-------
lithopone cadmium yellow pigment, as well as from the lithopone
cadmium red pigment operations.
Table 11-7 presents the wastewater
concentrations for each type of pigment.
Other Plants Visited
flow and pollutant
Six plants producing cadmium pigments and/or salts were' visited
during the program period, but not sampled. A description of the
individual products and treatment facilities for those plants
visited is given in the discussion below.
Plant F101 manufactures cadmium sulfate and cadmium pigments. At
present there is no wastewater treatment facility at this plant
for treatment of process wastewater. All process wastewaters are
discharged to a POTW. Plant personnel are investigating several
alternatives to reduce or eliminate the discharge of process
water pollutants. One alternative is the use of soda ash
neutralization to treat the effluent from the pigment quenching
operation. The neutralized effluent would be discharged, and the
cadmium carbonate precipitate would be recovered and recycled. A
second alternative consists of recycling the quenching effluent
directly. This second alternative has not been demonstrated, and
some technical problems including safe handling of the hydrogen
sulfide gas that could be evolved during recycling, may be
difficult to solve. .
Plant F128 manufactures cadmium sulfate, cadmium nitrate and
cadmium pigments, as well as other chemical products. All of the
cadmium pigment plant wastewater except that emanating from the
drying operations and air scrubbers is discharged to an in-plant
receiver. The wastewater is treated with alkali and then
filtered. The filter cake is either sold for recovery of cadmium
or disposed of in a chemical waste landfill. The effluent from
cadmium treatment joins the wastewater from the drying operations
and air scrubbers in a separate in-plant receiver. The receiver
carries the wastewaters generated from the rest of the plant
processes, as well as the above-mentioned treated cadmium
wastewater, to the main wastewater treatment facility. The
wastewater is neutralized with lime, settled and filtered in a
dual-media filter before discharge to surface waters. The sludge
from settling is filtered in a filter press and the filter cake
is disposed of in a chemical landfill. The filtrate is recycled
to the wastewater treatment facility, as is the backwash
wastewater from the periodic backwashing of the dual-media
filter.
187
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Plant FIT7 manufactures cadnuum sulfate and cadmium chloride as
well as a variety of other metal salts. Process wastewater from
cadmium salts production are treated separately. These are very
small flows consisting of leaks, spills and washups. Treatment
consists of the addition of caustic (NaOH) to the collection sump
until the pH is around 10. The sump is then pumped out through a
small filter press, and the filtrate is discharged directly to
surface waters. The residue is sent to solids disposal.
Plant F107 manufactures cadmium nitrate and a variety of other
metal salts. There is no treatment facility at this plant and
all wastewaters are discharged to a POTW.
Plant FIT9 manufactures cadmium nitrate and a variety of other
metal salts. All process wastewater from production of metal
products undergo combined treatment. This consists of
neutralization tanks where pH is adjusted to 8.7 - 9.0 with
caustic. The neutralized waste is sent to a settling basin for
settling. The settled wastewater is then sent to a flash mix
tank where flocculating agents are added and then on to a tube
settler for additional solids removal. The overflow discharges
to a municipal treatment plant while the underflow goes to a
sludge holding tank where it then undergoes filtering in a filter
press and disposal in a chemical landfill. Supernatant and
filtrate from sludge handling is recycled to the treatment
facility.
Plant FT 45 manufactures cadmium chloride and a variety of other
inorganic and organic compounds. All process wastewaters from
the entire plant which cannot be recycled are sent to the
combined plant wastewater treatment facility. Here the waste is
equalized, neutralized with lime slurry to pH 9.5 - 10.2,
agitated, and settled in clarifiers. The overflow from the
clarifiers is sent to the organics removal portion of the WWTF
where it receives biological treatment and is discharged directly
to surface waters. Sludge is dewatered and disposed of as solid
waste.
Toxic Pollutant Concentrations
Thirteen toxic pollutants were found at detectable concentrations
in the raw wastewater at the two sampled plants. The maximum
concentrations observed are given in the table below.
Pollutant
Antimony
Arsenic
Maximum Concentration
Observed (ug/1)
540
190
188
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TABLE 11-8. TOXIC POLLUTANT RAW WASTE DATA-CADMIUM PIGMENTS
Average Daily Pollutant Concentrations and Loads
mg/1
kg/kkg
Plant Designation
Pollutant
Antimony
Cadmium
Thallium
Selenium
Zinc
Lead
Nickel
Copper
(PR)
F102(i)
0
0
1040
47
0
0
29
1
25
1
0
0
0
0
0
0
.19
.00874
.0
.8
.14
.00644
.7
.37
.1
.154
.25
.0115
.18
.00828
.097
.00446
(PY)
F134(2)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.54
.0566
.49
.0514
.064
.0067
.26
.00273
.20
.0210
.3
.0315
.15
.0157
.061
.00640
(LR)
F134(2)
0
0
6
0
0
0
2
0
0
0
0
0
0
0
0
0
.225
.00176
.76
.0530
.003
.00002
.0
.0157
.035
.00027
.081
.00063
.008
.00006
.026
.00020
(LY)
F134<2)
0
0
11
0
0
0
0
0
2
0
0
0
0
0
0
0
.24
.00237
.14
.110
.002
.00002
.005
.00005
.12
.0209
.072
.0071
.0072
.00007
.015
.00015
Overall
Average
0
0
264
12
0
0
7
0
6
0
0
0
0
0
0
0
.30
.0174
.6
.0
.052
.00330
.99
.347
.86
.299
.18
.0127
.086
.00603
.05
.00280
(1) Data from three 24-hour composite samples, averaged, from
the combined total raw waste sampling point.
(2) Data from three days of composite samples collected from
individual batches, flow proportioned from each raw waste
stream for that particular day and then averaged over the
three days.
(PR) Pure Red Pigments.
(PY) Pure Yellow Pigments.
(LR) Lithopone Red Pigments.
(LY) Lithopone Yellow Pigments.
189
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TABLE 11-9. TOXIC POLLUTANT TREATED EFFLUENT DATA
CADMIUM PIGMENTS
Average Daily Pollutant Concentrations and Loads
mg/1
kg/kkg
Pollutant
Antimony
Cadmium
Thallium
Selenium
Zinc
Lead
Nickel
Copper
(PR)
F102(i)
0.21
0.00898
92.0
3.93
0.21
0.00898
0.19
0.00813
0.26
0.00111
0.18
0.0077
0.23
0.00984
0.29
0.0124
(PY)
F134(2)
0.33
0.0407
0.106
0.0131
0.047
0.00580
0.11
0.0136
0.027
0.00333
0.115
0.0142
0.056
0.00691
0.027
0.00333
(LR)
F134(2)
0.2
0.00181
0.41
0.00371
0.001
0.00001
3.12
0.0282
<0.026
<0. 00024
<0.078
<0. 00071
0.0086
0.00008
0.016
0.00014
(LY)
F134(2)
0.1
0.00195
0.13
0.00254
0.001
0.00002
0.01
0.00020
0.069
0.00135
0.15
0.00293
0.014
0.00027
0.01
0.00020
Overall
Average
0.21
0.0134
23.2
0.987
0.065
0.00370
0.86
0.0125
<0.095
<0. 00151
<0.13
<0. 00640
0.077
0.00430
0.085
0.00327
(1) Data from three 24-hour composite samples, averaged.
(2) Data from composite samples collected from individual
batches over three days and averaged.
(PR) Pure Red Pigment.
(PY) Pure Yellow Pigment.
(LR) Lithopone Red Pigment.
(LY) Lithopone Yellow Pigment.
190
-------
Cadmium
Chromium
Copper
Lead
Nickel
Selenium
Thallium
Zinc
Bis(2-chloroethyl) ether
Bis (2-ethyhexyl) phthalate
Chloroform
Methylene chloride
1,400,000
400
250
530
420
81,000
190
62,000
84
24.4
40.3
14.8
Data was obtained at Plants FT02 (one type of cadmium pigment)
and F134 (three different cadmium pigments). The organic
compounds bis(2-ethylhexyl) phthalate and -chloroform were present
in high concentrations in the supply water at one plant. In
addition, phthalates and methylene chloride are generally found
at this concentration as a result of sample contamination from
the plasticizers in tubing and laboratory glassware cleaninq
procedures. y
Section 5 of this report describes the methodology of the
sampling program. In the cadmium pigments industry, nine days of
sampling were conducted at Plants F102 and F134. This involved
15 different sampling points for raw and treated wastewater
streams. The evaluation of toxic metals content of these
process-related wastewater streams was based on 507 analytical
data points. Sampling for organic pollutants generated another
1,824 data points.
In Table 11-8, the toxic pollutant raw wastewater data from the
sampling program are presented, as the average daily
concentrations and unit loadings found at the individual plants
and pigment processes. The overall averages were calculated and
shown also to present a situation as if a single plant were
making all four types of pigments at the same time and they
combined the wastes into one raw wastewater stream which could
occur at the four discharging plants. The toxic pollutant
concentrations and unit loadings in the treated effluents from
the sampling program are presented in Table 11-9 for the four
pigment types sampled.
POLLUTION ABATEMENT OPTIONS
Toxic Pollutants of Concern
The toxic pollutants found in significant amounts are the heavy
metal components of the raw materials and product, as well as the
191
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impurities found in the raw materials. The primary pollutant is
cadmium, which is present throughout the process train. Selenium
and zinc are the second most abundant pollutants and of course
depend on which pigment (red or yellow) is being produced. Since
all plants produce both pigments, both of these metals would be
present in significant amounts at all plants.
The other toxic metals of concern found were lead, antimony,
copper, nickel and thallium. These are present in trace amounts
due to impurities in the raw materials and subsequently removed
during processing of the cadmium pigments. The presence or
absence of these five trace metals at significant levels in the
wastewater may depend mainly on the levels present as impurities
in the materials as well as the degree of purification of the
materials to remove them. The fact that these metals are found
in such small concentrations could present problems in monitoring
due to analytical variability. For example, one plant exhibited
higher concentrations of some of these metals in the treated
effluent than were found in the raw wastewater.
All the process contact wastewater generated in the cadmium
pigments subcategory contain dissolved cadmium and pigment
pafticulates.
Existing Control and Treatment Practices
A description of the individual treatment facilities for those
plants visited was given previously. In addition, the following
information was obtained for the remaining plants.
Plant F110 manufactures the basic cadmium sulfide pigment. The
process wastewater from this plant is sent to the plant treatment
facility where it is neutralized with lime to pH 12. The
wastewater is then sent to a lagoon for settling. The solids are
dredged to the sides of the lagoon and there is no discharge of
wastewater from the lagoon. The plant is located in an arid
region of the country.
Plant F125 manufactures cadmium nitrate and other metal salts.
Wastewaters from the cadmium process are combined with the other
product process wastes and treated together. Treatment consists
of equalization, sedimentation, pH adjustment with NaOH, and a
series of lined and unlined impoundments before discharge to
surface waters.
Plant No. F123 produces small quanities of cadmium chloride.
This plant discharges no wastewater. All process wastewater is
incorporated in the product.
192
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Plant F124 produces cadmium nitrate as well as other metal salts.
Treatment of wastewaters for the entire plant consists of
alkaline precipitation, clarification, filter press filtration,
multi-media filtration, pH adjustment and sedimentation in ponds
before discharging directly to surface waters.
Other Applicable Control and Treatment Technologies
Cadmium pigment plants commonly have a cadmium recovery system
which uses alkaline or ferrous sulfide precipitation followed by
settling and/or filtration. Effluent from the recovery systems
still contains considerable amounts of cadmium and further
treatment should be applied before discharge. Further treatment
by lime precipitation and clarification, followed by sand or
dual-media filtration would remove more residual cadmium.
Process Modifications and Technology Transfer Options
One cadmium pigment manufacturer employs a continuous turbidity
monitor as part of the wastewater treatment system. The
monitoring device is located downstream of a cadmium scavenger
filter press and upstream of the final treated discharge.
Wastewater not meeting turbidity standards is automatically
pumped back to treatment and again sent through the filter press.
This offers the advantage of reducing the- variations in
performance of treatment and aids in control of suspended solids.
Control of suspended solids at pigment facilities is essential to
reduction of effluent concentrations of cadmium, selenium, and
zinc in the final discharge.
Several cadmium pigment producers practice segregation of process
wastewater from other products manufactured to enable recovery of
cadmium-containing solids. Typically, cadmium-containing
wastewater streams are segregated for wastewater treatment/solids
recovery, and sludges obtained are sold for recovery of metal
values. Treated wastewater is then either discharged or
commingled with other wastewater streams for further treatment.
