flow rate is unavailable
XI-23
-------
Terminal Cleaning - This process is associated with glass encap-
sulated capacitor manufacturing. Annealing at high temperatures
results in coating the copper leads with a copper oxide. To remove
the oxide, the leads are dipped into a mild acid solution and
rinsed. Ceramic capacitors also require leadicleaning. These
capacitors are washed in a mild detergent solution to remove
excess solder flux. This process is characterized by a flow of
76 to 114 liters per hour and fluctuating concentration levels at
the visited plants. '
f '
Glass Cutting - This process is uniquely associated with glass en-
capsulated capacitors. Special cutting disksiare hydraulically
lowered through a bar of uncut capacitors which have been fabrica-
ted as a group. Water sprayed over the bar and spinning disk cools
the disk and flushes away sawed glass particles (kerf). A visited
plant had a flow rate of 679 liters per hour (180 gal/hr) and high
solids content in this manufacturing process raw wastewater stream.
Penetrant Inspection - This process is not unique to the capacitor
industry. .This method of inspecting parts foi: minute cracks and
flaws is used extensively in many industries.| This process was
observed at a glass encapsulated capacitor manufacturer. The ca-
pacitor was dipped into a solution, passed under a UV light for
examination, and then washed, rinsed, and dried. The wastewater
discharge from this process results from the wash and rinse steps.
Ball Mill Washdown - Ceramic capacitor manufacturing requires re-
gular (usually daily) cleariout of the ball mill. The procedure
requires that an operator hose down the interior of the ball mill
and the surrounding area. The wastewater discharge rate is a func-
tion of the frequency that the ball mill is cleaned. The wastewater
discharge rate varies widely according to the size of the ball mill,
actual pounds of specific batches, and operator variability in
cleaning. However, this does not affect the pollutant discharge
mass associated with washdowns.
Ink Manufacturing'- This process is not unique to the capacitor in-
dustry. However, precious metal ink applicable for use in capaci-
tors warrants distinct consideration. Precious metals are dissolved
in strong acids (such as sulfuric and nitric acid) and then processed
with proprietary precipitation reactions. There are numerous decant,
filtering, and mixing steps. The 1,797 liter/hr (475 gal/hr) water
discharge rate sampled at one plant is characterized by strong acids
and bases. The discharge rate is affected by,the number of water pro-
ducing reactions and the total amount of precipitate formed. These
wastewater producing reactions will vary from;plant to plant, depen-
ding upon the exact ink produced and type of equipment used.
Etching - (tantalum dry and wet slug capacitots) - Sintered
tantalum pellets are treated with very dilute , solutions of nitric
and phosphoric acids to generate a tantalum o^ide dielectric coat-
ing. The low water discharge rate, estimated!to be 38 liters/hr
(10 gal/hr) at a visited plant, is characterized by batch dumps of
the very weak solutions of the above acids and water from subsequent
rinsing. I
Xl-24
-------
Etching - (aluminum electrolytic) - Aluminum foil is electrochemi-
cally etched in very strong acid solutions. The objective is to
roughen the metal, producing a surface with increased effective
area, iThe process flow rate is estimated to be 310 liters/hr (100
gal/hr) at a contacted facility and is characterized by batch dumps
of high concentrations of acid and dissolved metal and subse-
quent water rinsing.
Forming - (tantalum dry slug) - Etched capacitors are dipped in a
viscouis solution of manganese nitrate. The capacitors are then
placed in a heated steam atmosphere where manganese oxide forms
over the tantalum oxide film. This process was observed to have
a very low discharge rate of manganese nitrate solutions, estima-
ted at 19 liters/hr (5 gal/hr) at a visited plant.
!. " •
Reforming - (tantalum dry slug) - After forming, the capacitors are
dipped into a dilute solution of nitric and phosphoric acid. The
operation eliminates voids in the oxide surface. The discharge was
estimated to be 36 liters/hr (10 gal/hr) at a visited plant and is
characterized by batch dumps of the dilute acids and subsequent
water rinsing.
Other - (Bar Wash) (tantalum dry slug) - At one visited plant, groups
of capacitors were attached to a stainless steel bar which was used
as a holding fixture during manufacture. The bar is separated from
the capacitors during one of the final operations. The bar is then
placed in a bar wash where mangnaese nitrate/oxides are removed by
alternating a mild alkaline cleaner and rinse cycles. The discharge
rate is 114 liters/hr (30 gal/hr) at the visited plant and is charac-
terized by high solids content.
Formation Reactions - (tantalum foil) - Tantalum foil is electro-
chemically reacted to form an oxide film in various types of mildly
acidic glycol solutions. Two of the visited- plants processed tanta-
lum foil with different solutions and different equipment. The
wastes are characterized by batch dumps of acid solutions and
subsequent water rinsing.
Formation Reactions - (aluminum electrolytic) - Etched aluminum foil
is electrochemically reacted in dilute solutions of ammonium penta-
borate,. The discharge rate is estimated to be 380 liters/hr (100
gal/hr) at a visited plant and is a mildly acidic solution with vari-
able solids content and subsequent water rinsing.
Wastewater Analysis Data
Specific capacitor manufacturing operations were observed and sampled
at three facilities. Each sample taken was analyzed for all toxic
pollutants and a number of non-toxic metals and other pollutants
as listed in Table 11-4. Process raw waste, incoming water, and
treated effluent wastewater characteristics for individual plants are
presented in tables 11-5 through 11-7.
XI-25
-------
TABLE 11-4
POLLUTANT PARAMETERS ANALYZED
TOXIC ORGANICS
1. Acenaphthene 46.
2. Acrolein 47.
3. Acrylonitrile 48.
4. Benzene 49.
5. Benzidine 50.
6. Carbon Tetrachloride(Tetracliloroniethane) 51.
7. Chlorobenzene 52.
8. 1,2,4-Trichlorobenzene 53.
9. Hexachlorbenzene 54.
10. 1,2-Dichlorethane 55.
11. 1,1,1-Trichloroethene 56.
12. Hexachloroethane 57.
13. 1,1-Dichloroethane 58.
14. 1,1,2-Trichlroethane 59.
15. 1,1,2,2-Tetradiloroethane 60.
16. Qiloroethane 61.
17. Bis(Chlocomethyl)Ether 62.
18. Bis(2-Chlorc3ethyl)Ether 63.
19. 2-Chloroethyl Vinyl Ether(Mixed) 64.
20. 2-Chloronaphthalene 65.
21. 2,4,6-Trichlorophenol 66.
22. Parachloromsta Cresol 67.
23. Chloroform( Trichloronethane) 68.
24. 2-Chlorophenol 69.
25. 1,2-Dichlorobenzene 70.
26. 1,3-Dichlorobenzene 71.
27. 1,4-Dichlorobenzene 72.
28. 3,3'-Dichlorobenzidine 73.
29. 1,1-Dichloroethylene 74.
30. 1,2-Trans-Dichloroethylene 75.
31. 2.4-Dichlorophenol 76.
32. 1,2-Dichloropropane 77.
33. l,2-Dichloropropyler>e(l,3-Dichloropropene) 78.
34. 2,4-Dimathylphenol 79.
35. 2,4-Dinitro toluene 80.
36. 2,6-Dinitrotoluene 81.
37. 1,2-Diphenylhydrazine 82.
38. Ethylbenzene 83.
39. Pluoranthene 84.
40. 4-ChlorophenylPhynyl Ether 85.
41. 4-BronophenylPhenyl Ether 86.
42. Bis(2-Chloroisopropyl}Ether . 87.
43. Bis(2-CM.oroethoj!y)Methane 88.
44. Msthylene Chloride (Dichlororoethane) 89.
45. Methyl Chloride(Chloromethane) 90.
Methylbroraide (Brcsnomethane)
Bromoform (Tribrononethane)
Dichlorobrononethane
Trichloroflucaromethane
Dichlorodiflujoromethane
Chlorodibrcsmcmethane
Hexachlorc±)utadiene
Hexachlorocyclopentadiene
Isophorone
Naphthalene
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
2,4-Dinitrophenol
4,6-Dinitro-o-cresol
N-Nitrosod imethylamine
N-Nitrosodiphenylamine
N-Nitrosodi-N^-Propylamine
Pentachlorophenol
Phenol
Bis(2-Ethylhe3^1)Phthalate
Butyl Benzyl Phthalate
Di-N-Butyl Phthalate
Di-N-Octyl Phthalate
Diethyl Phthalate
Dimethyl Phthalate
1,2-Benzanthracene(Benzo(A)Anthracene)
Benzo(A) Pyrene (3,4-Benzo-Pyrene)
3,4-Benzofluoranthene(Benzo (B)Fluoranthene)
11,12-Benzofluoranthene(Benzo(K)Fluoranthene)
Chrysene :
Aoanaphthylene
Anthracene i
1,12-Benzoperylene (Benzo {on) -Perylene)
Fluorene
Phenanthrene
1,2,5,6-Dibenzathracene(Dibenzo(A,H)Anthracene)
Indeno(1,2,3-DC)Pyrene(2,3-o~PhenylenePyrene)
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Vinyl Chloride (Chloroethylene)
Aldrin
Dieldrin
XI-26
-------
TABLE 11-4 Con't
TOXIC ORGANICS CON'T
91. Chlordane(TechnicalMixtureandMetabolites)
92. 4,4'-DDT
93. 4,4'-DDE(P,P'-DDX)
94. 4,4'-DDD(P,P'-TDE)
95. Alpha-Endosulfan
96. Beta-Endosulfan
97. Endosulfan Sulfate
98. Endrin
99. Endrin Aldehyde ;
100. Heptachlor
101. HeptachlorEpoxide(BHC-Hexachlorocyclo-
hexane)
102. Alpha-BHC
103. Beta-BHC
104. Garnma-BHC(LIndane)
105. Delta-BHC(PCB-Polychlorinated
106. PCB-1242(Arochlor 1242)
107. PCB-1254(Arochlor 1254)
108. PCB-1221(Arochlor 1221)
109. PCB-1332(Arochlor 1232)
110. PCB-1248(Arochlor 1248)
111. PCB-1260(Arochlor 1260)
NON-TOXIC METALS
Calcium
Magnesium
Aluminum
Manganeses
Vanadium
Boron ;
Barium
Molybdenum
Tin
Yttrium i
Cobalt :
Iron !
Titanium j
OTHER POIjLUTANTS
Oil & Grease
Total Organic Carbon
Biological Oxygen Demand
Total Suspended Solids
Phenols
Fluoride J
Xylenes '
Alkyl Epcixides
112. PCB-1016(Arochlor 1016)
113. Toxaphene
129. 2,3,5,8-Tetrachloridibenzo-P-Diox.in (TCDD)
TOXIC METALS
114.
115.
117.
118.
119.
120.
121.
122.
123.
124.
125.
126.
127.
128.
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
• Zinc
XI-27
-------
TABLE 11-5
CERAMIC AND TANTALUM SLUG AND BOIL PROCESS WASTES
(PLRNT ID# 19116)
Stream Identification
Plow Rate Liters/Hour
Duration Hours/Day
Sarple 10 No.
TOXIC ORGANICS
04 Benzene
23 Chloroform
30 1,2 Transdichloroethylene
38 Ethylbenzene
39 Fluorantheno
44 Methylene Chloride
55 Napthalene
65 Phenol
66 Bls(2-ethylhexyl)Phthalate
68 Di-N-Butyl Phthalate
76 Chrysene
84 Pyrene
86 Toluene
87 Triehloroethylene
Total Toxic Organics
TOXIC METALS
114 Antimony
115 Arsenic
117 Beryllium
118 Cadmium
119 Chromium
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
Total Toxic Metals
NON-TOXIC METALS
Aluminum
Barium
Boron
Calcium*
Cobalt
Iron
Magnesium*
Manganese
Molybdenum
Sodium*
Tin
Titanium
Vanadium
yttrium
Total Non-Toxic Metals
Tcnperatura °c
121 Cyanide, Total
Col & Grease
Total Organic Carbon.
Biological Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
* Matals Not Included In Totals
B-Concentraction found in blank sample
mg/1
Ceraraic
kg/day
Ball Mill
Wash
1130
24
3577
< 0.010B
< 0.010B
< 0.01
< 0.010
< 0.010
<'0.010B
< 0.010B
0.000
< '0.005
< 0.003
< 0.001
, 0.007
< 0.001
0.022
0.003
< 0.001
< b.ooi
< 0.003
0.127
'< 0.025
0.035
0.194
< 0.001
0.010
0.204
10.690*
< 0.001
0.067
3.137*
. 0.005
< 0.001
2.684*
0.008
< 0.001
0.015
* o.ooi •
0.309
5.5
20
5.000
<'4.00
0.00019
0.0006
0.00008
0.0034
0.00095
0.00522
0.00027
0.0055
0.288
0.0018
0.085
0.00014
0.0728
0.00022
0.0004
0.00833
0.136
mg/1
Ceramic
1797
24
3578
< 0.010B
< 0.010
< 0.010B
< 0.01
< 0.010
< 0.010
< 0.010B
0.027B
0.027
< 0.005
< 0.003
< 0.001
• 0.006
0.061
0.389
0.213
< 0.001
0.056
< 0.003
0.034
< 0.025
0.269
1.028
0.903
3.025
0.800
11.767*
0.005
1.513
3.311*
0.031
0.004
370.64*
0.044
2.770
0.035
< 0.001
9.130
8.9
23
56.0
38.0
56.0
kg/day
Ink. Mfg.
0.0012
0.0012
0.00026
0.00263
0.01678
0.00919
0.00242
0.00147
0.0116
0.0444
0.0389
0,1305
0.0345
0.5075
0.00022
0.06525
0.1428
0.00134
0.00017
15.985
0.0019
0.1195
0.00151
0.3938
2.415
1.639
2.415
mg/1
Tantalun
295
24
3579
< 0.010
< iQ.OlOB
i
[
< O.&lOB
<" 0.01
< 0.010
< 0.010
< 0.010B
0.06B
0.06
< ;o.oos
< t0.003
<-:o.ooi
;0.005
< 0.001
;0.030,
< 0.001
.< 0.001
< 0.001
< 0.003
< 0.005
< 0.025
< 0.030
0.035
< 0.001
0.020
0.218
0.920*
< 0.001
0.038
0.263*
< '0.001
0.001
1.741*
0.002
< 0.001
< 0.001
< b.ooi
I0.279
5.5
26
8.000
24.000
0.021
kg/day
mg/1
kg/day
Slug & Foil Final Effluent
0.00042
0.00042
0.00004
0.00021
0.00025
0.00014
0.00153
0.00651
0.00027
0.00186
9254
24
3580
< 0.010
< 0.010B
< 0.010
< 0.010
< 0.010
< OiOlOB
< 0.01
< 0.01
< 0.01
< 0.01
..< 0.01
< 0.01
< 0.01B
1.40B
1.40
< 0.005
< 0.003
< 0.001
0.006
0.017
0.049
0.050
< 0.001
0.028
0.003
0.010
< 0.025
0.067
0.16
0.227
1.127
0.317
0.006*
0.014
0.299
2.257*
0.000007 0.010
0.0123
0.00001
0.00196
0.0566
0.169
0.00015
0.003
67.203*
0.041
0.078
0.022
< 0.001
2.138
7.0
24
121
246
20
0.012
0.250
0.311
0.311
0.00133
0.00378
0.0109
0.0111
0.0062
0.00067
0.0022
0.0149
0.05041
0.0504
0.150
0.0704
0.001
0.0031
0.0664
0.5013
0.0022
0.00067
14.926
0.0091
0.0173
0.0049
0.4745
26.651
54.636
4.442
0.00267
0.0555
XI-28
-------
o
O
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O O O
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O O O
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rH T-l C4 i-l rH
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-------
c- in iM er>
•-I ro eg in CM
o o -I
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s
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o
rHco* o co * ro in * in
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CMOCOHOOrHOO'S'OOOOin
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V V VVVVV
tO (u
XI-3,0
-------
CM
in vo in oo
in CM o t-(
i o 1-1 o
o o o' o
in in
o o in
co o in in t— co o >-<
lD
in
ON *H CO
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c*> co o
in
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o o o
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"Q* <(j« 00 f»4
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CO
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O O
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in in
o o in
o o in o r- co o *-i
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§
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o o
in o <-) in o i-<
O O O
v v
* O O f
v v
XI-31
-------
TABLE 11-6 (Com)
GLASS ENCAPSULATED AND CERAMIC PROCESS WASTES
(PLANT ID# 31072)
Stream Identification
Flow Rate Liters/Hr
Duration Hours/Day
Sanple ID No.
TOXIC ORGANICS
mg/1 kg/day
Ceramic Ball Mill
0.394
24
03740
04 Benzene
23 Chloroform
30 1,2 Transdichloroethylene
38 Ethylbenzene Not
44 Methylene Chloride Analyzed
66 Bis (2-ethylhexyl) Phthalate
68 Di-N-Butyl Phthalate
70 Diethyl Phthalate
84 Pyrene
86 Toluene
87 Trichloroethylene
Total Toxic Organics
114 Antimony
115 Arsenic
117 Berylium
118 Cadmium
119 Chromium
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
Total Toxic Metals
NON-TOXIC METALS
Aluminum
Barium
Boron
Calcium*
Cobalt
Iron
Magnesium*
Manganese
Molybdenum
Sodium*
Tin
Titanium
Vanadium
yttrium
Total Non-Toxic Metals
pH
Temperature °C
121 Cyanide, Total
Oil & Grease
Total Organic Carbon
Biochemical Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
< 0.013
. 0.0121**
< 0.02
0.02
0.237
0.067
1.10
< 0.001
0.191
< 0.002
< 0.001
< 0.001
170.00
171.63
30.5
51700.
0.337
1750.0*
4.080
11.20
26.7*
0.174
13.6
466.0*
62.5
91.5
17.900
2.280
51934.
9.7
25
< 0.005
NA***
279
< 1
1010
< 0.005 •
1.15
0.0000001
0.0000002
0.000002
0.00000063
0.00001
0.000002
0.0016
0.00161
0.00029
0.489
0.000003
0.0165
0.000038
0.00011
0.00025
0.0000016
0.00013
0.0044
0.0006
0.00087
0.00017
0.000022
0.4912
0.000264
0.00955
0.0000011
mg/1 kg/day
Ceramic Line Treatment
1232
8
03741
Not
Analyzed
0.002
< 0.002
0.001
0.007
0.007
0.031
0.107
< 0.001
< 0.005
< 0.002
0.005
< 0.001
0.355
0.515
0.201
158.0
0.554
9.52*
0.181
0.155
2.2*
0.050
6.84
28.2*
2.05
53.1
0.160
0.006
221.3
6.4
24
< 0.005
44.60
116
17.9
214
< 0.005
1.15
0.00002
0.00001
0.000069
0.000069
0.00031
0.00105
0.000049
0.00345
0.00503
0.00198
1.557
0.00546
0.09383
0.00178
0.00153
0.02168
0.00049
0.0674
0.278
0.0202
0.523
0.00158
0.000059
2.181
0.4395
1.143
0.176
2.109
0.0113
* Metals Not Included In The Totals
**I-Interference present
*** NA-not analyzed
XI-32'
-------
TABLE 11-7
TANTALUM SLOG PROCESS WASTES
(PLANT ID# 09062)
Stream Identification
Flow Rate Liters/Hour
Duration Hours/Day
Sample 10 Mo.
TOXIC ORGANICS
04 Benzene
23 Chloroform
44 Methylene Chloride
45 Methyl chloride
66 Bis(2-ethylhexyl)Phthalate
68 Di~N-Butyl Phthalate
70 Diethyl Phthalate
86 Toluene
87 Tridiloroethylene
Total Priority Organics
114 Antimony
115 Arsenic:
117 Beryllium
118 Cadmium
119 Chromium
120 Copper
122 Lead :
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 Thallivim
128 Zinc
Total Toxic Metals
NON-TOXIC M3TALS
Aluminum
Barium .
Boron
Calcium*
Cobalt I
Iron
Magnesium*
Manganese
Molybdenum
Sodium*
Tin :
Titaniisn
Vanadium
Yttrium
Total Non-Toxic Metals
Temperciture °C
121 Cyanide, Total
Oil & Ofrease
Total Organic Carbon
Biological Oxygen Demand
Total Suspended Solids
Phenols
Fluoride
mg/1 kg/day
Incoming Water
24
03759
0.001
0.005
0.01
0.01
0.01
0.05
0.03
0.001
0.11
0.01
0.006
0.05
0.14
0.35
0.14
0.02
0.09
13.06*
0.01
0.37
1.52*
0.01
0.03
9.64*
0.01
C 6.01
0.02
0.01
24.84
8.1
24
C 0.005
0.000
4
0.000
0.20
< 0.001
0.49
rng/1 kg/day
Bar And Rack Wash
114
24
03761
Not
mg/1 kg/day
Total Raw Waste
3298
24
03760
Not
mg/1 kg/day
Final Effluent
3298
24
03758
.
< O.Olf
1.3CT
0.10
Analyzed
< 0.001
< 0.005
< 0.01
C 0.
' 0.
0.
0.
<. 0.
0.
0.
0.
<0.
0.
0.
5.
0.
0.
4.
0.
2.
0.
0.
0.
5.
0.
0.
0.
0.
19.
7.
24
0.
0.
2
75
2.
C 0.
'8.
01
24
04
06
001
37
005
017
05
05
777
03
02
18
64*
02
53
53*
53
07
72*
02
15
09
01
36
8
005
000
18
001
000
0.
0.
0.
0.
0.
0.
0007
0001
0002
001
00005
00014
0.00219
0.
0.
0.
014
00005
0005 J
0.013
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
00005
007
0015
0015
0002
016
00005
0004
0002
00003
05398
005
21
006
02
Analyzed
< 0.001
< 0.005
< 0.01
< o.
0.
0.
0.
< 0.
0.
< 0.
0.
< 0.
0.
1.
0.
0.
0»
4.
0.
2.
0.
4.
0.
18.
0.
0.
0.
< 0.
30.
7.
24
< 0.
0.
125
75
56
< 0.
1.
01
04
85
03
001
08
005
009
05
17
219
51
01
09
18*
01
38
43*
10
03
67*
03
02
01
01
38
0
005
000
001
27
0.
0.
003
067
0.0024
0.
0.
0.
0.
0.
0.
0064
0007
013
0925
04
0008
0.0071
0.
0.
0.
0.
0.
0.
1.
0.
0.
0.
2.
0.
5.
4.
0.
33
0008
19
03
32
0024
48
0024
0016
0008
3988
89
94
43
10
0.
0.
< 0.
0.
0.
< 0.
1.
< 0.
< 0.
< 0.
< 0.
0.
024
013
01
01-U
02?
oP
332
001
005
010
01
05
0.06
0.
< 0.
0.
< 0.
05
001
15
005
0
0
0
0
0
0
.0017
.1017
.004
.0048
.004
.012
< 0.006
< 0.
0.
0.
0.
0.
0.
05
29
60
97
02
08
11.13*
< 0.
"0.
1.
4.
0.
122.
0.
0.
0.
0.
140.
7.
24
< 0.
0.
109
62
1.
< 0.
4.
01
68
28*
26
04
33*
02
01
03
03
75
7
005
000
0
0
0
0
0
0
0
0
0
.023
.0478
.077
.0016
.006
.88
.054
.10
.34
0.0032
9
0
0
0
0
11
.68
.0016
.0008
.0024
.0024
.1398
8.63
0
001
700
4
0
.91
.08
0.37
* Metals Not Included In Totals
B
.-concentration found in Sample Blank
XI-33
-------
Tables 11-5 through 11-7 present sampling analysis data for detected
parameters in raw process wastewaters and treated effluents for
those plants sampled within the capacitor subcategory. Pollutant
parameters are grouped according to toxic organics, toxic metals,
non-toxic metals, and other pollutants. Total pollutant concen-
trations are presented as well as mass loadings of those pollu-
tant parameters. Mass Loadings were derived by multiplying con-
centration by the flow rate and the hours per day that a particu-
lar process is operated. Some entries were left blank for one of
the following reasons: the parameter was not detected; the con-
centration used for the kg/day calculation is less than the lower
quantifiable limits or not quantifiable. The kg/day is not inclu-
ded in totals for calcium, magnesium, and sodium. The kg/day is
not applicable to pH. Totals do not include values preceded by
"less than".
The following conventions were followed in quantifying the levels
determined by analysis:
Trace Levels - Pollutants detected at levels too low to be
quantitatively measured are reported as the value preceded
by a "less than" (<) sign. All other pollutants are repor-
ted as the measured value.
Mass Load - Total daily discharge in kilograms/day of a par-
ticular pollutant is termed the mass load. This figure is -
computed by multiplying the measured concentration (mg/1) by
the water discharge rate expressed in liters per day.
Sample Blanks - Blank samples of organic-free distilled water
were used to detect contamination of water samples. These
sample blank data are not subtracted from the analysis results,
but rather, are shown as a (B) next to 1:he pollutant found in
both the sample and the blank. The tables show figures for
total measurable jto'xic organics, toxic and non-toxic metals,
total suspended solids and fluorides.
. Blank Entries - Some entries were left blank for one of the
following reasons: the parameter was not detected; kg/day
is not given when the concentration is lower than the mini-
mum detectable limit or not quantifiable; kg/day is not given
and not included in totals for calcium,;magnesium, and sodium;
kg/day is not applicable to pH.
Table 11-5 presents sampled results from a plant producing ceramic
and wet tantalum slug capacitors. This facility is unique in that
it produces its own precious metal inks, and the waste treatment
system is shared by other processes. All organics detected were at
trace levels. The ink manufacturing process showed higher levels
of "toxic and non-toxic metals than did the ceramic ball mill
operation and the tantalum foil operation.
XI-34
-------
Table 11-6 presents sampling results from a plant producing glass
encapsulated capacitors and ceramic capacitors. The glass capaci-
tor manufacturing operations discharge directly to the municipal
treatment system with no treatment. The glass line produces waste
associated with lead cleaning, inspection, and glass cutting. The
glass cutting operation produces high concentrations of total lead.
The ceramic line discharges first to a settling basin and then to the
municipcil treatment system. Wastewater in the settling basin in-
cludes ceramic capacitor lead cleaning, cooling tower blowdown,
boiler blowdown, and water deionizer backwash. The ceramic line
produces significant quantities of barium.
Table 11-7 presents analysis results from a plant producing dry
tantalum slug capacitors. The waste treatment system handles
manufacturing process wastewater, cooling tower and boiler blow-
down, arid water deionizer backwash. The raw waste was observed
to be quite cloudy, and the effluent clarity was variable. Most
of the dry tantalum slug capacitor manufacturing processes are dry,
but the wet process of reforming and forming has a discharge rate
of approximately 19 liters/hr (5 gal/hr). This facility utilized a
rack washer that cleaned the stainless steel bars to which the capa-
citors were soldered as they went through all manufacturing process
steps. |
i :
Summary of Raw Waste Stream Data
Table 11-8 summarizes pollutant concentration data for capa-
citor (excluding ball mill wastewaters) raw waste streams sampled
in the capacitor subcategory. Minimum, maximum, mean, and flow
weighted mean concentrations were determined using all raw waste
streams sampled. The flow weighted mean concentration was cal-
culated by dividing the total mass rate (ing/day) by the total flow
rate (liters/day) for all parameters sampled.
Table 11-6 presents the raw waste concentrations of pollutants
analyzed (excludes toxic organics) for a batch Ball Mill Wash
(Plant ID 31072, Stream-03740). The settling step effluent data
is also presented. The difference in flow rate represents flow
from another ball mill wash and contact cooling waters that were
not sampled. A sludge sample was not taken so a mass balance
approach cannot be used to determine the concentrations in the
unsamplesd streams.
Potenticil pollutant parameters were selected from Table 11-6 and
Table 11-8 for sampled raw waste streams based upon their occur-
rence arid concentration in the sampled streams. Table 11-9 pre-
sents the flow weighted mean pollutant concentrations of capaci-
tor raw waste streams and a ball mill raw waste stream (Plant
31072, Stream 03740). Those pollutants not detected or at trace
levels in the sampled streams have been listed in Table 11-10 for
capacitor (excluding ball mill waste) raw waste and in Table 11-11
for ball mill wastes.
XI-35
-------
TABLE 11-8
CAPACITOR SUBCATEGORY
SM"MAR¥ OF CAPACITOR RAW WASTE DATA (EXCLUDES BALL MILLING)
Min. Cone. Max. Cone.
Parameter mg/1 mg/1
TOXIC ORGANICS
Oil 1,1,1-trichlorethane < 0.01 0.014;
023 Chloroform < 0.01 0.047
044 Methylene chloride < 0.01 0.09 |
087 Trichlorethylene 0.06 0.27
Mean Cone.
mg/1
0.012
0.0154
0.033
0.165
Flow Weighted
Mean Cone.
mg/1
0.0129
0.0125
0.0159
0.0323
TOXIC METALS
114 Antimony < 0.001
115 Arsenic < 0.003
119 Chromium < 0.001
120 Copper . 0.016
122 lead < 0.001
124 Nickel < 0.001
126 Silver < 0.001
128 Zinc < 0.001
NON-TOXIC METALS
Aluminum < 0.001
Barium < 0.001
Boron 0.09
Calcium 0.92
Iron 0.038
Magnesium 0.263
Manganese 0.001
Sodium 1.741
Tin 0.002
Titanium < 0.001
Vanadium < 0.001
Phenols < 0.005
Oil and Grease 0.0
Total Suspended Solids 0.0
Total Organic Carbon 2.0
Biochemical Oxygen Demand 1.7
Fluoride 0.1
pH 3.2
0.093
0.012
1.06 ,
0.85 ,
32.0 ;
0.37 i
0.055
5.5 '
5.03;
3.025,
0.8 '
11.7671
2.53
3.311
4.10 '
370.64 I
0.315
2.77
0.09
0.27
348.0
218.0 '
125.
75.0
8.0
8.9
0.0215
0.0055
0.180
0.241
4.138
0.07
0.0155
0.764
0.00880
0.00463
0.05672
0.056072
1.2844
0.0683
0.0162
0.2354
0.887
0'.628
0.255
5.782
0.866
1.649
0.589
61.0
0.098
0.406
0.018
0.074
43.5
72.9
42.313
29.29
1.724
6.4
0.57041
0.9627
0.31746
6.51178
1.7997
1.438
2.2499
122.31
0.04341
0.8425
0.01763
0.0053
9.1997
136.7
88.538
55.438
4.512
XI-36
-------
TABLE 11-9
CAPACITOR SUBCATEGORY
SUMMARY OF TOTAL RAW WASTE
(Includes Ball Milling)
Parameter
120. Copper
122. Lead
128. Zinc
Aluminum
Barium
Iron
Manganese-
Total Suspended Solids
Oil & Grease
Flow Weighted
Mean Concentration (mg/1)
0.818
1.874
0.359
0.835
6.305
2.627
3.28
130.6
9.2
XI-37
-------
TABLE 11-10 '
POLLUTANT PARAMETERS NOT DETECTED IN
CAPACITOR RAW WASTE STREAMS i
(EXCLUDING BALL MILL WASTES) !
TOXIC CRGANICS
2. Acrolein 61.
3. Acrylonitrile 63.
5. Benzidine 71.
6. Carbon Tetrachloride(Tetrachloromethane) 73.
7. Chlorobenzene 74.
8. 1,2,4-Trichlorobenzene 78.
9. Hexachlorbenzene 79.
10. 1,2-Dichlorethane 81.
12. Bexachloroethane 82.
13. 1,1-Dichloroethane 83.
14. 1,1,2-Trichlorethane 85.
15. 1,1,2,2-Tetrachloroethane 88.
16. CWLoroethane 89.
17. Bis(ChloronBthyl)Ether 90.
18. Bis(2-Chloroethyl Vinyl Ether (Mixed) 91.
19. 2-Chloronaphthalene 92.
22. Parachlorometa Cresol 93.
25. 1,2-Dichlorobenzene 94.
26. 1,3-Dichlorobenzene 95.
27. 1,4-DicW.orobenzene 96.
29. 1,1-Dichloroethylene 97.
31. 2,4-DicW.orphenol 98.
32. 1,2-Dichloropropane 99.
33. If2-Dichloroprc^ylene(lf3-Dichloropropene) 100.
34. 2,4-Dinethyphenol 101.
35. 2,4-Dinitrotoluene 102.
37. l,2-Diphen7lhydrazine 103.
40. 4-ChlorophenylEhenyl Ether 104.
41. 4-Broirophenyl Ether 105.
42. Bis (2-Chloroiscpropyl) Ether 106.
45. Methyl Chloride (Chloronethane) 107.
46. Methylbromide (Bromanethane) 108.
47. Bronoforra (Tribromomethane) 109.
49. Trichlorofluoronethane 110.
50. Dichlorodifluororaethane 111.
51. Chlorodibroncmethane 112.
52. Hexachlorobutadiene 113.
53. Hexachlorocydopentadiene . 129.
54. Isophorone
56. Nitrobenzene
N-Nitrosod imenthylamine
N-Nitrosod i-N-Propylamine
Dimethyl Phthalate
Benzo(A)Pyrene (3,4-Benzo-Pyrene)
3,4-Benzofluoranthene(Benzo(B)Fluoranthene)
Anthracene
1,12-Benzoperylene (Benzo( GHI) -Perylene)
Phenanthrene
1,2,5,6-Dibenzathracene(Dibenzo(A,H) Anthracene)
Indeno(1,2,3-DC)Pyrene(2,3-o~PhenylenePyrene)
Tetrachloroethylene
Vinyl Chloride (Chloroethylene)
Aldrin -,
Dieldrin
Chlordane (Technical Mixture and Metabolites)
4,4'-DDT
4,4'-DDE(P,P'-DDX)
4,4'-DDD(P,P'-TDE)
Alpha-Endosulfan
Beta-Endosulfan
Endosulfan Sulfate
Endrin
Endrin Aldehyde
Heptachlor
Heptachlor Epoxide(BHC-hexachlorocyclohexane)
Alpha-BHC
Beta-BHC
Gamma-BHC(Lindane)
Dslta-BHC(PCB-Polychlorinated Biphenyls)
PCB-1242(Arochlor 1242)
PCB-1254(Arochlor 1254)
PCB-1221(Arochlor 1221)
PCB-1232(Arochlor 1232)
PCB-1248(Arochlor 1248)
PCB-1260(Arochlor 1260)
PCB-1016(Arochlor 1016)
Toxaphene
2,3,7,8-Tetrachlorodibenzo-P-Dioxin(TCDD)
Xylenes
Alkyl Epoxides
XI-38
-------
TABLE 11-10 (Continued)
POLLUTANTS ONLY DETECTED AT TRACE LEVELS
CAPACITOR (EXCLUDING BALL MILL WASTE) RAW WASTE
TOXIC ORI3ANICS
01 Acenaphthene
04 Benzene
21 2,4,6-Trichlorophenol
24 2-Chlorophenol
28 3,3-Dichlorobenz idine
36 2,6-Dinitrotoluene
38 Ethylbenzene
43 Bis(2-Chloroethoxy) Methane
48 Dichlorobronethane
58 4-Nitrophenol
64 Pentachlorophenol
65 Phenol
66 Bis (2-ethylhexyl) Phthalate
TOXIC METALS
115 Arsenic
117 Beryllium
123 Mercury
127 Thallium
67. Butyl Benzyl Phthalate
68. Di-N-Butyl Phthalate
69 Di-N-Cctyl Phthalate
70 Diethyl Phthalate
72 1,2-Benzanthracene
75 11,12-Benzofluoranthene
76 Chrysene
77 Acenaphthylene
80 Fluorene
84 Pyrene
86 Toluene
87 Trichloroethylene
112 PCB-1016
NON-TOXIC METALS
Molybdenum
XI-39
-------
TABLE 11-10 (Continued)
DETECTED IN CAPACITOR (EXCLUDING BALL MILL WASTES) RAW WASTE STREAMS
AT LEVELS TOO LOW TO REQUIRE TREATMENT*
Parameter
Toxic Metals
118 Cadmium
121 Cyanide
Mean Cone.
mg/1
0.005
<0.0!05
Non-Toxic Metals
Cobalt
Yttrium
0.03
0.004
* These parameters do not require treatment because 1) the raw
waste concentration is less than the daily maximum figure (See
Table 11-12), or 2) no performance data is; available for treat-
ment of these parameters.
