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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
24
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
<0.01
0.01
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<0.001
<0.04
<0.004
<0.005
<0.025
0.169
0.274
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0.825
0.031
0.018
0.016
0.003
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0.039
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0.008
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0.242
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0.007
0.887
32.23
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43.971
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89894
24
3948
0.062
<0.010
0.570
<0.010
<0.010
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.
VIII-5
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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.
VIII-6
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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
-------
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m
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0
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CU
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o
-l-l
Q
I
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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
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00 OJ t~ O
O iH iH m O
ro
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OJ4J
\o
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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
Level 2 Treated*
Effluent
(kg/year)
0
0
0
0
623.781
* =* 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
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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
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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
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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
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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
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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
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. 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
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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
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IX-19
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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
-------
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Si
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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'*
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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
c o
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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
37
7
8.2
6.9
20
1
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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:
PHOSPHIDE
WAFERS
APPLY
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EXPOSURE
DEVELOP
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DEVELOP
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DENOTES LIQUID WASTE GENERATION
FIGURE 10-2
LED PRODUCTION
X-7
-------
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FIGURE 10-3
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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