In the case of POTW dischargers, much cadmium, selenium, and zinc
can be prevented from accumulating in POTW - generated sludges by
using wastewater stream segregation and recovery technology.
The use of filter aids to improve filter performance is
commonplace in inorganic chemicals manufacturing processes.
Transfer of this technology to wastewater treatment processes may
facilitate decreasing suspended solids concentrations in
wastewater treatment filtrates. For example, plant F102 employs
polyelectrolyte addition to improve clarification performance in
a tube settler. The identification and use of effective
flocculants and other settling aids could contribute
193
-------
significantly toward enhancing effluent quality in this
subcategory. *
An overall reduction in water use at cadmium pigments facilities
might be obtained by the following approaches:
1
2.
3.
Recycle of filter washwater
process, where possible;
during pigment finishing
Use of noncontact cooling water for make-up water in
the salt and pigment process (this would reduce overall
water use, but not pollutant discharges);
Limit excessive usage of washwater
wastewater, where possible;
and • other process
4. Recycle of scrubber wastewater where possible.
As shown on Tables 11-3 and 11-5, the major water use by far at
cadmium pigments plants is direct and indirect process contact
wastewater resulting from cleaning impurities from the crude
pigments. This cleaning is necessary to produce a saleable
product,^and the^amount of water used for cleaning depends upon
of impurity, and the demands of the
the amount
the product,
^ ' — — —•«£*• •-— *. wjf f MIAVA wtis^ wdiiciiiuo
customer. Therefore, while the above suggestions may save water
at those plants that can implement them, no specific technology
was identified which could be applied at all plants and result in
a significant reduction in the amount of wastewater discharged to
treatment.
Best Management Practices
If contact is possible with leakage, spillage of raw materials or
product, all storm water and plant site runoff should be
collected and directed to the plant treatment facility. This
contamination can be minimized by indoor storage of chemicals
proper air pollution control, and development of an effective
spill prevention and control program.
A11°tner contact wastewater including leaks, spills, and
washdowns should be contained and treated because this practice
may enhance recovery of raw materials and product.
If solids from the wastewater treatment plant are hazardous and
disposed or stored on-site, provision must be made to control
leachates and permeates. Leachates and permeates which contain
toxic pollutants should be directed to the treatment system for
further treatment.
194
-------
Advanced Treatment Technology
Cadmium pigments wastewater contains fugitive pigment particles
which in turn contain significant concentrations of cadmium?
Z.nC' L°W concentrations of suspended solids must
P ensure reduction of these toxic metals in
dlschar<3es- Level 1 plus Level 2 technology will be
as a minimum to achieve these low concentrations. The
effectiveness oi: these technologies can be enhanced by addition
locculaHng aaents Prior to clarification and bythe use of
? Urmedria ^tration (as opposed to filter press
) for Level 2. To illustrate the above, plant FT 02
practices cadmium recovery followed by further treatment
consisting of pH adjustment, clarification, and sand flltralion
to achieve an average cadmium concentration of 0.07 mg/1.
Selection of Appropriate Technology and Equipment
Technologies for Different Treatment Levels
A. Level 1
treatment consists of alkalinp
°C Settl^g-i and final 1- adjustmen of the
i necessarv- Sludges generated are dewatered in a
P !S °r. c?"«cted and disposed of in a hazardous waste
t r; /f rrt ofthe treatment system, a holding basin sized
even? of tr^f^"^ of.infli;«nt is provided as a safeguard in the
m
i
followed
?te? ^s the addition of caustic soda. This
clarification/settling (if the wastewater
fclrif i SUitable' a tub? Settl2r may be sJJStltSS
tor a clarifier to conserve space . Sludge is removed from the
clanfier and directed to a filter press for dewatering Pits
^ the filter Pres^ for thftempo^y s?orage ol
??r?ge t? Peri°dicaliY transported to a hazardous
tO the head
aceDtabl li wastewater stream is adjusted to an
acceptable level by acid addition prior to discharge if
moitorin Astern is installed at the discharge
] techn°10^ is to remove heavy
^-^ Wa? not selected as the basis for BPT because
provides inadequate removal of fine suspended cadmium
195
_
-------
hydroxide particles. Currently, only three facilities still
employ Level 1 treatment alone.
B.
Level 2
Level 2 treatment consists of granular media filtration of the
Level 1 effluent for further removal of cadmium hydroxide
precipitates and other solids from the wastewater. This
technology is portrayed in Figure 10-11. In practice, when Level
2 technology is added to Level 1, final pH adjustment would be
reconfigured to occur after filtration not prior to it. The
objective of Level 2 treatment technology in this subcategory is
to achieve, at a reasonable cost, more effective removal of toxic
metals than provided by Level 1. Filtration will both increase
treatment system solids removal and decrease the variation in
solids removal exhibited by typical clarifier performance.
Level 2 treatment was selected as the basis for BPT because it
represents a typical and viable industry practice for the control
of suspended solids, cadmium, zinc and selenium. Currently seven
of twelve plants in this subcategory have Level 2 or equivalent
treatment technology. Four of the six direct dischargers have
Level 2 treatment already installed. Two plants have no
discharge and would not incur additional costs.
Equipment for Different Treatment Levels
A. Equipment functions
Conventional sludge dewatering by a filter press is used for
sludge removed by the clarification/settling system. In the
cadmium pigments segment, this sludge has value and may be
recovered. The sludge from the filter press is either disposed
of- off-site in a hazardous material landfill or sent to an off-
site cadmium reclaiming/recovery operation. If a tube settler is
used, backwash from the settler as well as from the granular-
media filters 'is returned to the influent holding basin. All
equipment is conventional and readily available.
B. Chemical Handling
Caustic soda (50 percent NaOH) is used to precipitate heavy
metals in Level 1. Sulfuric acid (concentrated) may be used to
reduce the pH of the wastewater prior to discharge.
C. Solids Handling
Treatment sludges for cadmium pigments generated by Level 1 are
dewatered in a filter press. The solids may be disposed of off-
196
-------
site in a hazardous material landfill or sent to an off-site
cadmium reclaiming/recovery operation. Level 2 filter backwash
may be sent to the head of the plant or, if the solids
concentration is sufficiently high, may be sent directly to the
filter press. Cadmium salts wastewater treatment sludges are not
dewatered since the low volume typically produced does not
justify the use of a filter press.
Treatment Cost Estimates
In the cadmium pigments and salts subcategory, two model plants
were chosen, one representing the cadmium pigments segment and
the other representing the cadmium salts segment. In each case
two treatment options were considered. Costs for two model
plants were developed because there are significant differences
between the production and amounts of wastewater generated even
though the wastewaters have similar chemical characteristics.
General
ranges. and wastewater flow characteristics have been
earlier in this section and are summarized in Table 11-
:,, lhere*rir six direct dischargers, four indirect dischargers,
and two plants which achieve zero discharge. ouu«y«rfi,,
A. Cadmium Pigments
During development of the model plant characteristics, only data
rSS-H 5® £acilities. wnich manufacture cadmium pigments were
considered. However, since pigment production is universally
preceded by manufacture of cadmium salts and since cadmium salts
manufacture generates small volumes of wastewater, both source!
nfanrrh^ffr -T"e COI?bined for the purpose of defining modi!
S,,S \- 5 K acteristics. In fact, most wastewater flow information
supplied by industry for pigment plants did not differentiate
* fc 0 salts production and to
The model plant production rate of 711 metric tons per year
represents the average production for all discharging pigment
tin d™r;^JhV?del Pla^ Unit fl°W Of 92'4 cubic »2t2?s/S25ic
ton was obtained by computing the average unit flow for the three
discharging facilities for which detailed water use information
was available (see Table 11-5). Since zero discharge fJSlUtiS
were "°t included in the computation, the average unit flow value
is greater than if zero discharge (zero unit flow) facilities
ODerate^f «n *M°8t discha^ing cadmium pigment facUitiS
««, ! S ? ay per year basis' so the model plant was also
assumed to operate on a similar schedule. The daily discharge
197
-------
volume (262 cubic meters) was derived from the model plant
characteristics listed above. These characteristics were used as
the basis for treatment cost estimates at all levels.
Material usage for all levels was estimated as follows:
Chemical Amount Treatment Level
NaOH (50% sol.)
H2S04 (100%)
445 kg/day
52.4 kg/day
(1)
(1)
Total solid waste generated is estimated at 0.18 cubic meters/day
for Level 1 and 0.018 cubic meters/day for Level 2. The sludge
is assumed to be dewatered to 50% solids by volume.
Model Plant Treatment Costs. On the basis of the model plant
specifications and design concepts presented earlier and in
Section 10, the estimated costs of treatment for one model with
two levels are shown in Table 11-10. The cost of Level 2 is
incremental to Level 1.
B. Cadmium Salts
During development of the model plant characteristics, only those
facilities producing cadmium salts not destined for production of
cadmium pigments were considered salt producers. The model plant
for the cadmium salts segment has a production rate of 169 metric
tons per year. This figure was obtained by computing the average
production for discharging cadmium salt producers. The model
plant operating schedule of 150 days per year was based on the
average of operating days reported for discharging salt
producers. The unit flow value of 0.058 cubic meters/kkg was
obtained by computing the average unit flow for those facilities
where wastewater flow information was available (see Table 11-4).
The daily discharge volume (0.07 cubic meters) was obtained by
multiplying daily production by the unit flow value. These data
were used as the basis for treatment cost estimates at all
levels.
Material usage for both levels was estimated as follows:
Chemical Amount Treatment Level
NaOH (50% sol.)
H2SO* (100%)
0.12 kg/day
0.014 kg/day
(1)
(1)
Total solid waste generated is estimated at 0.0012 cubic
meters/day for Level 1 and 0.001 cubic meters per day as Level 2.
The sludge is assumed to contain 2% solids by volume.
198
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TABLE 11-10. WATER EFFLUENT TREATMENT COSTS AND RESULTING
WASTE-LOAD CHARACTERISTICS FOR MODEL PLANT
SUBCATEGORY: Cadmium Pigments Subgroup
ANNUAL PRODUCTION:
DAILY FLOW: 262
PLANT AGE:
711
METRIC TONS
NA
CUBIC METERS
YEARS PLANT LOCATION:
' ' NA
a. COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS
COST CATEGORY
Facilities
Installed Equipment
(Including Instrumentation)
Engineering
Contractor Overhead and Profit
Contingency
Land
Total Invested Capital
Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Waste Disposal) 112 4 89
Residual Waste Disposal 2*7 0*3
COSTS ($1,000) TO ATTAIN LEVEL
1234 5
23.0
168.6 29.4
38.3 5.9
34.5 5.3
26.4 4.1
290.8 44.7
47.3 7.3
Total Annual Cost
b.
162.4 16.5
Parameter
pH
TSS
Cd
Se
Zn
RESULTING WASTE-LOAD CHARACTERISTICS
• Long-Terra Avg.
Concentration (mg/1)
„ „ «. , , , After Treatment To Level
Untreated(mg/11 12345
Avg. Cone.
5-6
750
265
8
6.9
6-9
13
4.3
0.2
0.26
6-9
9.3
0.076
0.2
0.04
c. TREATMENT DESCRIPTION
199
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TABLE 11-11. WATER EFFLUENT TREATMENT COSTS AND RESULTING
WASTE-LOAD CHARACTERISTICS FOR MODEL PLANT
SUBGATEGORY: Cadmium Salts Subgroup
ANNUAL PRODUCTION:
DAILY FLOW: 0.07
PLANT AGE: NA
169
METRIC TONS
CUBIC METERS
YEARS PLANT LOCATION:
NA
a. COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS
COSTS ($1,000) TO ATTAIN LEVEL
COST CATEGORY 12345
Facilities
Installed Equipment
(Including Instrumentation)
Engineering
Contractor Overhead and Profit
Contingency
Land
Total Invested Capital
Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Waste Disposal) 4.1
Residual Waste Disposal
4.7 0.1
RESULTING WASTE-LOAD CHARACTERISTICS
Long-Term Avg.
Concentration (mg/1)
After Treatment To Level
m 1.2 3 4 5
1.9
0.4
0.3
0.3
2.9
0.5
4.1
0.1
0.2
Negl.
Negl.
Negl.
0.2
Negl.
0.1
Negl.
Total Annual Cost
Parameter
PH
TSS
Cd
Se
Zn
b . RES
Avg. Cone.