XI-4O
-------
, TABLE 11-11
POLLUTANT PARAMETERS NOT ANALYZED IN
BALL MILL RAW WASTE
(PLANT ID 31072, STREAM 03740)
TOXIC ORGANICS
1. Acenaphthene
2. Acrolein
3. Acrylonitrile
4. Benzene
5. Benzidine
6. Carbon Itetrachloride (Tetrachloromethane)
7. Chlorobenzene
8. 1,2,4-Trichlorobenzene
9. Hexachlorbenzene
10. 1,2-Dichlorethane
11. 1,1,1,-iTrichloroethene
12. Hexachloroethane
13. 1,1-Dichloroethane
14. 1,1,2-Trichlorethane
15. 1,1,2,2-Tetrachloroethane
16. Chlqroethane
17. Bis(Chloromethyl)Ether
18. Bis(2-Chloroethyl)Ether
19. 2-Chloroethyl Vinyl Ether (Mixed)
20. 2-Chlorcaiaphthalene
21. 2,4,6-Trichlorophenol
22. Parachloroneta Cresol
24. 2-Chlorophenol
25. 1,2-Dichlorobenzene
26. 1,3-Dichlorobenzene
27. 1,4-Diehlorobenzene
28. 3,3'-Dichlorobenzidine
29. 1,1-Dichloroethylene
30. 1,2-Trains-Dichloroethylene
31. 2,4-Dichlorphenol
32. 1,2-Dichloropropane
33.1,2-Dichloropropylene(1,3-Dichloropropene)
34. 2,4-Dimethylphenol
35. 2,4-Dinitrotoluene
36. 2,6-Dinitrotoluene
37. 1,2-Diphenylhydrazine
38. Ethylbenzene
39. Fluoranthene
40. 4-ChloirphenylPhenyl Ether
41. 4-BronophenylPhenyl Ether
42. Bis(2-Chloroisopropyl)Ether
43. Bis(2-Oiloroethoxy)Methane
45. Methyl Chloride (Chloronethane)
46. roethylbromide (Broroomethane)
47. Bromoform (Tribromemethane)
48. Dichlorobromomethane
49. Trichlorofluoromethane
50. Dichlorodifluoromethane
51. Chlorodibrononethane
52. Hexachlorobutadiene
53. Hexachlorocyclopentadiene
54. Isophorone
55. Naphthalene
56. Nitrobenzene
57. 2-Nitrophenol
58. 4-Nitrophenol
59. 2,4-Dinitrophenol
60. 4,6-Dinitro-o-cresol
61. N-Nitrosodimenthylamine
62. N-Nitrosodiphenylamine
63. N-Nitrosodi-N-Propylamine
64. Pentachlorophenol
67. Butyl Benzyl Phthalate
69. Di-N-Cctyl Phthalate
70. Diethyl Phthalate
71. Dimethyl Phthalate
72. 1,2-Benzanthracene(Benzo(A)Anthracene >
73. Benzo(A).Pyrene (3,4-Benzo-Pyrene)
74. 3,4-Benzofluoranthene(Benzo(B)Fluoranthene)
75. 11,12-Benzofluoranthene(Benzo(K)Fluoranthene)
76. Chrysene
77. Acenaphthylene
78. Anthracene
79.1,12-Benzoperylene(Benzo(GHI)-Perylene)
80. Fluorene
81. Phenanthrene
82. l,2,5,6-Dibenzathracene(Dibenzo(A,H)Anthracene
83. Indeno(l,2,3-DC)Pyrene(2,3-o-PhenylenePyrene)
84. Pyrene
85. Tetrachloroethylene
88.'Vinyl Chloride (Chloroethylene)
89. Aldrin
90. Dieldrin
91. Chlordane (Technical Mixture and Metabolites)
XI-41
-------
TABLE 11-11 (Continued)
FOLLOTANT PARAMETERS NOT ANALYZED FOR
BALL MILL RAW WASTE ;
(PLANT ID 31072, STREAM 03740)
92. 4,4'-DDT
93. 4,4'-DDE(P,PI-DDX)
94. 4,4'-DDD(P,P'-TDE)
95. Alpha-Endosulfan
96. Beta-Endosulfan
97. EndosoLfan Sulfate
98. Endein
99. Endrin Aldehyde
100. Heptachlor
101. Hepfcachlor Epoxide (BHC-Hexachlorocyclo-
hexane)
102. Alpha-BHC
103. Beta-BHC
104. Gamma-BHC(Lindane)
105. Delta-BHC(PCB-Polychlorinated Biphenyls)
106. PCB-1242(Arochlor 1242)
107. PCB-1254(Arochlor 1254)
108. PCB-1221(Arochlor 1221)
109. PCB-1232(Arochlor 1232)
110. PCB-1248(Arochlor 1248)
111. ,PCB-1260(Arochlor 1260)
112. PCB-1016(Arochlor 1016)
113. Toxaphene
129. 2,3,7,8-Tetrachlorodibenzo-P-Dioxin (TCDD)
Xylenes
Alkyl Epoxides
XI-42
-------
TABLE 11-li (Continued)
POLLUTANTS DETECTED ONLY AT TRACE LEVELS
BALL MILL RAW WASTE
TOXIC METALS
114.
117.
123.
125.
126.
127.
Antimony
Beryllium
Mercury
Selenium
Silver
Thallium
XI-43
-------
TABLE 11-11 (Continued)
POLLUTANT PARAMETERS DETECTED AT LEVELS
TOO LOW TO BE EFFECTIVELY TREATED*
Toxic Metals
115. Arsenic
118. Cadmium
124. Nickel
Mean Concentration
0.012 (I)
0.02
0.191
These parameters do not require treatment because 1) the raw
waste concentration is less than the daily maximum figure (See
Table 11-12), or 2) no performance data is available for treat-
ment of these parameters.
I - Lab Interference ;
XI-44
-------
Treatment-In-Place
The seven plants visited in the capacitor subcategory have a wide
range of treatment-in-place. One plant had no waste treatment;
another plant had no wet processes and no wastewater discharge. The
treatment-in<-place observed at the remaining five plants is discussed
below.
Plant 19116 (Reference Table 11-5 for sampling data), Ceramic,
Tantalum Slug, and Tantalum Foil Capacitors
This plant produces a variety of capacitors, three types of
which result in wastewater discharges. The facility is quite
old, but the plumbing for the manufacturing process is rela-
tively new. Many manufacturing operations are manual, which
results in variable discharge rates and pollutant concentra-
tions. All manufacturing process wastewater discharges are
mixed in a 11,355 liter (3,000 gallon) settling/mixing tank
which receives wastes from other manufacturing processes as
well. An automatic pH sensor activates sulfuric acid or
sodium hydroxide pumps to adjust the pH before the treated
flow is discharged through a weir equipped with an automatic
flow recorder. Since there is no provision for sludge settling
and removal, the overall system only pH adjusts the wastewater
prior to discharge.
Plant 31072 (Reference Table 11-6 for sampling data), Glass
Encapsulated and Ceramic Capacitors
Both types of capacitors produced at this plant result in
wastewater discharges. The glass capacitor line dischar-
ges directly to the municipal treatment system without treat-
ment. The ceramic capacitor line has two discharges which
share a settling basin with boiler blowdown, cooling tower
blowdown, and water deionizer backwash. There is no pH adjust-
ment or chemical addition of any kind. There is a relatively
infrequent clean-out (twice per year) of the settling basin.
The raw process wastewater samples were collected prior to
mixing with the non-process wastewater discharges.
Plant 09062 (Reference Table 11-7 for sampling data), Dry
Tantalum Slug Capacitors
This facility has one process line and produces dry tantalum
slug capacitors. Basically the manufacturing process steps
utilize very little water .(977 liters or 258 gph), but the
ancillary operations produce a large volume of water by com-
parison. The ancillary operations include cooling tower blow-
down, boiler blowdown, and water deionizer backwash. The total
XI-45
-------
raw waste sample includes all wastes prior to settling and pH
adjustment. The settling basin is cleaned infrequently (approx-
imately twice per year) and the aerator/mixer causes some
settled solids to become re-entrained and subsequently dis-
charged. The pH adjustment is automatically performed by ad-
ding either sulfuric acid or sodium hydroxide directly into
the final outfall. The pH adjustment mechanism is primarily
for the blowdown and backwash operations. The process line
effluent has a steady and nearly neutral pH. Tantalum slug
process discharge appears cloudy due to the presence of man-
ganese nitrate.
Plant 40082, Aluminum Electrolytic and Tantalum Foil Capacitors
This facility producing both aluminum electrolytic and tanta-
lum foil capacitors is quite small and does not contain the
major wet process of aluminum etching which is normally asso-
ciated with aluminum electrolytic capacitor manufacturing.
However, this plant does perform the aluminum electrolytic
formation reactions for aluminum electrolytic capacitor man-
ufacture. Wastewaters from this process are characterized
by high solids content and slightly acidic pH. This facili-
ty discharges one of its process lines directly to a munici-
pal treatment system and the other to a sand filter which
discharges to a drainage ditch. The tantalum foil line dumps
spent ammonium bromide and methanol directly into the munici-
pal treatment system without treatment.
Plant 41154, Ceramic Capacitors
This facility produces ceramic capacitors and uses incoming
municipal water for ball milling and mixing. Wastewater
from these processes is treated in a portable sand filter
and discharged to a municipal treatment system.
POTENTIAL POLLUTANT PARAMETERS
Potential pollutants present in wastewater frpm the capacitor
(excluding ball mill wastes) raw waste that might require treat-
ment prior to discharge include:
120 Copper
122 Lead
128 Zinc
Aluminum
Barium
Iron
Manganese !
Total Suspended Solids
Oil & Grease
pH
Potential pollutants present in raw wastewater from a sampled ball
mill wash (Plant ID 31072) are:
XI-46
-------
119 Chromium
128 Zinc
Total Suspended
Solids
122 Lead
Barium
This wash was mixed with an unsampled ball mill waste stream prior
to settling. The settling treatment step at Plant ID 31072 cannot
be fully evaluated after review of sampling data. (See Table 11-6,
Plant ID 31072, Stream 03741, Ceramic Line Treatment). Potential
pollutcints present in settling effluent at concentrations requir-
ing further or additional treatment include:
Barium
Titanium
Oil & Grease
Total Organic Carbon
Total Suspended Solids
Tables 11-10 and 11-11 lists pollutants other than those selected
above that were analyzed in capacitor (excluding ball milling)
and the ball mill process raw waste streams sampled for the
capacitor subcategory. Each pollutant is listed in the appro-
priate grouping as being not detected (organics were not analyzed
in the case of ball milling), detected only at trace levels, or
detected at levels too low to be effectively treated prior to
discharge.
APPLICABLE TREATMENT TECHNOLOGIES
Based on the selected pollutant parameters and treatment-in-place
(See Table 11-2) in the capacitor industry, the following tech-
nologies are applicable for wastewater treatment:
- 1 pH Adjustment
Chemical precipitation and clarification
Oil removal
Sludge dewatering
Polishing Filtration
These specific treatment components are discussed in detail in
Section XII of this report.
Recommended Treatment Systems
Three levels of treatment are proposed for the capacitor manufac-
turing facilities. Figures 11-7 through 11-11 present schematic
diagrams of the three levels of treatment proposed for capacitor
facilities. Level 1 represents the minimum treatment found for
those facilities that had any treatment and consists of pH adjust-
ment prior to discharge and for ball mill discharge, pH adjustment
and settling. Capacitor manufacturing operations often result in
pH fluctuations that could fall outside pretreatment regulations.
XI-47
-------
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XI-48
-------
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XI-51
-------
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XI-5 2
-------
The Level 2 treatment systems (See Figures 11-8 and 11-9) contain
chemical precipitation and sedimentation (for solids and metals
removal)/ neutralization, vacuum filtration and contract hauling
of the dewatered sludge (an oil skimmer is included for treatment
of capacitor raw waste excluding ball milling). This type of sys-
tem would lower effluent concentrations for all of the visited
facilities. None of the visited facilities had a Level 2 treat-
ment system presently in-place.
The Level 3 treatment systems (See Figures 11-10 and 11-11) are a
Level 2 treatment system with a polishing filter after the neu-
tralization step. The polishing filter reduces the total suspen-
ded solids concentration with attendant incidental reduction of
various metals concentrations.
Performance of Observed Treatment Systems
The actual performance of Level 1 treatment systems have been
sampled as in-place technologies for the capacitor subcategory.
Table 11-12 presents effluent analysis data for those plants
which treat manufacturing process wastewater prior to discharge.
Minimum, maximum, mean, and flow weighted mean concentrations
are shown for each potential pollutant parameter previously
selected. Data from individual effluent streams utilized in the
formation of these tables were presented in Tables 11-5 through
11-7.
Performance of Recommended Treatment Systems
Performance of the recommended treatment systems for capacitor
raw Weistes and ball milling wastes for Levels 1, 2, and 3, are
presented in Table 11-13. Performance figures are based upon
data from treatment component performance observed in other
industries. This performance data can be used for the capacitor
Iridustry because of the similarity of the raw wastes. Section
XII describes the treatment components and the performance
levels achievable. Table 11-14 compares the performance for
the recommended treatment systems in Section XII to the obser-
ved treatment performance at visited capacitor and ball mill
facilities. Table 11-15 presents the daily maximum, 30-day
average and long-term average pollutant concentrations as ob-
served in other industries for Level 2 and 3 treatment.
Estimated Cost of Recommended Treatment Systems
The determination of estimated costs for recommended treatment sys-
tem components is discussed in Section XII of this report. Tables
11-16 through 11-24 present the estimated costs for each of the
recommended treatment systems discussed previously.
XI-53
-------
TABLE 11-12
CAPACITOR SUBCATEQORY
PERFORMANCE OF OBSERVED LEVEL 1 TREATMENT SYSTEMS
Treated Capacitor (Excluding Ball Mill Wastes) Raw waste - Effluent concentration *
Parameter
120 Copper
122 Lead
128 Zinc
Aluminum
Barium
Iron
Manganese
Total Suspended
Solids
Oil & Grease
PH
Minimum mg/1 Maximum mg/1 Mean mg/1
0.049
0.05
0.067
0.227
0.02
0.299
0.01
1.0
0
7.0
0.06
0.05
0.29
0.97
1.127
0.68
4.26
20
0
7.7
0.054
0.05
0.18
0.6
0.57
0.49
2.14
10.0
0
7.4
Flow Weighted
Mean Concentra-
tion (mg/1)
0.053
0.050
0.0126
0.422
0.837
0.398
1.13
15.
119
122
128
Treated Ball Milling Raw Waste - Effluent Concentration **
Barium
Total Suspended
Solids
Chromium
Lead
Zinc
1581
214
0.007
0.107
0.355
*Plant ID 19116 and 09062
**KLant ID 31072
XI-5 4
-------
TABLE 11-13
CAPACITOR SUBCATEGORY
PERFORMANCE OF RECOMMENDED TREATMENT SYSTEMS
I ' .' *
Treated Capacitor (Excludes Ball Milling) Raw Waste - Effluent Concentration
Parameter
120 Copper
122 Lead
128 Zinc
Aluminum
Barium
Iron
Manganese
Total Suspended Solids
Oil & Grease
pH
Level 1 *
Recommended
Treatment
NC**
NC
NC
NC
NC
NC
NC
NC
NC
7.0
Level 2
(mg/1)
NC
0.05 -
NC
NA***
NA
0.797
NA
17.8
NC
NC
Level 3
(mg/D
0.368
0.034
NC
NA
NA
0.257
NA
12.7
7.1
NC
TREATED BALL MILL RAW WASTE
i EFFLUENT CONCENTRATION
119 Chromium 0.007**** NC
122 Lead 0.107**** 0.05
128 Zinc 0.355**** NC
Barium 158**** NA.
Total Suspended Solids 214**** 17.8
NC
0.034
0.247
NA
17.8
*pH adjustment
**NC - No change in performance from previous level
***NA "• Data is unavailable
****0bserved Treatment - Plant ID 31072
XI-5 5
-------
TABLE 11-14
CAPACITOR SUBCATEGORY
COMPARISON OF OBSERVED VERSUS
RECOMMENDED TREATMENT
Treated Capacitor Raw Waste (Excludes Ball Milling)
Effluent Concentration (mg/1)
Level 1*
Parameter Observed
120 Copper 0.053
122 Lead 0.05
128 Zinc 0.0126
Aluminum 0.422
Barium 0.837
Iron 0.398
Manganese 1.13
Total Suspended Solids 15
Oil & Grease 0
pH 7.4
Level 1
Recommended
NC**
NC
NC
NC
NC
NC
NC
NC
NC
7.0
Ball Milling Raw Waste -
Effluent Concentrations (mg/1)
Parameter
119 Chromium
122 Lead
128 Zinc
Barium
Total Suspended
Solids
pH
Level 1
Observed
0.007
0.107
0.355
158.
214.
9.7
Level 1
Recommended
NA***
NA
NA
NA
17.8
7.0
*See Table 11-12
**NC - No change in concentration from raw waste
***NA - Data Not Available
XI-5 6
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XI-66
-------
Three costs have been estimated for each level of treatment for the
capacitor subcategory. The cost of the systems differs because flow
rates that are input to these systems change the size of the compon-
;ents needed. The flow rates used in the determination of system
costs are characteristic of the flows observed at sampled plants
within the industry.
BENEFIT ANALYSIS
This section presents an analysis of the industry-wide benefit
estimated to result from applying the three levels of treatment
previously discussed in this section to the total process waste-
water generated by the capacitor subcategory. This analysis esti-
mates the amount of pollutants that would not be discharged to the
environment if each of the three levels of treatment were applied
on a subcategory-wide basis. An analysis of the benefit versus
estimated subcategory-wide cost for each of the treatment levels
is also; provided.
Industry-wide Costs
i
By multiplying the total annual cost of each level of treatment
at various flow rates by the number of plants estimated to exist
in each; flow regime in the industry, a subcategory-wide cost
figure is estimated. Table 11-25 presents this tabulation for
capacitor raw wastes excluding ball milling, and for ball mil-
ling raw wastes. These figures represent the investment and
annual costs for each treatment level for capacitor waste
streams: and ball milling. This calculation does not make any
allowance for waste treatment that is currently in-place at
capacitor facilities.
Industry-wide Cost and Benefit
Tables tll-26 and 11-27, present the estimates of total annual
cost to the capacitor subcategory to reduce pollutant discharge
for the treatment of capacitor (excluding ball milling) waste--
water and ball milling wastewater, respectively. These tables
also present the benefit of reduced pollutant discharge for the
capacitor subcategory resulting from the application of the three
levels ,of recommended treatment. Benefit was calculated by mul-
tiplying the estimated number of liters discharged by the sub-
category times the performance attainable by each of the recom-
mended treatment systems as presented in Table 11-13. Values
are presented for each of the selected subcategory pollutant
parameters.
'i
The column "Raw Waste" shows the total amount of pollutant that
would be discharged to the environment if no treatment were employed
by any jfacility in the industry. The Levels 1, 2, and 3 treatment
columns show the amount of pollutants that would be discharged if
any of ithese three levels of treatment were applied to the total
wastewater estimated to be discharged by the capacitor subcategory.
XI-67
-------
TABLE 11-25 ,
CAPACITOR SUBCATEGORY
INDUSTRY-WIDE COST ANALYSIS
(MILLIONS OF DOLLARS)
Capacitor' (Excluding Ball Milling) Wastewaters
Treatment Schemes
Investment*
Annual Costs
Capital Cost
Depreciation
Operation & Maint.
Energy & Power
Total Annual Cost
Level 1
12.75
Level 2
14.26
Level 3
16.287
1.075
2.551
1.171
0.00544
4.803
1.202
2.852
1.237
0..0315
5.323
1.373
3.257
1.732
0.039
6.402
*Cost analysis based on 116 plants estimated to be discharging
wastewater - medium size plant costs have been multiplied by this
number of plants. v j
XI-68
-------
TABLE 11-25 (CON'T)
CAPACITOR SUBCATEGORY
INDUSTRY-WIDE COST ANALYSIS
(MILLIONS OF DOLLARS)
Ball Milling Wastewater Treatment Schemes
Investment*
Annual Costs
Capital Cost
Depreciation
r-
Operation & Maint,
\ ' . V • \
Energy & Power
i '
Total Annual Cost
Level 1
0.554
Level 2
1.229
Level 3
1.326
0.0467
0.111
0.157
0.0016
0.175
0
0
0
0
0
.104
.246
.099
.0099
.458
0,
0,
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0.
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112
265
128
0103
51 6 \
*Cost analysis based on 7 plants estimated to be conducting a
ball milling process - medium size plant costs have been mul-
tiplied by this number of plants.
XI-69
-------
TABLE 11-26 '
CAPACITOR SUBCATEQORY - INDUSTRY COST?
AND BENEFIT ANALYSIS
Treated Capacitor Raw Vfeste - Excludes Ball Milling
LEVEL 1 LEVEL 2
Raw Wfeste Treatment Treatment
Parameter kg/year kg/year kg/year
Plow (Million Liters Per Year)* 571.9 571.9 571.9
120 Copper 320.7 NC** '>, NC
122 Lead 734.6 NC ! 28.60
128 Zinc 134.6 NC ' NC
Aluminum 326.2 NC NA***
Barium 550.6 NC NA
Iron 1029.3 NC 455.8
Manganese 1286.8 NC NA
Oil & Qrease 5261.5 NC NC
Total Suspended Solids 78182.0 NC ' 10179.8
pH 6.4 7.0 NC
Annual Cost (Million Dollars) - 4.803
5.323
LEVEL 3
Treatment
kg/year
571.9
210.5
19.4
NC
NA
NA
147.0
NA
4060.5
7263.1
NC
6.402
*Based on 116 plants (See Table 11-25)
**NC - No change in concentration due to additional treatment
***NA - Data not available
XI-70
-------
CAPACITOR SUBCATEQORY
COST AND BENEFIT ANALYSIS
Treated Ball Mill Raw Waste
Parameter
Flow (Million Liters Per Year)1
119 Chromium
120 Lead
128 Zinc
Barium
Total Suspended Solids
pH
Annual Cost (Million Dollars)
Raw Waste**
kg/year
24.5
LEVEL 1
Treatment
kg/year
24.5
LEVEL 2
.Treatment
kg/year
24.5
LEVEL 3
Treatment
kg/year
24.5
5.81
26.95
4165.0
1266650.
24745.
NC
NC
NC
2871
5243.
7.0
0.175
NC
1.23
NC
NA
436.1
NC
0.458
NC
0.83
6.05
NA
311.15
NC
0.516
NA - Data not available
NC - No change in concentration due to additional treatment
*Based on 7 plants (See Table 11-25)
**One saripled ball nail stream, Plant ID 31072
XI-71
-------
-------
SECTION XII
CONTROL AND TREATMENT TECHNOLOGY
INTRODUCTION
This section describes the treatment techniques, currently used
or available to remove or recover wastewater pollutants normally
generated by Electrical and Electronic Components (E&EC) manu-
facturing plants. Included are a discussion of treatment system
performance transferable from the Metal Finishing Category data
base and a discussion of individual treatment technologies and
in-plant technologies. The technologies presented are appli-
cable to the entire E&EC manufacturing industry for both direct
and indirect dischargers and reflect the entire E&EC manufacturing
data base.
To minimize the total mass of pollutants discharged in E&EC
manufacturing, a reduction in either concentration or flow or
both is required. Several techniques are being employed to
effect a significant reduction in total pollution. These
techniques can be readily adapted to other existing facilities
and include:
1.
2.
3.
4.
Avoidance of unnecessary dilution. Diluting waste
streams with unpolluted water makes treatment more
expensive (since most equipment costs are directly
related to volume of wastewater flow) and more diffi-
cult (since concentrations may be too low to treat
effectively). ' Precipitated material may also be
redissolved by unpolluted water.
Reduction of flow to pollution -generating processes.
Use of counter cur rent, spray, and fog rinses greatly
reduces the volume of water requiring treatment.
After proper treatment, the mass of a pollutant
that remains in the solution is a function of the
volume of water. Hence, less water, less pollutant
discharged.
Treatment under proper conditions. The use of the
proper pH can greatly enhance pollutant precipita-
tion. Since metallic ions precipitate best at various
pH levels, waste segregation and proper treatment at
the optimum pH will produce improved results. The
prior removal of compounds which increase the solu-
bility of waste materials will aloow significantly
more efficient treatment of the remaining material.
An example is the segregation of complexed wastes
from wastewater containing noncomplexed metals.
Timely and proper disposal of wastes. Removal of
sludge from the treatment system as soon as possible
XII-1
-------
in the treatment process minimizes returning pollut-
ants to the waste stream through resolubilization.
One plant visited during the MFC study (ID 23061)
utilized a settling tank in their treatment system
that required periodic cleaning. Such cleaning had
not been done for some time, and our analysis of both
their raw and treated wastes shpwed little difference
Subsequent pumping out of this settling tank resulted
in an improved effluent (reference Table 12-1).
Once removed from the primary effluent stream, waste
sludges must be disposed of properly. If landfills
are used for sludge disposal, the landfill must be
designed to prevent material from leaching back into
the water supply. Mixing of waste sludges which
might form soluble compounds should be prevented. If
sludge is disposed of by incineration, the burning
must be carefully controlled to prevent air pollution.
A licensed scavenger may be substituted for plant
personnel to oversee disposal of the removed sludge.
TABLE 12-1
COMPARISON OF WASTEWATER AT PLANT ID 23061
BEFORE AND AFTER PUMPING OF SETTLING TANK
Parameter
Cyanide, Amen, to
Chlorination
Cyanide, Total
Phosphorus
Silver
Gold
Cadmium
Chromium,
Hexavalent
Chromium, Total
Copper
Iron
Fluoride
Nickel
Lead
Tin
Zinc
Total Suspended
Solids
Concentration (mg/1)
Before Sludge Removal
Concentration (mg/1)
After Sludge Removal
Total Raw
Waste
0.007
0.025
2.413
0.001
0.007
0.001
0.005
0.023
0.028
0.885
0.16
0.971
0.023
0.025
0.057
17.0
Treated
Effluent
0.001
0.035
2.675
0.001
0.010
0.006
0.105
0.394
0.500
3.667
0.62
1.445
0.034
0.040
0.185
36.00
Total Raw
Waste
0.005
0.005
14.35
0.002
0.005
0.005
0.005
0.010
0.127
2.883
0.94
0.378
0.007
0.121
0.040
67.00
Treated
Effluent
0.005
0.05
13.89
0.003
0.005
0.002
0.005
0.006
0.034
1.718
0.520
0.312
0.014
0.134
0.034
4.00
XII-2
-------
TRANSFER OF PERFORMANCE
The similarity of raw wastes between the E&EC Category and the
Metal Finishing Category (MFC) allows the transfer of waste treat-
ment technologies and their proven performance to the E&EC Category,
This transfer of treatment technology performance is necessary to.
provide support for the E&EC Category from the larger Metal Finish-
ing Category data base. Information used in the preparation of
the Metal Finishing Category data base was gathered from industry
visits and sampling, an industry-wide survey, a literature
survey, and telephone contacts.
The following subsections will present waste treatment technol-
ogy performance transferred from the Metal Finishing Category
as well as a discussion of the individual waste treatment tech-
nologies, their application, and performance.
TREATMENT SYSTEM PERFORMANCE
This section presents performance attainable by treatment
systems recommended for use in the E&EC Category. This per-
formance data has been transferred from the Metal Finishing
Category due to the similarity of raw wastes produced by these
two categories.
The following breakdown will be utilized in this discussion
of wastewater treatment system performance:
Hydroxide Precipitation/Sedimentation - Metals removal by
chemical precipitation and sedimentation.
Polishing Filtration - Metals removal by chemical precipi-
tation, sedimentation, and polishing
filtration.
Skimming - Oils removal.
Carbon Adsorption - Total Toxic Organics (TTO) removal.
Hydroxide Precipitation/Sedimentation
The core of the metals removal waste treatment system is a
hydroxide precipitation/sedimentation mechanism. Hydroxide
precipitation/sedimentation includes pH adjustment, precipitation,
flocculation, and sedimentation. Hydroxide precipitation/sedi-
mentation may be carried out with equipment such as clarifiers,
tube settlers, settling tanks, sedimentation lagoons, and various
filtration devices using hydroxide or sulfide precipitation.
Some raw wastes require pretreatment before going to solids
removal. Hexavalent chromium bearing wastes must undergo chemical
reduction in order to reduce hexavalent chromium to trivalent
chromium (This step is not necessary if sulfide precipitation is
being used in the solids removal operation because the hexavalent
chromium is reduced in the precipitation reaction).
XII-3
-------
Performance of a properly operating Hydroxide precipitation/
sedimentation system (shown in Figure 12-1 with its sources of
wastes) is demonstrated by effective solids settling, which is
indicated by low effluent levels of total suspended solids (TSS)
Effective solids settling depends upon maintaining the system
pH at the level needed to form metal hydroxides. Generally a
pH range of 8.5 to 9.5 is considered optimum for hydroxide pre-
cipitation with mixed metal wastes.
To establish the treatment system performance characteristics,
visited plants employing hydroxide precipitation/sedimentation
treatment were selected from the Metal Finishing Category data
base. The files for these plants were then examined to ensure
that only properly operating facilities :were included in the
performance data base by establishing criteria to eliminate the
data for improperly operating systems. The criteria for elimin-
ating improperly operating treatment systems were, as follows:
1.
Date with an effluent TSS level greater than 50 mg/1 were
deleted. This represents a level of TSS above which no
well-operated treatment plant should be discharging.
Figure 12-2 shows effluent TSS concentrations vs. per-
centile distribution. As is shown in the graph, there is
an abrupt increase in slope (approximately 5.8:1) at the
50 mg/1 level. Deleting data above this concentration
still includes nearly seventy percent of the data base.
The following presentation of TSS a;nd metals concentrations
for plants 20073 and 20083 shows that a low level of TSS
in indicative of low effluent metal; concentrations.
Plant ID 20073 (mg/1 )
Day 1
Day 2
Day 3
TSS
Cu
Ni
Cr
Inf.
702.
64.6
53.8
162.
Eff.
11.
.812
.448
1.47
Inf.
712.
97.1
52.5
175.
Eff.
14
.875
!.478
1.89
Inf.
124.
91.2
89.7
220.
Eff.
33.
1.37
1.12
2.85
XII-4
-------
Chromium
Bearing
Wastes
Metals
Wastes
Hexavalent
Chromium
Reduction
Precipitation
Sed imentation
Sludge
Discharge
FIGURE 12-1
TREATMENT OF METALS WASTES BY
HYDROXIDE PRECIPITATION/SEDIMENTATION
XI I- 5
-------
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XII-6
-------
Plant ID 20083 (mg/1 )
Day 1
Day 2
Day 3
Inf.
Eff.
Inf.
Eff.
Inf.
Eff.
Day 4
Inf.
Eff.
TSS
Cu
Ni
24.0
56.2
103
145
2.75
6.13
18.0
57.7
153
23.0
0.38
0.91
15.0
39.3
82.8
27.0
0.21
0.77
10.0
50.0
87.1
97.0
2.44
4.75
2. Plants with alkaline precipitation systems that operated at
an average effluent pH of less than 7.0 were deleted. An
alkaline precipitation system will not work properly in
this pH range, as is illustrated by the following data from
plant 21066.
Plant ID 21066 (mg/1)
Day 2
Inf. Eff.
Day 1
Inf. Eff.
Avg. effluent pH
TSS
Cr
Zn
NA
48.0
5.36
114
5.4
448
3.74
150
NA
61.0
8.99
I'll
5.1
371
1.28
140
Proper control of pH is absolutely essential for favorable perfor-
mance of precipitation/sedimentation technologies. This is illus-
trated by results obtained from a sampling visit to manufacturing
plant 47432 (not a metal finishing plant) as shown in the follow-
ing table (concentrations are in mg/1}:
In
Day 1
pH Range 2.4-3.4
TSS 39
Copper 312
Zinc 250
•i
Lead 0.16
Nickel 42.8
Day 2
Day 3
Out
8.5-8.7
8
0.22
0.31
0.03
0.78
In
1.0-3.0
16
120
32.5
0.16
33.8
Out
5.0-6.0
19
5.12
25
0.04
0.53
In
2.0-5.0
16
107
43.8
0.15
36.6
Out
6.5-8,1
7
0.66
0.66
0.04
0.46
XI 1^
-------
This plant utilizes lime precipitation and pH adjustment followed
by flocculant addition and sedimentation. Samples were taken be-
fore and after the system. On day two effluent pH was allowed to
range below 7 for the entire day, and the effluent metals control
was less effective than on days one and three. In general, better
results will be obtained in chemical precipitation systems when pH
is maintained consistently at a level between 8.5 and 9.5. It can
be clearly seen that the best results were produced on day one when
the effluent pH was kept within the recommended range for the entire
day.
3. Plants which had effluent flows significantly greater than
the corresponding raw waste flows were deleted. The in-
crease in flows was assumed to be dilution by other waste-
waters.
4. Plants that experienced difficulties in system operation
during the sampling period were excluded. These difficulties
included a few hours operation at very low pH (<4.0),
observed operator error,an inoperative chemical feed system,
improper chemical usage, improperly maintained equipment,
high flow slugs during the sampling period, and excessive
surface water intrusion (heavy rains).
The following procedure was followed for each metal pollutant para-
meter in ord,er to eliminate spurious background metal readings.
The mean effluent concentration of each parameter was calculated
and when a raw waste concentration was less than the mean effluent
concentration for that parameter, the corresponding effluent reading
was deleted from the data set. The mean was recalculated using
points not removed initially, and the process was repeated in an
interative loop until all raw waste concentrations were greater
than the calculated mean effluent concentration. The deletion
of these points prevents the calculation of unrealistically low
effluent concentrations from the waste treatment systems due to
low raw waste pollutant loadings. |
Plots of raw waste concentration vs. effluent concentration were
generated for total suspended solids, cadmium, total chromium,
copper, iron, lead, nickel, zinc, and fluorides. These plots
are shown in Figures 12-3 through 12-11. The mean effluent
concentrations for these parameters were then computed and are
presented in Table 12-2.
XII-8
-------
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TABLE 12-2
TREATMENT OP METALS BY HYDROXIDE PRECIPITATION/SEDIMENTATION
MEAN EFFLUENT CONCENTRATIONS
Parameter mg/1
Total Suspended Solids 17.8
Cadmium .012
Chromium, Total I .572
Copper .814
Iron : .797
Lead .050
Nickel .942
Zinc .551
Fluorides 15.3
Table 12-3 presents the values for daily and 30-day average maximum
variability factors that were established for the Electroplating
Category. The derivation and development of these are reported
in detail in the Development Document for Existing Source Pretreat-
ment Standards for the Electroplating Point Source Category
(EPA 440/ 1-79/003, August 1979). These values were used in
conjunction with the mean effluent concentrations tabulated in
Table 12-2 to establish the daily maximum and 30 day average
concentrations presented in Table 12-4 for treatment of metals
using hydroxide precipitation/sedimentation.
TABLE 12-3
SUMMARY OF DAILY AND 30-DAY AVERAGE
MAXIMUM VARIABILITY FACTORS
Variability Factor
Pollutant
Total Suspended Solids*
Cyanide, Total
Cyanide, Amenable
Cadmium
Chromium, Total
Chromium, Hexavalent
Copper
Iron*
Lead
Nickel
Zinc
Silver
Fluorides*
Oil and Grease*
Total Priority Organics
Daily Max.
2.9
5.
5,
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,0
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3.9
5.2
3.2
2.9
2.9
2.9 i
3.0 I
2.9 •
2.9
2.9
2.9
30-Day-Avg.
1.3
1.5
1.5
1.3
1.4
1.5
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
*Miniraum variability factor selected; further effort needed to
establish final value.
XII-18
-------
TABLE 12-4
HYDROXIDE PRECIPITATION/SEDIMENTATION SYSTEMS CONCENTRATIONS
Concentration (mg/1)
Pollutant
Total Suspended Solids
(118) Cadmium
(119) Chromium
(120) Copper
Iron
(122) Lead
(124) Nickel
(128) Zinc
Fluorides
Daily Max.
51.6
0.04
2.23
2.61
2.31
0.15
2.73
1.65
44.4
30-Day-Ave.
23.1
0.02
0.80
1.06
1.04
0.07
1.23
0.72
19.9
The data collection portfolios (DCP's) received from non-visited
facilites were also sorted for plants which utilize hydroxide
precipitation/sedimentation treatment systems. Of these plants,
fifty reported effluent concentration data. The raw waste data
were very fragmented and could not be correlated with the effluent
data. Consequently, only effluent concentration statistics were
generated, and the pe-rcentile distribution for these effluent
concentrations are presented in Figures 12-12 through 12-20.
Because these plants were not visited, it is not possible to know
which plants were not operating properly and should be deleted.
The dally maximum concentrations that were presented in Table 12-4
are overlayed onto these distribution plots for direct comparison
of the visited plant sampling data with these DCP data.
Figures 12-21 through 12-29 present effluent concentrations for the
entire metal finishing data base. The graphs include all data points
including those that were removed during the determination of the
pollutant mean effluent concentrations for a properly operating
treatment system. Data are presented for nine pollutants and the
daily maximum concentration for each pollutant is overlayed for .
comparison.
Polishing Filtration
Polishing filtration treatment systems for metal wastes removal
is identical to the hydroxide precipitation/sedimentation treatment
system with the addition of filtration devices after the primary
solids removal devices. The purpose of these filtration units is
to "polish" the effluent, that is, remove suspended solids such
as metal hydroxides which did not settle out in the solids removal
devices. The filters also act as a safeguard against pollutant
discharge if an upset should occur in the solids removal devices.
XII-19
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100
FIGURE 12-12;
DCP DATA FOR TSS EFFLUENT; DISTRIBUTION
XII-20
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FIGURE 12-14
DCP DATA FOR CHROMIUM EFFLUENT DISTRIBUTION
100
XII-22
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FIGURE 12-16
DCP DATA FOR IRON EFFLUENT DISTRIBUTION
100
XII-24
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FIGURE 12-18
DCP DATA FOR NICKEL EFFLUENT DISTRIBUTION
XII-26
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100
FIGURE 12-19
DCP DATA FOR ZINC EFFLUENT DISTRIBUTION
XII-27
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Plants were selected that were visited and'sampled and were
operating polishing filtration type treatment system. Plants with
poorly operating treatment systems were then deleted from the data
set using the same exclusion criteria detailed previously.
Plots of raw waste vs. effluent were generated for the following
parameters: total suspended solids, cadmium, total chromium,
copper, iron, lead, nickel, zinc, and fluorides. These plots
are presented as Figures 12-30 through 12-38. The mean effluent
concentrations for these parameters were calculated and are
presented in Table 12-5„
TABLE 12-5
POLISHING FILTRATION MEAN EFFLUENT CONCENTRATIONS
Parameter
Total Suspended Solids
(118) Cadmium
(119) Chromium, Total
(120) Copper
Iron
(122) Lead
(124) Nickel
(128) Zinc
Fluorides
mg/1
12.7
.011
.319
.368
.257
.034
.550
.247
4.76
The^variability factors presented in Table 12-3 were used in
conjunction with the mean effluent concentrations shown in
Table 12-5 to establish the daily maximum and 30-day average
concentrations listed in Table 12-6 for the polishing filtra-
tion treatment of common metals. Table 12-7 provides a list-
ing of Metal Finishing Category plants in the data base which
have a polishing filtration system.
TABLE 12-6 ;
POLISHING FILTRATION TREATMENT SYSTEM CONCENTRATIONS
Pollutant
Total Suspended Solids
(118) Cadmium
(119) Chromium
(120) Copper
Concentration (mg/1)
Daily Max. 30-Day-Avg.
36.8
0.03
1.24
0.18
16.5
.015
0.45
0.48
XII-38
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XII-47
-------
TABLE 12-6 (Con't)
POLISHING FILTRATION SYSTEM CONCENTRATIONS
Pollutant
Iron
(122) Lead
(124) Nickel
(128) Zinc
Fluorides
Concentration (mg/1)
Daly Max. 30-Day-Avg
0.75
0.10
1.60
0.74
13.8
0.33
0.04
0.72
0.32
6.19
TABLE 12-7
METAL FINISHING PLANTS WITH POLISHING FILTRATION SYSTEMS
FOR METALS
04140
04151
06062
06131
11096
11182
12075
12077
13031
13033
19069
27042
28121
30159
30519
30927
31021
31022
31033
31044
33070
33073
33110
36048
36082
36102
38223
40047
44150
45041
The data collection portfolios (DCP's) received from non-visited
facilities were also screened for plants which, have polishing
filtration treatment system. Of these plants, twenty reported
effluent concentration data. Effluent concentration statistics
were generated and the percentile distribution for these effluent
concentrations are presented in Figures 12-39 through 12-47. Be-
cause these plants were not visited, it is not possible to know
which plants were not operating properly and should be deleted.
The daily maximum concentrations that were presented in Table 12-6
are overlayed onto these distribution plots for direct comparison
of the visited plant sampling data with these DCP data.
Figures 12-30 through 12-38 present effluent concentration as a
function of raw waste concentration for the entire metal finishing
polishing filtration data base. Data are presented for pol-
lutants and the daily maximum concentration for each pollutant
is overlayed for comparison. Table 12-8 summarizes the percent-
age of the metal finishing data base that is in compliance with
the daily maximum concentration limitation for the sampled plants,
the entire sampled data base, and the DCP data base.
XII-48
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FIGURE 12-42
DCP DATA FOR COPPER EFFLUENT DISTRIBUTION
XII-52
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XII-54
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XII-55
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100
FIGURE 12-46
DCP DATA FOR ZINC EFFLUENT DISTRIBUTION
XII-56
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XII-57
-------
TABLE 12-8
PERCENTAGE OF MFC DATA BASE BELOW THE DAILY
MAXIMUM CONCENTRATION LIMITATION FOR POLISHING FILTRATION
Pollutant
Cadmium
Chromium, Total
Copper
Iron
Lead
Nickel
Zinc
Fluorides
Sampled Plants
After Deletions
100.0
100.0
85.7
93.3
100.0
91.7
88.2
88.9
All Sampled
Plants
100.0
100.0
88.2
87.5
100.0
92.8
88.2
88.9
DCP Data Base
46.1
88.8
90.0
75.0
62.5
100.0
63.6
66.7
Summary tables are provided to show a direct comparison of the
mean, daily maximum, and 30-day average for hydroxide precipita-
tion/sedimentation and polishing filtration. Table 12-9 presents
a comparison on the mean concentrations and Table 12-10 lists the
daily maximum and 30-day average concentrationsj for each.
TABLE 12-9 ;
HYDROXIDE PRECIPITATION/SEDIMENTATION AND POLISHING FILTRATION
MEAN CONCENTRATION COMPARISON
Pollutant
Concentration (mg/1)
Hydroxide
Precipitation/Sedimentation
Total Suspended Solids
(118) Cadmium
(119) Chromium
(120) Copper
Iron
(122) Lead
(124) Nickel
(128) Zinc
Fluorides
17.8
.012
.572
.814
.797
.050
.942
.551
15.3
Polishing
Filtration
12.7
.011
.319
.368
.257
.034
.550
.247
4.76
TABLE 12-10
HYDROXIDE PRECIPITATION/SEDIMENTATION AND POLISHING FILTRATION
LIMITATION COMPARISON
Concentration (mg/1)
Hydroxide
Precipitation/Sedimentation
Parameter
Daily Max.
Total Suspended
Solids 51.6
(118) Cadmium 0.04
(119) Chromium 2.23
30-Day-Ave.
23.1
0.02
0.80
Polishing
Filtration
Daily Max. 30-Day-Ave,
36.8
0.03
1.24
16.5
.015
0.45
XII-58
-------
; TABLE 12-10 (Con't)
HYDROXIDE PRECIPITATION/SEDIMENTATION AND POLISHING FILTRATION
LIMITATION COMPARISON
Parameter
(120) Copper
Iron
(122) Lead
(124) Nickel
(128) Zinc
Fluorides
Concentration (mg/1)
Daily Max. 30-Day-Ave. Daily. Max. 30-Day-Ave.
2.61
2.31
0.15
2.73
1.65
44.4
1.06
1.04
0.07
1.23
0.72
19.9
1.18
0.75
0.10
1.60
0.74
13.8
0.48
0.33
0.04
0.72
0.32
6.19
Treatment of Oils and Total Toxic Organ! cs
The following paragraphs present the oily waste performance data
for combined wastewater in the Metal Finishing Category data base
identify the mean concentrations established 'for oils and total
toxic organics, define the concentration limitations, and com-
pare these limitations with the sampled data base and the DCP data
base for chemical precipitation/sedimentation and polishing
filtration treatment systems.
Combined Wastewater Performance for Oils - Hydroxide Precipitation/
Sedimentation and Oil Skimming
Figure 12-48 presents the oil and grease performance data for the
treatment system data base for properly operating systems. From
these data the following performance was established for oil and
grease in combined wastewater for hydroxide precipitation/sediment-
ation and oil skimming.
: Oil and Grease Performance Data
(Combined Wastewater - Hydroxide Precipitation/Sedimentation and
Skimming)
Mean Effluent Concentration 11.9 mg/1
Variability Factors (from Table 12-13) 2.9/1.3
Daily Maximum Concentration 34.5 mg/1
30-day Average Concentration 15.5 mg/1
Figure 12-49 presents the oil and grease performance data for the
sampled data base, and Figure 12-50 presents the data collection
portfolio (DCP) responses for effluent oil and grease concentrations
from facilities that incorporate hydroxide precipitation/sedimenta-
tion and oil skimming treatment. The daily maximum concentration is
overlayed on each of these for comparison. The percentage of oil
and grease effluent concentrations that are less than the daily
maximum concentration limitation are 100% for the data base com-
prised of properly operating systems, 90.3% for the MFC data base
and 71% for the MFC DCP data base.
XII-59
-------
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(t/6ui)
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XII-60
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XII-61
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XII-62
-------
Figure 12-51 presents the oil and grease concentration data for
the polishing filtration treatment system data base. From these
data, excluding the outlier at an effluent concentration of 56 mg/1
which exceeds the hydroxide precipitation/sedimentation and oil
skimming daily maximum concentration limitation, the following
performance results1.
Oil and Grease Performance Data
(Combined Watewater - PojJ.shing_ Filtration!
Mean Effluent Concentration
Variability Factor
Daily Maximum Concentration
30-day Average Concentration
7.1 mg/1
2.9/1.3
20.6 mg/1
9.2 mg/1
Figure 12-52 shows the data collection portfolio (DCP) effluent
concentration distribution for oil and grease from plants that in-
corprate a polishing filtration treatment system. The percen-
tages of combined wastewater oil and grease effluent concentrations
that are less than the daily maximum concentration limitation
are 88.9% for the MFC sampled data base and 100% for the MFC
DCP data base.
Combined Wastewater Performance for Total Toxic Organics
As discussed in Section -X, the pollutants designated Parameters
1 through 88 and 106 through 112 on Table 10-3 are toxic organics
that commonly occur in the E&EC Category as solvent cleaners or
oil additives. These have been grouped together for control and
are identified as Total Toxic Organics, (TTO). Figure 12-53
presents the raw waste concentration distribution for the Total
Toxic Organics, (TTO), in Metal Finishing Category wastewaters.
The mean concentration of these TTO is 11.3 mg/1 for the entire
Metal Finishing Category data base. However, there are three
high outliers (802., 285., and 74.2 mg/1) on Figure 12-53.
These are considered to result from the direct discharge of
TTO from some source, such as solvent degreaser sumps or spent
solvent storage, because TTO should enter wastewater streams only
from cleaning operations as rinses. Removal of these three
outliers as data not representative of acceptable TTO disposal
lowers the raw TTO mean concentration to 0.38 mg/1. This mean
raw TTO concentration is considered characteristic for waste-
waters with proper TTO management practices being applied. Table
12-11 presents raw and effluent total toxic organics performance
from treatment systems in the Metal Finishing Category data base
that have raw waste concentrations in the same order of magnitude
as the 0.38 mg/1 mean raw waste concentration.
The treatment technique recommended for the removal of TTO from
manufacturing process wastewater from semiconductor manufactur-
ing and dielectric fluid use is carbon adsorption. Carbon
adsorption is discussed in detail later in this section.
XII-63
-------
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XII-66
-------
TABLE 12-11
J. W J.JT\±J J. \.'**-L,Nrf VA-W^J*.*^* •*-*** i
Plant ID
02032 :
04071
06090
06091
06960
17050
19068
21051
27046 i
30054
Mean Concentration
Concentration
Raw TTO
1.247
0.121
0.238
0.486
0.149
0.189
1.083
0.477
0.297
0.421
0.179
0.225
0.608
0.44
(mg/1)
Effluent TTO
0.077
0.081
0.040
0.052
0.019
0.079
0.030
0.047
0.020
0.012
0.020
0.016
0.012
0.067
0.04
Based upon the data of Table 12-11,
summarized.
the following performance is
Total Toxic Organic Performance - Metal Finishing Category
Mean Effluent Concentration
Variability Factor
Daily Maximum Concentration
30-day Average Concentration
Do 04 mg/1
2,9/1.3
0.12 mg/1
0305 mg/1
XII-67
-------
INDIVIDUAL TREATMENT TECHNOLOGIES
™* ProYides descriptions of individual recovery and
treatment technologies that are used or intended for use in most
plants engaged in E&EC manufacturing. Each description includes
a functional description and discussions of application and per-
formance, advantages and limitations, operational factors of reli-
ability, maintainability, and solid waste aspects, and demonstra-
tion status.
Table 12-12 lists the technologies and shows their specific
application to E&EC manufacturing and the page on which they
are described. Table 12-13 shows the applications of each
technology in terms of the waste characteristics subcategories
listed above.
HYDROXIDE PRECIPITATION |
Dissolved' heavy metal ions are often chemically precipitated as
hydroxides so that they may be removed by physical means such
2on?S S2f2t^i°^ ^ration, or. centrifugation. Reagents com-
monly used to effect this precipitation include alkaline compounds
such as lime and sodium hydroxide. Calcium hydroxide precipitates
triyalent chromium and other metals as metal hydroxides and pre-
cipitates phosphates as insoluble calcium phosphate. These treat-
ment chemicals may be added to a flash mixer or rapid mix tank, or
?infC!:;;YH~0 fc?? ?<|dimentation device. Because metal hydroxides
tend to be colloidal in nature, coagulating agents may also be
added to facilitate settling. Figure 12-54 illustrates typical
raeS£tionPaevicetati°n equipment as wel1 as, the associated sedi-
After the solids have been removed, final pH adjustment may be
required to reduce the high pH created by the alkaline tSatSSnt
chemicals.
XH-68
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XII-70
-------
RAPID SEDIMENTATION
AND CONTINUOUS
GRAVITY DRAINAGE
TUBE
CLARIFICATION
INLET
WASTEWATER
CHEMICALS
RAPID
MIX TANK
FLOCCULATOR
DRIVE
COLLECTION
TROUGH
J'W I
CLARIFIED
EFFUENT
FLOCCULATOR
SLUDGE
FLOCCULATOR
TUBE
CLARIFIER
SLUDGE COLLECTOR
SLUDGE
SIPHON
FIGURE 12-54
CHEMICAL PRECIPITATION AND SEDIMENTATION
IW A CLARIFIER
•'XII-71
-------
Application and Performance
Hydroxide precipitation is used in the E&EC Category for precipita-
tion of dissolved metals and phosphates. It can be utilized in
conjunction with a solids removal device such as a clarifier or
filter for removal of metal ions such as iron, lead, tin, copper,
zinc, cadmium, aluminum, mercury, manganese, cobalt, antimony,
arsenic, beryllium, molybdenum, and trivalent chromium. The pro-
cess is also applicable to any substance that can be transformed
into an insoluble form like soaps, phosphates, fluorides, and
a variety of others.
The performance of hydroxide precipitation depends on several
variables. The most important factors affecting precipitation
effectiveness are:
1.
2.
3.
Addition of sufficient excess anibns to drive the
precipitation reaction to completion.
Maintenance of an alkaline pH throughout the precip
itation reaction and subsequent settling (Figure
12-55 details the solubilities of; various metal
hydroxides as a function of pH).
Effective removal of precipitated, solids (see
appropriate solids removal technologies).
If the treatment chemicals are not present in slight excess concen
trations, some metals will remain dissolved in the waste stream.
Advantages and Limitations
Hydroxide precipitation has proven to be -an effective technique
for removing many pollutants from industrial wastewater. It
operates at ambient conditions and is well suited to automatic
control. Lime is usually added as a slurry when used in hy-
droxide precipitation. The slurry must be kept well mixed and
the addition lines periodically checked to prevent blocking,
which may result from a buildup of solids. The use of hydroxide
precipitation does produce large quantities of sludge requiring
disposal following precipitation and settling. The use of treat-
ment chemicals requires caution because of the potentially
hazardous situation involved with the storage and handling of
those chemicals. Recovery of the precipitated species is some-
times difficult because of the homogeneous nature of most
hydroxide sludges (where no single metal hydroxide is present
in high concentrations) and because of the difficulty in smelt-
ing which results from the interference of calcium compounds.
XII-72
-------
5 6 7 8 9 10 II 12 13
2 3
1. Plotted data for metal sulfides based on experimental data listed
in Seidell's solubilities.
2. Solubilities for metal hydroxides are taken from Curves by Freedmari
and Shannon,"Modern Alkaline Cooling Water Treatment," Industrial
Water Engineering, Page 31, {Jan./Feb. 1973).
FIGURE 12-55
COMPARATIVE SOLUBILITIES OF METAL HYDROXIDES
AND SULFIDE AS A FUNCTION OF pH
XII-73
-------
Operational Factors
Reliability: The reliability of hydroxide precipitation is high,
although proper monitoring, control, and pretreatment to remove
interfering substances is required.
Maintainability; The major maintenance needs involve periodic
upkeep of monitoring equipment, automatic feeding equipment,
mixing equipment, and other hardware. Removal of accumulated
sludge is necessary for efficient operation of precipitation/
sedimentation systems.
Solid Waste Aspects; Solids which precipitate out are removed
in a subsequent treatment step. Ultimately, the solids must be
properly disposed of. Proper disposal practices are discussed
later in this section under Treatment of Sludges,
Demonstration Status
Hydroxide precipitation of metals is a classic waste treatment
technology used by most industrial waste treatment systems.
As noted earlier, sedimentation to remove precipitates is dis-..
cussed separately; however, both techniques have been illustrated
in Figure 12-54.
SEDIMENTATION
Sedimentation is a process which removes solid particles from a
liquid waste stream by gravitational force. The operation is
effected by reducing the velocity of the feed stream in a large
volume tank or lagoon so that gravitational settling can occur.
Figure 12-56 shows two typical sedimentation devices.
Wastewater is fed into a high volume tank or lagoon where it loses
velocity and the suspended solids are allowed" to settle out. High
retention times are generally required (the plants in the data base
used retention times ranging from 1 to 48 hours). Accumulated
sludge can be collected and removed either periodically or contin-
uously and either manually or mechanically.
XII-74
-------
Stdimantstion Basin
Inlet Zone
Inlet Liquid
Baffles To Maintain
"Quiescent Conditions
Settled Particles Collected
And Periodically Removed
Circular Clarifier
Partfcle«Trajlctdrve
« "«.
Outlet Zone
Outlet Liquid
Belt-Type Solids Collection Mechanism
Inlet Liquid
Circular Baffle
Annular Overflow Weir
Outlet Liquid
Settling Zone
Revolving Collection
Mechanism
Settling Particles
Settled Particles "T Collected And Periodically Removed
1 Sludge Drawoff
FIGURE 12-56
REPRESENTATIVE TYPES OF SEDIMENTATION
XII-75
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Inorganic coagulants or polyelectrolytic flocculants are added
to enhance coagulation. Common inorganic coagulants include
sodium sulfate, sodium aluminate, ferrous or ferric sulfate, and
ferric chloride. Organic polyelectrolytes vary in structure,
but all usually form larger floccules than coagulants used alone.
The use of a clarifier for sedimentation reduces space requirements,
reduces retention time, and increases solids removal efficiency.
Conventional clarifiers generally consist of a circular or rec-
tangular tank with a mechanical sludge collecting device or with
a sloping funnel-shaped bottom designed for sludge collection.
In advanced clarifiers, inclined plates, slanted tubes, or a
lamellar network may be included within the clarifier tank in
order to increase the effective settling area. A more recently
developed "clarifier" utilizes centrifugal force rather than
gravity to effect the separation of solids from a liquid. The
precipitates are forced outward and accumulate against an outer
wall, where they can later be collected. A fraction of the sludge
stream is often recirculated to the clarifier inlet, promoting
formation of a denser sludge.
Application 1
Sedimentation is used in the E&EC Category to remove precipitated
metals, phosphates, and suspended solids. Because most metal
ion pollutants are easily converted to solid metal hydroxide
precipitates, sedimentation is of particular.use in industries
associated with metal finishing and in other industries with hiqh
concentrations of metal ions in their wastes. In addition to
heavy metals, suitably precipitated materials effectively removed
by sedimentation/clarification include aluminum, manganese, cobalt,
arsenic, antimony, beryllium, molybdenum, fluoride, and phos-
phate.
A properly operating sedimentation system is capable of efficient
removal of suspended solids, precipitated metal hydroxides, and
other impurities from wastewater. The performance of the process
depends on a variety of factors, including the effective charge on
the suspended particles (adjustments can be made in the type and
dosage of flocculant or coagulant) and the types of chemicals
used in prior treatment. It has been found t;hat the site of floc-
culant or coagulant addition may significantly influence the
effectiveness of sedimentation. If the flocculant is subjected
to too much mixing before entering the settling device, the
agglomerated complexes may be broken up and the settling effec-
tiveness diminished. At the same time, the flocculant must
have sufficient mixing in order for effective set-up and settling
to occur. Most plant personnel select the line or trough leading
into the clarifier as the most efficient site for flocculant
addition. The performance of sedimentation is 'a function of the
XII-76
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retention time, particle size and density, and the surface area of
the sedimentation catchment.
Sampling visit data from plant 40063, a metal finishing and por-
celain enameling facility, exemplify efficient operation of a
chemical precipitation/settling system. The following table pre-
sents sampling data from this system, which consists of the addition
of lime and caustic soda for pH adjustment and hydroxide precipita-
tion, polyelectrolyte flocculant addition, and clarification. Sam-
ples were taken of the raw waste influent to the system and of the
clarifier effluent. Flow through the system is approximately
18,900 LPH (5000 GPH). Concentrations are given in mg/1. The ef-
fluent pH shown in the table reflects readjustment with sulfuric
acid after solids removal. Parameters which were not detected are
listed as ND.
Day 2
Day 3
pH Range
TSS
Al
Co
Cu
Fe
Mn
Ni
Se
Ti
Zn
jwwjr
Inf.
9.2-9.6
4390
37.3
3.92
0.65
137
175
6.86
28.6
143
18.5
Eff .
8.3-9.8
9.0
0.35
ND
0.003
0.49
0.12
ND
ND
ND
0.027
Inf.
9.2
3595
38.1
4.65
0.63
110
205
5.84
30.2
125
16.2
Eff.
7.6-8.1
13
0.35
ND
0.003
0.57
0.012
ND
ND
ND
0.044
Inf.
9.6
2805
29.9
4.37
0.72
208
245
5.63
27.4
115
17.0
Eff.
7.8-8.2
13
0.35
ND
0.003
0.58
0.12
ND
ND
ND
0.01
TSS levels were below 15 mg/1 on each day, despite raw waste
TSS concentrations of over 2800 mg/1. Effluent pH was maintained
at approximately 8 or above, lime addition was sufficient to
precipitate most of the dissolved metal ions, and the flocculant
addition and clarifier retention served to effectively remove
the precipitated solids.
XII-77
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Advantages and Limitations !
The major advantage of simple sedimentation is the simplicity of
the process itself - the gravitational settling of solid parti-
culate waste in a holding tank or lagoon. The major disadvantage
of sedimentation involves the long retention times necessary to
achieve complete settling, especially if the specific gravity
of the suspended matter is close to that of water.
A clarifier is more effective in removing slow settling suspended
matter in a shorter time and in less space than a simple sedimen-
tation system. Also, effluent quality is often better from a
clarifier. The cost of installing and maintaining a clarifier is,
however, substantially greater than the costs associated with
sedimentation lagoons.
Inclined plate, slant tube, and lamellar clarifiers have even
higher removal efficiencies than conventional Iclarifiers, and
greater capacities per unit area are possible. Installed costs
for these advanced clarification systems are claimed to be one
half the cost of conventional systems of similar capacity.
Operational Factors ;
Reliability; Sedimentation is a highly reliable technology for
removing suspended solids and precipitates. Proper treatment
of the wastewater prior to sedimentation (precipitation and coagu-
lant addition) is essential for continued efficient operation.
Those advanced clarifiers using slanted tubes, inclined plates,
or a lamellar network may require pre-screening of the waste in
order to eliminate any fibrous materials which could potentially
clog the system.
Maintainabil i ty ; When clarifiers are used, the associated system
utilized for chemical pretreatment and sludge dragout must be
maintained on a regular basis. Routine maintenance of mechanical
parts is also necessary. If lagoons are used, little maintenance
is required other than periodic sludge removal.
Waste Aspects; Rather large quantities of sludge are generated
and can be dewatered to facilitate handling. Further appropriate
disposal is required (see Treatment of Sludges).
Demonstration Status
Sedimentation in conjunction with hydroxide precipitation (the
Option 1 system) represents the typical method of solids removal
and is employed extensively in industrial waste treatment. The
advanced clarifiers are just beginning to appear in significant
numbers in commercial applications, while the centrifugal force
"clarifier" has yet to be used commercially. Sedimentation or
clarification is used in 13 plants in the E&EC Category.
Xii-78
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SULFIDE, PRECIPITATION
Hydrogen sulfide or soluble sulfide salts such as sodium sul-
fide are used to precipitate many heavy metal sulfides. Since
most metal sulfides are even less soluble than metal hydroxides
at alkaline pH levels, greater heavy metal removal can be ac-
complished through the use of sulfide rather than hydroxide
as a chemical precipitant prior to sedimentation. The solu-
bilities of metallic sulfides are pH dependent and are shown
in Figure 12-56.
Sampling data from three industrial plants using sulfide preci-
pitation are presented in Table 12-14. Concentrations are given
in mg/1.
Table 12-14
Sampling Data From Sulfide
Precipitation/Sedimentation Systems
Data Source Reference 1
Treatmemt
Lime, FeS, Poly-
Electrolyte,
Settle, Filter
Reference 2
Lime, FeS, Poly-
Electrolyte,
Settle, Filter
Reference 3
NaOH, Ferric
Chloride", NaS,
Clarify (1 stage)
Cr, T
Cu
Fe
Ni
Zn ;
Reference:
Raw
5.0-6.8
25.6
32.3
.52
39.5
Eff.
8-9
<.01
<.04
.10
<.07
Raw
7.7
.022
2.4
108
.68
33.9
Eff.
7.38
<.020
0.6
Raw
27
11.4
18.3
.029
.060
Eff.
6.4
<.005
<.005
.003
.009
1. Treatment of Metal Finishing Wastes by Sulfide Precipitation,
EPA Grant No. S804648010
2. Industrial Finishing, Vo. 35, No. 11, Nov. 1979, p. 40 (Raw
waste sample taken after chemical addition).
3. Visit Plant 27045. Concentrations are two day averages.
In all-cases except iron, effluent concentrations are below 0.1 mg/1
and in many cases below 0.01 mg/1 for the three plants studied.
Sampling data from several chlorine/caustic inorganic chemicals
manufacturing plants using sulfide precipitation reveal effluent
mercury concentrations varying between 0.009 and 0.03 mg/1. (Cal-
span Report No. ND-5782-M-72). As can be seen in Figure 7-65, the
solubilities of PbS and Ag2S are lower at alkaline pH levels than
bench scale tests conducted on several types of metal finishing
wastewater (Centec Corp; EPA Contract 68-03-2672) indicate that
metals removal to levels of less than 0.05 mg/1 and in some
XII-79
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cases less than 0.01 mg/1 are common in systems using sulfide
precipitation followed by clarification. Some of the bench scale
data, particularly in the case of lead, do not support such low
effluent concentrations. However, no suspended solids data were
provided in these studies. TSS removal is a reliable indicator
of precipitation/sedimentation system performance. Lack of these
data makes it difficult to fully evaluate the bench tests and in-
sufficient solids removal can result in high metals concentrations
Lead is consistently removed to very low levels (less than 0.02
rag/1) in systems using hydroxide precipitation and sedimentation.
Therefore one would expect even lower effluent concentrations of
lead resulting from properly operating sulfide precipitation sys-
tems due to the lower solubility of the lead sulfide compound.
Of particular interest is the ability of the,-ferrous sulfide pro-
cess to precipitate hexavalent chromium (Cr ) without prior re-
duction to the trivalent state as is required in the hydroxide
process, although the chromium is still precipitated as the hy-
droxide. When ferrous sulfide is used as the precipitant, iron
and sulfide act as reducing agents for the hexavalent chromium.
2FeS
2Fe(OH)3 + 2Cr(OH)3 + 2S'
2OH"
In this case the sludge produced consists mainly of ferric hydrox-
ides and chromic hydroxides. Some excess.hydroxyl ions are pro-
duced in this process, possibly requiring a downward re-adjustment
of pH to between 8-9 prior to discharge of the treated effluent.
Advantages and Limitations
The major advantage of the sulfide precipitation process is that
due to the extremely low solubilities of most metal sulfides, very
high metal removal efficiencies can be achieved. Also, the sulfide
process has the ability to remove chromates-and dichromates with-
out preliminary reduction of the chromium to its trivalent state.
In addition, it will precipitate metals complexed with most com-
plexing agents. However, care must be taken to maintain the pH
of the solution above approximately 8 in order to prevent the gen-
eration of toxic hydrogen sulfide has. For: this reason ventilation
of the treatment tanks may be a necessary precaution in some in-
stallations. The use of ferrous sulfide virtually eliminates the
problem of hydrogen sulfide evolution, however. As with hydroxide
precipitation, excess sulfide must be present to drive the
precipitation reaction to completion. Since sulfide itself is
toxic, sulfide addition must be carefully controlled to maximuze
heavy metals precipitation with a minimum of.excess sulfide to
avoid the necessity of posttreatment. At very high excess sul-
fide levels and high pH, soluble mercury-sulfide compounds may
also be formed. Where excess sulfide is present, aeration of
the effluent stream can aid in oxidizing residual sulfide to the
less harmful sodium sulfate (Na2So.). The cost of sulfide pre-
cipitants is high in comparison with hydroxide precipitating agents,
and disposal of metallic sulfide sludges may pose problems.
Speculation is that with improper handling or disposal of sulfide
precipitates, hydrogen sulfide may be released to the atmosphere
XII-80
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creating a potential toxic hazard, toxic metals may be leached
out into surface waters, and sulfide might oxidize to sulfate and
release dilute sulfuric acid to surface waters. An essential
element in effective sulfide precipitation is the removal of
precipitated solids from the wastewater to a site where reoxidation
and leaching are not likely to occur. .
Operational Factors
Reliability; The reliability of sulfide precipitation is high,
although proper monitoring, control, -and pretreatment to re-
move interfering substances is required.
Maintainability; The major maintenance needs involve periodic
upkeep of monitoring equipment, automatic feeding equipment,
mixing equipment, and other hardware. Removal of accumulated
sludge is necessary for efficient operation of sulfide pre-
cipitation systems.
Solid Waste Aspects; Solids which precipitate but are removed
in a subsequent treatment step. Ultimately, the solids must be
properly disposed of. There is disagreement over the accepta-
bility of s'ulfide and other sludges for landfill, as discussed
above.
Demonstration Status
Pull scale commercial sulfide precipitation units are in opera-
tion at numerous installations.
PRESSURE FILTRATION •
Description of the Process
Pressure filtration is achieved by pumping the liquid through a
filter material which is impenetrable to the solid phase. The
positive pressure exerted by the feed pumps or other mechanical
means provides the pressure differential which is the principal
driving force. Figure 12-58 represents the operation of one
type of pressure filter.
A typical pressure filtration unit consists of a number of
plates or trays which are held rigidly in a frame to ensure
alignment and are pressed together between a fixed end and a
traveling end. On the surface of each plate is mounted a
filter made of cloth or a synthetic fiber. The wastewater is
pumped into the unit and passes through feed holes in the trays
along the length of the press until the cavities or chambers
between the trays are completely filled. The solids in the
water are then entrapped, and a cake begins to form on the
XII-81
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PERFORATED
BACKING PLATE
\
FABRIC
FILTER MEDIUM
INLET
SLUDGE
FABRIC
FILTER MEDIUM
SOLID
RECTANGULAR
END PLATE
SOLIDS
AND FRAMES ARE PRESSED
DURING FILTRATION
FILTERED LIQUID OUTLET
RECTANGULAR
METAL PLATE
RECTANGULAR FRAME
FIGURE 12-58
PRESSURE FILTRATION
XII-82
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surface of the filter material. The water passes through the
fibers, and the solids are retained. .
At the bottom of the trays are drainage ports. The filtrate is
collected and discharged to a common drain. As the filter
medium becomes coated with sludge, the flow of filtrate through
the filter drops sharply, indicating that the capacity of the ,
filter has been exhausted. The unit must then be cleaned of
the sludge. After the cleaning or replacement of the filter
media, the unit is again ready for operation.
Application and Performance T
Pressure filtration is a technique which can be found in many
industry applications concerned with removing solids from their
waste stream.. In a typical pressure filter, chemically"pre-
conditioned sludge detained in the unit for one to three hours
under pressures varying from 5 to 13 atmospheres exhibited
final moisture content between 50 and 75 percent.
Advantages and ^Limitations • : -.•'•',.
The pressures which may be applied to a sludge for removal of
water by filter presses that are currently available range from
5 to 1,3 atmospheres. Pressure filtration .may also reduce the
amount of chemical pretreatment required. The sludge, retained
in the form of the filter cake, has a higher percentage of
solids] than either a centrifuge or vacuum filter yield. Thus,
the sludge can be easily accommodated by materials handling
systems.
Two disadvantages associated with pressure filtration in the
past have .been the short life of the filter cloths and lack of
automation. New synthetic fibers have largely offset the first
of these problems. Also, units with automatic feeding and
pressing cycles are now available.
For larger operations, the relatively high space requirements,
as compared to those of a centrifuge, also can be considered as
a disadvantage,
Operation Factors
Reliability; Assuming proper pretreatments design, and control,
pressure filtration is a highly dependable system.
I
Maintainability; Maintenance consists of periodic cleaning or
replacement of the filter media, drainage grids, drainage
piping, filter pans, and other parts of the system. If the
removal of the sludge cake is not automated, -additional time is
required for this operation. *
XII-83
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Solid Waste Aspects; Because it is generally drier than other
types of sludges, the filter sludge cake can be handled with
relative ease. Disposal of the accumulated sludge may be
accomplished by any of the accepted procedures.
Demonstration Status
Pressure filtration is a commonly used technology that is
currently utilized in a great many commercial applications.
Pressure filtration is used in several E&EC plants.
MEMBRANE FILTRATION I
Description of the Process
Membrane filtration is a technique for removing precipitated
heavy'metals from a wastewater stream. It must therefore be
preceded by those treatment techniques which will properly
prepare the wastewater for solids removal. Typically, a membrane
filtration unit is preceded by cyanide and chromium pretreatment
as well as pH adjustment for precipitation of the metals.
These steps are followed by addition of a!proprietary chemical
reagent which causes-the metal precipitate to be non-gelatinous,
easily d.ewatered, and highly stable. The resulting mixture of
pretreated wastewater and reagent is continuously recirculated
through a filter module and back into a recirculation tank.
The filter module contains tubular membranes. While the reagent-
metal precipitate mixture flows through the inside of the
tubes, the water and any dissolved salts permeate the membrane.
The permeate, essentially free of precipitate, is alkaline,
non-corrosive, and may be safely discharged to sewer or stream.
When the recirculating slurry reaches a concentration of 10 to
15 percent solids, it is pumped out of the system as sludge.
Application and Performance :
Membrane filtration can be used in E&EC manufacture in place of
sedimentation or clarification to remove precipitated metals
and phosphates. Membrane filtration systems are being used in
a number gf industrial applications, particularly in the metal
finishing industry and have also been used for heavy metals
removal ,in the paper industry. They have potential application
in coil coating, porcelain enameling, battery, and copper and
copper alloy plants.
The permeate is guaranteed by one manufacturer to contain less
than the effluent concentrations shown in the following table,
regardless of the influent concentrations. These claims have
been largely substantiated by the analysis of water samples at
various plants including those shown for comparison in the
table.
Xll-84
-------
WASTEWATER CONSTITUENT
MEMBRANE FILTER EFFLUENT; mq/1
Guarantee Plant #19066
Plant #31022
Raw
Treated
Raw
Treated
Aluminum 0.5
Chromium, hexavalent 0.03
Chromium, total 0.02
Copper; 0.1
Iron 0.1
Lead 0.05
Cyanide 0.02
Nickel' 0.1
Zinc 0.1
TSS —-
Advantages and Limitations
0.46 0.01
4.13 0.018
18.8 0.043
288 0.3
0.652 0.01
<0.005 <0.005
9.56 0.017
2.09 0.046
632 <0.1
5.25
98.4
8.00
21.1
0.288
<0.005
194
5.00
13.0
<0.005
0.057
0.222
0.263
0.01
<0.005
0.352
0.051
8.0
A major advantage of the membrane filtration system rs that
installation can utilize most of the conventional end-of-pipe
system that may already be in place. Also, the sludge is
highly stable in an alkaline state. Removal efficiencies are ,
excellent, even with sudden variation of pollutant input rates.
However, the effectiveness of the membrane filtration system
can be limited by clogging of the filters. Because a change in
the pH of the waste stream greatly intensifies the clogging
problem, the pH must be carefully monitored and controlled.
Clogging can force the shutdown of the system and may interfere
with production.
Operational Factors
Reliability; Membrane filtration has been shown to be a very
reliable system, provided that the pH is strictly controlled.