Untreated (
5-6
750
265
8
6.9
6-9
13
4.3
0.2
0.26
6-9
9.3
0.076
0.2
0.04
c. TREATMENT DESCRIPTION
LEVEL 1: Alkaline precipitation, clarification, pH adjustment
LEVEL 2: Filtration
200
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incremental to Level l . COSt of Levgl 2 is
Basis for Regulations
Basis for BPT Limitations
A. Technology Basis
,,»
Sir 1 -:£S
would not be affected P tS have "°
B. Flow Basis
and thus
C. Selection of Pollutants to be Regulated
201
-------
concentrations observed of toxic pollutants detected during
screening and verification sampling at several plants are also
presented earlier in this section. Data from Appendix A on the
performance of in-place industry treatment systems was also
utilized in developing the list of pollutants to be regulated.
Based upon the occurrence of treatable levels of specific toxic
metals, cadmium, lead, selenium, and zinc were selected as
candidate toxic pollutants for BPT regulations. Antimony,
arsenic, chromium, copper, mercury, nickel, silver, and thallium
were detected but at less than treatable levels.
Consideration of the raw wastewater concentrations presented
earlier, industry data, and information in Section 8 related to
the effectiveness of hydroxide precipitation, clarification and
filtration leads to the selection of cadmium, selenium, and zinc
as toxic pollutants to be regulated. As discussed in Section 8,
proper control of zinc concentrations will also achieve control
of lead, so that lead was not selected for regulation.
D. Basis of BPT Pollutant Limitations
Limitations are presented as both concentrations (mg/1) and loads
(kg/kkg), and the relationship between the two is based on the
unit flow rate of 92.4 m'/kkg for cadmium pigments and 0.058
mVkkg for cadmium salts.
BPT limitations, which apply to all process wastewater.
discharged, are presented in Table 11-V2 (Cadmium pigments) and
Table 11-13 (Cadmium salts).
1. Conventional Pollutants
a. pH
The treated effluent is to be controlled within the
range' of 6.0 - 9.0. This limitation is based upon the
data presented in Appendix B .of the Development
Document for Proposed Effluent Guidelines for Phase I
Inorganic Chemicals (Ref. 2) and the JRB study (Ref.
3).
b. TSS
Since no long-term monitoring data for TSS is available
from any cadmium pigments or cadmium salts
manufacturing plant, the BPT limitations for TSS are
based on an average of long-term TSS monitoring data
from Plants A and K as presented in Appendix A of the .
202
-------
USe the same Level 2
for frh * • contro1 TSS that is proposed
for plants employing filtration. Variability factorS
-
30-dav average;
mVkkg)
24-hour maximum;
(1000
(100° 1/m3)
Similarly, for the cadmium salts segment:
30-dav average.
(100°
24-hour max imum :
(1000
2. Toxic Pollutants
a. Cadmium
respectively.
Lons for the
follows:
30-day average;
(0.15 mg/l)(92.4
) (kg/10« mg) (TOOO
203
_
-------
* 0.014 kg/kkg
24-hour maximum;
(0.46 mg/l)(92.4 mVkkg) (kg/10* mg) (1000
= 0.043 kg/kkg
Similarly, for the cadmium salts segment:
30-day average;
(0.15 mg/l)(0.058 mVkkg) (kg/10« mg) (1000 1/m')
= 0.0000087 kg/kkg
24-hour maximum;
(0.46 mg/l)(0.058 mVkkg) (kg/10« mg) (1000 1/m3)
« 0.000027 kg/kkg
b. Selenium
The BPT limitations for selenium are based upon
screening and verification sampling at Plant F102 since
no plant could be found with long-term effluent
monitoring data for selenium. Screening and
verification data from plant F134 was not used because
it was not producing pure cadmium reds and had a low
selenium raw waste load. Since there is insufficient
data to derive reliable variability factors for
selenium, the variability factors of 2 for a 30-day
average and 6 for a 24-hour maximum from treatment
system performance for cadmium from Plant F128 were
used yielding selenium limitations of 0.4 and 1.2 mg/1
respectively. Thus, utilizing these values, mass
limitations computed for cadmium pigments are as
follows:
30-day average;
(0.4 mg/1)(92.4 mVkkg) (kg/10« mg) (1000 1/m*)
= 0.037 kg/kkg
24-hour maximum;
(1.2 mg/1) (92.4 mVkkg) (kg/10« mg) (1000 1/m*)
=0.11 kg/kkg
Similarly, for cadmium salts:
30-day average;
(0.4 mg/1) (0.058 mVkkg) (kg/10«) (1000 1/m*)
= 0.000023 kg/kkg
24-hour maximum:
204
-------
TABLE 11-12. BPT EFFLUENT LIMITATIONS FOR
CADMIUM PIGMENTS
Conventional
Pollutants
TSS
(4)
Toxic
Pollutants
Cadmium
Selenium
Zinc
Long-Term
Avg.(mq/11
9.3
(U
0.076(2)
0.2(3)
0.04(2)
VFR
1.8/3.0.
(ID
Cone. Basis
(mq/1)
30-day
avg.
17
24-hr,
max.
28
2/6(2) 0.15 0.46
2/6(2) o.4 1.2
1.67/3.0(2) 0.067 0.12
Effluent Limit
(kg/kkg)
30-day
avg.
1.57
24-hr.
max.
2.59
0.014 0.043
0.037 0.11
0.0062 0.011
VFR - Variability Factor Ratio
(1) Based upon long-term data at Plants A and K (Phase I)
(2) Based upon long-term data at Plant F128.
(3) Based upon screen sampling at Plant F102.
(4) Also applicable to NSPS and BCT.
(5) Also applicable to BAT and NSPS.
205
-------
TABLE 11-13. BPT EFFLUENT LIMITATIONS FOR CADMIUM SALTS
Conventional
Pollutants
Long-Term
Avg.
VFR
Cone. Basis Effluent Limit
(mg/1) Ckg/kkg)
3u-day z'4-hr. 30-day 24-hr.
avg.
max.
avg.
max.
TSS
(4)
Toxic
Pollutants
Cadmium
Selenium *• '
9.3CD
0.076*-2)
0 2C3)
\f • Lt
0.04
1.8/3.0^) 17
28
0.001
0.0016
2/6
2/6
(2)
(2)
0.15
0.4
0.46 0.0000087 0.000027
1.2 0.000023 0.000070
,C2)
1.67/3.01 J 0.067 0.12 0.0000039 0.0000070
VFR - Variable Factor Ratio (30-day avg./24-hr, max.)
(1) Based upon long-term data at Plants A and K(Phase I)
(2) Based upon long-term data at Plant F128.
(3) Based upon screen sampling at Plant F102.
(4) Also applicable to NSPS and BCT,
(5) Also applicable to BAT and NSPS.
206
-------
(k9/'°*
(100°
c. Zinc
concentfauon for "nc^o?9 0 04 IST^S .'*•"*
factors deveiopld fS^inSVthlt p?ak werfllj'"
30-dav average;
0°
('°00
2 4 -hour max imum
Similarly, for the cadmium salts segment
30-dav average;
24-hour maximum;
Basis for BCT Effluent Limitations
EPA is not prooosina an <- •
TSS under BCT since we haveTLn^f "gfnt limitations than BPT for
would remove additional amounts of JS? "^ technology which
is equal to the BPT llmitationl. S * r€SUlt' BCT for TSS
Basis for BAT Effluent Limitations
Application of Advanced Level Treatment
207
-------
TABLE 11-14. BAT EFFLUENT LIMITATIONS FOR CADMIUM PIGMENTS
AND SALTS SUBCATEGORY
a. Cadmium Pigments (Flow basis 92.4 m3/kkg)
Concentration
(mg/1)
Effluent
Limitations
Toxic
Pollutants
Cadmium
Selenium
Zinc
L.T.A.
(mg/1)
0.076
0.2
0.04
VFR
2/6
2/6
1.67/3.0
30-day
avg.
0.15
0.4
0.067
24-hr.
max.
0.46
1.2
0.12
30-day
avg.
0.014
0.037
0.0062
24-hr.
max.
0.043
0.11
0.011
b- Cadmium Salts (Flow basis 0.058 mVkkg)
Cadmium
Selenium
Zinc
0.076
0.2
0.04
2/6
2/6
1.67/3.0
0.15 0.46 0.0000087 0.000027
0.4 1.2 0.000023 0.000070
0.067 0.12 0.0000039 0.0000070
L.T.A. * Long-terra average achievable level.
VFR s Variability Factor Ratio; ratio of the 30-day average
variability factor to the 24-hour maximum variability factor.
208
-------
For BAT, the Agency is proposing limitations based on treatment
consisting of Level 1 plus Level 2 (BPT) technology. Toxic
pollutants limited by the proposed BAT regulation are cadmium,
selenium, and zinc at the same concentration levels and loadings
proposed for BPT. No additional technology which would remove
significant quantities of additional pollutants is known.
A. Technology Basis
Alkaline precipitation followed by clarification', dewatering of
the sludge in a filter press, and filtration of the clarifier
effluent followed by pH adjustment (if necessary) used for BPT is
the same as for BAT.
B. Flow Basis
A unit wastewater flow rate of 92.4 mVkkg of cadmium pigments
and 0.058 mVkkg of cadmium salts has been selected for BAT (same
as BPT).
C. Selection of Pollutants to be Regulated
Toxic Pollutants
The toxic pollutants cadmium, selenium, and zinc have been
selected at the same concentration levels and loadings proposed
for BPT. Table 11-14 presents the BAT limitations for the
Cadmium Pigments and Salts Subcategory.
Basis for NSPS Effluent Limitations
For NSPS, the Agency is proposing limitations equal to BPT
because no additional technology that removes significant
quantities of additional pollutants is known. The pollutants
limited include pH, TSS, cadmium, selenium, and zinc which are
listed in Table 11-12 (cadmium pigments) and Table 11-13 (cadmium
salts).
Basis for Pretreatment Standards
The Agency is proposing PSES and PSNS that are equal to BAT
limitations because BAT provides better removal of cadmium,
selenium, and zinc than is achieved by a well operated POTW with
secondary treatment installed and, therefore, these toxic
pollutants would pass through a POTW in the absence of
pretreatment. Pollutants regulated under PSES and PSNS are
cadmium, selenium, and zinc.
209
-------
Using the summary data presented in Tahi<= 11 in 4-u *
Cadmium; Raw Waste = 265 mg/1
BAT = 0.076 mg/1
Percent Removal = [ (265-0. 076)•*( 265) 1 (100)
" 99.97%
Selenium; Raw Waste = 8 mg/1
BAT =0.2 mg/1
Percent Removal = [(8-0.2)*(8)](100)
= 97.5%
ZiH£s Raw Waste =6.9 mg/1
BAT =0.04 mg/1
Percent Removal = I (6.9-0.04M6.9) ] (100)
» 99.4%
i^iiSrK^ts.'Ssss,?1 s/srs tS pSsriM
study for other toxic metals ranged from 19% to 66%. We pres^l
sSle?luln removals are in that range. Therefore siSce th»
Existing Sources
There are currently four indirect discharger cadmium pigments and
b Ca'°r F°r «m lor
New Sources
210
-------
- K ??n?!?t standards for New Sources (PSNS), the Agency is
M^l^tations based on NSPS. Since NSPS is equal to BAT,
Table ll-i2 (cadmium pigments) and Table 11-13 (cadmium salts
£or the
211
-------
SECTION 11
REFERENCES
1. Kirk and Othmer, Encyclopedia of Chemical Technology, Wiley-
Interscience, 3rd ed., Vol. 4, pp 397-411, (1978).
2. U.S. Environmental Protection Agency, "Development Document
for Effluent Limitations Guidelines and Standards for the
Inorganic Chemicals Manufacturing Point Source Category,"
EPA Report No. 440/1-79-007, June 1980.
3. JRB Associates, Inc., "An Assessment of pH Control of
Process Waters in Selected Plants," Draft Report to the
Office of Water Programs, U.S. Environmental Protection
Agency, 1979.
212
-------
SECTION 12
COBALT SALTS INDUSTRY
INDUSTRIAL PROFILE
General Description
The cobalt salts considered in this subcateqorv are cobalf
chloride, cobalt nitrate, and cobalt sulfate Each lilt has
i??11^1^ how?ver many uses are «~» £ *» s;
ind* in fhhreS SaJtS.are USed as Catalysts, soil
salts ha™ f« «* *e ..manufacture of inks. Two of the cobalt
salts have found uses in the manufacture of pigments and vitamins
and various applications in the ceramics industry. The status of
cobalt as a strategic material combined with recent changes
* *
Table 12-1 presents the industry profile for cobalt salts.
wastewater flow as a function of unit production is ve?y low
General Process Description and Raw Materials
hdrhi- af? Prod"ced by reacting cobalt metal with either
hydrochloric, sulfuric, or nitric acid. The reactions for the
formation of the cobalt salts under consideration arl?