Improper pH can result in the clogging of the membrane. Also,
surges in the flow rate of the waste stream must be eliminated
in order to prevent solids from passing through the filter and
into the effluent. ,
Maintainability; The membrane filters must be regularly monitored
and cleaned or replaced as necessary. Depending on the composi-
tion of the waste stream and its flow rate, cleaning of the
filters may be required quite often. Flushing with hydrochloric
acid will usually suffice. In addition, the routine maintenance
of pumps, valves, and other plumbing is required.
Solid Waste Aspects; When the recirculating reagent-precipitate
slurry reaches 10 to 15 percent solids, it is pumped out of the
system. It can then be disposed of directly or it can undergo
a dewatering process. The sludge's leaching characteristics
are such that the state of South Carolina has approved the
sludge for landfill, provided that an alkaline condition be
maintained. Tests carried out by the state indicate that even
XII-85
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at the slightly acidic pH of 6.5, leachate from a sludge contain-
ing 2600 mg/1 of copper and 250 mg/1 of zinc contained only 0.9
rag/1 of copper and 0.1 mg/1 of zinc.
Demonstration Status
There are approximately twenty membrane filtration systems pre-
sently in use by the metal finishing and other industries.
Bench scale and pilot studies are being run in an attempt to
expand the list of pollutants for which this system is known to
be effective.
No data have been reported showing the use of membrane filtration
in E&EC manufacturing plants. However, it is used in electro-
plating plants and the technology can be transferred to the
electronics industry discharge.
GRANULAR BED FILTRATION
Description of the Process
Filtration is basic to water treatment technology, and experience
with the process dates back to the 1800's. Filtration occurs
in nature as the surface ground waters are purified by sand.
Silica sand, anthracite coal, and g"arnet are common filter
media used in water treatment plants. These are usually
supported by gravel. The media may be used,singly or in combin-
ation. The multi-media filters may be arranged to maintain-
relatively distinct layers by virtue of balancing the forces of
gravity, flow, and buoyancy on the individual particles. This
is accomplished by selecting appropriate filter flow rates
(gpm/sg ft), media grain size, and density.
Granular bed filters may be classified in terms of filtration
rate, filter media, flow pattern, or method of pressurization.
Traditional rate classifications are slow sand, rapid sand, and
high rate mixed media. In the slow sand filter, flux or hydraulic
loading is relatively low, and removal of collected solids to
clean the filter is therefore relatively infrequent. The
filter is often cleaned by scraping off the inlet face (top) of
the sand bed. In the higher rate filters, cleaning is frequent
and is accomplished by a periodic backwash, opposite to the
direction of normal flow.
A filter may use a single medium such as sand or diatomaceous
earth, but dual and mixed (multiple) media filters allow higher
flow rates and efficiencies. Trfe dual media filter usually
consists of a fine bed of sand under a coarser bed of anthracite
coal. The coarse coal removes most of the influent solids,
while the fine sand performs a polishing function. At the end
of the backwash, the fine sand settles to the bottom because it
is denser than the coal, and the filter is ready for normal
operation. The mixed media filter operates on the same principle,
with the finer, denser media at the bottom and the coarser,
XII-86
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less dense media at the top. The usual arrangement is garnet
at the bottom (outlet end) of the bed, sand in the middle, and
anthracite coal at the top. Some mixing of these layers occurs
and is, in fact, desirable.
The flow pattern is usually top-to-bottom, but other patterns
are sometimes used. Upflow filters are sometimes used, and in a
horizontal filter the flow is horizontal. In a biflow filter,
the influent enters both the top and the bottom and exits
laterally. The advantage of an upflow filter is that with an
upflow backwash the particles of a single filter medium are
distributed and maintained in the desired coarse-to-fine
(bottom-to-top) arrangement. The disadvantage is that the bed
tends to become fluidized, which ruins filtration efficiency.
The biflow design is an attempt to overcome this problem.
The usual granular bed filter operates by gravity flow. However,
pressure filters are also used. Pressure filters permit higher
solids loadings before cleaning and are advantageous when the
filter effluent must be pressurized for further downstream
treatment. In addition, pressure filter systems are often less
costly for low to moderate flow rates.
Figure 12-59 depicts a granular bed filter. It is a high rate,
dual media, gravity downflow filter, with self-stored backwash.
Both filtrate and backwash are piped around the bed in an
arrangement that permits upflow of the backwash, with the
stored filtrate serving as backwash. Addition of the indicated
coagulant and polyelectrolyte usually results in a substantial
improvement in filter performance.
Auxiliary filter cleaning is sometimes employed in the upper
few inches of filter beds. This is conventionally referred to
as surface wash and is accomplished by water jets just below
the surface of the expanded bed during the backwash cycle.
These jets enhance the scouring action in the bed by increasing
the agitation.
An important feature for successful filtration and backwashing
is the ; underdrain. This is the support structure for the bed.
The underdrain provides an area for collection of the filtered
water without clogging from either the filtered solids or the
media grains. In addition, the underdrain prevents loss of the
media with the water, and during the backwash cycle it provides
even flow distribution over the bed. .Failure to dissipate the
velocity head during the filter or backwash cycle will result
in bed upset and the need for major repairs.
Several standard approaches are employed for filter underdrains.
The simple'st one consists of a parallel porous pipe imbedded
under ai layer of coarse gravel and manifolded to a header pipe
for effluent removal. Other approaches to the underdrain
system are known as the Leopold and Wheeler filter bottoms.
Both of these incorporate false concrete bottoms with specific
XII-87
-------
INFLUENT
VALVE
DRAIN
FIGURE 12-59
GRANULAR BED FILTRATION EXAMPLE
XII-88
-------
porosity configurations to provide drainage and velocity head
dissipation.
Filter system operation may be manual or automatic. The filter
backwash cycle may be on a timed basis, a pressure drop basis
with a terminal value wich triggers backwash, or a solids
carryover basis from turbidity monitoring of the outlet 'stream.
All of these schemes have been successfully used.
Application and Performance
Granular bed filters can be used in E&EC manufacturing plants
to remove residual solids from clarifier effluent. Filters in
wastewater treatment plants are often employed for polishing
following clarification, sedimentation, or other similar oper-
ations. Granular bed filtration thus has potential application
to nearly all industrial plants. Chemical additives which
enhance the upstream treatment equipment may or may not be
compatible with or enhance the filtration process. It should
be borne in mind that in the overall treatment system, effective-
ness and efficiency are the objectives, not the performance of
any single unit. The volumetric fluxes for various types of
filters "are as follows:
Slow Sand
Rapid Sand
High Rate Mixed Media
2.04 - 5.30 1/min/sq m
40.74 - 81.48 1/min/sq m
122.2 - 611 1/min/sq m
Suspended solids are commonly removed from wastewater streams
by filtering through a deep 0.3-0.9 m (1-3 feet) granular
filter bed. The porous bed formed by the granular media can be
designed to removal practically all suspended particles. Even
collodial suspensions (roughly 1 to 100 microns) are adsorbed
on the surface of. the media grains as they pass in close
proximity in the narrow bed passages.
Properly operating filters following some pretreatment to
reduce suspended solids well below 200 mg/1 should produce
water with less than 10 mg/1 TSS. Pretreatment with inorganic
or polymeric coagulants can improve poor performance.
Advantages and Limitations
The principal advantages of granular bed filtration are its low
initial and operating costs and reduced land requirements over
other methods,to achieve the same level of solids removal.
However, the filter may require pretreatment if the solids
level is high (above 100 to 150 mg/1). Operator training is
fairly high due to controls and periodic backwashing, and
backwash must be stored and dewatered to be disposed of
economically.
XII-89
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Operational Factors
Reliability; The recent improvements in filter technology have
significantly improved filtration reliability. Control systems,
improved designs, and good operating procedures have made
filtration a highly reliable method of water treatment.
Maintainability; Deep bed filters may be operated with either
manual or automatic backwash. In either case, they must be
periodically inspected for media attrition, partial plugging,
and leakage. Where backwashing is not used, collected solids
must be removed by shoveling, and filter media must be at least
partially replaced.
Solid Waste Aspects; Filter backwash is generally recycled
within the wastewater treatment system, so that the solids
ultimately appear in the clarifier sludge stream for subsequent
dewatering. Alternatively, the backwash stream may be dewatered
directly or, if there is no backwash, the collected solids may
be suitably disposed. In either of these situations there is a
solids disposal problem similar to that of clarifiers.
Demonstration Status '•
Deep bed filters are in common use in municipal treatment
plants. Their use in polishing industrial clarifier effluent is
increasing, and the technology is proven and conventional.
ULTRAFILTRATION
Description of the Process
Ultrafiltration (UF) is a process using semipermeable polymeric
membranes to separate emulsified or colloidal materials dis-
solved or suspended in a liquid phase by pressurizing the
liquid so that it permeates the membrane. The membrane of an
ultrafilter forms a molecular screen which separate molecular
particles based on their differences in size, shape, and chemical
structure. The membrane permits passage of solvents and lower
molecular weight solutes while barring dissolved or dispersed
molecules above a predetermined size. At present, an ultrafilter
is capable of removing materials with molecular weights in the
range of 1,000 to 100,000.
In an ultrafiltration process, the feed solution is pumped
through a tubular membrane unit. Water and some low molecular
weight materials pass through the membrane under the applied
pressure of 0.767 kg/cnr (10 to 100 psig). Emulsified oil
droplets and suspended particles are retained, concentrated,
and removed continuously. In cpntrast to'ordinary filtration,
retained materials are washed off the membrane filter rather
than held by the filter. Figure 12-60 illustrates the ultrafil-
tration process.
XII-90
-------
ULTRAFILTRATION
\
MACROMOLECULES
J*
P=10-50 PSI %
MEMBRANE
M
WATER SALTS
•MEMBRANE
PERMEATE
u
O- • r»* *r> * O * • * * O * O« •' • *
FEED* *Q * ^>«»* ^. •* °* *;o* *. 'CONCENTRATE
• 6 *o • o . e ° e / ° o * ° ^
T
O OIL PARTICLES oDISSOLVED SALTS AND LOW-
MOLECULAR-WEIGHT ORGANICS
FIGURE 12-60
SIMPLIFIED ULTRAFILTRATION FLOW SCHEMATIC
XII-91
-------
The pore structure of the membrane acts as a filter, passing
small particles, such as salts, while blocking larger emulsified
and suspended matter. The pores of ultrafiltration membranes
are much smaller than the blocked particles. Therefore, these
particles cannot clog the membrane structure. Clogging of the
membrane by particles near the minimum removal size can be
minimized by proper selection of the membrane to suit the
wastewater to be treated.
Once a membrane is chosen that provides maximum attainable
removal of the desired particles, the next most important
design criterion is the membrane capacity or flux. Flux is the
volume of water passed through the membrane area per unit time.
The standard units are cu m/day/sq m (gpd/sq ft). The typical
flux is 0.42 to 8.48 cu m/day/sq m (5 to 1000 gph/sq ft). Both
membrane equipment and operating costs increase with the membrane
area required. It is, therefore, desirable to maximize flux.
Membrane flux is normally dependent on operating pressure,
temperature, flux velocity, solids concentration (both total
dissolved solids and total suspended solids), membrane permeabil-
ity, membrane thickness, and fluid viscosity. Membrane flux is
also affected by the surface tension of the solution being
processed. With a fixed geometry, membrane flux will increase
as the^fluid velicity is increased in the system. This increase
in fluid velocity will require greater capacity and more horse-
power. Less membrane area is, therefore, required per unit of
effluent to be treated with higher fluid velocities; membrane
replacement and initial capital costs decrease. Opposing these
cost decreases is the increase in power and its resultant cost.
Application and Performance
i
Oltrafiltration has potential application to E&EC manufacturing
plants for separation of oils and residual solids from a variety
of waste streams and for regeneration of alkaline baths associated
with ancillary metal working and metal cleaning. Successful
commercial use has been thoroughly demonstrated for separation
of emulsified oils from wastewater. Over one hundred such
units are now in operation in the United States, treating
emulsified oils from a variety of industrial processes. Currently
operating units have capacities of from a few hundred gallons a
week to 50,000 gallons per day. Concentration of oily emulsions
to 60% oil or more is possible. Oil concentrates of 40% or
more are generally suitable for incineration, .and the permeate
can be treated further and in some cases recycled back to the
process. In this way, it is possible to eliminate contractor
removal costs for oil from some oily waste streams.
Work is currently being done in ultrafiltration systems to
purify alkaline cleaning baths for re-use. In this application,
the contaminated caustic solution is pumped through the ultra-
filter, and oil and particulate matter are concentrated within
the membrane. The alkaline cleaner solution permeates the
XII-92
-------
membrane and can be returned to the process bath. The membrane
is designed to withstand pH within the range of 9-13. Contami-
nants present in the concentrate are further concentrated,
reclaimed, incinerated,*or dispoiled of brother means.
The following test data indicate ultrafiltration performance
(note that UP is not intended to remove dissolved solids):
Contaminant
Oil (freon extractable)
COD
TSS
Total Solids
Feed (mg/1)
1230
8920
1380
2900
Permeate (mg/1)
4
148
13
296
The removal percentages shown are typical, but they can be
influenced by pH and othe-r conditions.
The permeate or effluent from the ultrafiltration unit is
normally of a quality that can be reused in industrial applica-
tions or discharged directly. The concentrate from the ultrafil-
tration unit can be disposed of readily by incineration for oil
wastes or by standard end-of-pipe oil and solids removal from
the low-volume concentrate.
Advantages and Limitations
Ultrafiltration is sometimes an attractive alternative to
chemical treatment because of lower capital equipment; install-
ation and operating costs; very high oil* removal efficiency,
independent of influent oil content; little, if any, pretreatment
required; and because of its compact equipment, which utilizes
only a small amount of floor space. It provides a positive
barrier between oil and effluent. This eliminates the possibility
of oil discharge which might occur due to operator error.
A limitation of ultr.afiltration for treatment of process effluents
is its narrow temperature range (181[?C to 301[?C) for satisfactory
operation. Membrane life is decreased with higher temperatures,
but flux increases at elevated temperatures. Therefore, surface
area requirements are a function of temperature arid become a
tradeoff between initial costs and replacement costs for the
membrane. In addition, ^ultrafiltration is unable to handle
certain solutions. Strong oxidizing agents, solvents, and
other organic compounds can cause dissolution of the membrane.
Fouling is sometimes a problem.
Operational Factors
Reliability; The reliability of an ultrafiltration system is
dependent on the proper filtration of incoming waste streams to
prevent damaging the membrane.
XII-93
-------
Maintainability; A limited amount of regular maintenance is
required for the pumping system. In addition, membranes must
be periodically changed. Maintenance associated with membrane
plugging can be reduced to selection of a membrane with optimum
physical characteristics.
Solid Waste Aspects: Ultrafiltration is used primarily for
recovery of solids and liquids. It therefore eliminates solid
waste problems when the solids (e.g., paint solids) can be
recycled to the process. Otherwise, the stream containing
solids must be treated by end-of-pipe equipment.
Demonstration Status
The ultrafiltration process is well developed and commercially
available for treatment of wastewater or recovery of certain
liquid and solid contaminants. However, no E&EC manufacturing
plants have reported using ultrafiltration.
ION EXCHANGE ;
Description of the Process
Ion exchange is a process in which ions, held by electrostatic
forces to charged functional groups on the: surface of the ion
exchange resin, are exchanged for ions of [similar charge from
the solution in which the resin is immersed. This is classi-
ied as a sorption process because the exchange occurs on the
surface of the resin, and the exchanging ion must undergo a
phase transfer from solution phase to solid phase. Thus, ionic
contaminants in a waste stream can be exchanged for the harmless
ions of the resin. j
I
Although the precise technique may vary slightly according to
the application involved, a generalized process description
follows. The wastewater stream being treated passes through a
filter to remove any solids, then flows through a cation exchanger
which contains the ion exchange resin. Here, metallic impurities
such as copper, iron, and trivalent chromium are retained. The
stream then passes through the anion exchanger and its associated
resin. Hexavalent chromium, for example, is retained in this
stage. If one pass does not reduce the contaminant levels
sufficiently, the stream may then enter another series of
exchangers. Many ion exchange systems are;equipped with more
than one set of exchangers for this reason;
The other major portion of the ion exchange process concerns
the regeneration of the resin, which now hcblds those impurities
retained from the waste stream. An ion exchange unit with in-
place regeneration is shown in Figure 12-6:).. Metal ions such
as nickel are removed by an acidic cation exchange resin, which
is regenerated with hydrochloric or sulfuric acid, replacing
the metal ion with one or more hydrogen ions. Anions such as
dichromate are removed by a basic anion exchange resin, which
XII-94
-------
WASTE WATER CONTAINING
DISSOLVED METALS
Oft OTHER IONS
HEGENERANT TO REUSE.
TREATMENT, OR DISPOSAL
OIVERTER VALVE
REGENERANT
SOLUTION
DIVERTED VALVE
METAL—FREE WATER
FOR REUSE OR DISCHARGE
FIGURE 12-61
ION EXCHANGE W!TH REGENERATION
XII-95
-------
is regenerated with sodium hydroxide, replacing the anion with
one or more hydroxyl ions. The three principal methods employed
by industry for regenerating the spent resin are:
A) Replacement Service; A replacement service replaces the
spent resin with regenerated resin, and regenerates the
spent resin at its own facility. The service then has the
problem of treating and disposing of the spent regenerant.
B) In-Place Regeneration; Some establishments may find it
less expensive to do their own regeneration. The spent
resirt column is shut down for perhaps an hour, and the
spent resin is regenerated. This results in one or more
waste streams which must be treated in an appropriate
manner. Regeneration is only performed as the resins
require it.
C) Cyclic Regeneration; In this process, the regeneration of
the spent resins takes place in alternating cycles with
the ion removal process. A regeneration frequency of
twice an hour is typical. This very short cycle time
permits operation with a very small quantity of resin and
with fairly concentrated solutions, resulting in a very
compact system. Again, this process varies according to
application, but the regeneration cycle generally begins
with cfaustic being pumped through the anion exchanger,
carrying out hexavalent chromium, for example, as sodium
dichromate. The sodium dichromate stream then passes
through a cation exchanger, converting the sodium dichro-
mate to chromic acid. After concentration by evaporation
or other means, the chromic acid cai|i be returned to the
process line. Meanwhile, the catioiji exchanger is regener-
ated with sulfuric acid, resulting in a waste acid stream
containing the metallic impurities temoved earlier.
Flushing the exchangers with water completes the cycle.
Thus, the wastewater is purified and, in this example,
chromic acid is recovered. The ion exchangers, with newly
regenerated resin, then enter the ion removal cycle again.
Application and Performance '
I
Ion exchange could be used in E&EC manufacturing plants for
recovery of copper, zinc, or other metals from process chemical
baths and rinses associated with manufacturing.
The list of pollutants for which the ion exchange system has
proven effective include aluminum, arsenic, cadmium, chromium
(hexavalent and trivalent), copper, cyanide, gold, iron, lead,
manganese, nickel, selenium, silver, tin, zinc and more. Thus,
it can be applied to a wide variety of industrial concerns.
Because of the heavy concentrations of metals in their waste
water, the electronic and metal finishing industries utilize
ion exchange in several ways. As an end-of-pipe treatment, ion
exchange is certainly feasible, but its greatest value is in
XIi-96
-------
recovery applications. It is commonly used, however, as an
integrated treatment to recover rinse water and process chemicals.
Also, plating facilities utilize ion exchange to concentrate
and purify their plating baths. In addition to electronics,
ion exchange is finding applications in the photographic industry
for purification, in battery manufacturing for heavy metals
removal, in the chemical industry, the food industry, the
nuclear industry, the pharmaceutical industry, the textile
industry, and others. Ion exchange is already in use in the
E&EC manufacturing industry for production of deionized water,
which is used in large amounts in manufacturing semiconductors,
TV and CRT's and fluorescent lamps.
Ion exchange is highly efficient at recovering metal finishing
chemicals. Recovery of chromium, .nickel, phosphate solution,
and sulfuric acid from anodizing is commercial A chromic acid
recovery efficiency of 99.5% has been demonstrated. Typical
data (Bg/1) for purification of rinse water have been reported
as follows:
Parameter
All Values mg/1
Zinc (Zn)
Cadmium (Cd)
Chromium (Cr+3)
Chromium (Cr+6)
Copper (Cu)
Iron ( Fe )
Nickel (Ni)
.Silver (Ag)
Tin (Sn)
Cyanide (CN)
Manganese (Mn)
Aluminum (Al)
Sulf ate (SO )
Lead (Pb)
Gold (Au)
Plant
Prior To
Purifi-
cation
14.8
5.7
3.1
7.1
4.5
7.4
6.2
1.5
1.7
9.8
4.4
5.6
—
A
After
Purifi-
cation
0.40
0.00
0.01
0.01
0.09
Of\ i
. 01
0.00
0.00
0.00
0.04
0.00
00 f\
. 20
-
Plant
Prior To
Purifi-
cation
-
™
"""
— •
43.0
—
1.60
9.10
1.10
3.40
210.00
1.70
2.30
B
After"
Purifi-
cation
-
~
0.10
0.01
0.01
0.10
0.09
2.00
0.01
0.10
Advantages and Limitations
Ion exchange is a versatile technology applicable to a great
many situations. This flexibility, along with its compact
nature and performance, make ion exchange a very effective
method of waste -water treatment. However, the resins in these
systems can prove to be a limiting factor. The thermal limits
of the anion resins, generally placed in the vicinity of 60°C,
could prevent its use in certain situations. Similarly, nitric
acid, chromic acid, and hydrogen peroxide can all damage the
resins as will iron, manganese, and copper when present with
XII-97
-------
sufficient concentrations of dissolved oxygen. Removal of a
particular trace contaminant may be uneconomical because of the
presence of other ionic species that are preferentially removed.
The cost of the regenerative chemicals can be high. In addition,
the waste streams originating from the regeneration process are
extremely high in pollutant concentrations, although low in
volume. These must be further processed for proper disposal.
Operational Factors '<
Reliability; With the exception of occasional clogging or
fouling of the resins, ion exchange has been shown to be a
highly dependable technology assuming proper prior treatment of
the waste stream has taken place.
i
Maintainability; Along with the normal maintenance of pumps,
valves,,and other hardware, the regeneration process constitutes
the largest portion of the maintenance requirements. Unless
the cyclic type regeneration is used, the regeneration, process
inevitably involves the shutdown of the ion exchange units as
well as additional labor costs. In most cases, however, the
regeneration process can be effected quickly and easily.
Solid Waste Aspects; Few, if any, solids accumulate within the
ion exchangers, and those which do appear are removed by the
regeneration process. Proper prior treatment and planning can
eliminate solid buildup problems altogether. In fact, use of
ion exchange for recovery avoids sludge generation that would
result from end-of-pipe treatment. I
Demonstration Status i
All the applications mentioned in this document are available
for commercial use. The research and development in ion exchange
is focusing on improving the quality and efficiency of the
resins, rather than new applications. Work is also being done
on a continuous regeneration process whereby the resins are
contained on a fluid-transfusible belt. Thte belt passes through
a compartmented tank with ion exchange, washing, and regeneration
sections. The resins are therefore continually used and regenerated
No such system, however, has been reported ;to be beyond the
pilot stage.
No data have been reported showing the use of ion exchange in
treating effluents from E&EC manufacturing plants. However,
ion exchange is used in the production of dpionized water for
the semi-conductor and electron tube industries.
REVERSE OSMOSIS \
\
Description of the Process !
The process of osmosis involves the passage of a liquid through
a semipermeable membrane from a dilute to a;more concentrated
XII-98
-------
solution. Reverse osmosis (RO) is an operation in which
pressure is applied to the more concentrated solution, forcing
the permeate to diffuse through the membrane and into the more
dilute solution. This filtering action produces a concentrate
and permeate on opposite sides of the membrane. The concentrate
can then be further treated or returned to the original operation
for continued use, while the permeate water can be recycled to
for reuse. Figure 12-62 represents a reverse osmosis system.
As illustrated in Figure 12-63, there are three basic configura-
tions used in commercially available RO modules: tubular,
spiral-wound, and hollow fiber. All of these operate on the
principle described above, the only difference being their
mechanical and structural design characteristics.
The tubular membrane module utilizes a porous tube with a
cellulose acetate membrane-lining. A common tubular module
consists of a length of 2.54 cm (1 inch) diameter tube wound on
a supporting spool and encased in a plastic shroud. Feed water
is driven into the tube under pressures varying from 40.8 -
54 4 a1-m (600-800 psi). The permeate passes through the walls
of the"tube and is collected in a manifold while the concentrate
is drained off at the end of the tube. A less widely used
tubular RO module uses a straight tube contained in a housing,
under the same operating conditions.
Spiral-wound membranes consist of a porous backing sandwiched
between two cellulose acetate membrane sheets and bonded along
three ^dges. The fourth edge of the composite sheet is attached
to a large permeate collector tube. A spacer screen is then
placed on top of the membrane sandwich and the entire stack is
rolled around the centrally located tubular permeate collector.
The rolled up package is inserted into a pipe able to withstand
the high operating pressures employed in this process, up to
54.4 atm (800 psi) with the spiral-wound module. When the
system is operating, the pressurized product water permeates
the membrane and flows through the backing material to the
central collector tube. The concentrate is drained off at the
end of the container pipe and can be reprocessed or sent to
further treatment facilities.
The hollow fiber membrane configuration is made up of a bundle
of polyamide fibers of approximately 0.0076 cm (3 mils) OD and
0.0043 cm (1.7 mils) ID. A commonly used hollow fiber module
contains several hundred thousand of the fibers placed in a
long tube, wrapped around a flow screen, and rolled into a
soiral. The fibers are bent in a U-shape and their ends are
supported by an epoxy bond. The hollow fiber unit is operated
under 27.2 atm (400 psi), the feed water being dispersed from
the center of the module through a porous distributor tube.
Permeate flows through the membranes to the fiber interiors and
is collected at the ends of the fibers.
XII-99
-------
MACROMOLECULES
i AND
SOLIDS
=430 PS1
MEMBRANE
WATER
PERMEATE (WATER)
FEED
MEMBRANE CROSS SECTION.
IN TUBULAR. HOLLOW FIBER,
OR SPIRAL-WOUND CONFIGURATION
;.:(.-.•:. .f^/.-'-f "
• •o» % -O * • V • dL 'P. • ' . •
« 9
•p :
> O *P * O » « , t. ft? P. 4 *! °
•' )• •'••••' f'.'•*'j.*-(.
O SALTS OR SOLIDS
• WATER MOLECULES
CONCENTRATE
(SALTS)
FIGURE 12-62
i
SIMPLIFIED REVERSE OSMOSIS SCHEMATIC
i
XII-100 !
-------
KJMtATt MWESIVt tOUNO
SPIRAL M00UU
d-MINS MIMIRANC
SPIRAL MEMBRANE MODULE
fWow Support Tubi
with Mtmbr«n»
Product Wmr Pcrmutt Flow
BwckW. \
»—» Wmr \
' Fad Flow/\
(±
? I ** 'if
Product Wrtff
Brin*
Conc«ntr»»
Flow
TUBULAR REVERSE OSMOSIS MODULE
CONCENTRATE
SNAP RING OUTLET
ROW
OPEN ENDS
OF FIBERS
EPOXY
TUBE SHEET
trntNGSEAIi.
POROUS
BACK-UP DISC
END PLATE
SHAPRHK5
PERMEATE
FIBER
SHELL
•0- RING SEAL
POROUS FEED END PLATE
DISTRIBUTOR TUBE
HOLLOW FIBER MODULE
FIGURE 12-63
REVERSE OSMOSIS MEMBRANE CONFIGURATIONS
XII-101
-------
The hollow fiber and spiral-wound modules have a distinct
advantage over the tubular system in that they are able to load
a very large membrane surface area into a relatively small
volume. However, these two membrane types are much more suscep-
tible to fouling than the tubular system, which has a larger
flow channel. This characteristic also makes the tubular
membrane much easier to clean and regenerate than either spiral-
wound or hollow fiber modules. One manufacturer claims that
their helical tubular module can be physically wiped clean by
passing a soft porous polyurethane plug under pressure through
tne module. i
|
Application and Performance <
!
The largest industrial wastewater application of reverse osmosis
has been in plating to recover nickel and rinse water from
nickel deposition rinses. Reverse osmosis is used to close the
loop between plating and rinsing operations in the metal finish-
ing industry. The overflow from the first rinse in a counter-
current setup is directed to a reverse osmosis unit, where it
is separated into two streams. The concentrated stream contains
dragged out process chemicals and is returned to the process
bath to replace the loss of solution due ,to evaporation and
dragout. The dilute stream (the permeate!) is routed to the
last rinse tank to provide water, for the jrinsing operation.
The rinse flows from the last tank to the first tank and the
cycle is complete. :
i
The closed-loop system described above may be supplemented by
the addition of a vacuum evaporator after the RO unit in order
to further reduce the volume of reverse osmosis concentrate.
The evaporated vapor can be condensed andi returned to the last
rinse tank or sent on for further treatment. Another" variation
is to increase the rate of evaporation inl the process bath to
make room for reverse osmosis concentrate^.
,.^ s^own that R0 can generally be applied to most acid
metal baths with a high degree of performance, providing that
the membrane unit is not overtaxed. The limitations most
critical here are the allowable pH range and maximum operating
pressure for each particular configuration.. Application to
chromic acid and very high pH systems has | not been successful.
Plant 33065, a metal finishing facility, has a reverse osmosis
unit on its nickel plating line. The sampling results (mg/1)
of the raw input, permeate, and concentrate are shown below.
XII-102
-------
Parameter
Input
Permeate
Concentrate
TSS 1.0
Copper i .617
Nickel : . 276.
Chromium, Total .050
Zinc .846
Cadmium <.005
Tin -417
Lead <.01
2.0
.092
81.
.033
.159
<.005
.375
.067
20,700
.051
17.6
.006
.500
.021
One manufacturer claims that several RO units are being used to
dewater sludges generated by photographic processes. Reverse
osmosis has also been effective in removing zinc from diazo
solutions in laboratory experiments. Another company has
demonstrated the usefulness of RO in removing cutting oils and
machining coolants from wastewater streams in a pilot plant
operation.
Severa] new membrane materials are under development. A Japanese
firm has conducted experiments with a new RO membrane consisting
of a polybenzimidazolone (PBIL) polymer. The manufacturer
claims that it can handle a pH range from 1 to 12, temperatures
as high as 601I?C and is resistant to oxidation by chromic acid.
Test results for acid copper plating have been encouraging. In
contrast, performance of a polybenzimidazole (PBI) membrane has
been disappointing. Another membrane is being considered for
treatment of cyanide plating baths and has shown pH tolerance
in the 1 to 13 range. It is made up of a crosslinked poly-
ethyleneimine structure and is claimed to exhibit excellent
stability and RO performance. A polyamide composite membrane
also shows promise for both acid and alkaline cyanide service,
and a polyfurfury1 alcohol hollow fiber composite membrane is
effective for acid copper solutions. The only membranes readily
available commercially are the three described earlier, and
their overwhelming use has been for the recovery of various
acid metals plating baths.
Advantages and Limitations
The major advantage of reverse osmosis for handling process
effluents is its ability to concentrate dilute solutions for
recovery of salts and chemicals with low power requirements.
No latent heat of vaporization or fusion is required for effect-
ing separations; the main energy requirement is for a high
oressure pump. It requires relatively little floor space for
comllct? high capacity units, and it exhibits good recovery and
rejection rates for a number of typical process solutions.
Capital and operating costs are relatively low. A limitation
of the reverse osmosis process for treatment of process effluents
is its limited temperature range for satisfactory operation.
For cellulose acetate systems, the preferred limits are 18.3 to
XII-103
-------
29.4 degrees C (65 to 85 degrees F); higher temperatures will
increase the rate of membrane hydrolysis and reduce system
life, while lower temperatures will result in decreased fluxes
with no damage to the membrane. Another limitation is inability
to handle certain solutions. Strong oxidizing agents, strongly
acidic or basic solutions, solvents, and other organic compounds
can cause dissolution of the membrane. Poor rejection of some
compounds such as borates and low molecular weight organics is
another problem. Fouling of membranes by slightly soluble
components in solution or colloids has caused failures, and
fouling of membranes by feed waters with high levels of suspended
solids can be a problem. A final limitation is inability to
treat or achieve high concentration with some solutions. Some
concentrated solutions may have initial osmotic pressures which
are so high that they either exceed available operating pressures
or are uneconomical to treat.
Operational Factors
Reliability; Very good so long as the proper precautions are
taken to minimize the chances of fouling or degrading of the
membrane. Sufficient testing of the waste stream prior to
application of an RO system will provide.the information needed
to insure a successful application. [
I
Maintainability; Membrane life is estimated to fall between 6
months and 3 years, depending on the use cif the system. Down
time for flushing or cleaning is on the order of 2 hours as
often as once each week; a substantial portion of maintenance
time must be spent on cleaning any prefilters installed ahead
of the reverse osmosis unit. t
Solid Waste Aspects; In a closed loop sys'tem utilizing RO
there is a constant recycle of concentrate: and a minimal amount
of solid waste. Prefiltration eliminates kiany solids before
they reach the module and helps keep the buildup to a minimum.
These solids require proper disposal.
Demonstration Status ]
\
There are presently at least one hundred reverse osmosis waste-
water applications in a variety of industries. In addition to
these, there are thirty to forty units being used to provide
pure process water for several industries.
Despite the many types and configurations of membranes, only
the spiral-wound cellulose acetate membrane has had widespread
success in commercial applications. Reverse osmosis is used in
the E&EC industry for the production of ultrapure process water
for semiconductor manufacturing. !
XII-104
-------
CHEMICAL CHROMIUM REDUCTION
Description of the Process
Reduction is a chemical reaction in which electrons are trans-
ferred to the chemical being reduced from the chemical initiat-
ing the transfer (the reducing agent). Sulfur dioxide, sodium
bisulfite, sodium metabisulfite, and ferrous sulfate form
strong reducing agents in aqueous solution and are, therefore,
useful in industrial waste treatment facilities for the reduction
of hexavalent chromium to the trivalent form. The reduction
enables the trivalent chromium to be separated from solution in
conjunction with other metallic salts by alkaline precipitation.
Gaseous sulfur dioxide is a widely used reducing agent and pro-
vides a good example of the chemical reduction process. Reduc-
tion using other reagents is chemically similar. The reactions
involved may be illustrated as follows:
3
3
3 H2O
3 H2S03
Cr2(S04)3 + 5 H20
The above reaction is favored by low pH. A pH of 2 to 3 is
normal for situations requiring complete reduction. At pH
levels above 5, the reduction rate is slow. Oxidizing agents
such as dissolved oxygen and ferric iron interfere with the
reduction process by consuming the reducing agent.
I
A tyoical treatment consists of two hours retention in an
equalization tank followed by 45 minutes retention in each of
two reaction tanks connected in series. Each reaction tank has
an electronic recorder-controller device to control process
conditions with respect to pH and oxidation reduction potential
(ORP). Gaseous sulfur dioxide is metered to the reaction tanks
to maintain the ORP within the range of 250 to 300 millivolts.
Each of the reaction tanks is.equipped with a propeller agitator
designed to provide approximately one turnover per minute.
Following reduction of the hexavalent chromium, the waste is
combined with other waste streams for final adjustment to an
appropriate alkaline pH to remove chromium and other metals by
precipitation and sedimentation. Figure 12-74 shows a continuous
chromium reduction system.
Application and Performance
Chromium reduction is used in the E&EC manufacturing industry
for treating photolithographic solutions and rinses which con-
tain hexavalent chromium. The main application of chemical
reduction to the treatment of wastewater is in the reduction of
hexavalent chromium to trivalent chromium. Rinse waters and
cooling tower blowdown are two major sources of chromium in
waste streams. A study of an operational waste treatment
XII-105
-------
= 2
";x
=12
in a
a
H
a
UJ
Ui
XII-106
-------
facility chemically reducing hexavalent chromium has shown that
a 99.7% reduction efficiency is easily achieved. Final concen-
trations of 0.05 mg/1 are readily attained, and concentrations
down tb 0.01 mg/1 are documented in the literature.
i - I
Advantages and Limitations
The major advantage of chemical reduction of hexavalent chromium
is that it is a fully proven technology based on years of ex-
perience. Operation at ambient conditions results in minimal
energy consumption, and the process, especially when using
sulfur dioxide, is well suited to automatic control. Further-
more, the equipment is readily obtainable from many suppliers,
and operation is straightforward.
One limitation of chemical reduction of hexavalent chromium is
that for high concentrations of chromium, the cost of treatment
chemicals may be correspondingly high. When this situation
occurs, other treatment techniques are likely to be more
economical. Chemical interference by oxidizing agents is
possible in the treatment of mixed wastes, and the treatment
itself may introduce pollutants if not properly controlled..
Storagie and handling of sulfur dioxide is somewhat hazardous.
Operational, Factors
Reliability; Maintenance consists of periodic removal of
sludge, the frequency of which is a function of the input
concentrations of detrimental constituents.
Solid Waste Aspects; Pretreatment to eliminate substances
which will interfere with the process may often be necessary.
This process produces trivalent chromium which can be controlled
by further treatment. There may, however, be small amounts of
sludge collected due to minor shifts in the solubility of the
contaminants. This sludge can be processed by the main sludge
treatment equipment.
Demonstration Status
The reduction of chromium waste by sulfur dioxide or sodium
bisulfite is a classic process and is used by numerous plants
employing chromium compounds in pickling and non-contact cooling
operations. Chemical chromium reduction is used in one E&EC
manufacturing plant.
SKIMMING
,
Description of the Process
Pollutants with a specific gravity less than water will often
float unassisted to the surface of the wastewater. Skimming is
used to remove these floating wastes. Skimming normally takes
place in a tank designed to allow the floating debris to rise
XII-107
-------
and remain on the surface, while the liquid flows to an outlet
located below the floating layer. Skimming devices are therefore
suited to the removal of non-emulsified oils from raw waste
streams. Common skimming mechanisms include the rotating drum
type, which picks up oil from the surface1of the water as it
rotates. A knife edge scrapes oil from t^ie drum and collects
it in a trough for disposal or reuse. The water portion is
then allowed to flow under the rotating drum. Occasionally, an
underflow baffle is installed after the drum; this has the ad-
vantage of retaining any floating oil which escapes the drum
skimmer. The belt type skimmer is pulledtvertically through
the water, collecting oil from the surface which is again
scraped off and collected in a tank. Gravity separators, such
as the API type, utilize overflow and underflow baffles to skim
a floating oil layer from the surface of the wastewater. An
overflow-underflow baffle allows a small amount of wastewater
(the oil portion) to flow over into a trough for disposition or
reuse, while the majority of the water flows underneath the
baffle. This is followed by an overflow baffle, which is set at
a height relative to the first baffle such that only the oil
bearing portion will flow over the first baffle during normal
plant operation. A diffusion device, such as a vertical slit
baffle, aids in creating a uniform flow th'rough the system and-
increasing oil removal efficiency. ;
Application and Performance
Oil skimming is used in the E&EC manufacturing industry to
remove free oil from many different process wastewater streams.
Skimming is applicable to any waste stream containing pollutants
which float to the surface. It is commonliy used to remove free
oil, grease, and soaps. Skimming can be u^sed in conjunction
with air flotation or clarification in ord|er to increase its
effectiveness. ;
The removal efficiency of a skimmer is partly a function of the
retention time of the water in the tank. [Larger, more buoyant
particles require less retention time than; smaller particles.
Thus, the efficiency also depends on the composition of the
waste stream. The retention time required^ to allow flotation
and subsequent skimming varies from 1-15 mjinutes, depending on
the wastewater characteristics.
API or other gravity-type separators tend [to be more suitable
for use where the amount of surface oil flbwing through the
system is consistently significant. Drum and belt type skimmers
are applicable to waste streams which evidence smaller amounts
of floating^oil and where surges of floating oil are not a
problem. Using an API separator system in conjunction with a
drum type skimmer would be a very effectiv^ method of removing
floating contaminants from nonemulsified oily waste streams.
Examples of the performance of these systems are shown in the
following tabulation: |
XII-108
-------
Plant Skimmer Type
06058 API
0(5058 Belt
06041 Drum
11477 Belt
Oil &
Grease
In. (rag/1)
149779.
19.4
232.
61.
Oil &
Grease
Out (mg/1)
17.9
8.3
63.7
14.
Advantages and Limitations
Skimming as a pretreatment is effective in removing naturally
floating waste material and improves the performance of subsequent
downstream treatments.
Many pollutants, particularly dispersed or emulsified oil, will
not float "naturally" but require additional treatments.
Therefore, skimming alone will not remove all the pollutants
capable of being removed by more sophisticated technologies.
I
Operational Factors
i
Reliability; Because of its simplicity, skimming is a very re-
liable technique.
Maintainability; A mechanical skimming mechanism requires
periodic lubrication, adjustment, and replacement of worn
parts.
Solid Waste Aspects; The collected layer of debris must be
disposed of in an approved manner. Because relatively large
quantities of water are present in the collected wastes,
incineration is not always a viable disposal method.
Demonstration Status
Skimmi|ng is a common operation utilized extensively in industrial
waste treatment systems and is used by 3 plants in the present
data b£se.
COALESCING
Description of the Process
,i
The basic principle of coalescing involves the preferential
wetting of a coalescing medium by oil droplets which accumulate
on the1 medium, and then rise to the surface of the solution.
The most important requirements for coalescing media are wett-
ability for oil and large surface area.
Coalescing stages may be integrated with a wide variety of
gravity oil separation devices, and some systems may incorporate
XII-109
-------
several coalescing stages. In general, provision of preliminary
oil skimming treatment is desirable to avoid overloading the
coalescer. One commercially marketed system for oily waste
treatment (See Figure 12-65) combines coalescing with gravity
separation. In this unit, the oily waste enters the separator,
where the large droplets immediately move t:o the top surface of
the separator because of the specific gravity differential.
The^smaller droplets enter the corrugated plate area where
laminar flow produces coalescing of the oil droplets. The oil
droplets deposit on the surface of the plates and stream upward
through weep holes in the plates to the surface, where adjustable
skimmers remove the oil. Heavy solids are ideposited in the
entrance chamber before the oily wastewater enters the plate
area. |
I
Application and Performance j
i
Coalescing is not used in the E&EC industry for treatment of
oily wastes. i
Advantages and Limitations |
Coalescing allows removal of oil droplets too finely dispersed
for conventional gravity separation/skimming technology. It
can also significantly reduce the residence; times (and therefore
separator volumes) required to achieve separation of oil from
some wastes. Because of their simplicity, coalescing oil
separators provide generally high reliability and low capital
and operating costs. Coalescing is not generally effective in .
removing soluble or chemically stabilized emulsified oils. To
avoid plugging, coalescers must be protectejd by pretreatment
from very high concentrations of free oil ahd grease and suspended
solids. Frequent replacement of prefiltersi may be necessary
when raw waste oil concentrations are high.j
Operational Factors }
Reliability; Coalescing is inherently highly reliable because
there are no moving parts, and the coalescing substrate is
inert in the process and therefore not subject to frequent
regeneration or replacement requirements. Large loads or
inadequate prior treatment, however, may result in plugging or
bypassing of coalescing stages. !
Maintainability; Maintenance requirements are generally limited
to replacement of the coalescing medium on am infrequent basis.
Solid Wastes Aspects >
i
No appreciable solid waste is generated by this process, but
when coalescing occurs in a gravity separator the normal solids
accumulation is experienced. !
XII-110
-------
m
H
«
D
O
M
o
E-i
CO
M
O
en
o
XII-111
-------
Demonstration Status i
Coalescing has been fully demonstrated in|the copper and copper
alloys industry and in other industries generating oily waste-
water. It has not been observed in the EsiEC manufacturing
industry. j
CARBON ADSORPTION l
Description of the Process
Carbon adsorption in industrial wastewater treatment involves
passing the wastewater through a chamber containing activated
carbon. The use of activated carbon has been proven to be
applicable for removal of dissolved organics from water and
wastewater. In fact, it is one of the most efficient organic
removal processes available. This process is reversible, thus
allowing activated carbon to be regenerated and reused by the
application of heat and steam.
The term activated carbon applies to any amorphous form of
carbon that has been specially treated to give high adsorption
capacities. Typical raw materials include coal, wood, coconut
shells, petroleum base residues and char from sewage sludge
pyrolysis. A carefully controlled process bf dehydration,
carbonization, and oxidation yields a product which is called
activated carbon. This material has a high, capacity for adsorp-
tion, 500-1500 square meters/gram, resulting from a large number
of internal pores. Pore sizes generally rahge from 10-100
angstroms in radius. i
Activated carbon removes organic contaminants from water by the
process of adsorption, or the attraction and accumulation of
one substance on the surface of another. Activated carbon has
a preference for organic compounds and, because of this selec-
tivity, is particularly effective in removing organic compounds
from aqueous solutions. i
i
Some important but general rules based on considerations relating
to carbon adsorption capacity are:
Higher surface area will give a greater adsorption capacity.
Larger pore sizes will give a greaterjadsorption capacity
for large molecules. i
Adsorptivity increases as the solubility of the solute
decreases. For hydrocarbons, adsorption increases with
molecular weight. ;
Adsorption capacity will decrease with! increasing
temperature. I
For solutes with ionizable groups, maxjimum adsorption
will be achieved at a pH corresponding to the minimum
lonization.
XII-112
-------
The rate of adsorption is also an important consideration. For
example; while capacity is increased with the adsorption of
higher molecular weight hydrocarbons, the rate of adsorption is
decreased. Similarly, while temperature increases will decrease
the capacity, they may increase the rate of removal of solute
from solution.
Carbon adsorption requires pretreatment to remove excess sus-
pended solids, oils, and greases. Suspended solids in the
influent should be less than 50 ppm to minimize backwash require-
ments? £ downflow carbon bed can handle much higher levels (up
to 2000 ppm), but frequent backwashing is required. Backwashing
more than two or three times a day is not desirable; at 50 ppm
suspended solids, one backwash will suffice. Oil and grease
should be less than about 10 ppm. A high level of dissolved
inorganic material in the enfluent may cause problems with
thermal! carbon reactivation (i.e., scaling and loss of activity)
unless appropriate preventive steps are taken; such steps might
include pH control, softening, or the use of an acid waste on
the carbon prior to reactivation.
Activated carbon is available in both powdered and granular
form. The equipment necessary for a granular activated carbon
adsorption treatment system consists of the following: a
preliminary clarification or filtration unit to remove the bulk
of suspended solids; two or three adsorption columns packed
with activated carbon similar to the one shown in Figure 12-66;
a holding tank located between the adsorbers; and liquid transfer
pumps. Unless a reactivation service is utilized, a furnace
and associated quench tanks, spent carbon tank, and reactivated
carbon tank are necessary for reactivation. •
Powdered carbon is less expensive per unit weight than granular
carbon and may have slightly higher adsorption capacity but it
does have some drawbacks. For example, it is more difficult to
regenerate; it is more difficult to handle (settling characteris-
tics may be poor); and larger amounts may be required than for
granular systems in order to obtain good contact. One innova-
tive powdered carbon system uses wet oxidation for regeneration
instead of fluidized bed incineration. This technique has been
applied mainly to municipal treatment but can be used in
industrial systems.
The necessary equipment for a two stage powdered carbon unit is
as follows: four flash mixers, two sedimentation units, two
surge tanks, one polyelectrolyte feed tank, one dual media
filter, one filter for dewatering spent carbon, one carbon wet-
ting tank, and a furnace for regeneration of spent carbon.
!
Thermal regeneration, which destroys adsorbates, is economical
if carbon usage .is above roughly 454 kg/day (1000 Ibs/day).
Reactivation is carried out in a multiple hearth furnace or a
rotary kiln at temperatures from 870 °C to 988°C. Required
XII-113
-------
WASTE WATER
INFLUENT
DISTRIBUTOR
WASH WATER
BACKWASH
BACKWASH
REPLACEMENT CARBON
SURFACE WASH
MANIFOLD
liRBON REMOVAL. PORT
TREATED WATER
SUPPORT PI-ATE
i
FIGURE 12-66 |
ACTIVATED CARBON ADSORPTION IcOLUMN
XII-114
-------
residenpe times are of the order of 30 minutes. With proper
control, the carbon may be returned to its original activity;
carbon losses will be in the range of 4-9% and must be made up
with fr^sh carbon. Chemical regeneration may be used if only
one solute is present which can dissolve off the carbon. This
allows material recovery. Disposal of the carbon may be required
if use is less than approximately 454 kg/day (1000 Ibs/day)
and/or a hazardous component makes regeneration dangerous.
I
A new type of carbonaceous adsorbent is made by pyrolizing ion
exchange resins. These spherical adsorbents appear to have the
best characteristics of adsorbent resins and activated carbon.
They have a greater physical strength, attrition resistance,
and regeneration flexibility than either activated carbon or
polymeric resins. One type is particularly suited for halo-
genated organics and has greater capacity than selected carbons
for compounds such as 2-chloroethyl ether, bromodichloromethane,
chloroform, and dieldrin. Another type (based on a different
polymeric resin) is best suited for removing aromatics and
unsaturated hydrocarbons. A third type has a particularly high
capacity (46 mg/1 or 46.45 kg/cu m (2.9 Ib/cu ft) at 2000 mg/1)
for phenol and other relatively polar organic molecules. These
adsorbents are commercially available but have not yet been
proven in large scale operation.
Application and Performance
The principle liquid-phase applications of activated carbon
adsorption include sugar decolorization; municipal water purifi-
cation;! purifications of fats, oils, foods, beverages and
Pharmaceuticals; and industrial/municipal wastewater treatment.
Potentially, it is almost universally applicable because trace
organics are found in the wastewater of almost every industrial
plant. I
Carbon adsorption, when applied to well-treated secondary effluent,
is capable of reducing COD to less than 10 mg/1 and BOD to
under 2 mg/1. Removal efficiencies may be in the range of 30%
to 90% and vary with flow variations and different bed load-
ings. Carbon loadings in tertiary treatment plants fall within
the range of 0.25 to 0.87 kg of COD removed per kg of carbon,
and if ;the columns are operated downflow, over 90% suspended
solids jreduction may be achieved.
Quite frequently, segregated industrial waste streams are
treated with activated carbon. The contaminants removed
include BOD, TOC, phenol, color, cresol, polyesters, polynitro-
phenol/| toluene, p-nitrophenol, p-chlorobenzene/ chlorophenols,
insecticides, cyanides and other chemicals, mostly organic.
The flows being treated are generally small in comparison with
tertiary systems (less than 75,700 liters/day [20,000 gpd]).
XII-H5
-------
Thermal reactivation of the carbon does not become common until
flows are above 227,100 liters/day (60,000 gpd). Some installa-
tions reactivate their carbon chemically and; the adsorbate is
recovered. Recoverable adsorbates are known1to include phenol,
acetic acid, p-nitrophenol, p-chlorobenzene,ip-cresol, and
ethylene diamine. Carbon loadings approach one kg COD removal
per kg carbon in installations where the adsbrbates are easily
adsorbed and present in relatively high concentrations. In
other cases, where influent concentrations are lower and where
the adsorbates are not readily adsorbed, much lower loadings
will result. For example, it was determined;that brine wastewaters
containing 150-750 ppm phenol and 1500-1800 ppm acetic acid
could be reduced to about 1 ppm phenol and 100-200 ppm acetic
acid with phenol loadings in the range of 0.09-0.16 kg per kg
and acetic acid loadings in the range of 0.0^-0.06 kg per kg.
Prom metal finishing, loadings for cyanide removal have been
found to be on the order of 0.01 kg for influent concentrations
around 100 ppm. Loadings, for removal of hexavalent chromium
have been shown to be as high as 0.07 kg/kg carbon at 100 ppm
and 0.14 kg/kg carbon at 1000 ppm.
EPA isotherm tests have indicated that activated carbon is very
effective in adsorbing 65 percent of the organic priority
pollutants and reasonably effective for another 22 percent.
Specifically, for the organics of particular interest, activated
carbon was very effective in removing 2,4-dimethylphenol,
fluoranthene, isophorone, naphthalene, all plithalates, and
phenanthrene. It was reasonably effective on 1,1,1-trichloroethane,
1,1-dichloroethane, phenol, and toluene. Table. 12-15 summarizes
the treatability effectiveness for most of the organic priority
pollutants by activated carbon as compiled by, EPA. Table 12-16
summarizes classes of organic compound together with examples
of organics that are readily adsorbed on carbon.
Table 12-17 summarizes results from a carbon [adsorption treatment
system developed by a private concern under an EPA grant. The
results of this study show removal of organids to a level
exceeding 90%. The results also show high removal of s.ome
organics (i.e. benzene, toluene, 1,1,1-trichioroethane) and
little or no removal of others. j
Advantages and Limitations !
The major benefits of carbon treatment include applicability to
a wide variety of organics, with high removal efficiency.
Inorganics such as cyanide, chromium, and mercury are also
removed effectively. Variations in concentration and flow rate
are well tolerated. The system is compact, and recovery of
adsorbed compounds often occurs during thermal regeneration.
Xll-116
-------
! TABLE 12-15
Classes of Organic Compounds Adsorbed on Carbon
Organic
Chemical Class
Aromatic Hydrocarbons
Polynuclear Aromatics
Chlorinated Aromatics
Phenolics
Chlorinated Phenolics
*High Molecular Weight Aliphatic
and Branch Chain Hydrocarbons
Chlorinated Aliphatic Hydrocarbons
*High Molecular Weight Aliphatic
Acids land Aromatic Acids
*High Molecular Weight Aliphatic
Amines; and Aromatic Amines
! • ' ', ' " '
*High Molecular Weight Ketones,
Estersj, Ethers & Alcohols
Surfactants
i
I
Soluble! Organic Dyes
Examples of Chemical Class
benzene, toluene, xylene
naphthalene, anthracene
biphenyls
chlorobenzene, polychlorinated
biphenyls, aldrin, endrin,
toxaphene, DDT
phenol, cresol, resorcenol
and polyphenyls
trichlorophenol
pentachlorophenol
gasoline, kerbsine
1,1,1-Trichlorbethane,
trichloroethylene, carbon
tetrachloride, perchloro-
ethylene
tar acids, benzoic acid
aniline; toluene diamine
hydroquinone, polytheylene
glycol
alkyl benzene sulfbnates
methylene blue, Indigo
carmine
*High Molecular Weight includes compounds in the range of 4 to 20
carbon: atoms
XII-117
-------
Table 12-16 |
TREATABILITY RATING OF PRIORITY POLLUTANTS UTILZING CARBON ADSORPTION
Priority Pollutants
*Removal Rating
Priority Pollutants
*Removal Ratir
1. acenaphthene H
2. acrolein L
3. acrylonitrile L
4. benzene M
5. benzidine H
6. carbon tetrachloride M
(tetrachloromethane)
7. chlorobenzene H
8. 1,2,4-trichlorobenzene H
9. hexachlorobenzene H
10. 1,2-dichloroethane M
11. 1,1,1-trichloroethane M
12. hexachloroethane H
13. 1,1-dichloroethane M
14. 1,1,2-trichloroethane M
IS. 1,1,2,2-tetrachloroethane H
16. chlorcethane L
17. bis(chloromethyl) ether
18. bis(2-chloroethyl) ether M
19. 2-chloroethyl vinyl ether L
(mixed)
20. 2-chloronaphthalene H
21. 2,4t6-trichlorophenol H
22. parachlorometa cresol H
23. chloroform (trichloromethane) L
24. 2-chlorophenol . H
25. 1,2-dichlorobenzene H
26. 1,3-dichlorobenzene H
27. 1,4-dichlorobenzene H
28. 3,3-dichlorobenzidine H
29. 1,1-dichloroethylene L
30. 1,2-trans-dichloroethylene L
31. 2,4-dichlorophenol H
32. 1,2-dichloropropane M
33. 1,2-dichloropropylene H
(1,3,-dichloropropene)
34. 2,4-dimethylphenol H
35. 2,4-dinitrotoluene H
36. 2,6-dinitrotoluene H
37. 1,2-diphenylhydrazine H
38. ethylbenzene M
39. fluoranthene H
40. 4-chlorophenyl phenyl ether H
41. 4-bromophenyl phenyl ether H
42. bis(2-chloroisopropyl) ether M
43. bis(2-chloroethoxy)methane M
44. methylene chloride L
(dichloromethane)
45. methyl chloride (chlororaethane) L
46. methyl bromide (bromomethane) L
47. bromoform (tribromomethane) H
48. dichlorobromcmethane M
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
-------
CARBON ADSORPTION
TABLE 12-17
(AS REPORTED
Parameter Influent (mg/1)
Phenol
Phenol ios (class
test)*^
4-Nitrophenol
2, 6-Dinitro-o-cresol
1 , 3-Dichlorobenzene
1 , 4-Diciilorobenzene
bis(2-E1:hylhexyl)
ph thai ate
2,4-Dinitrotoluene
2, 6-Dinitrotoluene
Chloroform
Bromoform
Carbon tetrachloride
Dichl orobromome thane
Trichlorofluorome thane
Chi orod ibromome thane
1,1, 1-Tr ichloroe thane
Trichloroethylene
Tetrachloroethylene
Chlorobenzene
Benzene
Toluene
Ethvl benzene
0.440
0.627
0.056
0.011
ND
0.720
0.002
2.000
1.900
0.950
0.910
0.095
0.054
0.920
0.081
0.018
0.060
0.062
1.900
0.160
0.680
0.029
UNDER EPA GRANT)
Effluent (mg/1)
0.018
0.197
0
0
ND
0.470
0.001
0.330
0.450
0.051
0.100
0.006
0
0.013
0
0
0.006
0.007
0.012
0
0.004
0.007
% Removal
96
69
>99
>99
-
35
67
84
76
95
89
94
>99
99
>99
>99
90
88
>99
>99
>99
78
XII-119
-------
If carbon cannot be thermally desorbed, Jit must be disposed of
along with any adsorbed pollutants. Whejn thermal regeneration
is utilized, capital and operating costs' are relatively high.
Cost surveys show that thermal regeneration is generally economi-
cal when carbon usage exceeds about 454 [kg/day (1,000/lb-day) .
Carbon cannot remove low molecular weight or highly soluble
organics. It also has a low tolerance for suspended solids,
which must be removed to at least 50 ppm in the influent water.
Operational Factors i
i
Reliability; This system should be veryj reliable assuming
upstream protection and proper operation and maintenance proce-
dures . ]
\
Maintainability; This system requires periodic regeneration or
replacement of spent carbon and is dependent upon raw waste
load and process efficiency. .
Solid Waste Aspects; Solid waste from tjiis process is contami-
nated activated carbon that requires disposal. If the carbon
undergoes regeneration, the solid waste problem is reduced
because of much less frequent replacement.
i
Demonstration Status
'Carbon adsorption systems have been demonstrated to be practical
and economical for the reduction of COD,'BOD and related para-
meters in secondary municipal and industrial wastewaters; for
the removal of toxic or refractory organics from isolated
industrial waste-waters; for the removal! and recovery of certain
organics from wastewaters; and for the removal, at times with
recovery, of selected inorganic chemicals from aqueous wastes.
Carbon adsorp-tion must be considered a viable and economic
process for organic waste streams containing up to 1-5% of
refractory or toxic organics; its applicability for removal of
inorganics such as metals, although demonstrated in a few
cases, is probably much more limited. ;
l
Although carbon adsorption has not been observed in any E&EC
manufacturing facilities, it could be useful in removing trace
organics from wastewater. [
GRAVITY SLUDGE THICKENING j
Description of the Process I
In the gravity thickening process, dilute sludge is fed from a
primary settling tank or clarifier to a thickening tank. Rakes
stir the sludge gently to densify the slikdge and to push it to
XII-120
-------
a central collection well. The supernatant is returned to the
primary settling tank. The thickened sludge that collects on
the bottom of the tank is pumped to dewatering equipment or
hauled away. Figure 12-67 shows the construction of a gravity
thickener.
Application and Perfrmance
Thickeners are generally used in facilities where the sludge is
to be further dewatered by a compact mechanical device such as
a vacuum filter or centrifuge. Doubling the solids content in
the thickener substantially reduces capital and operating cost
of the subsequent dewatering device and also reduces cost for
hauling. The process is potentially applicable to almost any
industrial plant.
Organic sludges from sedimentation units of one to two percent
solids concentration can usually be gravity thickened to six to
ten percent; chemical sludges can be thickened to four to six
percent.j
Advantages and Limitations
The principal advantage of a gravity sludge thickening proces
is thatiit facilitates further sludge dewatering. Other advan-
tages are high reliability and minimum maintenance requirements.
Limitations of the sludge thickening process are its sensitivity
to the flow rate through the thickener and the sludge removal
rate. These rates must be low enough not to disturb the thickened
sludge.
I
Operational Factors
Reliability; Reliability is high assuming proper design and
operation. A gravity thickener is designed on the basis of
square feet per pound of solids per day, in which the required
surface!area is related to the solids per square meter per day
(pounds per square foot per day).
Maintainability; Twice a year, a thickener must be shut down
for lubrication of the drive mechanisms. Occasionally, water
must be pumped back through the system in order to clear sludge
pipes.
Solid Waste Aspects; Thickened sludge from a gravity thickening
process will usually require further dewatering prior to disposal,
incineration, or drying. The clear effluent may be recirculated
in part; ,or it may be subjected to further treatment prior to
discharge.
XII-121
-------
SLUDGE PUMP
OVERFLOW
RECYCLED
THROUGH
PLANT
FIGURE 12-67
MECHANICAL GRAVITY THICKENING
XII- 122
-------
Demonstration Status
:
Gravity sludge thickeners have not been observed in E&EC manufac-
turing plants, but are used throughout other industry segments
to reduce water content to a level where the sludge may be
efficiently handled. Further dewatering is usually practiced
to minimize costs of hauling the sludge to approved landfill
areas.
CENTRIFUGATION
Description of the Process
Centrifugation is the application of centrifugal force to
separate solids and liquids in a liquid/solid mixture or to
effect concentration of the solids. The application of centri-
fugal force is effective because of the density differential
normally found between the insoluble solids and the liquid in
which they are contained. As a waste treatment procedure,
centrifugation is applied to dewatering of sludges. One type
of centrifuge is shown in Figure 12-68.
There are three common types of centrifuges: the disc, basket,
and conveyor type. All three operate by removing solids under
the influence of centrifugal force. The fundamental difference
between the three types is the method by which solids are
collected and discharged.
In the disc centrifuge, the sludge feed is distributed between
narrow channels that are present as spaces between stacked
conical Idiscs. Suspended particles are collected and discharged
continuously through small orifices in the bowl wall. The
clarified effluent is discharged through an overflow weir.
A second type of centrifuge which is useful in dewatering
sludges is the basket centrifuge. In this type of centrifuge,
sludge feed is introduced at the bottom of the basket, and
solids collect at the bowl wall while clarified effluent over-
flows the lip ring at the top. Since the basket centrifuge
does not: have provision for continuous dischare of collected
cake, operation requires interruption of the feed for cake
discharge for a minute or two in a 10 to 30 minute overall
cycle.
The third type of centrifuge commonly used in sludge dewatering
is the conveyor type. Sludge is fed through a stationary feed
pipe into a rotating bowl in which the solids are settled out
against the bowl wall by centrifugal force. From the bowl
wall, tliey are moved by a screw to the end of the machine, at
which point whey are discharged. The liquid effluent is dis-
charged through ports after passing the length of the bowl.
XII-123
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LIQUID
OUTLET
SLUDGE
INLET
CYCLOGEAR
IMPELLER
FIGURE 12-68
CENTRIFUGA-tlON
XII-124
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Application and Performance
Virtually all of those industrial waste treatment systems
producing sludge can utilize centrifugation to dewater it.
Centrifugation is currently being used by a wide range of
industrial concerns. The performance of sludge dewatering by
centrifugation depends on the feed rate, the rotational velocity
of the drum, and the sludge composition and concentration.
Assuming proper design and operation, the solids content of the
sludge can be increased to 20-35 percent.
Advantages and Limitations
Sludge 'dewatering centrifuges have minimal space requirements
and show a high degree of effluent clarification. The operation
is simple, clean, and relatively inexpensive. The area required
for a centrifuge system installation is less than that required
for a filter system or sludge drying bed of equal capacity, and
the initial cost is lower.
Centrifuges have a high power cost that partially offsets the
low initial cost. Special consideration must also be given to
providing sturdy foundations and soundproofing because of the
vibration and noise that result from centrifuge operation.
Adequate electrical power must also be provided since large
motors are required.. The major difficulty encountered in the
operation of centrifuges has been the disposal of the concen-
trate which is relatively high in suspended, non-settling
solids.
l
Operational Factors
Reliability; Its reliability is high, assuming proper control
of factors such as sludge feed, consistency, and temperature.
Pre-treatment such as grit removal and coagulant addition may
be necessary. Pretreatment requirements will vary depending on
the composition of the sludge and on the type of centrifuge
employed.
Maintainability; Maintenance consists of periodic lubrication,
cleaning, and inspection. The frequency and degree of inspec-
tion required varies depending on the type of sludge solids
being dewatered and the maintenance service conditions. If the
sludge is abrasive, it is recommended that the first inspection
of the rotating assembly be made after approximately 1,000
hours of operation. If the sludge is not abrasive or corrosive,
then the initial inspection might be delayed. Centrifuges not
equipped with a continuous sludge discharge system require
periodic shutdowns for manual sludge cake removal.
xil-125
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Demonstration Status j
i
Sludge beds have been in common use in both municipal and
industrial facilities for many years. However, protection of
ground water from contamination is not Always adeqaute. Sludge
bed drying is used in one plant in the present data base.
VACUUM FILTRATION I
Description of the Process
In wastewater treatment plants, sludge dewatering by vacuum
filtration is an operation that is generally accomplished on
cylindrical drum filters. These drums have a filter medium
hich may be cloth made of natural or synthetic fibers, coil
springs, or a wire-mesh fabric. The drum is suspended above
and dips into a vat of sludge. As the dtfum rotates slowly, part
of its circumference is subject to an internal vacuum that
draws sludge to the filter medium. Water is drawn through the
porous filter cake to a discharge port, jand the dewatered
sludge, loosened by compressed air, is scraped from the filter
mesh. Because the dewatering of sludge'on vacuum filters is
relatively expensive per kilogram of water removed, the liquid
sludge is frequently thickened prior to iprocessing. A vacuum
filter is shown in Figure 12-69. j
Application and Performance i
i
Vacuum filters are frequently used both ;in municipal treatment
plants and in a wide variety of industries for dewatering
sludge. They are most commonly used in larger facilities, which
have a thickener to double the solids content of clarifier
sludge before vacuum filtering. The function of vacuum filtra-
tion is to reduce the water content of sludge, so that the
proportion of solids increases from aboujt 5 percent to about 30
percent. . j
i
Advantages and Limitations j
Although the initial cost and area requirement of the vacuum
filtration system are higher than those iof a centrifuge, the
operating cost is lower, and no special provisions for sound
and vibration protection need be made. [The dewatered sludge
from this process is in the form of a mo;ist cake and can be
conveniently handled. j
Operational Factors j
!
Reliability: Vacuum filter systems have1 proven reliable at
many industrial and municipal treatment facilities. At present,
the largest maunicipal installation is at the West Southwest
wastewater treatment plant of Chicago, Illinois, where 96 large
filters were installed in 1925, functioned approximately 25
years, and then were replaced with larger units. Original
XII-126
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DIRECTION OF ROTATION
FABRIC OR WIRE
FILTER MEDIA
STRETCHED OVER
REVOLVING DRUM
VACUUM
SOURCE
CYLINDRICAL
FRAME
LIQUID
THROUGH
MEDIA BY
MEANS OF
VACUUM
SOLIDS SCRAPED
OFF FILTER MEDIA
e*
.**
SOLIDS COLLECTION
HOPPER
INLET LIQUID
TO BE
FILTERED
FILTERED LIQUID
FIGURE 12-69
VACUUM FILTRATION
XII-127
-------
vacuum filters at Minneapolis-St. Paul, Minnesota now have over
38 years of continuous service, and Chicago has some units with
similar or greater service life. j
Maintainability; Maintenance consists of the cleaning or
replacement of the filter media, drainag|e grids, drainage
piping, filter pans, and other parts of the equipment. Experi-
ence in a number of vacuum filter plants indicates that mainte-
nance consumes approximately 5 to 15 percent of the total time.
If carbonate buildup or other problems are unusually severe,
maintenance time may be as high as 20 percent.
If intermittent operation is to be employed, the filter equipment
should be drained and washed each time it is taken out of
service and an allowance for wash time should be made in the
selection of sludge filtering schedules.!
Solid Waste Aspects; Vacuum filters generate a solid cake.
All of the metals extracted from the plant wastewater are
concentrated in the filter cake as hydroxides, oxides, sulfides,
or other salts. These metals are subject, to leaching into
ground water, especially under acid conditions.
F
Demonstration Status i
i
Vacuum filtration has been widely used for many years. It is a
fully proven, conventional technology foi: sludge dewatering.
Vacuum filtration is used in four plants i in the present data
base.
SLUDGE DISPOSAL j
There are several methods of disposal of sludges from industrial
wastewater treatment. The two most common techniques are
land-filling by the company on its own property and removal by
licensed contractor to an outside landfill or reclamation
point. Other disposal techniques used for industrial waste
sludges include incineration, lagooning, 'evaporative ponds, and
pyrolysis. This latter technique produces a dewatered ash or
sludge which requires ultimate disposal by either contractor
hauling or on-site landfilling. j
i
IN-PROCESS POLLUTION CONTROL TECHNIQUES !
— , ___ !
Introduction ;
In general, the most cost effective pollution reduction tech-
niques available to any industry are thosje which prevent the
entry of pollutants into process wastewatler or reduce the
volume of waste water requiring treatment. These "in-process"
controls can increase treatment effectiveness by presenting the
pollutants to treatment in smaller, more Iconcentrated waste
streams from which they can be more compljetely removed, or by
XII-128
-------
eliminating pollutants which are not readily removed or which
interfere with treatment of other pollutants.. They also
frequently yield economic benefits both in decreased waste
treatment costs and in decreased consumption or recovery of
process materials. Many in-process control techniques are
applicable to E&EC manufacturing plants at the present time and
will see increasing use as plants are modernized and outdated
equipment is replaced.
i •
While some in-process pollution control techniques such as
water recycling and good housekeeping are of general applica-
bility/ many are applicable only to specific types of processes.
Subsequent sections address in-process pollution control tech-
niques of general applicability and those applicable to E&EC
processes, rinses and quenches.
Generally Applicable In-Process Techniques
Recycle of process wastewater, reduction of water use, waste
stream segregation, and general good housekeeping practices are
applicable to the reduction of pollution discharges from all
subcategories. All may frequently be effected with minimal
capital investment and can achieve substantial reductions in
treatment costs and pollutant discharges.
Nearly all semiconductor and fluorescent lamp plants recycle
some process wastewater streams. The most commonly recycled
streams include deionized water rinse and phosphor deposition
discharges. Electroplating rinse water is also recycled at some
facilities. In general, some treatment is required to allow
process wastewater reuse in this industry, but the required
treatment is generally less than that needed for discharge. At
present, the most common treatment practices prior to recycle
in E&EC manufacturing are solids removal and deionized water
reprocessing.
Where recycle is presently practiced, the percentage of water
reused varies from approximately 50% to 100%. Factors which
limit the extent of recycling include build-up of dissolved
solids to levels unsuitable for further use. This limitation
may often be overcome by the application of more advanced
treatment techniques than those presently in common use for
recycle. Other factors limiting recycling and treatment
required for water reuse are specific to different process
operations and are discussed further in each of the ensuing
sections.
Examples of water recycling and reuse characterized by sampling
during this study are shown in .Table 12-18. Similar recycle
and reuse systems are reported throughout the E&EC manufacturing
products industry segment. In general, the examples of recycling
encountered do not encompass all operations of a particular type
within the plant, but they clearly demonstrate the feasibility
of a tvigh degree of wastewater recycle and reuse for some E&EC
manufacturing subcategories.
XII-129
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PLANT
ID
06143
11114
15606
28063
30047
35035
36173
42044
TABLE 12-18
IN-PROCESS TECHNOLOGIES AT E&EC PLANTS
PRODUCT
Semiconductors
RECYCLE STOEAM
SOURCE
Total raw waste
TV Tubes Phosphor application
Carbon & Graphite Impregnation Quench
19101 Semiconductors
Total raw waste
Carbon & Graphite Machining Waste
Carbon & Graphite Machining Waste
Semiconductors Total raw waste
Carbon & Graphite Machining Waste
Semiconductors
Total raw waste
%RECYGLE
i
55
100
65
100,
NARRATIVE DESCRIPTION
Increasing recycle to
65-75%
R/0 water recycle.
Phospher reclaim
All water recycled except
evaporation, make-up
water added
Just beginning production.
Recycle may be as high
as 80%.
Filter out carbon, add rust
inhibitor and recycle.
100, Settle carbon and recycle
100: Carbon bearing waste stream
I goes to clarifier and is
j returned to process.
: Sludge is contractor
i removed.
80! Projected 90% recycle
by 1981.
XII-130
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Recycle is highly effective in reducing pollutant discharges,
often eliminating the discharge completely. Where a discharge
remains, the volume requiring treatment is greatly reduced,
making |the application of advanced treatment techniques more
economically attractive.
Many production processes in E&EC manufacturing plants operate
intermittently or at widely varying production rates. The
practice of shutting off water during periods when the process
is inoperative and of adjusting flow rates during periods of
low activity can prevent much unnecessary dilution of wastes
and reduce the volume of water to be treated and discharged.