Co + 2HC1 - CoCl2 + H2
Co + H2S04'= CoS04 + Hj,
Co + 2HN03 = Co(N03)2 + H2
Sid.)"* Pr°d"~d b^«°»P°^tion
The production of a cobalt salt is a batch process consistino of
step
a:
chemical addition and filtration may be SecessSry
213
-------
TABLE 12-1. SUBCATEGORY PROFILE &&TA FOR ©SHALT
Number of Plants in Subcategory
Total Subcategory Production Rate
Minimum
Maximum
Total Subcategory Wastewater Discharge
Minimum
Maximum
Types of Wastewater Discharge
Direct
Indirect
Zero
10
>3, 000 kkg/yr
<4.5 kkg/yr
Confidential
>4@
19 m 3/3 ay
5
3
2
214
-------
WATER USE AND WASTEWATER SOURCES
Water Use
Wastewater Sources
Noncontact Cooling Water
"
Direct Process Contact
cto
215
_
-------
o
=1
•o
o
W
I
3 2
O t«
« ^
T
U
01
4J J3
> 5 "*"
U
CO |
*TJ
2
§ §
O 0)
•O W
0 C§
A
•3J
u XI
C^, J*
0)^ 3 <^
y Vi
to 01
U «^
<3 -^
O
•H C4/^ ^
M
OJ
^ AJ
J § 3
^ ^ O &0
~ u G
•J. ^ en fl
' 1
U
-a y
•H 3
^" UJ VJ
•H U
h-i CM
t-4
to n) o>
•aw r-i
^^ -H o »-i y
on y
W -H 0)
Q Crf
erf
o
w
H
£
I
U
n
3
o
d
o
H
si
§
erf
g
3
Cft
en
u
o
CM
N
W
Z
td
O
216
-------
TABLE 12-2. WATER USAGE AT COBALT SALTS FACILITIES
Flow (mVkkg of Cobalt Salts)
Plant Designation
WATER USE
F117(2)
F117(3)
Noncontact
Cooling
Direct Process
Contact
Indirect Process
Contact
Maintenance
Air Pollution
Scrubbers
Noncontact
Ancillary
TOTALS
1.65
NA
NA
1.33
NA
NA
1.65
1.33
NA Flow volume not available.
No information.
(1) Values indicated only for those plants that reported
separate and complete information.
(2) Cobalt Chloride.
(3) Cobalt Sulfate.
Source: Section 308 Questionnaires and Plant Visit Reports
217
-------
TABLE 12-3. WASTEWATER FLOW AT COBALT SALTS FACILITIES(D
Flow (m3/kkg of Cobalt Salts)
WASTEWATER SOURCE
Direct Process
Contact
Indirect Process
Contact
Maintenance
Air Pollution
Scrubbers
F117(2) F117(3)
0 0
0 0
0.083 NA
0^ QC4)
TOTAL PROCESS
WASTEWATER DISCHARED
0.083
Noncontact
Cooling
Noncontact
Ancillary
NA Plow volume not available.
No information.
(1) Values indicated only for those plants that reported
separate and complete information. p«"eu
(2) Cobalt Chloride.
(3) Cobalt Sulfate.
(4) Wastewater recycled within plant.
Source: Section 308 Questionnaires and Plant Visit Reports
218
-------
Maintenance
Washdowns, cleanups, spills, and pump leaks are periodic and
account for the remaining wastewater.
Table 12-3 presents information on sources and quantities of
wastewater produced in the production of cobalt salts.
DESCRIPTION OF PLANTS VISITED
Six of the 10 plants producing cobalt salts were visited.
Unfortunately, at the time of sampling none of these plants were
producing cobalt salts, so that it was not possible to sampll
wastewater streams associated with cobalt salt production.
plant
tO those
At Plant Fl 19 cobalt chloride, cobalt nitrate, and cobalt sulfate
are produced in addition to many other inorganic compounds. All
process wastewater from production of metal products is pH-
fs311™? £° 8'7 I*?:0 with. Caustic. The neutralized wastewater
aL ??«£ ^ *> Set"in9 basin- Flocculating agents are then added
and flow is directed to a tube settler for additional solids
removal The overflow is discharged to a POTW, and the underflow
ifnrfSrLiS? \ siudge hol<3ing tank. The supernatant from the
sludge holding tank is recycled to the settling basin and the
sludge is filtered in a filter press. The filtrate is sent back
Plant F113 produces cobalt chloride and cobalt sulfate. All
process wastewater is discharged to a POTW without treatment
except neutralization.
1c produces cobalt chloride, cobalt nitrate and cobalt
™* K?epa^ate t'i;eatment systems are provided for both the
cobalt chloride and cobalt nitrate processes. Each treatment
system consists of caustic addition (to pH 10) and filtration
SUlfate
Plant F107 produces cobalt nitrate as well as other metal salts.
All process wastewater is discharged to a POTW without treatment.
hni«IJ8 Produces Cobalt nitrate along with other products.
The plant has a combined wastewater treatment system with
wastewater from all production processes going to the treatment
system. The treatment system consists of equalization, chemical
219
-------
addition, precipitation, sedimentation, and final pH adjustment
before discharge to surface waters.
Plant F145 produces cobalt chloride and cobalt nitrate in minor
quantities in addition to many other chemicals. Wastewater from
all production processes, both organic and inorganic are treated
in the plant treatment system. Treatment processes used are lime
precipitation, clarification, sludge dewatering and biological
treatment.
POLLUTION ABATEMENT OPTIONS
Toxic Pollutants of Concern
The toxic pollutants present in cobalt salt process wastewaters
depend upon the purity of the sources and the nature of the raw
materials being used. Toxic metals which are known to be present
in the raw materials are copper, lead, nickel, and zinc. Most of
the impurities will be removed in the purification step and
disposed of as a solid sludge. There are no raw wastewater data
because cobalt salts were not being produced during sampling at
the plants visited. However, data submitted by one facility
indicated that 4,000 mg/1 of cobalt might be expected in a raw
wastewater stream. Nickel and copper are also expected to be
present in wastewater streams at treatable levels because those
metals are present in the cobalt raw material.
Existing Control and Treatment Practices
Wastewater treatment practices for plants visited were previously
described above. Provided below are the treatment practices at
the four plants not visited.
Plant F124 produces cobalt sulfate and cobalt nitrate as well as
other metal salts. Treatment of wastewaters for the entire plant
consists of alkaline precipitation, clarification, filter press
filtration, multi-media filtration, pH adjustment and
sedimentation in ponds before discharging directly to surface
waters.
Plant FT39 produces cobalt sulfate and cobalt chloride as well as
other metal salts. Treatment of wastewaters for the entire plant
consists of equalization, sedimentation, filtration, and
neutralization before discharge to surface waters.
Plants F150 and F138 have no discharge, as all process wastewater
is disposed of by a waste contractor.
Other Applicable Control/Treatment Technologies
220
-------
Process Modifications and Technology Transfer Options
2L.J?™"1/ ai^ie _?^c?ss_.wastewater is generated in this
1.
2.
back into
Minimizing product changes by careful product
scheduling and by increasing the number of reactors.
1.
2.
lime) may be advantageous when used as
wastewater treatment for the following
reduces or eliminates the problem of scale
reaction time
Caustic soda treatment results in a
reduction in sludge volume; and
significant
contfins high. concentrations of . the
WhiCh may be "claimed and
Best Management Practices
recycle. To implement this technology, rwcle olilno
221
-------
If solids from the wastewater treatment plant are disposed or
stored on-site, provision must be made to control leachates and
permeates. Leachates and permeates which contain toxic
pollutants should be directed to the wastewater treatment system
for further treatment.
Advanced Treatment Technology
No demonstrated advanced treatment technology has been identified
for this subcategory.
Selection of Appropriate Technology and Equipment
Technologies for Different Treatment Levels
A. Level 1
Level 1 treatment consists of alkaline precipitation,
clarification or settling, dewatering of the sludge in a filter
press followed by pH adjustment if necessary. This technology is
illustrated by Figure 10-.10. A holding basin sized to retain 4-6
hours of flow is provided.
The initial treatment step is the addition of caustic soda. This
is followed by clarification/settling (if the wastewater
characteristics are suitable, a tube settler may be substituted
for a clarifier to save space). Sludge is removed from the
clarifier and directed to a filter press for dewatering. Pits
are provided at the filter press for the temporary storage of
sludge. The sludge is periodically transported to a hazardous
material landfill. The pH of the treated wastewater stream is
adjusted to an acceptable level by acid addition prior to
discharge if necessary. A monitoring system is installed at the
discharge point. The objective of Level 1 technology is to
remove heavy metals and suspended solids.
B. Level 2
Level 2 treatment consists of the addition of granular media
filtration following clarification in the Level 1 treatment
system. This technology is illustrated in Figure 10-11. Level 2
technology has been selected as a means of achieving improved
removal of metal hydroxide precipitates and other suspended
solids.
Level 2 treatment was selected as the basis for BPT because it
represents a typical and viable industry practice for the control
of suspended solids, cobalt, nickel and copper. Currently four
of five direct discharge plants in this subcategory have Level 2
222
-------
or equivalent treatment technology.
Two additional plants have
not incur
Equipment for Different Treatment Levels
A. Equipment Functions
Conventional sludge dewatering by a filter press is used for
sludge removed by the clarification/settling system. The sludge
SS^S? f11^-?!;888^8 disPosed of off-site in a hazardous
material landfill. If a tube settler is used, backwash from the
settler is returned to the influent holding basin. Likewise, if
granular media filters are used, backwash water is returned to
the influent holding basin. After .mixing in a tank, the
S?SSlSeS l!,filte?ed prior to PH Adjustment (if necessary) and
discharged. All equipment is conventional and readily available.
B. Chemical Handling
soda<50 Pfrcent NaOH) is used to precipitate heavy
d fi£ »eV?\l' Sujfuric acid (concentrated) may be used to
reduce the pH of the wastewater prior to discharge.
C. Solids Handling
Treatment sludges generated by Level 1 are dewatered in a filter
"** be disP°sed of off-site in a hazardous
or sent to an off-site cobalt
ion. Level 2 filter backwash may be
K uplant or' if the solids concentration is
high, may be sent directly to the filter press.
Treatment Cost Estimates
General
n™«n, ran«es. and wastewater flow characteristics have been
presented earlier in this section and are summarized in Table 12-
2. There are five direct dischargers, three indirect
dischargers, and two plants which have no discharge.
The average production rate for the five plants providina
separate and complete production data is 358 metric tons per yea?
nr«v^L3Vera?e 2? "5 operating days per year. Only one plant
provided relieable flow data but that flow data is believed
rh£^SrtatiVS °f- °°balt salts Production based on process
chemistry and engineering visits to six plants by the Agency and
223
-------
TABLE 12-4. WATER EFFLUENT TKfcATMENT COSTS AND RESULTING
WASTE-LOAD CHARACTERISTICS FOR MODEL PLANT
SUBCATEGORY: Cobalt Salts
ANNUAL PRODUCTION:
DAILY FLOW: p.26
PLANT AGE:
358
METRIC TONS
NA
CUBIC METERS
YEARS PLANT LOCATION:
NA
a.
COST CATEGORY
COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS
COSTS ($1,000) TO ATTAIN LEVEL
12345
Facilities
Installed Equipment
(Including Instrumentation)
.Engineering
Contractor Overhead and Profit
Contingency
Land
Total Invested Capital
Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Waste Disposal) 6.0
Residual Waste Disposal - -
6.6
1.3
1.2
0.9
10.0
1.6
6.0
1.0
0.4
0.1
0.1
0.1
0.7
0.1
0.2
Negl,
Total Annual Cost
b.
8.6
0.3
RESULTING WASTE-LOAD CHARACTERISTICS
Avg. Cone.
Parameter Untreated (mg/1)
pH
TSS
Co
Cu
Ni
5-8
290
4,000
5'
5
Long-Term Avg.
Concentration (mg/1)
After Treatment To Level
2345
6-9
13
1.3
0.96
0.96
6-9
9.3
0.97
0.69
0.69
c. TREATMENT DESCRIPTION
LEVEL 1: Alkaline precipitation, clarification, pH adjustment
LEVEL 2: Filtration
224
-------
Material usage for both levels was estimated as follows:
Chemical Amount Treatment'
NaOH (50 percent sol.)
H2SO« (100 percent)
Level
1
2
3.3 kg/day
0.05 kg/day
(1)
(1)
Solid Waste
0.024
0.00004
Basis for Regulation
Basis for BPT Limitations
A. Technology Basis
B. Flow Basis
sub c°*ts, for the
representative of the group. ° /kkg W3S sele^ted as being
C.
Selection of Pollutants to be Regulated
225
-------
The selection of pollutants for which specific effluent
limitations are being established is based on an evaluation of
the wastewater data from discharge monitoring reports,
consideration of the raw materials used in the process,
literature data, permit applications, and the treatability of the
toxic pollutants.
Tables 8-1 through 8-14 summarize the achievable concentrations
of toxic metal pollutants from the literature using available
technology options, other industries, and treatability studies.
Water use and discharge data are presented earlier in Section 12
together with generalized process characteristics. Data from
Appendix A on the performance of inplace industry treatment
systems were also utilized in developing the list of pollutants
to be regulated.
Copper and nickel are commonly found as secondary constituents of
many cobalt ores, therefore the two toxic metals would be
expected to occur in raw materials used in production of cobalt
salts. The copper and nickel impurities would be carried over in
the process wastewater, and therefore these two metals were
selected as candidate toxic metals for BPT regulations. The
non-conventional pollutant, cobalt, was also selected for
limitation. Lead and zinc were not selected for limitation
because, as described in Sections 7 and 8, control of copper and
nickel will provide adequate control of lead and zinc.
Consideration of industry data and information in Section 8
related to the effectiveness of hydroxide precipitation,
clarification and filtration lead to the selection of cobalt,
copper and nickel as pollutants to be regulated.
D. Basis of BPT Pollutant Limitations
Limitations are presented as both concentrations (mg/1) and loads
(kg/kkg), and the relationship between the two is based on the
unit flow rate of 0.083m3/kkg.
BPT limitations, which apply to all
discharged, are presented in Table 12-5.
1. Conventional Pollutants
process wastewater
a. pH
The treated effluent is to be controlled within
the range of 6.0 - 9.0. This limitation is based
upon the data presented in Appendix B of the
Development Document for Proposed Effluent
226
-------
Guidelines for Phase I Inorganic
1) and the JRB study (Ref. 2).
Chemicals (Ref
b. TSS
2.
The BPT limitations for TSS are based upon an
average of long-term data from Plants A and K
(Phase I Development Document). Both plants are
using dual-media filtration to reduce TSS and
toxic metals which is the technology basis for the
proposed BPT for the cobalt salts subcategory.
Therefore, the TSS effluent quality should be the
same for cobalt salts plants as for plants A and
K. No long- term TSS data from Phase II plants
using dual- media filtration is available. A
long-term average of 9.3 mg/1 (the average of both
plants) was used to- develop the discharge
limitations for plants employing filtration.
Variability factors, also obtained from Plants A
and K, of 1.8 for a monthly average and 3.0 for a
24 hour maximum were used yielding TSS
concentration limits of 17 mg/1 and 28 mg/1,
respectively. Thus utilizing tb^sc values, one
obtains TSS mass limitation;, ..or the cobalt salts
subcategory of:
30-day average;
(17 mg/1 )(0.083mVkkgHkg/10« mgHlOOO l/m*)
= 0.0014 kg/kkg
24-hour- maximum , <.
(28 mg/1 )(0.083mVkkg)( kg/10« mg)(1000 l/m*)
• 0.0023 kg/kkg
Non-Conventional Pollutants
a. Cobalt
The BPT Limitations for cobalt are based on long-
term monitoring data from Plant 124 presented in
Appendix A. The plant is achieving a long-term
average concentration of 0.97 mg/1. Variability
factors of 1.44 for a 30-day average and 3.75 for
a 24-hour maximum were used yielding cobalt
limitations of 1.4 and 3.6 mg/1 respectively.
Thus, utilizing these values, mass limitations may
be obtained as follows:
227
-------
30-day average;
(1.4 mg/1)(0.083mVkkg)(kg/1 0« mg)(1000 1/m')
= 0.00012 kg/kkg
24-hour maximum;
(3.6 mg/1 )(0.083mVkkg) (kg/1 6* mg)(1000 1/m3)
= 0.00030 kg/kkg
3. Toxic Pollutants
a. Copper
Since there is no long-term monitoring data for
copper from any cobalt salts manufacturing plants,
the BPT limitations for copper are based on the
long-term monitoring data for nickel at Plant
F124. Plant F124 manufactures cobalt salts and
nickel salts. The BAT effluent limitations for
the nickel sulfate subcategory, which were
supported by our treat- ability study for the
nickel sulfate subcategory (see Section 14) show
that the copper and nickel concentrations in
effluent from the Level 2 treatment system are the
same in nickel sulfate wastewater. Since thes
treatment system is the same for cobalt salts and
nickel salts, and at least half the existing
dischargers in the cobalt salts subcategory also
manufacture nickel sulfate or other nickel salts
and commingle the wastewater for treatment, it is
reasonable to assume that the copper concentration
in treated cobalt salts wastewater is the same as
the nickel concentration in that wastewater. The
long-term average nickel concentration in treated
wastewater at Plant F124 is 0.69 mg/1, with
variability factors of 1.52 for a 30-day average
and 4.83 for a 24-hour maximum. Using these
figures, the corresponding copper concentrations
are 1.0 and 3.3 mg/1 respectively. Utilizing
these figures, mass limitations for copper are
calculated as follows:
30-day average;
(1.0 mg/1) (0.083mVkkgXkg/10* mg)(1000 l/m*)
= 0.000083 kg/kkg
24-hour maximum;
228
-------
TABLE 12-5. BPT EFFLUENT LIMITATIONS FOR COBALT SALTS
Conventional
Pollutants
Long-Term
Avg.(mq/1)
TSS1
.(3)
9.3
Non-Convent i onal
Pollutants
.(4)
Cobalt
Toxic
Pollutants
Copper^)
Nickel'-4-'
0.97(2)
0.69C2)
0.69(2)
VFR
1.8/3.0
(1)
Cone. Basis
(mg/1)
30-day 24-hr,
avg. max.
17
1.44/3.75(2) 1.4
1.5.2/4,83(2) 1.0
1.52/4.83(2) i.o
28
Effluent Limit
(kg/kkg)
30-day 24-hr.
avg. max.
0.0014 0.0023
3.6 0.00012 0.0003
3.3 0.000083 0.00027
3.3 0.000083 0.00027
LTA - Long-term average achievable level.
VFR - Variability Factor Ratio (30-day avK./24-hr, max.)
(1) Bas^d upon long-term data at Plants A and K (Phase I)
(2) Based upon long-term data at Plant F124.
(3) Also applicable to NSPS and BCT.
(4) Also applicable to BAT and NSPS.
229
-------
(3.3 mg/l)(0.083 mVkkg) (kg/10« mg)(1000 1/m')
= 0.00027 kg/kkg
b. Nickel
The BPT limitations for nickel are based upon a
long-term average of 0.69 mg/1 obtained from 26
months of monitoring at Plant F124 (657 data
points). No other long-term monitoring data is
available from any cobalt salts manufacturing
plant with a Level 2 treatment system.
Variability factors of 1.52 for a 30-day average
and 4.83 for a 24-hour maximum were used yielding
nickel limitations of 1.0 and 3.3 mg/1
respectively. Utilizing these values, mass
limitations for nickel may be obtained as follows:
30-day average;
(1.0 mg/1) (0.083 mVkkg) (kg/10« mg)(1000 1/m')
* 0.000083 kg/kkg
24-hour maximum;
(3.3 mg/l)(0.083 mVkkg) (kg/1 0« mg)(1000 1/m')
(- 0.00027 kg/kkg
Basis for BCT Effluent Limitations
EPA is not proposing more stringent limitations for TSS under BCT
since we identified no other technology which would remove
significant additional amounts of TSS. As a result, BCT for TSS
is equal to the BPT limitations.
Basis for BAT Effluent Limitations
Application of Advanced Level Treatment
For BAT, the Agency is proposing limitations based on treatment
consisting of Level 1 plus Level 2 (BPT) technology because we
identified no other technology which would remove significant
additional amounts of pollutants. Pollutants limited by the
proposed BAT regulation are cobalt, copper and nickel at the same
concentration levels and loadings proposed for BPT.
A. Technology Basis
Alkaline precipitation, clarification, filtration, dewatering of
the sludge in a filter press, followed by pH adjustment if
230
-------
necessary, is used for BAT which is the same technology used for
B. Flow Basis
SB
°f
C. Selection of Pollutants to be Regulated
Toxic Pollutants
*nn n?n-c?™entional pollutant cobalt, and
and nickel have been selected at the same
and loadings proposed for BPT. Table
limitations for Cobalt Salts Subcategory
Basis for NSPS Effluent Limitations
Basis for Pretreatment Standards
iS Pr°P°sin9 pSES and PSNS that are equal
BAT
has
o^r'T" ""^ raw waste concentrations for the cobalt c?aifo
231
-------
that the copper and nickel are equally probable and together
account for about half the impurity in average commerical grade
cobalt. That is, for 99.5% pure cobalt, 0.25% is copper and
nickel, and the copper is assumed to be 0.125% and the nickel is
0.125% of the total metal. The primary source of the process
wastewater at cobalt salts manufacturing plants is spillage. We
assume that the spill contains cobalt and other impurities in the
same ratio as found in the purchased cobalt, i.e., copper and
nickel are each about 0.125% of the concentration of the cobalt
in the wastewater. Therefore, for a cobalt concentration of 4000
mg/1, the copper concentration would be 4000 x .00125 = 5 mg/1,
and the nickel concentration would also be 5 mg/1.
In the absence of any other raw waste data for cobalt salts
manufacturing the Agency has used these calculations to estimate
the percent removals for cobalt, copper, and nickel by applying
the selected BAT technology to the untreated wastewater. The
calculations for percent removals are as follows:
Cobalt; Raw waste * 4000 mg/1
BAT =0.97 mg/1
Percent Removal = [{4000 -0.97)] t (4000)] (100)
- 99.98%
Copper t Raw waste « 5 mg/1
BAT =0.69 mg/1
Percent Removal = [(5 - 0.69) t (5)] (100)
= 86.2%
Nickel; Raw waste = 5 mg/1
BAT « 0.69 mg/1
Percent Removal = [(5 - 0.69) t (5)] (100)
= 86.2%
These estimated removals are greater than the removals achieved
for copper (58%) and nickel (19%) by 25% of the POTWs in the "40
Cities" study (Fate of Priority Pollutants in Publicly Owned
Treatment Works. Final Report, EPA 440/1-82/303,
September, 1982). Limited information showing the removal of
cobalt is available but the removals by 25% of the POTWs in that
study for other toxic metals range from 19% to 66%. Presumably,
the removals for cobalt would be in that range. Therefore, since
BAT technology achieves a greater percent removal of cobalt,
copper, and nickel than is achieved by a well operated POTW with
232
-------
metalswould pass
Existing Sources
New Sources
^^
233
.
-------
SECTION 12
REFERENCES
U.S. Environmental Protection Agency, "Development Document
for Effluent Limitations Guidelines and Standards for the
Inorganic Chemicals Manufacturing Point Source Category,
EPA Report No. 440/1-79-007, June 1980.
JRB Associates, Inc., "An Assessment of pH Control of
ProceS tier's in Selected Plants," Draft Report to the
Office of Water Programs, U.S. Environmental Protection
Agency, 1979.
234
-------
SECTION 13
COPPER SALTS INDUSTRY
INDUSTRIAL PROFILE
General Description
The copper salts included in this subcategory are copper sulfate,
copper chloride, copper carbonate, copper nitrate, and copper
iodide. These compounds are produced by several different
processes.
A process description and discussion of the copper sulfate
industry can be found in the Phase I development document:
Development Document for Effluent Limitations
Guidelines and Standards for the Inorganic Chemicals
Manufacturing Point Source Category, EPA 440/1-82-007,
June 1982.
Briefly, copper sulfate is produced by reaction of copper, copper
oxide, or waste copper (such as spent plating bath) with sulfuric
acid:
Cu + H2 S04 = CuSO* + H2
The copper sulfate may be sold in solution as produced, or may be
purified and crystallized before sale as the solid. Detailed
process information and the results of screening and verification
sampling are provided in the Phase I development document.