Water may be shut off and adjusted manually or through auto-
•matically controlled valves. Manual adjustment involves minimal
capital cost but has been found to be somewhat unreliable in
practice. Production personnel often fail to turn off manual
valves when production processes are shut down and tend to
increase water flow rates to habitual levels "to insure good
operation". Automatic shutoff valves are used in many
industrial operations to turn off water flows when production
units are inactive. Automatic adjustment of flow rates accord-
ing to production levels requires more sophisticated control
systems incorporating temperature or conductivity sensors.
Further reduction in water use may be made possible by^changes
in production technique and equipment. For. example, the
installation of effective drag-out control measures or more
efficient rinsing equipment may substantially reduce requirements
for rinse water. Since these changes are most often specific
to certain operations, they are presented in the subcategory
discussions (Sections VI - XI).
The potential for reduction of water use at E&EC manufacturing
facilities is evident in the raw waste data and water use
descriptions presented in Sections VI - XI of this report.
While it may be argued that variations in water flow per unit of
production are the necessary result of variations in process
conditions, on-site observations indicate that they are more
frequently the result of imprecise control of water use. This is
confirmed by observations in the semiconductor subcategory in
which rinse water flows whether the product is being rinsed or not
The segregation of wastewater streams is a key element in
cost-effective pollution control. For example, separation of
non-contact cooling water from process wastewater prevents
dilutibn of the process wastes and maintains the purity of the
non-contact cooling water for subsequent reuse or discharge.
Similarly, the segregation of process waste streams differing
significantly in their chemical characteristics can reduce
treatment costs and increase effectiveness. Waste segregation
is a fairly common practice in the E&EC industry.
XII-131
-------
Mixing process wastewater with non-contact ; cooling water generally
r2?,,f?anSVerS? effect on treatment costs arid performance. The
resultant waste stream is usually too contaminated for continued
reuse in non-contact cooling applications
-------
1.
designed flow to it. Of particular concern in this regard is
the prevention of discharges of process pollutants to storm
sewers and area drains which flow without treatment to lakes,
streams, or rivers. This may be accomplished by spill prevention,
the use I of dikes around liquid storage and handling areas
(especially pickling acids and lubricating oils), the use of
frequent cleaning of trash screens, rapid repair of leaks, and
numerous other techniques.
The actions which constitute "good housekeeping" are specific
to individual plants depending upon plant layout, process
operations and equipment, materials used and other factors.
Costs are similarly site specific, but the requirement for good
housekeeping as an integral part of any effective pollution
control program is universal.
i
Rinsing;
There are five primary modes of rinsing that are potentially
applicable to E&EC manufacturing:
Single Running Rinse - This arrangement requires a
large volume of water to effect a large degree of
contaminant removal. Although in widespread use,
single running rinse tanks should be modified or
replaced by a more effective rinsing arrangement to
reduce water use. A countercurrent rinse or a "dead
rinse" followed by a single running rinse is more
effective than a single running rinse. In some
cases, the dead rinse can potentially be regenerated
electrolytically and returned to the process chemical
tank.
Countercurrent Rinse - For a countercurrent rinse
system, there is only one fresh water feed for a
serie of tanks, and it is introduced in the last
tank of the arrangement. The overflow from each tank
becomes the feed for the tank preceeding it. Conse-
quently, the concentration of contaminants decreases
rapidly from the first to the last tank. Counter-
current rinsing was observed to be operating success-
fully on semiconductor rinses in the E&EC manufacturing
industry.
Series Rinse - In a series rinse system, each tank
reaches its own equilibrium condition; the first
rinse having the highest concentration, and the last
rinse having the lowest concentration. The major
advantage of the series rinse over the countercurrent
system is that the tanks of the series can be individu-
ally heated or - level controlled since each has a
separate feed. The disadvantage of series rinses over
the countercurrent rinse is higher water use.
2.
XII-133
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4- Spray Rinse - Spray rinsing is considered the most
efficient of the various rinse techniques in contin-
uous dilution rinsing. The main concern encountered
is the efficiency of the spray; !i.e., the volume of
water contacting the part and re'moving contamination
compared to the volume of water Discharged. Spray
rinsing is well suited for washibg batches of small
items such as capacitors. !
5' Dead, Still, or Reclaim Rinses -I This form of rinsing
is particularly applicable for initial rinsing following
photoresist stripping or gold etching which typically
cause succeeding rinses to contain significant concen-
trations of organics or gold sal^s. A dead rinse
allows the concentration of contaminants such as
organic solvents or gold salts, which can then be
reclaimed when sufficient concentrations of contami-
nants are present.
I
Once a rinse system is selected, the rinse!water feed rate must
be controlled to minimize water use. For lines where production
rates and products are relatively constant!a fixed orifice may
be used with good success to control the fresh water feed.
This technique is inexpensive and has beenjreadily adapted to
automatic process lines. Orifices are notjsuited for operations
with fluctuating production rates or where materials have wide
variance in dragout volume. For these situations, conductivity
controllers or manually operated valves should be used.
i
A conductivity controller utilizes a conductivity cell to
measure the conductance of the solution which, for an electro-
lyte, is dependent upon the ionic concentration. The conduc-
tivity cell is tied to a controller which c>pens or closes a
solenoid on the make-up line. As the rinse becomes more contami-
nated, its conductance increases until the ,set point of the
controller is reached, causing the solenoid to open and allowing
makeup to enter. :
For rinse flows controlled by orifices or manually operated
valves, dead man valves "should be installed to shut-off the
flow rate or rinse water when the rinse is 'not in use. Manage-
ment must insure that these valves are not ;jammed open.
Quenching Operations i
In general, quench operations produce relatively large volume
effluents which contain low concentrations of most pollutants.
As a result treatment effectiveness is somewhat limited unless
in-process control techniques are employed.! Recycle and reuse
of the quench water and a reduction of water use can reduce the
volume of effluent requiring treatment and increase pollutant
concentrations to more treatable levels. In addition, total
pollutant loads may be reduced by process changes which decrease
the amounts of contaminants present on surfaces being quenched.
XII-134
-------
Water quenches are used in carbon and graphite manufacturing
plants'following extrusion and impregnation processes. The
quench water becomes somewhat contaminated with metals, suspended
solids, and lubricants, but the primary effect of this use is
elevation of the water temperature. Because only minor chemical
changes are produced in the quench solutions, extensive recycle
and reuse is possible without deleterious effects on production.
After extrusion, impregnation products are quenched in quench
baths. Some quench baths may contain either continuous discharges
with no recycle, or the processes are run with zero discharge.
Treatment provided prior to recycle includes settling and pH
adjustment, although a high percentage recycle of extrusion
effluent is also reported without prior treatment.
It is noteworthy that plants presently reporting zero discharge
of quench water do not treat for oil removal. This may be
attributed to the process materials used which do not release
oily wastes during quenching.
Reduction of wa.ter use in quenches may also significantly
reduce discharge volumes. Since quench processes typically are
intermittent operations, elimination of water flow during
periods of inactivity is one major method of reducing water
use. Further reductions may be achieved by efficient water
use. !
i
The moist complete reduction of pollutant discharges from quench
operations results from the elimination of the quench altogether.
Technically, this could be achieved at carbon and graphite
plants simply by not quenching products. This has been reported
at one large plant and at 12 medium and small plants contacted.
XII-135
-------
-------
SECTION XIII
COST OF WASTEWATER CONTROL AND TREATMENT
INTRODUCTION
This section presents estimates of the cost of implementation of
wastewater treatment and control components for the Electrical &
Electronic Components category. These cost estimates, together
with the treatment and control option performance presented in.
Sections VI, VII, VIII, IX, X, and XI provide a basis for evalua-
tion of the options presented and identification of the Level 1,
Level 2 and Level 3 treatment alternatives. The system cost esti-
mates based on the methodologies discussed in this section and pre-
sented in the appropriate subcategory sections also provide the
basis for the determination of the probable economic impact of
regulation at different pollutant discharge levels on the E & EC
category. In addition, this section addresses non-water quality
environmental impacts of wastewater treatment and control altern-
atives including air pollution, noise pollution, solid wastes,
and energy requirements.
To arrive at the cost estimates presented in this and earlier sub-
category sections, specific wastewater treatment technologies and
in-process control techniques from among those discussed in Section
XII were selected and combined in wastewater treatment and control
systems appropriate for each subcategory. As described in more
detail below, investment and annual costs for each system were
estimated based on wastewater flow rates and raw waste character-
istics for each subcategory as presented in Sections VI through XI.
Cost estimates are also presented for individual treatment
technologies included in the waste treatment systems. These
estimates assume that no waste treatment systems are presently
in place.
COST ESTIMATION METHODOLOGY
Cost estimation is accomplished using a computer program which
acceots inputs specifying the treatment system to be estimated,
chemical characteristics of the raw waste streams treated, flow
rates and operating schedules. The program accesses models f6r
specific treatment components which relate component investment
and operating costs, materials, and energy requirements to
influent flow rates and stream characteristics. Component
models are exercised sequentially as the components are en-
countered in the system to determine chemical characteristics
and flow rates at each point. Component investment and annual
costs are also determined and used in the computation of,total
system costs. Mass balance calculations are used to determine
the characteristics of combined streams resulting from mixing
XIII-1
-------
two or more streams and to determine the jvolume of sludges or
liquid wastes resulting from treatment operations such as sedi-
mentation, filtration, flotation, and oil separation.
Cost estimates are broken down into severlal distinct elements
in addition to total investment and annual costs: operation
and maintenance costs, energy costs, depreciation, and annual
costs of capital. The cost estimation program incorporates
provisions for adjustment of all costs to a common dollar base
on the basis of economic indices appropriate to capital equipment
and operating supplies. Labor and electrical power costs are
input variables appropriate to the dollar; base year for cost
estimates. These cost breakdown and adjustment factors as well
as other aspects of the cost estimation process are discussed
in greater detail in the following paragraphs.
i
Cost Estimation Input Data-
The waste treatment system descriptions input to the computer
cost estimation program include both a specification of the
waste treatment components included and a definition of their
interconnections. For some components such as holding tanks,
retention times or other operating parameters are also specified
in the input, while for others, such as reagent mix tanks and
clarifiers, these parameters are specified within the program
based on prevailing design practice in industrial waste treatment.
The waste treatment system descriptions may include multiple
raw waste stream inputs and multiple treatment trains. For
example, treatment of wastewater from semiconductor manufacture
includes segregation of dilute and concentrated acid streams,
separate treatment for each stream, and reuse of the dilute acid
wastewater stream.
The specific treatment systems selected for cost estimation for
each subcategory were based on an examination of raw waste
characteristics, consideration of manufacturing processes, and
an evaluation of available treatment technologies discussed in
each section. The rationale for selection of these systems is
presented in Sections .VI through XI. ;
The input data set also includes chemical .characteristics for
each raw waste stream specified as input to the treatment systems
for which costs are to be estimated. These characteristics are
derived from the raw waste sampling data presented in each
section. The pollutant parameters which a!re presently ac-
cepted as input by the cost estimation prdgram are shown in
Table 13-1. The values of these parameters are used in de-
termining materials consumption, sludge volumes, treatment
component sizes, and effluent characteristics. The list of input
XIII-2
-------
TABLE 13-1
POLLUTANT PARAMETERS
SYSTEM COST ESTIMATION PROGRAM
Parameter, Units
,i
Flow, mgd
pH, pH Units
I
Turbidity, Jackson Units
Temperature, Degree C
Dissolved Oxygen, mg/1
Residual chlorine, mg/1
Acidity, mg/1 CaCo^
Alkalinity, mg/1 CaCb3
I
Ammonia, mg/1
j
Biochemical Oxygen Demand, mg/1
Color/ Chloroplatinate Units
Sulfide, mg/1
Cyanides, mg/1
Kjeldahl Nitrogen, mg/1
i
Phenols, mg/1
Conductance, Micromho/cm
Total^Solids, mg/1
Total Suspended Solids, mg/1
Settleable Solids, mg/1
Aluminum, mg/1
Barium, mg/1
Cadmium, mg/1
Calcium, mg/1
Chromium, Total, nig/1
Copper, mg/1
Parameter, Units
Oil, Grease, mg/1
Hardness, mg/1 CaCojJ
Chemical Oxygen Demand, mg/1
Total Phosphates, mg/1
Polychlorobiphenyls,' mg/1
Potassium, gm/1
Silica, rag/1
Sodium, mg/1
Sulfate, mg/1
Sul-fite, mg/1
Titanium, mg/1
Zinc,, mg/1
Arsenic, mg/1
Boron, mg/1
Iron, Dissolved, mg/1
' Mercury, mg/1
Nickel, mg/1
Nitrate, mg/1
Selenium, mg/1
Silver, mg/1
i
Strontium, mg/1
Beryllium, mg/1
XIII-3
-------
TABLE 13-1 (cent)
POLUTANT PARAMETERS
SYSTEM COST ESTIMATION PROGRAM (Continued)
Parameter/ Units
Fluoride, mg/1
Iron, Total, rag/1
Lead, mg/1
Magnesium^ rag/1
Molybdenum, mg/1
Total Volatile Solids, mg/1
Parameter, Units
Antimony, mg/1
Bromide, mg/1
Cobalt, mg/1
|
Thallium, mg/1
fin
Tin, mg/1
Chromium, Hexavalent, mg/1
XIII-4
-------
parameters is expanded periodically as additional pollutants are
found to be significant in waste streams from industries under
study and as additional treatment technology cost and perform-
ance data becomes available. For the E & EC category, individual
subcategories commonly encompass a number of widely varying
waste streams which are present to varying degrees at different
facilities. The raw waste characteristics shown as input to
waste treatment represent a mix of these streams including all
significant pollutants generated in the subcategory and will not
in general correspond precisely to process wastewater at any
existing facility. The process by which these raw wastes were
defined is explained in each subcategory section.
The final input data set comprises raw waste flow rates for each
input stream for one or more plants in each subcategory addressed.
Typical flows encountered at existing facilities were used for
each E & EC subcategory to represent the treatment costs which
would be incurred in the implementation of each control and
treatment option offered. In addition, data corresponding to
the flow rates reported by each plant were input to the computer
to provide cost estimates for use in economic impact analysis.
System Cost Computation
A simplified flow chart for the estimation of wastewater
treatment and control costs from the input data described
above is presented in Figure 13-1. In the computation, raw
waste characteristics and flow rates for the first case are
used as input to the model for the first treatment technology
specified in the system definition. This model is used to
determine the size and cost of the component, materials and
energy consumed in its operation, and the volume and character-
istics of the stream(s) discharged from it. These stream
characteristics are then used as input to the next component(s)
encountered in the system definition. This procedure is
continued until the complete system costs and the volume of the
final effluent stream(s) and sludge or concentrated oil wastes
have been determined. In addition to treatment components, the
system may include mixers in which two streams are combined, and
splitters in which part of a stream is directed to another
destination. These elements are handled by mass balance cal-
culations and allow cost estimation for specific treatment of
segregated process wastes such as destruction of hexavalent chro-
mium bearing wastes prior to combination with other process wastes
for further treatment and representation of partial recycle of
wastewater.
XIII-5
-------
FIGURE 13-1 j
SIMPLIFIED LOGIC DIAGRAM;
SYSTEM COST ESTIMATION PROGRAM
NON-RECYCLE
SYSTEMS
INPUT
A) RAW WASTE DESCRIPTION
B) SYSTEM DESCRIPTION
C) 'DECISION" PARAMETERS
D) COST FACTORS
PROCESS CALCULATIONS !
A) PERFORMANCE - POLLUTANT
PARAMETER EFFECTS
B) EQUIPMENT SIZE
C) PROCESS COST
(RECYCLE SYSTEMS)
CONVERGENCE
A) POLLUTANT PARAMETER
TOLERANCE CHECK
(NOT WITHIN
TOLERANCE LIMITS)
(WITHIN TOLERANCE LIMITS)
COST CALCULATIONS :
A) SUM INDIVIDUAL PROCESS
COSTS ;
B) ADD SUBSIDIARY COSTS
C) ' ADJUST TO DESIRED DOLLAR
BASE ;
OUTPUT ;
A) STREAK DESCRIPTIONS ;
COMPLETE SYSTEM !
B) INDIVIDUAL PROCESS SIZEi
AND COSTS :
C) OVERALL SYSTEM INVESTMENT
' AND ANNUAL COSTS !
XIII-6
-------
As an example of this computation process, the sequence of
calculations involved in the development of cost estimates
for the simple treatment system shown in Figure 13-2 may be
described. Initially, input specifications for the treatment
system are read to set up the sequence of computations. The
subroutine addressing chemical precipitation and sedimentation in
a clarifier is then accessed. The sizes of the mixing tank and
clarification basin are calculated based on the raw waste flow rate
to provide 45-minute retention in the mix tank and 4 hour retention
with 1356 1/m surface loading in the'clarifier. Based on these
sizes, investment and annual costs for labor, supplies and for
the mixing tank and clarifier including mixers, clarifier
rakes and other directly related equipment are determined.
Fixed investment costs are then added to account for sludge
pumps, controls and reagent feed systems.
Based on the input raw waste concentrations and flow rates,
the reagent additions (lime, alum, and polyelectrolyte) are
calculated to provide fixed concentrations of alum and poly-
electrolyte and 10% excess lime over that required for
stqichiometric reaction with the acidity and metals present
in the waste stream. Costs are calculated for these materials,
and the suspended solids and flow leaving the mixing tank and
entering the clarifier are increased to reflect the lime solids
added and precipitates formed. These modified stream character-
istics are then used with performance algorithms for the clarifier
to determine concentrations of each pollutant in the clarifier
effluent stream. By mass balance, the amount of each pollutant
in the clarifier sludge may be determined. The volume of the
sludge stream is determined by the concentration of TSS which is
fixed at 4-5% based on general operating experience, and concen-
trations of other pollutants in the sludge stream are determined
from their masses and the volume of the stream.
The subroutine describing vacuum filtration is then called,
and the mass of suspended solids in the clarifier sludge stream
is used to determine the size and investment cost of the vacuum
filtration unit. Operating hours for the filter are calculated
from the flow rate and TSS concentration, and manhours required
for operation are determined. Maintenance labor requirements are
added as a fixed 'additional cost.
The sludge flow rate and TSS content are then used to determine
costs of materials and supplies for vacuum filter operation
including iron and alum added as filter aids and the electrical
power costs for operation. .Finally, the vacuum filter performance
algorithms are used to determine the volume and-characteristics
of the vacuum filter sludge and filtrate, and the costs of
contract disposal of the sludge are calculated. The recycle of
XIII-7
-------
Raw Waste
Lime Flocculant
L_L
Chemical
Addition
Mixing
Clarifier
Filtrate
1
Effluent
Vacuum
Filter
Sludge Contractor Removed
FIGURE 13-2
SIMPLE; WASTE TREATMENT ,SYSTEM
XIII-8
-------
vacuum filter filtrate to the chemical precipitation-clarification
system is not reflected in the calculations due to the difficulty
of iterative solution of such loops and the general observation
that the contributions of such streams to the total flow and
pollutant levels are in practice negligibly small. Allowance
for such minor contributions is made in the 20% excess capacity
provided in most components.
The costs determined for all components of the system are
summed and subsidiary costs are added to provide output specifying
total investment and annual costs for the system and annual
costs for capital, depreciation, operation and maintenance, and
energy. Costs for specific system components and the character-
istics of all streams in the system may also be specified as
output from the program.
Treatment Component Models.
The cost estimation program presently incorporates subroutines
providing cost and performance calculations for the treatment
technologies identified in Table 13-2. These subroutines have
been developed over a period of years from the best available
information including on-site observations of treatment system
performance, costs, and construction practices at a large number
of industrial facilities, published data, and information
obtained from suppliers of wastewater treatment equipment. The
subroutines are modified and new subroutines added as additional
data allow improvements in treating technologies presently
available and as additional treatment technologies are required
for the industrial wastewater streams under study. Specific
discussion of each of the treatment component models used in
costinq wastewater treatment and control systems for the
E & EC*category is presented later in this section where cost
estimation is addressed.
Cost estimation is provided by mathematical relationships in
each subroutine approximating observed correlations between
component costs and the most significant operational parameters
such as water flow rate, retention times, and pollutant concen-
trations. In general, flow rate is the primary determinant of
investment costs and of most annual costs with the exception of
matericils costs. In some cases, however, as discussed for the
vacuum filter, pollutant concentrations may also significantly
influence costs.
Cost Factors and Adjustments
As previously indicated, costs are adjusted to a common dollar
base and are generally influenced by a number of factors including:
Cost of Labor, Cost of Energy, Capital Recovery Costs and
Debt-Equity Ratio. These cost factors and adjustments are
discussed below.
XIII-9
-------
TABLE 13-2 j
i
TREATMENT TECHNOLOGY SUBROUTINES
Treatment Process Subroutines Presently Available
Spray/Fog Rinse
Countercurrent Rinse
Vacuum Filtration
Gravity Thickening
Sludge Drying Beds
Holding Tanks
Centrifugation
Equalization
Contractor Removal
Reverse Osmosis
Chemical Reduction of Chromium
Chemical Oxidation of Cyanide
Neutralization
Clarification (Settling Tank/Tube Settler)
API Oil Skimming
Emulsion Breaking (Chem/Thermal)
Membrane Filtration
Filtration (Diatomaceous Earth)
Ion Exchange - In-Plant Regeneration
Ion Exchange - Service Regeneration
Flash Evaporation
Climbing Film Evaporation
Atmospheric Evaporation
Cyclic Ion Exchange
Post Aeration
Sludge Pumping
Copper Cementation
Fluoride Removal (Lime Addition)
Sanitary Sewer Discharge Fee
Ultrafiltration
Submerged Tube Evaporation
Flotation/Separat ion
Wiped Film Evaporation
Trickling Filter
Activated Carbon Adsorption
Nickel Filter
Sulfide Precipitation
Sand Filter
Pressure Filter
Multimedia Granular Filter
Sump
Cooling Tower
Ozonation
Activated Sludge
Coalescing Oil Separator
Non Contact Cooling Basin
Raw Wastewater Pumping
Preliminary Treatment
Preliminary Sedimentation
Aerator - Final Settler
Chlorination
Flotation Thickening
Multiple Hearth Incineration
Aerobic Digestion
Treatment Process Subroutines Currently Being Developed
Peroxide Oxidation
Air Stripping (Ammonia Removal)
Arsenic Removal ;
Water Recycle or Reuse !
XIII-10
-------
Dollar Base - A dollar base of August 1979 was used for all
costs..
Investment Cost Adjustment - Investment costs were adjusted to
the aforementioned dollar base by use of the Sewage Treatment
Plant Construction Cost Index. This index is published quarterly
by the EPA Division of Facilities Construction and Operation.
The national average of the Construction Cost Index for
August 1979 was 337.8.
Supply Cost Adjustment - Supply costs such as chemicals were related
to the dollar base by the Producer Price Index, formerly called the
Wholesale Price Index. This figure was obtained from the U.S.
Department of Labor, Bureau of Labor Statistics, "Monthly Labor Review"
For August 1979 the "Industrial Commodities" Wholesale Price Index
was 240.3. Process supply and replacement costs were included in
the estimate of the total process operating and maintenance cost»
Cost of Labor - To relate the operating and maintenance labor costs,
the hourly wage rate for non-supervisory workers in sanitary ser-=
vices was used from the U.S. Department of Labor, Bureau of Labor
Statistics Monthly publication, "Employment and Earnings". For
August 1979, this wage rate was $6.71 per hour. This wage rate was
then applied to estimates of operation and maintenance man-hours
within each process to obtain process direct labor charges. To
account for indirect labor charges, 15 percent of the direct labor
costs was added to the direct labor charge to yield estimated total
labor costs. Such items as Social Security, employer contributions
to pension or retirement funds, and employer-paid premiums to vari-
ous forms of insurance programs were considered indirect labor costs „
Cost of. Energy - Energy requirements were calculated directly
within 'each process. Estimated costs were then determined by
applying an electrical rate of 4.5 cents per kilowatt hour.
Capital Recovery C_os_ts_ - Capital recovery costs were divided
into straight line five-year depreciation and cost of capital
at a thirteen percent annual interest rate for a period of five
years. The five year depreciation period was consistent with the
faster write-off (financial life) allowed for these facilities
even though the equipment life is in the range of 20 to 25
years.
XIII-H
-------
The annual cost of capital was calculated by using the capital
recovery factor approach. The capital recovery factor is nor-
mally used in industry to help allocate the initial investment
and the interest to the total operating cost of the facility.
It is equal to:
N
(1+i) -1
where i is the annual interest rate and N is the number of
years over which the capital is to be recovered. The annual
capital recovery was obtained by multiplying the initial
investment by the capital recovery factor.: The annual deprecia-
tion of the capital investment was calculated by dividing the
initial investment by the depreciation period N, which was
assumed to be five years. The annual cost of capital was then
egaal to the annual capital recovery minus the depreciation.
Debt-Equity Ratio - Limitations on new borrowings assume that debt
may not exceed a set percentage of the shareholders equity. This
defines the breakdown of the capital investment between debt
and equity charges. However, due to the lack of information
about the' financial status of various plants, it was not
feasible to estimate typical shareholders equity to obtain
debt financing limitations. For these reasons, no attempt was
made to break down the capital cost into debt and equity charges.
Rather, the annual cost of capital was calculated via the <
procedure outlined in the Capital Recovery[Costs section above.
Subsidiary Costs
The waste treatment and control system costs presented in
each subcategory subsection for end-of-pipe| and in-process waste
water control and treatment systems include subsidiary costs
associated with system construction and ope'ration. These
subsidiary costs include:
administration and laboratory facilities
garage and shop facilities
line segregation
i
yardwork 1
. land
engineering
j
legal, fiscal, and administrative
interest during construction
XIII-12
-------
Administrative and laboratory facility treatment investment
is the cost of constructing space for administration, laboratory,
and service functions for the wastewater treatment system.
For these cost computations, it was assumed that there was
already an existing building and space for administration,
laboratory, and service functions. Therefore, there was no
investment cost for this item.
For laboratory operations, an analytical fee of $105 (August 1979
dollars) was charged for each wastewater sample, regardless of
whether the laboratory work was done on or off site. This
analytical fee is typical of the charges experienced by Hamilton
Standard during the past several years of sampling programs.
The frequency of wastewater sampling is a function of waste-
water discharge flow and is presented in Table 13-3. This
frequency was suggested by the Water Compliance Division of
the USEPA.
For industrial waste treatment facilities being costed, no
garage and shop investment cost was included. This cost item
was assumed to be part of the normal plant costs and was not
allocated to the wastewater treatment system.
Line segregation investment costs account for plant modifications
to segregate wastes. The investment costs for line segregation-
included placing a trench in the existing plant floor and installing
the lines in this trench. The same trench was used for all pipes
and gravity feed to the treatment system was assumed. The
pipe was assumed to run from the center of the floor to a corner.
A rate of 2.04 liters per hour of wastewater discharge per
square meter of area (0.05 gallons per hour per square foot)
was used to determine floor and trench dimensions from waste-
water flow rates for use in this cost estimation process.
The yardwork investment cost item includes the cost of general site
clearing, intercomponent piping, valves, overhead and underground
electrical wiring, cable, lighting, control structures, manholes,
tunnels, conduits, and general site items outside the structural
confines of particular individual plant components. This cost is
typically 9 to 18 percent of the installed components investment
costs. For these cost estimates, an average of 14 percent was
utilized. Annual yardwork operation and maintenance costs are
considered a part of normal plant maintenance and were not
included in these cost estimates.
No new land purchases were required. It was assumed that the
land required for the end-of-pipe treatment system was already
available at the plant.
Engineering costs include both basic and special services. Basic
services include preliminary design reports, detailed design, and
XIII-13
-------
TABLE 13-3 ',
WASTEWATER SAMPLING FREQUENCY
Wastewater Discharge
(liters per day)
0 - 37,850
37,850 - 189,250
189,250 - 378,500
378,500 - 946,250
946,250+
Sampling Frequency
once per month
twice per month
once per week
twice per week
XIII-14
-------
certain office and field engineering services during construction
of projects. Special services include, improvement studies,
resident engineering, soils investigations, land surveys,
operation and maintenance manuals, and other miscellaneous
services. Engineering cost is a function of process installed
and yardwork investment costs and ranges between 5.7 and
14% depending on the total of these costs.
Legal, fiscal and administrative costs relate to planning and
construction of wastewater treatment facilities and include
such items as preparation of legal documents, preparation of
construction contracts, acquisition of land, etc. These costs
are a function of process installed, yardwork, engineering, and
land investment costs and range between 1 and 3% of the total
of these costs.
Interest cost during construction is the interest cost accrued
on funds from the time payment is .made to the contractor to the
end of the construction period. The total of all other pro'ject
investment costs (process installed? yardwork; land; engineering;
and legal, fiscal, and administrative) and the applied interest
affect this cost. An interest rate of 13 percent was used to
determine the interest cost for these estimates. In general,
interest cost during construction varies between 3 and 10% of
total system costs depending on the total costs.
COST ESTIMATES FOR INDIVIDUAL TREATMENT TECHNOLOGIES
Introduction
Table 13-4 lists those technologies which are incorporated
in the wastewater treatment and control options offered for the
E & EC category and for which cost estimates have been developed.
These treatment technologies have been selected from among the
larger set of available alternatives discussed in Section XII on
the basis of an evaluation of raw waste characteristics, typical
plant characteristics (e.g. location, production schedules,
product mix, and land availability), and present treatment
practices within the subcategories addressed. Cost estimates for
each technology addressed in this section include investment costs
and annual costs for depreciation, capital, operation and maintenance,
and energy.
Investment - Investment is the capital expenditure required to
bring the technology into operation. If the installation is a
package contract, the investment Is the purchase price of the
installed equipment. Otherwise, it includes the equipment cost,
cost of freight,, insurance and taxes, and installation costs.
XIII-15
-------
TABLE 13-4
E & EC CATEGORY
APPLICABLE TREATMENT TECHNOLOGIES
WASTE TREATMENT TECHNOLOGY
Clarification - Lime Precipitation; Continuous
Treatment
Clarification - Lime Precipitation; Batch
Treatment '
Clarification - Sulfide Precipitation; Continuous
Treatment
Clarification - Sulfide Precipitation; Batch
Treatment
Multimedia Filtration
Membrane Filtration
Reverse Osmosis
Vacuum Filtration ;
Holding and Settling Tanks
Chromium Reduction |
pH Adjustment
Contract Removal
IN-PROCESS CONTROLS
Water Recycle or Reuse
XIII-16
-------
Total Annual Cost - Total annual cost is the sum of annual costs
operation and maintenance (less energy),
for depreciation, capital,
and energy (as a separate function).
Depreciation - Depreciation is an allowance, based on tax
regulations, for the recovery of fixed capital from an in-
vestment to be considered as a non-cash annual expense. It
may be regarded as the decline in value of a capital asset
due to wearout and obsolescence.
Capital - The annual cost of capital is 'the cost, to the
plant, of obtaining capital expressed as an interest rate.
It is equal to the capital recovery cost (as previously dis-
cussed on cost factors) less depreciation.
Operation and Maintenance - Operation and maintenance cost
is the annual cost of running the wastewater treatment
equipment. It includes labor and materials such as waste
treatment chemicals. As presented on the tables, operation
and maintenance cost does not include energy (power or fuel)
costs because these costs are shown separately.
Energy - The annual cost of energy is shown separately,
although it is commonly included as part of operation and
maintenance cost. Energy cost has been shown separately
because of its importance to the nation's economy and natural
resources.
Lime Precipitation and Sedimentation
This technology removes dissolved pollutants by the formation
of precipitates by reaction with added lime and subsequent removal
of the precipitated solids by gravity settling in a clarifier.
Several distinct operating modes and construction techniques
are costed to provide least cost treatment over a broad range of
flow rates. Because of their interrelationships and integration
in common equipment in some installations, both the chemical
addition and solids removal equipment are addressed in a single
subroutine.
Investment Cost - .Investment costs are determined for this
technology for continuous treatment systems using either steel
or concrete tank construction, and for batch treatment using
steel tanks only. The least cost system is selected for each
.application. Continuous treatment systems-include controls,
reagent feed equipment, a mix tank for reagent feed addition and
a clarification basin with associated sludge rakes and pumps. Batch
treatment includes only reaction-settling tanks and sludge pumps.
Controls and reagent feed equipment: Costs for continuous
treatment systems include a fixed charge of $10817 covering an
XIII-17
-------
immersion pH probe and transmitter, pH monitor, controller, lime
slurry pump, 1 hp mixer, and transfer pump. In addition, an
agitated storage tank sufficient to hold one day's operating
requirements of a 30% lime slurry is included. Costs for this
tank are estimated based on the holding tank!costs discussed
later in this section and shown in Figure 13-17. Lime feed
to the slurry tank is assumed to be manual. Hydrated lime is
used and no equipment for lime slaking or handling is included '
in these cost estimates. At facilities with high lime
consumption mechanical lime feed may be used resulting in higher :
investment costs, but reduced manpower requirements in comparison "•
to manual addition. : '
Mix Tank: Continuous systems also include ai> agitated tank
providing 45 minutes retention for reagent addition and formation
of precipitates. When the clarifier is concrete, the mix tank is
also of concrete, below grade and adjacent to the clarification
basin. Costs shown in Figure 13-3 include both the mix tank
and clarifier as a single item. For steel construction, the
costs for the mix tank are based on holding tank costs shown in
Figure 13-17.
Clarifier: The clarifier size is calculated based on a hydrauii-c
loading of 1356 1/m and a retention time of 4 hours with a 20% ;
allowance for excess flow capacity. Costs for clarifiers shown in
Figure 13-3 include a mix tank as noted above, excavation (if needed),
installation, and associated equipment including a mixer and
clarifier rakes. For steel construction, costs are estimated
for a cylindrical above ground clarifier with sludge collection
equipment. The type of construction used is selected internally in
the cost estimation program to provide least ,cost.
Sludge Pumps: A cost of $3817 is included in the total capital
cost estimates regardless of whether steel or concrete construction
is used. This cost covers the expense for two centrifugal
sludge pumps.
To calculate the total capital cost for continuous lime precipita-
tion and sedimentation in a clarifier, the costs estimated for the
controls and reagent feed system, mix tank, clarifier and sludge
pump must be summed. ' |
For batch treatment, dual above-ground cylindrical carbon steel
tanks sized for 8 hour retention and 20% excess capacity are
used. If the batch flow rate exceeds 19697 liters per hour, (5204
gph), then costs for fabrication are included. To complete the
capital cost estimation for batch treatment, ;a fixed $3,817 cost is
included for sludge pumps as discussed above.:
XIII-13
-------
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XIII-19
-------
Operation & Maintenance Costs - The operation and maintenance costs
for the Chemical Precipitation/Clarification routine include:
1) Cost of chemicals added (lime, alum, and polyelectrolyte)
2) Labor (operation and maintenance);
3) Energy \
Each of these contributing.factors is discussed below.
[
CHEMICAL COST
Lime, alum and polyelectrolyte are added for metals and
solids removal. The amount of lime required is based on
equivalent amounts of various pollutant parameters present
in the stream entering the clarifier unit. The methods
used in determining the lime requirements are shown in
Table 13-5. Alum and polyelectrolyte additions are
calculated to provide a fixed concentration of 200 mg/1
of alum and 1 mg/1 of polyelectrolyte.
LABOR |
Figure 13-4 presents the manhour requirements for the
continuous clarifier system. For the batch system,
maintenance labor is assumed negligible and operation
labor is calculated from:
{man-hours for operation) = 390 + (.975) x (Ibs. lime added
per day)
ENERGY
The energy costs are calculated from the clarifier and
sludge pump horsepower requirements.
Continuous Mode '
The clarifier horsepower requirement is assumed constant over
the hours of- operation of the treatment system at a level of
0.0000265 horsepower per 3.8 Iph (1 gph) of flow influent to
the clarifier. The sludge pumps are assumed operational for
5 minutes of each operational hour at a level of 0.00212
horsepower per 3.8 Iph (1 gph) of sludge stream flow.
Batch Mode :
The clarifier horsepower requirement is assumed to occur for
7.5 minutes per operation hour at the following levels:
XIII-20
-------
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-------
TABLE 13-5
Lime Additions for Lime Precipitation
Stream Parameter
Lime Addition
kg/kg (Ibs/lb)
Aluminum
Antimony
Arsenic
Cadmium
Chromium
Cobalt
Copper
Iron (Dissolved)
Lead
Magnesium
Manganese
Mercury
Nickel
Selenium
Silver
Zinc
0.81
4.53
1.75
2.84
2.73
2.35
38
28
2.19
0.205
3.50
1.48
1,
1,
0.42
1,
3,
,45
,23
0.39
1.25
XIII-22:
-------
'. influent flow < 3944 Iph; 0.0048 hp/lph
influent flow >, 3944 Iph; 0.0096 hp/lph
The power required for the sludge pumps in the batch system is
the same as that required for the sludge pumps in the contin-
uous system.