Therefore, the following discussion will cover the other copper
salts included in this subcategory.
Most copper chloride is marketed as cuprous chloride (CuCl). It
is used as a catalyst, decolorizer, and desulfurizing agent in
the petroleum industry, in the denitration of cellulose> and for
many other applications. The other form of copper chloride is
cupric chloride, produced as an intermediate in some cuprous
chloride processes. Cupric chloride (CuClz) has many
applications such as a catalyst in a number of organic oxidation
reactions, in sweetening petroleum oils, a wood preservative, and
in other uses. Both cuprous and cupric chloride can be produced
as either a liquid solution or as dried crystals.
Copper carbonate (CuCO3) is produced as a dry product and is
normally produced for outside sale. It is used in pyrotechnics,
paint and varnish pigments, ceramic frits, in the electroplating
235
-------
TABLE 13-1. SUBCATEGORY PROFILE DATA FOR COPPER SALTS
(a) COPPER SALTS EXCLUSIVE OF COPPER SULFATE
Number of Plants in Subcategory
Total Subcategory Production Rate
Minimum
Maximum
Total Subcategory Wastewater Discharge
Minimum
Maximum
Types of Wastewater Discharge
Direct
Indirect
Zero
15
>3000 kkg/yr
<4.5 kkg/yr
640 kkg/yr
~2000 m3/day
0
1060 n»3/day
4
5
6
236
-------
TABLE 13-1.
(b)
SUBCATEGORY PROFILE DATA SUMMARY FOR COPPER SALTS
COPPER SULFATE^
Total Subcategory Capacity Rate
Total Subcategory Production Rate
Number of Plants in this Subcategory
308 Data on File for
With total capacity of
With total production of
Representing capacity
Representing production
Plant production range:
Minimum
Maximum
Average production
Median production
Average capacity utilization
Plant age range:
Minimum
Maximum
Waste water flow range:
Minimum
Maximum
Volume per unit product;
Minimum
Maximum
Indeterminate
27,300 kkg/year
16
10
38,850 kkg/year
21,420 kkg/year
78 percent
45 kkg/year
9,100 kkg/year
2,100 kkg/year
790 kkg/year
63 percent
3 years
52 years
0 cubic meters/day
45 cubic meters/day
0 cubic meter/kkg
23 cubic meter/kkg
(1) Source: page 632 of development Document for Effluent
Limitations Guidelines and Standards for the Inorganic Chemicals
Manufacturing Point Source Category, EPA 440/1-82/007; June,1982.
Sources of data are Stanford Research Institute, Directory of
Chemical Producers, U.S.A., 1977, U.S. Department of Commerce,
Current Industrial Reports, December, 1977; Energy and
Environmental Analysis, Inc.; Draft Report, "Preliminary
Economic Assessment of Effluent Limitations in the Inorganic
Chemical Industry," June, 1978 and "Economic Analysis of Proposed
Revised Effluent Guidelines and Standards for the Inorganic
Chemicals Industry," March, 1980.
237
-------
industry as a source of copper, and agriculturally as a fungicide
for treating seed.
Copper nitrate (Cu(N02)3) can be sold in crystal or solution
form. It is used in light-sensitive reproductive papers, as a
ceramic color, as a mordant and oxidant in textile dyeing and
printing, in nickel-plating baths and aluminum brighteners, and
as a catalyst for numerous organic reactions.
Copper iodide (Cul) is produced and sold in a powder form. It is
used as a catalyst in certain organic reactions, as an ice-
nucleating chemical, and as a coating in cathode ray tubes.
Table 13-1 is a profile data summary for the copper salts
subcategory.
There are 15 facilities producing copper salts. Six facilities
have no discharge, four discharge directly and five discharge
indirectly. Of the 15 producers of other copper salts, six are
known to produce copper sulfate as well.
Total annual production in this subcategory is estimated to be in
excess of 3,000 metric tons, while total daily wastewater flow is
estimated to be approximately 2,000 cubic meters. It has been
found that copper carbonate production accounts for over 90
percent of the wastewater flow in this subcategory.
General Process Description and Raw Materials
The four copper salts exclusive of copper sulfate are produced by
different processes, each discussed separately below.
Copper chloride is produced in two forms, cupric chloride (CuCl,)
and cuprous chloride (CuCl). Each product involves the reaction
of copper with chlorine, and may be produced in solid or solution
form. The general reactions are:
Cu
1/2 C1
CuCl
Cu + C12 = CuCl2
CuCl 2 + 3Cu + C12 = 4 CuCl
Copper chloride (cuprous or cupric) is manufactured in a solid
form by reacting chlorine and pure copper in a molten bath. The
molten copper chloride is withdrawn continuously and materials
are added to maintain the desired material balance. The molten
copper chloride is cast, cooled, and if desired, ground to a
powder .
238
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CuS04 + Na2C03 = CuC03 + NazS04
Cu(N03)2 + NazC03 = CuCO, + 2NaN03
copper arei
3Cu * S HNO, . 3Cu{NOj)2 t 2NO * 4H,0
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is rS^'^-^'-jrdis^1 L^i1?^"^ ^s"
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2Cu + I2 = 2CuI
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243
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iodide. A reducing agent may be used to prevent contamination of
the cuprous iodide by reacting with the liberated iodine. The
cuprous iodide slurry is collected, washed in a filter press,
dried, ground, and packaged. The second process requires finely
divided copper metal and elemental iodine. These are mixed and
fed into a furnace. Molten cuprous iodide flows from the bottom
into a mold which is cooled by water. Iodine vapor is collected
by a scrubber, settled and periodically reused. Figure 13-4
presents the general process diagrams for this product.
WATER USE AND WASTEWATER SOURCES
Water Use
The major use of water in the production of copper chloride is
noncontact cooling water. Direct contact process water is used
in the reaction process for copper chloride solution. In
addition, water is also used for air pollution control,
maintenance, washdowns, and noncontact ancillary uses.
The major water use in the production of copper carbonate is
direct contact process water used to wash the precipitated
product. Indirect process water is also used along with
noncontact ancillary uses.
Noncontact cooling water used in the crystallizer is the major
use of water in the production of copper nitrate in solid form.
Water is also used for air pollution control, maintenance,
washdowns, and noncontact ancillary uses.
In the production of copper iodide noncontact cooling water is
used in the furnace process and direct contact water may be used
for product washing in the solution process. Water may also be
used in air pollution control devices.
Table 13-2 presents a summary of available plant data on water
use.
Wastewater Sources
Noncontact Cooling Water
Noncontact cooling water is used to cool reaction vessels in the
production of the copper salts, with the exception of copper
carbonate. This wastewater stream should not be contaminated by
process leaks, and therefore can be discharged without treatment.
Direct Process Contact Water
244
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The direct contact water
ESS-ASS- 2! S
whil. refining solut?ons
Noncontact Ancillary
Indirect Process Contact
m?l°
most copper salts incln
-------
listed in the table do not. It is observed that the copper
carbonate facilities produce substantially more process
wastewater than do other copper salts facilities. This
difference is attributable to the greater quantities of wash
water required for removal of product impurities in the copper
carbonate production process. The typical wastewater flow at
copper sulfate plants is 0.94 mVkkg, and results from indirect
contract water use (See the Phase I Development Document, page
649).
DESCRIPTION OF PLANTS VISITED AND SAMPLED
Plants Sampled
Plant F130 produces cuprous chloride by the process shown in
Figure 13-5. The plant produces cuprous chloride, cupric
chloride and other inorganic compounds. Cupric chloride is used
almost entirely as an intermediate for cuprous chloride
production. The process used at this plant is similar to that
described previously for the production of copper chloride from
spent plating and etching solutions. The solutions contain
dilute cupric chloride and copper ammonium chloride. This
solution is then reacted with hydrochloric acid to form a more
concentrated cupric chloride solution. Equal amounts of cupric
chloride solution and copper metal are reacted together with
water and hydrochloric acid to produce the appropriate cuprous
chloride solution.
Wastewater originates from tank and drum washdown, and pump seal
leaks. All washes from tank and loading areas are directed to a
sump where it is collected and transferred to the wastewater
holding tank. All wastewater and sludge collected in the
wastewater tank is recycled into the process. Most of the water
used in the process is shipped with the product solutions.
During the sampling episode the pump seals were not leaking and
water wa's forced through the seals in order to take a sample.
Toxic pollutant concentrations and loads in Table 13-4 were taken
from tank and drum washes and not from the collection tank
because the tank is only periodically dumped and pollutants have
time to settle. Figure 13-5 shows wastewater sources and
sampling locations at Plant F130.
Plant F127 produces copper carbonate (Figure 13-6) as well as a
variety of other metal products and inorganic chemicals. The
process used at this plant is similar to that previously
described for the production of copper carbonate. Nearly all
water is used as direct contact water in dissolving, reacting,
and filter washing. Noncontact cooling water is not used in the
248
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= Sampling Point
FIGURE 13-5. PROCESS AND SAMPLING LOCATIONS FOR PLANT F130.
249
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process. A majority of the wastewater from the process consists
of reaction supernatant decants, filtrate, and filter wash water.
These wastewater streams are collected in a settling tank where
coarse particulates are settled out and recovered. The overflow
is sent to a thickener where additional copper is separated from
the wastewater. The settled sludge is recycled back to the
process while the thickener overflow is sent to the central
treatment system. Floor washings, leaks and spills are directed
to another thickener for copper recovery, and the overflow
discharged to the central treatment system. At the central
treatment system, copper carbonate wastewater is commingled with
wastewater from inorganic and organic chemicals manufacture, then
subjected to alkaline precipitation, aeration, and clarification
before discharge to surface waters. Figure 13-6 shows wastewater
sources and sampling locations at Plant F127. Since the central
wastewater treatment system treats wastewater from a variety of
products, and therefore may not be representative of copper
carbonate wastewater only, no sampling was performed at the
central treatment system. Table 13-4 presents the wastewater
loads and pollutant concentrations for the sampled streams.
Other Plant Visits
Nine plants in the Copper Salts Subcategory were visited but not
sampled. A description of the individual products, wastewater
treatment, and discharge status for those plants visited are
given below.
Plant F145 produces cupric chloride, copper nitrate and other
inorganic and organic compounds. The copper chloride process is
similar to the process previously described. The resulting
solution is purified, filtered to remove impurities, then
crystallized. The pure crystals are collected, dried, ground,
and sold. The residue from filtration is disposed of as solid
waste. Copper nitrate is produced similar to the process
previously described. The majority of water used is noncontact
cooling water with minimal usage of direct contact water.
Scrubber wastes, washings, filtrates, tank cleanouts, and leaks
or spills which cannot be recycled are sent to a central
treatment system where all plant wastewaters are treated.
Treatment consists of equalization, lime precipitation,
clarification and sludge dewatering. Overflow from this system
is then treated by biological treatment prior to discharge to
surface waters.
Plant FIT9 produces copper nitrate, copper iodide, and copper
carbonate. All processes are similar to those previously
described. Off- gases from the copper nitrate production are
exhausted though a condenser to recover nitric acid, and the off-
252
-------
t0
ca-rbonat
destr°y nitrogen oxides before
cotlecteTin
previously described process. Wastwater from all cheical
processes are combined and passed through a treatment svstem
consisting of equalization, alkaline precipitation! SrtUinS and
final pH adjustment before discharge to surface waters?
Th=nt Pfoduces cuprous chloride and other inorganic salts
The manufacturing process is similar to the previously described
of°CcoDt>er0r,n,?»?dUCi29 "£lte? CUprous M°'**° from the reScuIn
of copper metal and chlorine. All contact and noncontact
'
faci
wastewater
pretreated prior to discharge to a POTW
253
-------
process wastewater streams when visited. Since the lagoons are
unlined, percolation of some of the wastewater from the lagoons
into the subsoil could account for the fact that the plant had no
discharge when visited.
Plant F129 produces copper iodide by direct reaction of copper
and iodine. This plant has no discharge as all wastewater is
recycled since the plant uses pure raw materials only and does
not need a purification step. Plants that did not use pure raw
materials would need a purification step and thus would have a
discharge of process wastewater.
Summary of Toxic Pollutant Data
Thirteen toxic metals and four toxic organics were found at
detectable concentrations in the total combined raw wastewater at
the two sampled plants. The table below presents the maximum
daily concentrations observed for these pollutants found in the
total combined raw wastewater. No treated wastewater samples
were collected during the sampling program at these facilities.