Given the above requirements, operation and maintenance
costs are calculated based on the following:
$6.71 per man-hour + 15% indirect labor charge
$44.61/metric ton of lime
$48.55 metric ton of alum
$1.95/kg of polyelectrolyte
$0.045/kilowatt-hour of required electricity
Sulfide Precipitation - Sedimentation
This technology removes dissolved pollutants by the formation of
precipitates by reaction with sodium sulfide, sodium bisulfide,
or ferrous sulfide and lime, and subsequent removal of the
precipitate by settling. As discussed for lime precipitation
and sedimentation, the addition of chemicals, formation of
precipitates, and removal of the precipitated solids from the
wastewater stream are addressed together in cost estimation
because of their interrelationships and commonality of equipment
under some circumstances.
Investment Cost - Investment cost estimation procedures for sulfide
precipitation and sedimentation are identical to those for-lime
precipitation and sedimentation. Continuous treatment systems
using concrete and steel construction and batch treatment systems
are cosited to provide a least cost system for each flow range and
set of raw waste characteristics. Cost factors are also the
same as for lime precipitation and sedimentation.
Operation and Maintenance Costs - Costs estimated for the operation
and maintenance of a sulfide precipitation-and sedimentation system
are also identical to those for lime precipitation and sedimentation
except for the cost of treatment chemicals. Lime is added prior to
sulfide precipitation to achieve an alkaline pH of approximately
8.5-9 and will lead to the precipitation of some pollutants as
hydroxides or calcium salts. Lime consumption based on both neu-
tralization and formation of precipitates is calculated to provide
a 10% excess over stoichiometric requirements. Sulfide costs are
based on the addition of ferrous sulfate and sodium bisulfide (NaH&)
to form a 10% excess of ferrous sulfide over stoichiometric require-
ments for precipitation. Reagent additions are calculated as shown
in Table 13-6. Addition of alum and polyelectrolyte is identical
to that shown for lime precipitation and sedimentation as are labor
and energy rates.
XIII-23
-------
TABLE 13-6
Reagent Additions for Sulfide Precipitation
Stream Parameter
Cadmium
Calcium
Chromium (Hexavalent)
Chromium (Trivalent)
Cobalt
Copper
Lead
Mercury
Nickel
Silver
Tin
Zinc
Sodium Bisulfide Requirement
Ferrous Sulfate Requirement
Lime Requirement
Ferrous Sulfide Requirement
' kg/kg (Ibs/lb)
0.86
2.41
1.86
2.28
1.64
1.52
! 0.47
j 0.24
! 1.65
0.45
1 0.81
; 1.48
0.65* Ferrous Fulfide Requirement
1.5* Ferrous -Sulfide Requirement
0.49* FeSo4(lbs) + 3.96* NaHS(lbs)
+ 2.19* Ibs of Dissolved Iron
XIII-24
-------
The following rates are used in determining operating and
maintenance costs for this technology.
$6.71 per man-hour •*• 15% indirect labor charge
$48,55/metric ton of alum
$1.95/lb of polyelectrolyte
$44.61/metric ton- of lime
$0.15/kg of sodium bisulfide
$155.40/metric ton of ferrous sulfate
$0.045/kilowatt-hour of electricity
Multi-Media Filtration
This technology provides removal of suspended solids by filtration
through a bed of particles of several distinct size ranges. As a
polishing treatment after chemical precipitation and sedimentation
processes, multi-media filtration provides improved removal of
precipitates and thereby improved removal of the original
dissolved pollutants.
Investment Cost - The size of the multi-media filtration unit is
based on 20% excess flow capacity and a hydraulic loading of
0.58 mvlph. The investment cost, presented in Figure 13-5 as
a function of flow rate, includes a backwash mechanism, pumps,
controls, media and installation. Minimum cos|s are obtained
using a minimum filter surface area of 18.29 m .
! ' ,\
Operation and Maintenance Cost - The costs shown in Figure 13-6
for ooeration and maintenance include contributions of materials,
electricity and labor. These curves result from correlations
made with data obtained by a major manufacturer. Energy costs
are estimated to be 3% of total O&M.
Membrane Filtration
Membrane filtration includes addition of sodium hydroxide to form
metal, precipitates and removal of the resultant solids on a
membrane filter. As a polishing treatment, it minimizes solubility
of metal and provides highly effective removal of precipitated
hydroxides and sulfides.
Investment Cost - Based on manufacturer's data, a factor of $52.6
per 1 gph flow rate to the membrane filter is used to estimate
capital cost. Capital cost includes installation.
Operation and Maintenance Cost - The operation and maintenance
costs for membrane filtration include:
1) Labor
2} Sodium Hydroxide Added
3) Energy
XIII-25
-------
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Plow Rate
03
FIGURE
MULTIMEDIA FILTER
00
C
'Sny - s-renoa) 1203
XII1-26
-------
XIII-27
-------
Each of these contributing factors are discussed below.
LABOR ;
2 man-hours per day of operation are included.
SODIUM HYDROXIDE ADDITION
Sodium hydroxide is added to precipitate metals as
hydroxides or to insure a pH favorable to sulfide pre-
cipitation. The amount of sodium hydroxide required, is
based on equivalent amounts of various pollutant parameters
present in the stream entering the membrane filter. The
•method used to determine the sodium hydroxide demand is
shown below: :
POLLUTANT ;
Chromium, Total
Copper
Acidity
Iron, DIS
Zinc
Cadmium
Cobalt
Manganese
Aluminum
(Sodium Hydroxide Per Pollutant, kg/day)
(LPH) x Pollutant Concentration (mg/1)
ENERGY ;
i
The horsepower required is as follows:
two 1/2 horsepower mixers operating 34 minutes per
operational hour
two 1 horsepower pumps operating 37 minutes per
operational hour
one 20 horsepower pump operating 45 minutes per
operational hour .
i
Given the above requirements, operation and maintenance costs
are calculated based on the following: :
$6.71 per man-hour +.15% indirect labor charge
$0.059 per kg of sodium hydroxide required
$0.045 per kilowatt-hour of energy required
0.000508
0.000279
0.000175
0.00.0474
0.000268
0.000158
0.000301
0.000322
0.000076
AN
aOH x Flow Rate
XIli-28
-------
Reverse; Osmosis
This technology achieves the concentration of dissolved organic
and inorganic pollutants in wastewater by forcing the water
through serai-permeable membranes which will not pass the pollu-
tants. The water which permeates the membranes is relatively
free of: contaminants and suitable for. reuse in most manufacturing
process operations. A number of different membrane types and
constructions are available which are optimized for different
wastewater characteristics (especially pH and temperature).
Investment Cost - Investment cost data from several manufacturers
of RO equipment is summarized in the cost curve shown in Figure
13-7, The costs shown include a prefilter, chemical feed system,
scale inhibitor tank, high pressure pump, and permeators.
Installation is also included. Two different systems, one using
cellulose acetate membranes and suitable for concentrated bath
recovery and one using polyamide membranes which are tolerant
of a wider pH and temperature range are addressed. The polyamide
resin systems are applicable to treatment of electric lamp manu-
facturing wastewaters.
Operation and.Maintenance Cost - Contributions to operation and
maintenance costs includes
LABOR
The annual labor requirement is shown in Figure 13-8.
Labor cost is calculated using a $6.71 per hour labor rate
plus a 15% indirect labor charge.
MATERIALS
The annual cost of materials used in operation and maintenance
of.the reverse osmosis unit is shown in Figure 13-9. The
major component of the materials cost is the cost of
replacement of permeator modules which are assumed to have
a 1.5 year service life based on manufacturers' data.
POWER
! , ' " -
The horsepower requirements for reverse osmosis unit is shown
in Figure 13-10. This requirement is assumed to be constant
over the operating hours of the system being estimated. The
energy cost is determined using a charge of $0.045 per kilo-
watt-hour.
XIII-29
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XIII-33
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Vacuum Filtration
Vacuum filtration is widely used to reduce the water content
of high solids streams. In the E & EC industry, this technology
is applied to dewatering sludge from clarifiers, membrane filters
and other waste treatment units.
Investment Cost - The vacuum filter is sized based on a typical
loading of 1476 kilograms of influent solids per hour per square
meter of filter area (3 Ibs/ft -hr). The curves of cost versus
flow rate at TSS concentrations of 3% and 5% are shown in Figure
13-11. The investment cost obtained from this curve includes in-
stallation costs.
Operation and Maintenance Cost. |
LABOR i
The vacuum filtration subroutine may be run for off-site
sludge disposal or for on-site sludge incineration. For
on-site sludge incineration, conveyor transport is assumed,
and operating man-hours are reduced from those for off-site
disposal. The required operating hours per year varies with
both flow rate and the total suspended solids concentration
in" the influent stream. Figure 13-12 shows the variance
of operating hours with flow rate and TSS concentration.
Maintenance labor for either sludge disposal mode is fixed
at 24 manhours per year.
MATERIALS '
The cost of materials and supplies needed for operation and
maintenance includes belts, oil, grease, seals, and chemicals
required to raise the total suspended solids to the vacuum
filter. The amount of chemicals required (iron and alum) is
based on raising the TSS concentration to the filter by 1 mg/1
Costs of materials required as a function of flow rate and
unaltered TSS concentrations are presented in Figure 13-13.
ENERGY
Electrical costs needed to supply power for pumps and controls
are presented in Figure 13-14. As the required horsepower
of the pumps is dependent on the influent*TSS level, the costs
are presented as a function of flow rate and TSS level.
Holding Tanks
Tanks serving a variety of purposes in wastewater treatment and
control systems are fundamentally similar in design, construc-
tion, and cost. They may include equalization tanks, solution
holding tanks; slurry or sludge holding tanks, mixing tanks,
XIII-34
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XIII-38
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and settling tanks from which sludge is intermittently removed
either manually or by sludge pumps. Tanks for all of these pur-
poses are addressed in a single cost estimation subroutine with
additional costs for auxiliary equipment such as sludge pumps
added ais appropriate.
Investment Costs - Investment costs are estimated for either steel
or concrete tanks. Tank construction may be specified as input
data, or determined on a least cost basis. Retention time is spe-
cified as input data and, together with stream flow rate, determines
tank size. Investment costs for steel and concrete tanks sized for
0.5 days retention and 20% excess capacity are shown as functions
of stream flow rate in Figure 13-15. These costs include mixers,
pumps atnd installation.
Operation and Maintenance Costs - For all holding tanks except
sludge holding tanks, operation and maintenance costs are minimal
in comparison to other system O&M costs. Therefore only energy
costs for pump and mixer operation are determined. These energy
costs sire presented in Figure 13-16.. ,
For sludge holding tanks, additional operation and maintenance
labor requirements are reflected in increased O&M costs. The
required man-hours used in cost estimation are presented in .
Figure 13-17. Labor costs are determined using a labor rate
of $6.71 per manhour plus 15% indirect labor" charge.
Where tanks are used for settling as in lime precipitation and
clarification batch treatment, additional operation and maintenance
costs are calculated as discussed specifically for each technology.
Chromium Reduction
This technology provides chemical reduction of hexavalent chromium
under acid conditions to allow subsequent removal of the trivalent
form by precipitation as the hydroxide. Treatment may be provided
in either continuous or batch mode, and cost estimates are developed
for both. Operating mode for system cost estimates is selected on
a least cost basis.
Capital Cost - Cost estimates include all required equipment for
performing this treatment technology including reagent dosage,
reaction tanks, mixers and controls. Different reagents are pro-
vided for batch and continuous treatment resulting in different
system design considerations as discussed below.
For both continuous and batch treatment, sulfuric acid is added
for pH control. A 90 day supply is stored in a 25 percent
aqueous form in an above-ground, covered concrete tank, 0.305m
(1 ft) thick. . • - .
XIII-39
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For continuous chromium reduction the single chromium reduction
tank is sized as an above-ground cylindrical concrete tank with
a 0.305 ra (1 ft) wall thickness, a 45 minute retention time, and
an excess capacity factor of 1.2. Sulfur dioxide is added to con-
vert the influent hexavalent chromium to the trivalent form.
The control system for continuous chromium reduction consists of;
1 immersion pH probe and transmitter
1 !• immersion ORP probe and transmitter
1 pH and ORP monitor .
2 slow process controllers
1 sulfonator and associated pressure regulator
1 sulfuric acid pump
1 transfer pump for sulfur dioxide ejector
2 maintenance kits for electrodes, and miscellaneous
electrical equipment and piping
For batch chromium reduction, the dual chromium reduction tanks are
sized as above-ground cylindrical concrete tanks, 0.305 m (1 ft)
thick, with a 4 hour retention time, and an excess capacity factor
of 1.2. Sodium bisulfite is added to reduce the hexavalent chromium,
A completely manual system is provided for batch operation. Sub-
sidiary equipment includes: • •
1 ,' sodium bisulfite mixing and feed tank
1 metal stand and agitator collector
1 sodium bisulfite mixer with disconnects
1 ! sulfuric acid pump .
1 sulfuric acid mixer with disconnects
2 immersion pH probes
1 pH monitor, and miscellaneous piping
Capital costs for batch and continuous treatment systems are pre-
sented in Figure 13-18.
Operation and Maintenance - Costs for operating and maintaining
chromium reduction systems include labor, chemical addition, and
energy requirements. These factors are determined as follows:
LABOR
The labor requirements are plotted in Figure 13-19. Maintenance
of the batch system is. assumed negligible and is not shown.
CHEMICAL ADDITION
For the continuous system, sulfur dioxide is added according to
the following:
XIII-43
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+6
(Ibs S02/day) - (15 ..43) (flow to unit-MGD) (Cr mg/1)
In the batch mode, sodium bisulfite .is added in place of sulfur
dioxide according to the following:
(Ibs NaHS03/day) = (20.06) (flow to unit-MGD) (Cr
ENERGY
+6
mg/l)
A two horsepower motor is required for chemical mixing. The mixers
are assumed to operate continuously over the operational time of the
treatment system.
Given the above requirements, operation and maintenance costs are
calculated based on the following:
$6.71 per man-hour +• 15% indirect labor charge
$380/metric ton of sulfur dioxide
. 520/metric ton of sodium bisulfite
. $0 .045/kilowatt-hour of"'required electricity
pH Adjustment •
The adjustment of pH values is a necessary precursor to a number
of treatment operations and is frequently required to return waste
streams to a pH value suitable for discharge; following metals
precipitation. This is typically accomplished by metering an
alkaline or acid reagent into a mix tank under automatic feed-
back control.
Figure 13-20 presents capital costs for pH adjustment as a function
of the flow rate going into the units. The cost calculations are
based on,steel or concrete tanks with a 15 minute retention time
and an excess capacity of 20%. Tank construction is selected on
a least cost basis. Costs include a pH probe and control system,
reagent mix tanks, a mixer in the pH adjustment tank, and system
installation. [
Operation and Maintenance Costs
LABOR
The required labor as a function of flow rate is
presented in Figure 13-21. The cost of labor may be
calculated using a labor rate of $6.71 per hour plus a
15% indirect labor charge.
XIII-46
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XIII-48
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MATERIALS
Sodium hydroxide or sulfuric acid are added according to
th« stream pH and acidity or alkalinity. The amount of
lime or acid required may be calculated by the procedure
shown in Table 13^7. The cost of lime or acid added may
be determined using the rates of $0.06 per kg of sodium
hydroxide and $75.68 per metric ton of sulfuric acid.
ENERGY
Power, required for a mixer, is based on a representative
installation with one turnover per minute. The daily horse-
power requirement is 3 hp per 37,850 Iph flow rate. The
energy cost may be calculated using the rates of .8 kilo-
watts per horsepower and $.045 per kilowatt-hour.
Contract Removal
Sludge, waste oils, and in some cases concentrated waste solutions
frequently result from wastewater treatment processes. These may
be disposed of on-site by incineration, landfill or reclamation,
but are most often removed on a contract basis for off-site disposal.
System cost estimates presented in this report are based on contract
removal of sludges and waste oils. In addition, where only small
volumes of concentrated wastewater are produced, contract removal
for off-site treatment may represent the most cost-effective ap-
proach to water pollution abatement. Estimates of solution con-
tract haul costs are also provided by this subroutine and may be
selected in place of on-site treatment on a least-cost basis.
Investment Costs - Investment for contract removal is zero.
Operating Costs - Annual costs are estimated for contract removal
of total waste streams or sludge and oil streams as specified in the
input data. Sludge and oil removal costs are further divided into
wet and dry haulage depending upon whether or not upstream sludge
dewatering is provided. The use of wet haulage or of sludge de-
watering and dry haulage is based on least cost as determined by
annualized system.costs over a ten year period. Wet haulage
costs are always used in batch treatment systems and when the
volume of the sludge stream is less than 378.5 liters per day (100
gallons per day). Both wet sludge haulage and total waste haulage
differ in cost depending on the chemical composition of the water
removed. Wastes are classified as cyanide bearing, hexavalent chro-
mium bearing, or oily and are assigned different haulage costs as
shown below.
XII1-49
-------
Chemical
Lime
Sulfuric Acid
TABLE 13-7
NEUTRALIZATION CHEMICALS REQUIRED
Condition
. pH less than 6.5
pH greater than 8.5
A
""Hj
.00014
.00016
(Chemical demand, kg/day) « Ao x Flow Rate (LPH) x Acidity
(Alkalinity, mgCaC03/l)
XIII-50
-------
Waste Composition
^0.05 mg/1 CN~
-0,1 mg/1 Cr °
Oil & grease -TSS
All others
Haulage Cost
$0.16/liter
50.18/liter
$0.08/liter
$0.06/liter
Dry sludge haul costs are estimated at $0.08/liter and 40% dry
solids in the sludge.
In Process Treatment and Control Components •
Some inLprocess controls have been identified for application to E &
EC wastewaters, and these require in-process treatment or changes in
manufacturing facilities and capital equipment for which additional
costs must be estimated. For recycle and reuse of specific process
streams, the required equipment and resultant costs are discussed
in this subsection.
Water Recycle and Reuse
The costing of a water recycle or reuse system is basically a
water pumping application. Wastewaters are pumped from holding
areas following process use or treatment to process operation work
areas for recycle and reuse. The cost of a recycle or reuse water
feed system is based on the amount of water to be recycled, the
total pumping head required, the length and diameter of pipe, and
any needed excavation or installation.
Based on information collected from visited plants in the E&EC
Industry, wastawater flow rates vary from 75.7 liters per minute
(20 GPM) to 18,924 liters per minute (5000 GPM). Pump size, motor
drives, and pipe diameter are all related to flow rate.
Recycle and reuse system components have been sized for seven recycle
flow rates. The equipment specifications for these recycle .and
reuse systems are presented in Table 13-8. Total pumping head,
required horsepower, and pipe diameter vary based on alternative
system flow rates. Manufacturer supplied pump curves were used;
and pipe sizes were selected to reduce internal pipe resistance to
a minimal value. ' The required length is assumed to be 30.5 meters
(100 feet) in all cases. Total pumping head is assumed to increase
with flow rate and varies from 7.6 meters (25 feet) to 18.3 meters
(60 feet).
XIII-51
-------
TABLE 13-8 !
Alternative Recycle and Reuse System Specifications
Recycle/Reuse
Alternative
1
2
3
4
5
6
7
Flow Rate Horsepower
(LPM) (GPM)
75.7 20 1/2
379
1135
1892
3785
9462
18924
100
300
500
1000
2500
5000
2
5
10
I
20
5|0
125
Diameter
(CM) (IN)
10.2 4
15.2 6
25.4 10
25.4 10
30.5 12
61. 2'4
61.
24
XIII-52
-------
Motor Drives:
Pump, pipe, and motor drive costs are based on plant construction
cost data for 1979. Manufacturers equipment specifications and
cost data sheets were also used. For all alternatives, tax and
freight costs are not included. All cost items are discussed
below.
Investment Costs - Investment costs were determined for each al-
ternative recycle and reuse system and include pumps, motor drives,
valves, supports and foundations, pump and motor controls, and
water transport piping. The recycle investment costs are presented
in Table 13-9 for each alternative system. Component costs were
based on the following:
Pumps: : Estimated costs are for centrifugal type pumps.
Using the required recycle flow rates, pump
curves were utilized to estimate horsepower
requirements and motor speed for the assumed
i total pumping head for each recycle system.
Two pumps are costed, each having the required
flow capacity.
Estimated costs are for motor drives to supply
the required pumping horsepower. Squirrel cage
induction motors with magnetic starters (230/460.
Volt, A.C, 3 phase, 60 cycle) were costed. One
motor is required for each pump.
Piping:: Estimated costs are for ductile cost iron pipe
(Type III) with mechanical joints. Pipe diameters
vary with flow rate as presented in Table 12-8.
The length of pipe required in each case is assumed
to be 30.5 meters (100 feet).
Pipe and Motor Controls: Controls are required with each pump and
motor to adjust recycle flow. The costs of these
controls are dependent on recycle or reuse system
layout and internal requirements. For this analy-
sis, the control costs are estimated to be equal to
the investment costs of the pump and motor system
to be controlled.
Support and Foundations: Estimated costs for pipe supports and
pump foundations are plant specific. Foundation
requirements are based on pump and motor weights
while support system are related to pipe size. For
this analysis, support and foundation costs are esti-
mated to be equal to 50 percent of pump and motor
investment costs.
XIII-53
-------
TABLE 13-9
RECYCLE AND REUSE INVESTMENT COST
RECYCLE/REUSE
ALTERNATIVE
1
2
3
4
5
6
7
FLOW
RATE
(1pm)
75.7
379
1135
"1892
3785
9462
18924
INVESTMENT
COST
(Dollars)
8516
16113
28318
28968
38377
71957
87317
XIII-54;
-------
Valves: Estimated costs are for iron body globe and swing
check valves. Two glove valves and one check
i valve are required per pump. Valve size has been
equated with pipe diameters for each alternative
system costed.
Operation and Maintenance Costs
Operation and maintenance costs include labor and energy. The
annual cost of materials, supplies and labor for operation
and maintenance is estimated to be 4% of total investment cost
in this analysis. The energy costs are estimated utilizing pump
horsepcwer requirements for each alternative-system. The cost per
Kw houi
is assumed to be $0.045.
XIII-55
-------
ENERGY AND NON-WATER QUALITY ASPECTS
Energy and non-water quality aspects of the wastewater treatment
technologies described in Section XII are summarized in Tables
13-10 and 13-11. Energy requirements are listed, the impact on
environmental air and noise pollution is noted, and solid waste
processes are divided into two groups, wastewater treatment
processes on Table 13-10 and sludge and solids handling processes
on Table 13-11.
Energy Aspects
Energy aspects of the waistewater treatment processes are important
because of the impact of energy use on our natural resources and
on the economy. Electrical power and fuel requirements (coal,
oil, or gas) are listed in units of kilowatt hours per ton of dry
•olids for sludge and solids handling. Specific energy uses are
noted in the "Remarks" column.
Non-water Quality Aspects
It is important to consider the impact of each treatment process
on air, noise, and radiation pollution of the environment to
preclude the development of a more adverse environment impact.
In general, none of the liquid handling processes causes air pollu-
tion.. With sulfide precipitation, however, the potential exists
for evolution of hydrogen sulfide, a toxic gas. Proper control of
pH in treatment eliminates this problem. Incineration of sludges
or solids can cause significant air pollution which must be con-
trolled by suitable gag houses, scrubbers or stack gas precipita-
tors as well as proper incinerator operation and maintenance. None
of the wastewater treatment processes causes objectionable noise
and none of the treatment processes has any potential for radiation
hazards.
The solid waste impact of each wastewater treatment process is
indicated in two columns on Table 13-11. The first column shows
whether effluent solids are to be expected and, if so, the solids
content in qualitative terras. The second column lists typical
values for percent solids of sludge or residue.
The processes for treating the wastewaters from this category
produce considerable volumes of sludges. In order to ensure long-
term protection of the environment from harmful sludge constituents,
special consideration of disposal sites should be made by RCRA and
municipal authorities where applicable.
XIII-56
-------
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IBEATMEKT SYSTEM COST ESTIMATES
Estimates of the total cost of wastewater treatment and control sys-
tems for E & EC process wastewater incorporating the treatment and
control components discussed above were presented for the appropriate
product subcategories in Sections VI through XI. Cost estimates
corresponding to median (typical) flow rates in the subcategory
addressed were presented for each system in order to provide an
indication of the costs to be incurred in implementing each level
of treatment. Since plants in some subcategories report zero waste-
water discharge and will therefore incur zero treatment and control
costs, low flow rates used in cost estimation represent low flow
values at plants reporting wastewater and are not true minima for,the
subcategory. Raw waste characteristics were determined based on
sampling data as discussed in Sections VI through XI.
The system costs presented in Sections VI through XI include com-
ponent costs as discussed above and subsidiary costs including
engineering, line segregation, administration, and interest expense
during construction. In each case, it is assumed that none of the
specified treatment components and control measures are in place so
that the presented costs represent total costs for the systems.
Cost estimates presented in the.tables in Section VI through X.I are1
representative of costs typically incurred in implementing treatment
and control equivalent to the specific levels. They will not, in
general, correspond precisely to cost experience at any individual
plant. Specific plant conditions such as age, location, plant layout,
or present production and treatment practices may yield costs which
are either higher or lower than the presented costs. Because the
costs shown are total system costs and do not assume any treatment
in place, it is probable that most plants will require smaller
expenditures to reach the specified levels of control from their
present status.
The actual costs of installing and operting a Level 1 system at a
particular plant may be substantially lower than the tabulated
values. Reductions in investment and operating costs are possible
in several areas. Design and installation costs may be reduced by
using plant workers. Equipment costs may be reduced by using or
modifying existing equipment instead of purchasing all new equipment.
Application of an excess capacity factor, which increases the size
of most equipment foundation costs, could be reduced if an existing
concrete pad or floor can be utilized. Equipment size requirements
may be reduced by the ease of treatment (for example, shorter
retention time) of particular waste streams. Substantial reduc-
tion in both investment and operating cost may be achieved if a
plant requires a water use rate below that assumed in costing.
XIII-59
-------
SECTION XIV
ACKNOWLE DGEMENTS
The Environmental Protection Agency was aided lin the preparation
of this Development Document by Hamilton Standard, Division of
United Technologies Corporation. Hamilton Standard's effort was
managed by Mr. Daniel Lizdas, Mr. Robert Blaser and Mr. Jeffrey
Wehner. Mr. Richard Wilde and Mr. Lawrence McNamara directed
the engineering activities and field operations were under the
direction of Mr. Richard Kearns. Significant contributions were
made by Peter Formica, James Brown, James Steele, Remy Halm, James
Pietrzak, Robert Patulak and Raymond Levesque.
Ms. Lauren Zeise and Mr. Richard Kinch Of the EPA's Effluent
Guidelines Division served as Project Officers during the prep-
aration of this document. Mr. G. E. Stigall, Chief, Inorganics
Chemicals and Services Branch, Effluent Guidelines Division,
offered guidance and 'suggestions during this report.
Acknowledgement and appreciation is also given to Mrs. Lynne McDonnell,
Ms. Lori Kucharzyk, Ms. Kathy Maceyka, and Ms. Denise McKiernan of
Hamilton Standard, who worked so diligently to prepare, edit, publish
and distribute the manuscript.
Finally, appreciation is also extended to the plants that partici-
pated in and contributed data for the formulation of this document.
XIV-1
-------
SECTION XV
REFERENCES
1. Amick, Charles L., Fluorescent Lighting Manual, McGraw-
Hill, 3rd ed.f (1961).
2. Baumann, E.R., Diatomite Filtration of Potable Water, Ameri-
can Water Works Association Inc.
3. Beau, R.L. et al., Transformers for the Electric Power In-
dustry, McGraw-Hill (1959).
4. Bogle, W.S., Device Development, The Western Electric Engi-
neer, (July, 1973).
5. Burock, R. et al, Manufacturing Beam Lead, Insulated Gate,
Field Effect Transistor Integrated Circuits, Bell Labora-
tories Record, (Jan. 1975).
6. Cockrell, W.D., Industrial Electronics Handbook, McGraw-
Hill (1958).
7. Culver, R.H., Diatomaceous Earth Filtration, Chemical
Engineering, Vol. 17, No. 12 (Dec. 1975).
8. Elenbaas, W., Fluorescent Lamps and Lighting, (1959).
9. EPA, Final Rule Polychlorinated Biphenyls Manufacturing,
Processing, Distribution in Commerce, and Use Prohibition,
Federal Register, (May 31, 1979), Part IV.
10. EPA, Support Document/Voluntary Environmental Impact State-
ment and PCS Ban Economic Impact Analysis, EPA Office of
Toxic Substances Report, (April, 1979).
11. Forsythe, William E., Fluorescent and Other Gaseous Dis-
charge Lamps, (1948).
12. Funer, R.E., Letter to Robert Schaeffer, EPA Effluent Guide-
lines Div., E.I. duPont de Nemours and Company. Subject:
priority pollutant removal from wastewater by the PACT
process at the Chambers Works.
13. Gerstenberg, D. and J. Klerer, Anodic Tantalum Oxide Capa-
citors From Reactively Sputtered Tantalum, 1967 Proceed-
Tngs, Electronic Components Conference, Sponsored by IEEE,
EIA.
XV-1
-------
14. Gray, H.J., Dictionary of Physics, Longmans, Green and Co.,
London (1958).
15. Henney, K. and C. Walsh, Eds., Electronic Components Handbook,
McGraw-Hill (1975). :
16. Hewitt, Harry, Lamps and Lighting, American Elsevier Publish-
ing Co., (1966).
17. Hiyama, S. et al, 3500 uFV Wound-Foil Type Aluminum Solid
Electrolytic Capacitors, 1968 Proceedings, Electronic
Components Symposium, Sponsored by IEEE, EIA.
18. IBM, S/C Manufacturing Overview, IBM,'East Fishkill, N.Y.
19. IEEE Standards Committee, IEEE, Standard Dictionary of Elec-
trical and Electronic Terms, J. Wiley and Sons, (Oct, 1971).
20. Illuminating Engineering Society, IES,Lighting Handbook, 3rd
ed., (1962). '
21. Jowett, C.E., Electronic Engineering Processes, Business
Books, Ltd., (1972).
22. Kirk and Othmer, Encyclopedia of Chemical Technology, Vol. 17,
McGraw-Hill, (1968).
23. Knowlton, A.E., Standard Handbook for Electrical Engineers,
McGraw-Hill, (1957).
24. McGraw-Hill, Dictionary of Scientific and Technical Terms,
2nd Ed., McGraw-Hill (1978). :
25. McGraw-Hill, Encyclopedia of Science and Technology, McGraw-
Hill (1960).
26. Mclndoe, R.W., Diatomite Filter Aids, Pollution Engineering
Magazine.
27. Motorola, Small Signal Wafer Processing, Motorola, Phoenix,
AZ.
28. Oldham, W.G., The Fabrication of Microelectronic Circuits,
Scientific American (Sept., 1977). :
XV-2
-------
29. Phillips, A.B., Transistor Engineering, McGraw-Hill, (1962),
30. Puchstein, A.F. et al., Alternating Current Machines, J. Wiley,
(1954).
31. Transformer Consultants, Why Annual Transformer Oil Testing,
The Consultor, Transformer Consultants, P.O. Box 3575,
Akron, Ohio, 44310 (1978).
32. U.S. Department of Commerce, Bureau of the Census, 1977 Census
of Manufactures, Preliminary Statistics, Bureau of the Cen-
sus Reports No. MC 77-1-36 for SIC 3600-3699 Issued 1979.
33. U.S. Government, Public Law 94-469 Toxic Substances Control
Act, (Oct. 11, 1976).
34. Webster's Seventh New Collegiate Dictionary, G & C Merriam
Co., (1963).
XV-3
-------
-------
SECTION XVI
GLOSSARY
Absorb - To take up matter or radiation.
,t
- Federal Water Pollution Control Act Amended 1972.
Activate - To treat the cathode or target of an electron tube
irforder to create or increase its emission.
Adjustable Capacitor - The capacitance of adjustable capacitors
may be set at any one of several discrete values.
Adsorption - The adhesion of an extremely thin layer of molecules
- (of~gas, liquid) to the surface of solids (granular activated
carbon for instance) or liquids with which they ace in con-
tact.
Aging •- Allowing a permanent magnet, capacitor, meter or other
device to remain in storage for a period of time sometimes
with a voltage applied until the characteristics of the de-
vice become essentially constant.
Algicide - Chemicals used in the control of phytoplankton (algae)
inTbodies of water.
Aluminum Foil - Aluminum in the form of a sheet of thickness not
exceeding 0.005 inch.
anneal - To treat a metal, alloy, or glass with heat and then
- cool to remove internal stresses and to make the material
less brittle.
Anode - The collector of electrons in an electron tube. Also
known as plate; positive electrode.
Anodizing - An electrochemical process of controlled aluminum
- oxidation producing a hard, transparent oxide up to several
mils in thickness.
Assembly or Mechanical Attachment - The fitting together of pre-
" - viously manufactured parts or components into a complete
machine, unit of a machine or structure.
Autotrans former - A power transformer having one continuous
- winding that is tapped? part of the winding serves as the
primary and all of it serves as the secondary, or vice versa.
XVI-1
-------
Ballast - A circuit element that serves to limit an electric
current or to provide a starting voltage, as in certain
types of lamps, such as in fluorescent ceiling fixtures.
Binder - A material used to promote cohesion between particles
of carbon or graphite to produce solid carbon and graphite
rods or pieces.
Biochemical Oxygen Demand (BOD) - (1) The quantity of oxygen used
in the biochemical oxidation of organic matter in a specified
time, at a specified temperature, and under specified con-
ditions. (2) Standard test used in assessing wastewater
strength .
Biodegradable - The part of organic matter which can be oxidized
by bioprocesses, e.g., biodegradable detergents, food wastes,
animal manure, etc.
Biological Wastewater Treatment - Forms of wastewater treatment
in which bacteria or biochemical action is intensified to
stabilize, oxidize, and nitrify the unstable organic matter
present. Intermittent sand filters, contact beds, trickling
filters, and activated sludge processes are examples.
Breakdown Voltage - Voltage at which a discharge occurs between
two electrodes.
Bulb ~ ^ke glass envelope which incloses an I incandescent lamp
or an electronic tube.
Bushing - An insulating structure including a central conductor,
or providing a central passage for a conductor, with pro-
vision for mounting on a barrier, conducting or otherwise,
for the purpose of insulating the conductor from the barrier
and conducting current from one side of the barrier to
the other .
Busbar - A heavy rigid, metallic conductor, usually uninsulated,
used to carry a large current or to make a common connection
between several curcuits.
Calcining - To heat to a high temperature without fusing, as to
heat ^ unformed ceramic materials in a kiln, or to heat ores,
precipitates, concentrates or residues ;so that hydrates,
carbonates or other compounds are decomposed and volitile
material is expelled, e.g., to heat limestone to make lime.
Calibration - The determination, checking, or rectifying of the
graduation of any instrument giving quantitative measurements.
XVI-2
-------
Capacitance - The ratio of the charge on one of the conductors
— —ol: a capacitor to the potential difference between the
conductors.
Capacitor - Device composed of conducting plates or foils
separated by thin layers of dielectric with the plates on >.
either side of the dielectric having opposite charges
causing electrical energy to be stored in the polarized
dielectric.
Carbon - A nonmetallic chiefly tetravalent element found native
or as a constituent of coal, petroleum, asphalt, limestone,
etc.
Cathode - The primary source of electrons in an electron tube;
in directly heated tubes the filament is the cathode,
and in indirectly heated tubes a coated metal cathode sur-
rounds a heater.
Cathode Ray Tube - An electron-beam tube in which.the beam can
be focused to a small cross section on a luminescent screen
and varied in position and intensity to produce a visible
pattern.
Central Treatment Facility - Treatment plant which co-treats
process wastewaters from more than one manufacturing opera-
tion or co-treats process wastewaters with noncontact cooling
water or with non-process wastewaters (e.g., utility blow-
down, miscellaneous.runoff, etc.).
Centrifugation - The removal of water in a sludge and water slurry
by introducing the water and sludge slurry into a centrifuge.
- The sludge is driven outward with the water remaining near
the center. The dewatered sludge is usually landfilled.
Ceramic - A product made by the baking or firing of a non-metallic
"ilneral such as tile, cement, plaster, refractories, and
brick.
Chemical Coagulation - The destabilization and intitial aggregation
ol~colloidal and finely divided suspended matter by the addi-
tion of a floe-forming chemical.
Chemical Oxidation (Including Cyanide) - The addition of chemical
iigents to wastewater for the purpose of oxidizing pollutant
material.
Chemical Oxygen Demand (COD) - (1) A test based on the fact that all
organic compounds, with few exceptions, can be oxidized to
carbon dioxide and water by the action of strong oxidizing
XVI-3
-------
agents under acid conditions. Organic matter is converted
to carbon dioxide and water regardless of the biological
assimilability of the substances. One of the chief limita-
tions is its ability to differentiate between biologically
oxidizable and biologically inert organic matter. The
major advantage of this test is the short time required
for evaluation (2 hrs). (2) The amount of. oxygen required
for the chemical oxidation of organics in a liquid.