Pollutant
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Bis(2-ethylhexyl) phthalate
Tetrachloroethylene
Toluene
Methyl Chloride
Maximum Concentration
Observed (uq/1)
1,300
270
3
20
270
560,000
12,000
32
390
140
130
180
8,300
23
30 (28)*
27 (29)*
10*
*preserved samples
Section 5 of this
sampling program.
report describes the methodology of the
In the Copper Salts Subcategory, a total of
254
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TABLE 13-5.
DATA FOR SAMPLED
Average Daily Pollutant Concentrations and Loads
mg/1
kg/kkg
Plant Designation
Pollutant
Antimony
Arsenic
Chromium
Copper
Lead
Nickel
Selenium
Silver
Thallium
Zinc
F130(D
,
0.483
0.00047
0.100
0.00010
0.220
0.00021
351.333
0.342
5.717
0.00557
0.357
0.00035
<0.005
<0. 00001
0.055
0.00005
<0.104
<0. 00010
7.067
0.00688
•
F127C2)
— — — — — — — .
0.200
0.0105
0.103
0.00542
0.047
0.00248
107.000
5.63
0.148
0.00779
0.176
0.00927
0.069
0.00363
0.026
0.00137
0.041
0.00216
0.045
0.00237
— — — — — — — — __
Overall
Average
0.341
0.00550
0.102
w • -t W *•
0.00276
0.134
0.00135
229.167
2.99
2.947
0.00668
0.267
** • *• w »
0.00481
<0.037
<0.0018
0.04-1
0.00071
<0.073
<0.0011
3.556
0.00463
(1) Data from three daily grab samples,
(2) Copper carbonate wastewater.
Cuprous chloride wastewater.
255
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six days of sampling were conducted at two plants. Six different
wastewater streams were sampled and analyzed. The evaluation of
toxic pollutants in these streams was based on 234 data points
for toxic metals and 678 data points for toxic organics. In
Table 13-5, toxic metal pollutant raw wastewater data are
presented as average daily concentrations and loads for the two
sampled plants.
POLLUTION ABATEMENT OPTIONS
Toxic Pollutants of Concern
The major toxic pollutant of concern in the Copper Salts
Subcategory is copper. Other toxic metals found in significant
concentrations in process wastewaters are probably related to the
purity of the raw materials used. Antimony, arsenic, and nickel
occurred in process wastewaters from two of the sampled plants
while lead and zinc were found at significant concentrations at
only one plant. No toxic organics were found in significant
concentrations. Antimony, arsenic, copper, lead, nickel, and
zinc were also found at significant concentrations in raw waste
during screening and verification sampling at a copper sulfate
plant during Phase I (see the Phase I Development Document).
When impure raw materials are used, toxic metal impurities are
removed in the purification process through filtration or washing
of the product. These pollutants then occur in wastewater or as
solid wastes. Using pure raw materials, which are not always
available or economical, however, can often allow recycle of most
or all of the process wastewater.
Existing Control and Treatment Practices
Treatment and control practices conducted at plants that were
visited during this program were previously described. Presented
below are brief descriptions of treatment practices at other
plants producing copper salts.
Plant F115 produces copper carbonate. Process wastewaters are
treated in a system using alkaline precipitation, sedimentation,
and final pH adjustment prior to discharge to surface waters.
Plant F108 manufactures cuprous chloride by direct reaction of
copper and chlorine. No process wastewater is generated or
discharged from this process.
P1fntV F132 Prod"ces copper chloride by direct reaction of copper
and chlorine. Process wastewaters, which consist of only air
scrubber blowdown are treated in a system using sedimentation,
256
-------
and filtration.
air scrubber.
These treated wastewaters are recycled to the
---"" -,". Produces copper iodide by direct reaction of copper
and iodine. The only source of process wastewater is the air
scrubber, and all air scrubber water is recycled with no
blowdown.
Other Applicable Control and Treatment Technologies
Alkaline precipitation and clarification will remove copper and
most other toxic metals found in copper salts process wastes.
Filtration of the effluent from this treatment process would
further reduce metals and solids. Three of four direct
dischargers are currently using this technology or its
equivalent. . y
Process Modifications and Technology Transfer Options
9ne of the major sources of process wastewater in the subcategory
is copper carbonate washwater. The copper carbonate precipitate
which must be washed results from addition of soda ash to a
copper salt solution, usually copper sulfate. The washwater is
of relatively high pH (approximately pH 8r-9) and typically
contains low concentrations of most toxic metals. Optimum
removal of copper occurs at a pH of 8.5 to 9.0, however, elevated
concentrations of copper may occur in the wastewater in suspended
form. The application of Level 2 technology (sand or multi-media
riitration) at this point may produce a suitable quality effluent
without application of Level 1. Increased product yield (copper
carbonate) would result from the wastewater treatment system by
recovery of the copper carbonate from the filter.
A reduction in the volume of process contact wastewater generated
might be achieved by:
Recycling of scrubber water or use of scrubber water as
make-up for product solutions, where possible;
2. Minimizing product changes by careful product
scheduling, or, for multi-product facilities, by
increasing the number of reactors. This can result in
reducing the volume of washdown water required by
minimizing product changeover.
As shown on Table 13-3, all four plants with scrubbers are
£f™H"g theuscrubber water. Product scheduling is a management
perogative subject to customer demands. Consequently, the Agency
1
257
-------
has not identified any technology which would provide significant
reduction in water use in this industry.
Sludge volumes may be reduced by the use of caustic soda instead
of lime. This practice offers other advantages including reduced
scale formation and faster reaction times.
Best Management Practices
The best technology for the treatment of scrubber wastewater from
copper salts production is recycle, where technically feasible.
Implementation of this technology requires installation of piping
and pumping as needed. Scrubber liquors may be used as process
makeup. All four plants with air scrubbers are recycling the
scrubber liquor.
If contact is possible with leakage, spillage of raw materials or
product, all storm water and plant site runoff should be
collected and directed to the plant treatment facility. This
contamination can be minimized by indoor storage of chemicals,
proper air pollution control, and elimination of spills.
All other contact wastewater including leaks, spills, and
washdowns should be contained and treated.
If solids from the wastewater treatment plant are disposed or
stored on-site, provision should be made to control leachates and
permeates. Leachates and permeates which contain toxic
pollutants should be directed to the treatment system for further
treatment.
Advanced Technology
No demonstrated advanced technology was identified for this
subcategory.
Selection of. Appropriate Technology and Equipment
Technologies for Different Treatment Levels
A. Level 1
Level 1 treatment consists of alkaline precipitation,
clarification or settling, and final pH adjustment of the
effluent if necessary. Sludges generated are dewatered in a
filter press. As part of the treatment system, a holding basin
sized to retain 4-6 hours of influent is provided as a safeguard
in the event of treatment system shutdown. The treatment
technology is illustrated in Figure 10-10.
258
-------
B.
Level 2
259
-------
treatment, and a reduction in discharge of toxic metals to
receiving waters.
Equipment for Different Treatment Levels
A. Equipment Functions
Conventional sludge dewatering by a filter press is used for
sludge generated by the clarification/settling system. In some
cases, the sludge may be amenable to copper recovery. However,
off-site disposal in a hazardous material landfill is generally
assumed. If a tube settler is used instead of a clarifier,
backwash from the settler is returned to the influent holding
basin. Solids resulting from Level 2 filter backwash would be
handled as discussed in item C (Solids Handling) below. All
equipment is conventional and readily available.
B. Chemical Handling
Caustic soda (50 percent NaOH) is used to precipitate heavy
metals in Level 1. At all levels of treatment, sulfuric acid
(concentrated) may be used to reduce the pH of the treated
wastewater prior to discharge.
C. Solids Handling
Treatment sludges generated by Level 1 are dewatered in a filter
press. The solids may be disposed of off-site in a hazardous
material landfill or processed for copper recovery. Level 2
filter backwash may be sent to the head of the plant or, if the
solids concentration is sufficiently high, may be sent directly
to the filter press."
Treatment Cost Estimates
Based upon copper salt subcategory profile characteristics, two
model plants were selected for costing of Level 1 and Level 2
treatment -systems. The overall- ranges of production and
wastewater flow have been discussed earlier in this section and
summarized in Table 13-1. Since copper carbonate production
accounts for a large portion (>90 percent) of the process
wastewater generated in the subcategory, one set of model plant
wastewater flow characteristics are based upon flow attributable
to this product, and a separate model plant has been established
for the other copper salts.
Estimates of material usages for both treatment
copper salts segment are listed below:
levels in the
260
-------
3.0 kg/day
0.08 kg/day
of solid waste generated for both
salts segment are provided below:
Waste Source
^Amount
Level 1 sludge
Level 2 sludge
0.0176 m*/day
0.0018 mVday
in Table
Therefore, the Agency has combined
cubic meters calculated frSIhh. 3 ^? "astewater flow of
unit flow of 0.94 mVkkg (as found =<• ™ Uy PJ°du=tion and the
an operating schedule^ o£ ?02 Per sulfate Plants) with
«- I. th.
an annual production of
a
^ea^ent
Chemical
NaOH (50 percent sol.)
H2SO« (100 percent sol.)
Amount
87.3 kg/day
29.1 kg/day
Level
1
1
levels in
261
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TABLE 13-6. WATER EFFLUENT TREATMENT COSTS AND RESULTING
WASTE-LOAD CHARACTERISTICS FOR MODEL PLANT
SUBCATEGORY: Copper Salts Subgroup
ANNUAL PRODUCTION:
DAILY FLOW:
PLANT AGE:
85.2
METRIC TONS
0.8
NA
CUBIC METERS
YEARS PLANT LOCATION:
NA
a. COST OF TREATMENT TO ATTAIN SPECIFIED. LEVELS
COST CATEGORY
Facilities
Installed Equipment
(Including Instrumentation)
Engineering
Contractor Overhead and Profit
Contingency
Land
Total Invested Capital
Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Waste Disposal) 6.3
Residual Waste Disposal
COSTS ($1,000) TO ATTAIN LEVEL
1 23 4 5
0.7
6.6
1.5
1.3
1.0
11.1
1.8
6.3
0.7
0.4
0.1
0.1
0.1
0.7
0.1
0.2
0.1
Total Annual Cost
8.8
0.4
b. RESULTING WASTE-LOAD CHARACTERISTICS
Long-Term Avg.
Avg. Cone. Concentration (mg/1)
After Treatment To Level
12345
Parameter Untreated(mg/1)
pH
TSS
Cu
Ni
2.5
225
1,175
51.2
6-9
6-9
* 20
1.2 0.89
2.3 1.8
c. TREATMENT DESCRIPTION
LEVEL 1: Alkaline precipitation, clarification, pH adjustment
LEVEL 2: Filtration
*No performance data available for TSS in this subcagegory with Level 1
technology.
262
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TABLE 13-7. WATER EFFLUENT TREATMENT COSTS AND RESULTINf
WASTE-LOAD CHARACTERISTICS FOR MODEL
SUBCATEGORY: Copper Carbm.»t»
ANNUAL PRODUCTION: 155
DAILY FLOW:
PLANT AGE:
METRIC TONS
291
NA
CUBIC METERS
YEARS PLANT LOCATION:
NA
a. COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS
COST CATEGORY
Facilities
Installed Equipment
COSTS .($1,000) TO ATTAIN LEVEL
1
25.4
163.7
37.8
34.0
26.1
.Contractor Overhead and Profit
Contingency
Land
Total Invested Capital
Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Waste Disposal) 78 3
Residual Waste Disposal J 9
287.0
46.7
31.3
6.3
5.6
4.3
47.5
7.7
9.3
0.1
Total Annual Cost 17r Q .- ,
•i- £ 3 • ^7 Jl / « 1
b. RESULTING WASTE-LOAD CHARACTERISTICS
Ave Conr ^ Long-Term Avg.
*vg. uonc. ^Concentration (mg/1)
Parameter Untreatedfmc/ll i
Af|°r Trea.tment To Level
PH
TSS
Cu
Ni
2.5
225
1,175
51.2
6-9
*
1.2
2.3
6-9
20
0.89
1.8
c. TREATMENT DESCRIPTION
a available for TSS in this subcategory with
263
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Waste Source
Level 1 sludge
Level 2 sludge
Model Plant Treatment Costs
Amount
0.058 mVday
0.006 mVday
On the basis of the model plant specifications and design
concepts presented earlier and in Section 10, the estimated cost
of treatment for the model plant with two treatment levels are
shown in Tables 13-6 and 13-7. The cost of Level 2 is
incremental to Level 1.