Chemical Precipitation - (1) Precipitation induced by addition of
chemicals. (2) The process of softening water by the addition
of lime and soda ash as the precipitants.
Chlorination - The application of chlorine to water or wastewater
generally for the purpose of disinfection, but frequently
for accomplishing other biological or dhemical results.
Circuit Breaker - Capable of making, carrying, breaking currents
under normal curcuit conditions and make, carry, break
under abnormal i.e. shortcircuits.
Cleaning - The removal of soil and dirt (including grit and
grease) from a workpiece using water with or without a
detergent or other dispersing agent.
Coil 7 A number of turns of wire used to introduce inductance
into an electric circuit, to produce magnetic flux, or
to react mechanically to a changing magnetic flux.
Coil-Core Assembly - A unit made up of the coil windings of a
transformer placed over the magnetic core.
Coking - (1) Destructive distillation of coal to make coke.
(2) A process for thermally converting the heavy residual
bottoms of crude oil entirely to lower-boiling petroleum
products and by-product pertroleum coke^
Colloids - A finely divided dispersion of one material called the
dispersed phase" (solid) in another material which Is called
the "dispersion medium" (liquid). Normally negatively charged.
Composite Wastewater Sample - A combination of individual samples
of water or wastewater taken at selected intervals and mixed
in proportion to flow or time to minimize the effect of the
variability of an individual sample.
Concentric Windings - Transformer windings in which the low-voltage
winding is in the form of a cylinder next to the core, and
the high-voltage winding, also cylindrical, surrounds the
low-voltage winding.
XVI-4
-------
Conductor - A wire, cable, or other body or medium suitable for
carrying electric current.
Conduit - Solid of flexible metal or other tubing through which
insulated electric wires are run.
Contamination - A general term signifying the introduction into
water of microorganisms, chemicals, wastes or sewage which
renders the water unfit for its intended use.
Contractor Removal - The disposal of oils, spent solutions, or
iiludge by means of a scavenger service.
Conversion Coating - A metal-surface coating consisting of a com-
pound of the base metal.
Cooling Tower - A device used to cool water used in the manufacturing
"" processes before returning the water for reuse.
Copper - A common reddish chiefly univalent and bivalent metallic
—^element that is ductile and malleable and one of the best
conductors of heat and electricity.
Core ([Magnetic Core) - A quantity of ferrous material placed in
a coil or transformer to provide a better path than air
for magnetic flux, thereby increasing the inductance of the
coil and increasing the coupling between the windings of a
transformer.
Corona Discharge - A discharge of electricity appearing as a
"~ laluish-purple glow'on the surface of and adjacent to a
conductor when the voltage gradient exceeds a certain cri-
tical value; due to ionization of the surrounding air by
the high voltage.
Curing - A heating/drying process carried out in an enclosure
where the temperature is usually maintained at approximately
150C.
Current Carrying Capacity- The maximum current that can be con-
tinuously carried without causing permanent deterioration
of electrical or mechanical properties of a device or
conductor.
Dag (Aquadag) - A conductive graphite coating on the inner and
— ^outer side walls of some cathode-ray tubes.
Degreasing - The process of removing grease and oil from the surface
of the basis material.
XVI-5
-------
Dewaterinq - A process whereby water is removed from sludge.
Dicing ~ Sawing or otherwise machining a semiconductor wafer into
small squares or dice from which transistors and diodes can
be fabricated.
Die ~ A tool or mold used to impact shapes to or to form impres-
sions on materials such as metals and ceramics.
Pie Cutting (Also Blanking) - Cutting of plastic or metal sheets
into shapes by striking with a punch.
Dielectric - A material that does not permit the conductance
of electricity; an insulator.
Di-n-Octyl-Phthalate - A liquid dielectric that is presently
being substituted 'for a PCB dielectric fluid.
Diode (Semiconductor), (Also Crystal Diode., Crystal Rectifier) -
A^two electrode semiconductor device that utilizes the rec-
tifying properties of a p-n junction or point contact.
Discrete Device - Individually manufactured transistor, diode,
etc. '
Dissolved Solids - Theoretically the anhydrous residues of the dis-
solved constituents in water. Actually the term is defined
by the method used in determination. In water and wastewater
treatment, the Standard Methods tests are used.
Distribution Transformer - An element of an electric distribution
system located near consumers which changes primary distribu-
tion voltage to secondary distribution voltage.
Dopant - An impurity element added to semiconductor materials used
in crystal diodes and transistors.
Dragout - The solution that adheres to the part or workpiece and is
carried past the edge of the tank.
Dry Electrolytic Capacitor - An electrolytic capacitor with a paste
rather than liquid electrolyte.
prying Beds - Areas for dewatering of sludge by evaporation and
seepage.
£EY. slug - Usually refers to a plastic encased sintered tantalum
slug type capacitor.
XVI-6
-------
Dry Transformer - Having the core and coils neither impregnated
— with an insulating fluid nor immersed in an insulating oil.
Effluent - The quantities, rates, and chemical, physical, bio-
logical, and other constituents of waters which are discharged
from point sources.
Electrochemical Machining - The process whereby the workpiece
•" becomes the anode and a shaped cathode is maintained in
close proximity. Electrolyte is pumped between the
electrodes and a potential applied with the result that metal
is rapidly dissolved from the work piece in a selective man-
ner and the shape produced on the workpiece complements that
of the cathode.
Electrolyte - A nonmetallic electrical conductor in which current
Is carried by the movement of ions.
Electron Beam Lithography - Similar to photolithography - A fine
b"^m~of~electrons is used to scan a pattern and expose an
electron-sensitive resist in the unmasked areas of the ob-
ject surface.
Electron Discharge Lamp - An electron lamp in which light is pro-
duced by passage of an electric current through a metallic
vapor or gas.
Electron Gun - An electrode structure that produces and may con-
trol7~~focus, deflect and converge one or more electron
'beams in an electron tube.
Electron Tube - An electron device in which conduction of electri-
"city is provided by electrons moving through a vacuum or
gaseous medium within a gas tight envelope.
Electroplating - The production of a thin coating of one metal
on another by electrodisposition.
Emissive Coating - An oxide coating applied to an electrode to
enhance the emission of electrons.
Emulsion Breaking - Decreasing the stability of dispersion of
one liquid in another.
End-of-pipe Treatment - The reduction and/or removal of pollutants
by chemical treatment just prior to actual discharge.
Enitayial Layer - A (thin) semiconductor layer having the same
Eirystaline orientation as the substrate on which it is grown.
XVI-7
-------
Epitaxial Transistor - Transistor with one or more epitaxial layers,
Equalization - The process whe'reby waste streams from different
sources varying in pH, chemical constituents, and flow rates
are collected in a common container. The effluent stream
from this equalization tank will have a fairly constant flow
and pH level, and will contain a homogeneous chemical mixture.
This tank will help to prevent an unnecessary shock to the
waste treatment system. ;
Etch - To corrode the surface of a metal in order to reveal its
composition and structure.
Extrusion - Forcing the carbon-binder-mixture through a die under
extreme pressure to produce desireable shapes and characteris-
tics of the piece. ;
Field-effect Transistors - Made by the metal-oxide-semiconductor
(MOS) technique, differ from bipolar ones in that only one
kind of charge carrier is active in a single device. Those
that employ electrons are called n-MOS transistors? those
that employ holes are p-MOS transistors.
i
Filament - Metallic wire which is heated in an incandescent
lamp to produce light by passing an electron current through
it. A cathode in a fluorescent lamp that emits electrons
when electric current is passed through it.
Filtering Capacitor - A capacitor used in a power-supply filter
system to provide a low-reactance path for alternating cur-
rents _ and thereby suppress ripple currents, without affect-
ing direct currents.
.F.ixed, Capacitor - A capacitor having a definite capacitance
valve that cannot be adjusted.
Float Pauge.- A device for measuring the elevation of the surface
of a liquid, the actuating element of which is a buoyant
float that rests on the surface of the: liquid and rises
or falls^with it. The elevation of the surface is measured
by a chain or tape attached to the float.
Floe - A very fine, fluffy mass formed by the aggregation of fine
suspended particles,. ;
XVI-8
-------
Flocculation - In water and wastewater treatment, the agglomeration
—of colloidal and finely divided suspended matter after coagu-
lation by gentle stirring by either mechanical or hydraulic
means. In biological wastewater treatment where coagulation
is not used, agglomeration may be accomplished biologically.
Flocculator - An apparatus designed for the formation of floe in
water or sewage.
Fjiow-proportioned Sample - A sampled stream whose pollutants are
~ tpportioned to contributing streams in proportion to the
flow rates of the contributing streams.
Fluorescent Lamp - An electric discharge lamp in which phosphor
Suiterials transform ultraviolet radiation from mercury
vapor ionization to visible light.
Forming - Application of voltage to an electrolytic capacitor,
"eJectrolytia rectifier or semiconductor device to pro-
duce a desired permanent change in electrical characteris-
tics as part of the manufacturing process.
Frit S«»al - A seal made by fusing together metallic powders with
ITglass binder for such applications as hermatically sealing
ceramic packages for integrated circuits.
Funnel"- The rear, funnel shaped portion of the glass enclosure
of a cathode ray tube.
Fuse - Overcurrent protective device w/circuit opening fusible
part heated and severed by overcurrent passage.
Gate - One of the electrodes in a field effect transistor.
Getter - A metal coating found within a lamp that when activated
by an electric current absorbs residual water vapor and
oxygen from with a vacuum.
Glass - A hard, amorphous, inorganic, usually transparent,
brittle substance made by fusing silicates, sometimes
borates and phosphates with certain basic oxides and then
rapidly cooling to prevent crystallization.
Glow Lamp - An electronic device containing at least two elec-
trodes and an inert gas in which light is produced by a
negative glow close to the negative electrode when a
voltage is applied between the electrodes.
Grab Sample - A single sample of wastewater taken at neither set
time nor flow.
XVI-9
-------
Graphite - A soft black lustrous carbon that conducts electricity
as a constituent of coal, petroleum, asphalt, limestone,
etc.
Grease - In wastewater, a group of substances including fats,
waxes, free fatty acids, calcium and magnesium soaps,
mineral oil and certain other nonfatty' materials. The type
of solvent and method used for extraction should be stated
for quantification.
f
Grease Skimmer - A device for removing grease or scum from the
surface of wastewater in a tank. !
Green Body - A carbon rod or piece prior to baking usually soft
and quite easily broken.
Grid - An electrode located between the cathode and anode of
an^electron tube, which has one or more openings through
which electrons or ions can pass, and serves-to control the
flow of electrons from cathode to anode.
Grinding - The process of removing stock from a workpiece by the
use of abrasive grains held by a rigid or semi-rigid binder.
Hardness - A characteristics of water, imparted by salts of calcium,
magnesium, and iron such as bicarbonates, carbonates, sulfates,
chlorides, and^nitrates that cause curdling of soap, deposi-
tion of scale in boilers, damage in some industrial processes
and sometimes objectionable taste. It may be determined by
a standard laboratory procedure or computed from the amounts
of calcium and magnesium as well as iron, aluminum, manganese,
tarium, strontium, and zinc, and is expressed as equivalent
calcium carbonate.
HeavY Metals - A general name given to the ions of metallic ele-
ments such as copper, zinc, chromium, and nickel. They are
normally removed from wastewater by forming an insoluble
precipitate (usually a metallic hydroxide).
Holding Tank - - A reservior to contain preparation materials -so
as to be ready for immediate service. !
Hybrid Integrated Circuits - Part integrated, part discrete cir-
cuit.
Impact Extrusion - A cold extrusion process for producing tubular
components by stricking a slug of the metal, which has been
placed in the cavity of the die, with a punch moving at
high velocity.
. XVI-10
-------
impregnant - A material diffused into the carbon piece to provide
——the~desireable electronic characteristics of the piece.
Impregnate - To force a liquid substance into the spaces of a
porous solid in order to change its properties.
Incandescent Lamp - An electric lamp producing light in which a
metal1ic~rilament is heated white-hot in a vacuum by passage
of an electric current through it.
Industrial Wastes - The liquid wastes from industrial processes
ai~dlstinct from domestic or sanitary wastes.
Influent - Water or other liquid, either raw or partly treated,
flowing into a reservior basin or treatment plant.
In-Process Control Technology - The regulation and conservation of
"chimTcals and rinse water throughout the operations as opposed
to end-of-pipe treatment.
Insulating Paper - A standard material for insulating electrical
eiuijment, usually consisting of bond or draft paper coated
with black or yellow insulating varnish on both sides.
Insulation (Electrical Insulation) - A material having high elec-
—: trical resistivity and therefore suitable for separating
cidjacent conductors in an electric circuit or preventing
possible future contact between conductors.
Insulator - A nonconducting support for an electric conductor.
integrated Circuit - Assembly of electronic devices interconnected
into circuits.
Interleaved Winding - An arrangement of winding coils around,
a transformer core in which the coils are wound in the form
of a disk, with a group of disks for the low-voltage windings
stacked alternately, with a group of disks for the high-
voltage windings.
Intermittent Filter - A natural or artificial bed of sand or other
fine-grained material to the surface of which sewage is inter-
mittently added in flooding doses and through which it passes,
the opportunity being given for filtration and the maintenance
of aerobic conditions.
Ion Exchange - A reversible chemical reaction between a solid (ion
exchanger) and a fluid (usually a water solution) by means
of which ions may be interchanged from one substance to
another. The superficial physical structure of the solid is
not affected.
XVI-11
-------
Ion Exchange Resins - Synthetic resins containing active groups
(usually sulfonic, carboxylic, phenol, or substituted amino groups)
that give the resin the property of combining with or exchanging
ions between the resin and a solution.
Ion Implantation - A process of introducing impurities into the near
surface regions of solids by directing a beam of ions at the
solid. ,
Junction - A region of transition between two different semiconduc-
ting regions in a semiconductor device such as a p-n junction
or between a metal and a semiconductor.
Junction Box - A protective enclosure into which wires or cables are
led and connected to form joints.
Ini£e, Switch - Form of switch where moving blade enters stationary
contact clips. *
Klystron - An evacuated electron-beam tube in which an initial velo-
city modulation imparted to electrons in the* beam results
subsequently in density modulation of the beam; used as an
amplifier in the microwave region or as an oscillator.
Lagoon - A man-made pond or lake for holding wastewater for the
removal of suspended solids. Lagoons are also used as retention
ponds after chemical clarification to polish the effluent and to
safeguard against upsets in the clarifier; for stabilization of
organic matter by biological oxidation; for storage of sludge-
and for cooling of water.
Landfill - The disposal of ineret, insoluble waste solids by dumping
at an approved site and covering the earth.
Lapping - The mechanical abrasion or surface planning of the semi-
conductor water to produce desired surface and wafer thickness.
Lime - Any of a family of chemicals consisting essentially of calcium
hydroxide made from limestone (calcite) which is composed almost
wholly of calcium carbonates or a mixture of calcium and magnesium
carbonates.
Limiting Orifice - A device that limits flow by constriction to a
relatively small area. A constant flow can be obtained over a
wide range of upstream pressures.
Machining - The process of removing stock from a workpiece by forcing
a cutting tool through the workpiece removing a chip of basis
material. Machining operations such as turning, milling, drilling
boring, tapping, planing, broaching, sawing and cutoff, shaving,
threading, reaming, shaping, slotting, hobbing, filling, and cham-
fering are included in this definition.
XVI-12
-------
Magnaflux Inspection - Trade name for magnetic particle test.
Make-up* Water - Total amount of water used by any process/process
step.
Mandrel - A metal support serving as a core around which the metals
Ire wound and amealled to form a central hole.
Mask (Shadow Mask) - Thin sheet steel screen with thousands of
~~—' opertureFThrough which electron beams pass to a color picture
tube screen. The color of an image depends on the balance from
each of three electron beams passing through the mask, one beam
for each color.
Metal Oxide Semiconductor Device - A metal insulator semiconductor
structure in which the insulating layer is an oxide of the subs-
trate material; for a silicon substrate, the insulating layer is
silicon dioxide (SiO2).
*%
Mica - A group of aluminum silicate minerals that are characterized
by their ability to split into thin, flexible flakes because of
tlieir basal cleavage.
Miligrams Per Liter (mg/1) - This is a weight per volume designation
used TrTwater and wastewater analysis.
Mixed Media Filtration - A filter which uses two or more filter materials
o'f differing specific gravities selected so as to produce a tilter
uniformly graded from coarse to fine.
MQS - (See Metal Oxide Semiconductor)
Mount Assembly - Funnel neck ending of picture tube holding electron
gun(s).
National Pollutant Discharge Elimination System (NPDES) - The federal
mechanism for regulating point source discharge by means o£
permits.
Neutralization - Chemical addition of either acid or base to a solution
luch that the pH is adjusted to approximately 7.
Noncontact Cooling Water - Water used for cooling which does not come
Into~direct contact with any raw material, intermediate product,
waste product or finished product.
Non-Polar Capacitor - An electrolific capacitor having equal thicknesses
of oxide film and both the anode and cathode.
Oil Filled Capacitor - A capacitor whose conductor and insulating
"elements are immersed in an insulating fluid that is usually,
but not necessarily, oil.
XVI-13
-------
Outfall - The point or location where sewage or drainage discharges
from a sewer, drain, or conduit.
Oxide Mask - Oxidized layer of silicon wafer through which "windows"
are formed which will allow for dopants to be introduced into
the silicon.
Panel - The front, screen portion of the glass Enclosure of a cathode
ray tube.
PCB (Polychlorinated Biphenyl) - A colorless liquid, used as an
insulating fluid in electrical equipment. (The future use of PCB
for new transformers was banned by the Toxic Substances Control
Act of October 1976.)
gH ~ The negative of the logarithm of the hydrogen ion concentration
Neutral water has a pH value of 7. At pH lower than 7, a solution
is acidic. At pH higher than 7, a solution is alkaline.
Adjustment - A means of maintaining the optimum pH through the use
of chemical additives. Can be manual, automatic, or automatic
with flow corrections.
.Phase - One of the separate circuits or windings of a polyphase system,
machine or other apparatus.
Phase Assembly - The coil-core assembly .of a single phase of a trans-
former, i
Phosphate Coating - A conversion coating on metal, usually steel,
produced by dipping it into a hot aqueous solution of iron, zinc,
or manganese phosphate.
Phospaor - Crystalline inorganic compounds that produces light when
excited by ultraviolet radiation.
Photolithography - The process by which a microscopic pattern is trans-
ferred from a photomask to a meterial layer (e.g., SiO.,) in an
actual circuit. *
Photomask - A film or glass negative that has many high-resolution
images, used in the production of semiconductor devices and
integrated circuits.
jPhoton - A quantum of electromagnetic energy.
Photoresist - A light-sensitive coating that is applied to a substrate
or board, exposed, and developed prior to chemical etching; the
exposed areas serve as a mask for selective etching.
XVI-14
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Picture Tube - A cathode ray tube used in television receivers to
~~Produce an image by varying the electron beam intensity as the
beam is deflected from side to side and up and down to scan a
raster on the fluorescent screen at the large end of the tube.
Plate - (1) Preferably called the anode. The prinicpal electrode to
~~ which the electron stream is attracted in an electron tube.
(2) One of the conductive electrodes in a capacitor.
Polar capacitor - An electrolytic capacitor having an oxide film on
~~ only one foil or electrode which forms the anode or positive
terminal.
Pole Type Transformer - A transformer suitable for mounting on a pole
~~ or similar structure.
Polishing - The process of removing stock from a workpiece by the
~ action of loose or loosely held abrasive grains carried to the
workpiece by a flexible support. Usually, the amount of stock
removed in a polishing operation is only incidental to achieving
a desired surface finish or appearance.
Pollutant - The term "pollutant" means dredged spoil, solid wastes,
Incinerator residue, sewage, garbage, sewage sludge, munitions,
chemical wastes, biological materials, radioactive materials
heat, wrecked or discarded equipment, rock, sand, cellar dirt and
industrial, municipal and agricultural waste discharged into
waiter.
Pollutant Parameters - Those constituents of wastewater determined to be
detrimental and, therefore, requiring control.
Pollution Load - A measure of the unit mass of a wastewater in terms
~ "oTTts solids or oxygen-demanding characteristics, or in terms
of harm to receiving waters.
Polyelectrolytes - Used as a coagulant or a coagulant aid in water and
wastewater treatment. They are synthetic or natural polymers
containing ionic constituents. They may be cationic, anionic, or
nqnionic.
Power Regulators - Maintain constant output current for changes in
"temperature output load, line current and time.
Power Transformer - Transformer used at a generative station to step.up
™ the generated voltage to high levels for transmission..
Prechlorination - (1) Chlorination of water prior to filtration. (2)
Chlorination of sewage prior to treatment.
XVI-15
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Precipitate - The discrete particles of material rejected from a
liquid solution.
Pressure Filtration - The process of solid/liquid phase separation
effected by passing the more permeable liquid phase through a
mesh which is impenetrable to the solid phase.
Pretreatment - Any wastewater treatment process! used to reduce
pollution load partially before the wastewater is introduced
into a main sewer system or delivered to a treatment plant for
substantial reduction of the pollution load.
Primary Feeder Circuit (Substation) Transformers - These transfor-
mers (at substations) are used to reduce the voltage from the
subtransmission level to the primary feeder level.
Primary Treatment - A process to remove substantially all floating
and settleable solids in wastewater and partially to reduce the
concentration of suspended solids.
Primary Winding - Winding on the supply (i.e. input) side of a trans-
former irrespective of whether the transformer is of the step-
up or step-down type.
Priority Pollutant - The 129 specific pollutants established by the
EPA from the 65 pollutants and classes of pollutants as outlined
in the consent decree of June 8, 1976.
Process Waste Water - Any water which during' manufacturing or processing,
comes into direct contact with or results from the production or
use of any raw materials, intermediate product, finished product,
by-product, or waste product.
Process Water - Water prior to its direct contact use in a process
or operation. (This water may be any combination of raw water,
service water, or either process wastewater or treatment facility
effluent to be recycled or reused.)
Pyrolysis - The breaking apart of complex molecules into simpler units
by the use of heat, as in the pyrolysis of-heavy oil to make
gasoline.
Quenching - Shock cooling by immersion liquid or molten material into
a cooling medium (liquid or gas); used in metallurgy, plastics
forming and petroleum refining.
XVI-16
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Raceway - A channel used to hold and protect wires, cables or
busbars.
Rapid sandfliter - A filter for the purification of water where water
which has been previously treated, usually by coagulation and
sedimentation, is passed through a filtering medium consisting
of a layer of sand or prepared anthracite coal or other suitable
mciterial, usually from 24 to 30 inches thick and resting on a
sxipporting bed of gravel or a porous medium such as carborundum.
The filtrate is removed by a drain system. The filter is cleaned
periodically by reversing the flow of the water through the ,
filtering medium. Sometimes supplemented by mechanical or air
agitation during backwashing to remove mud and other impurita.es
that are lodged in the sand.
Raw Wastewater - Plan water prior to any treatment or use.
• '• .»•'.' ' . ' .
Rectifier - (1) A device for converting alternating current into direct
' current. (2) A nonlinear circuit component that, ideally, allows
current to flow in one direction unimpeded but allows no current
to flow in the other direction.
Recycled Water - Process wastewater or treatment facility effluent
.which is recirculated to the same process.
Resistor - A device designed to have a definite amount of resistance,
!used in circuits to limit current flow or to provide a voltage
drop.
Retention Time - The time.allowed for solids to collect in a settling
tank". Theoretically retention time is equal to the volume of
the tank divided by the flow rate. The actual retention time is
determined by the purpose of the tank. Also, the design residence
time in a tank or reaction vessel which allows a chemical reaction
to go to completion, such as the reduction of hexavalent chromium
or the destruction of cyanide.
Reused Water - Process wastewater or treatment facility effluent which
is further used in a different manufacturing process.
Rinse - Water for removal of dragqut by dipping, spraying, fogging,
etc.
Rolled Capacitor - Refers to the construction of a capacitor. Aluminum
foil with attached leads with at least one space larger is rolled
and inserted into a capacitor case.
Sanitary Sewer. - A sewer that carries liquid and water wastes from
residences, commercial buildings, industrial plants, and institu-
tions together with minor quantities of ground, storm, and surface
waters that are not admitted intentionally.
XVI-17
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Sanitary Water - The supply of water used for sewage transport
and the continuation of such effluents to disposal.
Secondary Settling Tank - A tank through which effluent from
some prior treatment process flows for the purpose of re-
moving settleable solids. :
Secondary Wastewater Treatment - The treatment of wastewater by
biological methods after primary treatment by sedimentation.
. Secondary Winding - Winding on the load (i.e. output) side of a
transformer irrespective of whether the transformer is of
the step-up or step-down type.
Sedimentation - Settling of matter suspended in water by gravity.
It is usually accomplished by reducing the velocity of the
liquid below the point at which it can transport the sus-
pended material. i
Semiconductor - A solid crystalline material whose electrical
conductivity is intermediate between that of a metal and
an insulator. i
Settleable Solids - (1) That matter in wastewater which will not
stay zn suspension during a preselected settling period,
such as one hour, but either settles to the bottom or floats
to the top. (2) In the Imhoff cone test, the volume of
matter that settles to the bottom of the cone in one hour.
Sewer ~ A Pipe or conduit, generally closed, but normally not
flowing full for carrying sewage and other waste liquids.
Silvering - The deposition of thin films of silver on glass, etc.
carried by one of several possible processes.
Skimming Tank - A tank so designed that floating matter will
rise and remain on the surface of the wastewater until re-
moved, while the liquid discharges continuously under cer-
tain walls or scum boards.
Sludge - The solids (and accompanying water and organic matter)
which are separated from sewage or industrial wastewater.
Sludge Cake - The material resulting from air drying or dewatering
sludge (usually forkable or spadable).
Sludge Disposal - The final disposal of solid wastes.
Sludge Thickening - The increase in solids concentration of sludge
in a sedimentation or digestion tank. '
XVI-18
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Snubber - Shock absorber.
Soldering - The process of joining metals by flowing a thin
'Tcapillary thickness) layer of nonferrous filler metal
into the space between them. Bonding results from the in-
timate contact produced by the dissolution of a small
.amount of base metal in the molten filler metal, without
fusion of the base metal. The term soldering is used
where the temperature range falls below an arbitrary
value, such as 425C (800F).
Solvent - A liquid capable of dissolving or dispersing one or
more other substances.
Solvent Degreasing - The removal of oils and grease from a
workpiece using organic solvents or solvent vapors.
Sputtering - A process to deposit a thin layer of metal on
a solid surface in a vacuum. Ions bombard a cathode which
emits the metal atoms.
Stacked Capacitor - Referes to the multiple layering of di-
electric and conducting surfaces, i.e. ceramic and glass
encapasulated.
Stamping - Almost any press operation including blanking,
shearing, hot or cold farming, drawing, blending, or coining.
Steel - An iron base alloy, malleable under proper conditions,
containing up to about 2% carbon.
Step-Down Transformers (Substation) - A transformer in which
the AC voltages of the secondary windings are lower than
those applied to the primary windings.
Step-Up Transformer - Transformer in which the energy transfer
iss from a low-voltage winding to a high-voltage winding
or windings.
Studs •• Metal pins in glass of picture tube onto which shadow
mask is hung.
Substation - Complete assemblage of plant, equipment, and
the necessary buildings at a place where electrical
energy is received (from one or more power-stations)
for conversion (e.g. from AC to DC by means of reactifiers,
rotary converters, for stepping-up or down by means of
transformers, or for control (e.g. by means of switch-
gear, etc.).
XVI-19
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Subtransmission (Substation) Transformers - At the end of
a transmission line, the voltage is reduced to the
subtransmission level (at substations) by subtransmission
transformers.
Suspended Solids - (1) Solids that either float on the surface
of, or are in suspension in water, wastewater, or other
liquids, and which are largely removable by laboratory
filtering. (2) The quantity of material removed from
wastewater in a laboratory test, as prescribed in "Stan-
dard Methods for the Examination of Water and Wastewater"
and referred to as non-filterable residue.
i'
Tantalum - A lustrous, platinum-gray ductile metal used in
making dental and surgical tools, penpoints, and electronic
equipment.
Tantalum Foil - A thin sheet of tantalum, ^usually less than
0.006 inch thick. |
Terminal - A screw, soldering lug or other point to which
electric connections can be made.
Testing - A procedure in which the performance of a product is
measured under various conditions.
Thermoplastic Resin - A material with a linear macro-molecular
structure that will repeatedly soften when heated and
harden when cooled; for example styrene, acrylics, cellu-
losics, polyethylenes, vinyls, nylons! and. fluorocarbons.
Thermosetting Resin - A plastic that solidifies when first heated
under pressure, and which cannot be rpmelted or remolded
without destroying its original characteristics; examples
are epoxics, melamines, phenolics and! ureas.
Transformer - Stationary apparatus for transforming, electrical
energy at one alternating voltage intp electrical energy
at another (usually different) alternating voltage, by
means of magnetic coupling (without change-of frequency).
Transistor - An active component of an electronic circuit con-
sisting of a small block of semiconducting material to
which at least three electrical contacts are made; used
as an amplifier, detector, or switch.
Trickling Filter - A filter consisting of an artificial bed of
coarse material, such as-broken stone, clinkers, slats, or
brush over which sewage is distributed and applied in
drops, films, or spray, from troughs, drippers, moving
distributors or fixed nozzles and through which it trickles
to the underdrain giving opportunity for the formation
of zoogleal slimes which clarify and oxidize the sewage.
XVI-20
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Trimmer Capacitors - These are relatively small variable ca-
paoitors used in parallel with larger variable or fixed
capacitors to permit exact adjustment of the capacitance of
the parallel combination.
Vacuum Filter - A filter consisting of a cylindrical drum mounted
on"a horizontal axis, covered with a filter cloth revolving
with a partial submergence in liquid. A vacuum is maintained
under the cloth for the larger part of a revolution to ex-
tract moisture and the cake is scraped off continuously.
Vacuum Metalizing - The process of coating a workpiece with
metal by flash heating metal vapor in a high-vacuum
chamber containing the workpiece. The vapor condenses on
all exposed surfaces.
Vacuum Tube - An electron tube evacuated to such a degree that
Its electrical characteristics are essentially unaffected
by the presence of residual gas or vapor.
Variable Capacitor - A capacitor whose capacitance can be
varied continuously by moving one set of metal plates
with Respect to another.
Voltage Breakdwon - The voltage necessary to cause insulation
failure.
Voltage Regulator - Like a transformer, it corrects charges in
current to provide continuous, constant current flow.
Welding - The process of joining two or more pieces of material
by applying heat, pressure or both, with or without
filler material, to produce a localized union through
fusion or recrystallization across the interface.
Wet Air Scrubber - Air pollution control device which produces
a~~wastewater stream.
Wet Capacitor - (See oil-filled capacitor)
Wet Slug Capacitor - Refers to a sinterted tantalum capacitor
where the anode is placed in a metal can, filled with an
electrolyte and then sealed.
Wet Tantalum Capacitor -. A polar capacitor the cathode of which
Ii a liquid electrolyte (a highly ionized acid or salt
solution).
Wet Transformer -• Having the core and coils immersed in an
insulating oil.
Yoke - A set of coils placed over the neck of a magnetically
deflected cathode-ray tube to deflect the electron beam
horizontally and vertically when suitable currents are
passed through them.
XVI-21
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APPENDIX A
PCB Use as a Dielectric Fluid
Polychlorinated biphenyl is an excellent dielectric fluid for
particular applications. It is inexpensive, fire resistant,
chemically stable and is only slightly soluble in water. Large
numbers of power factor correction capacitors and small paper/
foil or film/foil capacitors were previously manufactured using
PCB as a dielectric fluid. The smaller capacitors were used in
motor controls, fluorescent light ballasts and in the circuitry
of such common products as television sets, microwave ovens and
computers. PCB transformers in use in 1978 numbered 140,000
Accounting "for'2% of all oil filled transformers. The majority
of oil filled transformers are filled with a petroleum oil similar
to a low viscosity lubricating oil.
A ban on the "manufacture, processing or distribution" of PCB
fluids was enacted through the Toxic Substances Control Act of
October 11, 1976. PCB is considered toxic to both man and the
natural environment. Although the ban became effective on January
1, 1978, PCS manufacture was discontinued by the major suppliers
in 1977.
Although the PCB ban prohibits manufacture of PCB capacitors and
.transformers, the continued use of these components is allowable
for an indefinite period of time because they are considered
"totally enclosed". PCB was never used in oil filled circuit
breakers, and thus these components are not mentioned in the
regulations on PCB fluids.
The PCB Rule (appearing in the Federal Register on May 31, 1979)
outlines procedures for the disposal of PCB capacitors; for the
repair and reconditioning of PCB transformers; for the storage of
PCB fluids and fluids contaminated with PCB contaminated articles,
and for the disposal of PCB fluids and articles. These regulations
are summarized in Table A-l.
The major problems concerning PCB in the Electrical & Electronic
Components Category are the decontamination of plant equipment,
plant facilities and plant grounds, and the storage of PCB fluid.
At present, there is no legal means for disposing of PCB. Complete
records must be maintained on the PCB presently remaining in
equipment and on PCB currently in storage.
A-l
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TABLE A-l
SUMMARY - PCS RULE REGULATIONS CONCERNING
TRANSFORMERS AND CAPACITORS
(AFTER JULY 1, 1979) "•
DEFINITIONS
1. PCS Transformer - Transformer filled with dielectric fluid
containing > 500 mg/1 PCB. ;
2. PCB Contaminated Transformer - Transformer filled with
dielectric fluid containing between 50 and 500 mg/1 PCB.
3. PCB Capacitor - Capacitor containing PCB dielectric fluid.
4. PCB Fluid - Fluid containing in excess of 500 mg/1 of PCB.
5. PCB Contaminated Fluid. - Fluid containing between 50 mg/1
and 500 mg/1 of. PCB.
PRESENT USE - Regulation allows indefinite continued use of
totally enclosed PCB components including PCB capacitors and
PCB transformers (see below for PCB railroad transformers).
TRANSFORMER SERVICING -
PCB Tranformers; Can drain oil, filter oil, replace gaskets,
return oil.O.K. to reuse PCB oil Or use inventory PCB oil.
PCB Contaminated Transformers; Can drain fluid and rebuild
transformer i.e. remove and rewind coils.
Manufacture; It is illegal to manufacture PCB transformers
of PCB capacitors unless exemption is obtained from the EPA.
PCB Manufacture; The manufacture, processing or distribution
in commerce of PCB is prohibited without an exemption obtained
from the EPA.
PCB Railroad Transformers; Fluid in railroad transformers
must comply with the following schedule;,
[
Present - Jan. 1, 1982 100% PCB OK
Jan. lr 1982 - Jan. 1, 1984 £ 6% PCB OK
Jan. 1, 1984 - ON £ 1000 ppm PCB OK
A-2
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TABLE A-l (CONTINUED)
CAPACITOR DISPOSAL;
Companies previously involved in PCB capacitor manufacture and
PCB equipment manufacture may dispose of PCB capacitors by
1) approved incinerator, or 2) approved chemical waste landfill
(up until Jan 1, 1980). Individuals not involved in PCB
equipment manufacture may dispose of small PCB capacitors
as municipal solid waste. Large PCB capacitors must be
disposed according to 1) or 2) above.
TRANSFORMER DISPOSAL -
PCB Transformers; 1) approved incinerator, 2) chemical
waste landfill after transformer is drained of PCB and
subsequenctly flushed with a solvent. PCB contaminated
solvent disposal in an approved manner (see below).
i1 . •.-•--
PCB Contaminated Transformer: Drain transformer of PCB
contaminated fluid.
manner (see below).
regulated by rule.
PCB DISPOSAL -
Dispose of fluid in an approved
Transformer structure disposal not
PCB; Any fluid containing >500 mg/1 PCB must be disposed of
by incineration in an incinerator approved by the EPA.
PCB Contaminated Fluid; Fluids containing between 50 mg/1
and 500 mg/1 PCB can be disposed of: 1) in an approved
incinerator, 2) in a high efficiency boiler,.or 3) in an
approved chemical waste landfill.
PCB STORAGE
PCB and PCB contaminated fluid may be stored for eventual
disposal in any of several ways as outlined in the PCB
rule. e.g. drums in a diked building, in undamaged
PCB equipment until Jan 1, 1983, in large tanks or tank
cars of approved types.
*U.S. GOVERNMENT PRINTING OFFICE: 1980-311-726:3912
A-3
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United States
Environmental Protection
Agency
Official Business
Penalty for Private Use
$300
Special Fourth-Class Rate
Book
Postage and Fees Paid
EPA
Permit No. G-35
Washington DC 20460
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