Basis for Regulations
Basis for BPT Limitations
A. Technology Basis
For BPT, the Agency is setting limitations based upon alkaline
precipitation, clarification, granular media filtration,
dewatenng of the sludge in a filter press and final pH
adjustment of the effluent (if necessary). Three of the four
direct dischargers have Level 2 treatment. One of the five
indirect dischargers also has Level 2 installed. All copper
sulfate plants have this technology or its equivalent installed.
Six plants currently do not discharge copper salts process
wastewater, and will not incur additional costs for treatment.
B. Flow Basis
For the'copper salts segment of the Copper Salts Subcategory, a
unit flow rate of 0.94 m3/kkg was selected as representative.
This flow rate was derived as described above under model plant
treatment costs. The unit flow is the same as for copper
sulfate. w
For the copper carbonate segment of the Copper Salts Subcategory
a unit flow of 58.1 mVkkg was selected as being representative
of the group. This flow rate was derived as described above
under model plant treatment costs.
C. Selection of Pollutants to be Regulated
The selection of pollutants for which specific effluent
limitations are being established is based on an evaluation of
the raw wastewater data from screening and verification,
consideration of the raw materials used in the process,
literature data, historical discharge monitoring reports and
264
-------
discharge permit applications, and the treatability of the toxic
pollutants.
Tables 8-1 through 8-14 summarize the achievable concentrations
of toxic metal pollutants from the literature using available
technology options, information from other industries, and
treatability studies. Water use and discharge data are presented
earlier in this section together with generalized process
characteristics. Pollutant concentrations of raw wastewater
streams and a summary of maximum concentrations observed of toxic
pollutants detected during screening and verification sampling at
several plants are also presented earlier in this section. Data
from Appendix A on the performance of in-place industry treatment
systems were also utilized in developing the list of pollutants
to be regulated.
The following parameters were selected initially as candidate
toxic pollutants for BPT regulations: copper, nickel, lead and
zinc. These pollutants were observed at least once during
screening and verification sampling at concentrations considered
treatable. A number of other priority pollutant metals were
detected during screening and verification sampling, however,
concentrations were generally less than 0.3 mg/1. Arsenic and
selenium were also considered as toxic pollutants to be
regulated.
During Phase I, significant concentrations of arsenic were found
at a copper sulfate facility during screening and verification
sampling. However, average concentrations of arsenic at two
copper salts fsicilities during Phase II sampling were
approximately 0.1 ing/1. Therefore, arsenic was rejected as a
regulated pollutant. Arsenic was also not selected as a
regulated pollutemt in Phase I.
Selenium was also found during Phase I screening and verification
sampling in a treated effluent. However, selenium was not found
in the raw wastewater. The maximum concentration of selenium
found in a combined raw wastewater influent to treatment during
Phase II screening and verification sampling was 0.14 mg/1.
Consideration of the raw wastewater concentrations presented
earlier in this section, wastewater information obtained from
industry and from Phase I, and information presented in Section 8
on the effectiveness of hydroxide precipitation, clarification,
and filtration suggested a reduction in the number of parameters
to be regulated. Copper, nickel, and selenium were selected as
the toxic pollutants to be regulated. Since selenium was found
in Phase I in treated effluent but not the raw waste, selenium
was selected for regulation in Phase I, along with copper and
265
-------
nickel, to assure that excessive amounts
discharged after treatment.
of selenium were not
Control of the regulated parameters, copper, nickel and selenium,
will provide adequate control for arsenic, lead and zinc;
therefore no limitations are set for these three parameters.
D. Basis of BPT Pollutant Limitations
Limitations are presented as both concentrations (mg/1) and loads
(kg/kkg), and the relationship between the two is based on the
unit flow rates of 0.94 m'/kkg for copper salts and 58.1 m3 for
copper carbonate. BPT limitations, which apply to all process
wastewater discharged, are presented in Table 13-8 and 13-9.
1. Conventional Pollutants
a. pH
The treated effluent is to be controlled within
the range of 6.0 - 9.0. This limitation is based
upon the data presented in Appendix B of the
Development Document for Proposed Effluent
Guidelines for Phase I Inorganic Chemicals (Ref.
1) and the JRB study (Ref. 2).
b. TSS
The BPT limitations for TSS are based upon the
limitations promulgated for the copper sulfate
industry in Phase I. The long-term average of 20
mg/1 was used to develop discharge limitations.
Variability factors of 1.2 for a monthly average
and approximately 3.6 for a 24-hour maximum were
. used yielding TSS concentration limitations of 24
mg/1 and 73 mg/1 respectively. Thus, utilizing
these values, one obtains TSS mass limitations for
the Copper Salts subcategory of:
1
Copper Salts Segment
30-day average:
(24 mg/1) (0.94 mVkkgH kg/10* mgXlOOO l/m3)
- 0.023 kg/kkg
24-hour maximum;
(73 mg/1) (0.94 m'/kkg)(kg/10« mg)OOOO 1/m*)
266
-------
2.
= 0.069 kg/kkg
2- Copper Carbonate Segment
30-day average;
(24 mg/l)(58.1 mVkkg) (kg/10« mg)(1000 1/m')
=1.4 kg/kkg
24-hour maximum;
(73 mg/1) (58.1 mVkkg) (kg/10« mg)(1000 1/m*)
= 4.2 kg/kkg
Toxic Pollutants
a . Copper
The BPT limitations for copper are based on the
limitations promulgated in Phase I for copper
sulfate manufacture. During Phase I, a long-term
average concentration of 0.89 mg/1 copper was
derived, and estimated variability factors of l 2
and 3.6 were used to compute the 30-day average
and 24-hour maximum values of l.l and 3.2 mg/1
respectively. *
rno ic uvaiues' mass limitations for the
Copper Salts Subcategory may be obtained as
follows?
1 • Copper Salts Segment
30-day average;
mVkkg)(k9/10' nig) (1000 1/m,)
24-hour maximum;
2' Copper Carbonate Segment
30-day average;
(1.1 mg/1) (58.1 mVkkg) (kg/10* mg)(1000 1/m')
= 0.064 kg/kkg
267
-------
24-hour maximum;
(3.2 mg/l)(58.1 m'/kkg)(kg/10«mg)(1000 l/m»)
=0.19 kg/kkg
b. Nickel
The BPT limitations for nickel are based on the
limitations promulgated in Phase I for copper
sulfate manufacture. In Phase I, a long-term
average concentration of 1.8 mg/1 nickel was
derived, and estimated variability factors of 1.2
and 3.6 were used to compute the 30-day average
and 24-hour maximum values of 2.1 and 6.4 mg/l
respectively.
The mass limitations for nickel in the Copper
Salts Subcategory were derived as follows:
1. Copper Salts Segment
30-day average;
(2.1 mg/l)(0.94 mVkkg) (kg/10« mg)(1000 1/m')
* 0.0020 kg/kkg
24-hour maximum;
•(6.4 mg/1) (0.94 mVkkg)(kg/10« mg)(1000 1/m3)
- 0.0060 kg/kkg
2. Copper Carbonate Segment
30-day average;
(2. l'mg/1) (58.1 mVkkg) (kg/10« mg)(1000 l/m*)
0.12 kg/kkg
24-hour maximum
(6.4 mg/1) (58.1 mVkkg) (kg/10« mg)(1000 1/m')
=0.37 kg/kkg
Selenium
The BPT limitations for selenium are based on the
limitations promulgated in Phase I for copper
sulfate manufacture. During Phase I, a long-term
average concentration of 0.44 mg/1 selenium was
268
-------
derived, and estimated variability factors of 1 2
UUI5 ™'t Were used to comPute the 30-day average
and 24-hour maximum values of 0.53 and 1.6 ma/1
respectively. y
Utilizing these values, mass limitations for the
follows- Subcategory may be obtained as
1- Copper Salts Segment
30-day average;
-BM'OOO 1/k.)
24-hour maximum;
«n,,
* 0.0015 kg/kkg
2- Copper Carbonate Segment
30-clay average
( kg/1°*
24-hour maximim
Basis for BCT Effluent Limitations
l P^°P°Sing ai?X m°re Strin9ent limitations for TSS under
Basis for BAT Effluent Limitations
Application of Advanced Level Treatment
269
-------
TABLE 13-8. BPT EFFLUENT LIMITATIONS FOR COPPER SALTS
Coventional
Pollutants
Long-Term (1)
Avg.(mg/1)
20
VFR
CD
1.2/3.6
Cone. Basis
Qng/1)
30-day ^
avg. max.
24
73
Effluent Limit
(kg/kkg)
30-day 24-hr.
avg. max.
0.023 0.069
Toxic
Pollutants
Copper^-3)
Nickel^3)
Selenium^3)
0.89
1.8
0.44
1.2/3.6
1.2/3.6
1.2/3.6
1.1 3.2 0.0010 0.0030
2.1 6.4 0.0020 0.0060
0.53 1.6 0.00050 0.0015
VFR - Variability Factor Ratio
(1) Based upon limitations promulgated for the copper sulfate sub-
category in Phase I.
(2) Also applicable to NSPS and BCT.
(3) Also applicable to BAT and NSPS.
270
-------
TABLE 13-9. BPT EFFLUENT LIMITATIONS FOR COPPER CARBONATE
Conventional
Pollutants
(3)
TSS
Toxic
Pollutants
Copper
(2)
Nickel^
Seleniunr J
Long-Term
Avg.(mg/11
20
CD
VFR
(1)
1.2/3.6
Cone. Basis
(mg/l)
30-day 24-hr.
avg. max.
24
73
Effluent Limit
fkg/kkg-)
30-d
ay
avg .
1.4
24-hr.
max .
4.2
0.89
1.8 -
0.44
1.2/3.6
1.2/3.6
1.2/3.6
1.1
2.1
0.53
3.2
6.4
1.6
0.064
0.12
0.031
0.19
0.37
0.093,
VFR - Variability Factor Ratio
(1) Based upon limitations promulgated for the copper sulfate sub-
category in Phase I.
(2) Also applicable to BAT and NSPS.
(3) Also applicable to NSPS and BCT.
271
-------
TABLE 13-10. BAT EFFLUENT LIMITATIONS FOR COPPER SALTS
Toxic
Pollutants
Long-Term
(1)
Avg.(rng/1)
VFR
Cone. BasisLJJ Effluent Limit
Cmg/lj rkg/kkg-)
30-day24-hr. 30-day 24-hr.
Copper
Nickel
Selenium
0.
1.
0.
89
8
44
1.
1.
1.
2/3.
2/3.
2/3.
6
6
6
1.
2.
0.
1
1
53
3.2
6.4
1.6
0.
0.
0.
•" K •
0010
0020
00050
0.0030
0.0060
0.0015
VFR - Variability Factor Ratio
(1) Based upon limitations promulgated for the copper sulfate sub-
category in Phase I.
272
-------
TABLE 13-11. BAT EFFLUENT LIMITATIONS FOR COPPER CARBONATE
Cone. Basis(1) Effluent Limit
Cmg/D fkg/kkg)
1UJLJ.U
Pollutants
Copper
Nickel
Selenium
i-ong-iernr
Avg.Cmg/i)
0.89
1.8
0.44
*
1.2/3.6
1.2/3.6
1.2/3.6
30-day
avg.
1.1
2.1
'0.53
24-hr.
max.
3.2
6.4
1.6
• 30-day
avg.
0.064
0.12
0.031
24-hr.
max.
0.19
0.37
0.093
VFR - Variability Factor Ratio
(1) Based upon limitations promulgated for the copper sulfate sub-
category in Phase I.
273
-------
other technology which would remove significant additional
amounts of pollutants is known.
A. Technology Basis
Alkaline precipitation followed by clarification and filtration,
dewatering of the sludge in a filter press, followed by pH
adjustment (if necessary) form the selected BAT technology basis
(same as BPT).
B. Flow Basis
Unit wastewater flow rates of 0.94 mVkkg of copper salts and
58.1 mVkkg of copper carbonate have been selected for BAT (same
as BPT).
C. Selection of Pollutants to be Regulated
Toxic Pollutants
The toxic pollutants copper, nickel, and selenium have been
selected at the same concentration levels and loadings proposed
for BPT. Tables 13-10 and 13-11 present the BAT limitations for
the Copper Salts Subcategory.
Basis for NSPS Effluent Limitations
For NSPS, the Agency is proposing limitations equal to BAT since
no additional technology which would remove significant
additional amounts of pollutants is known. The pollutants
.limited include pH, TSS, copper, nickel, and selenium which are
listed in Table 13-8 and 13-9.
Basis for Pretreatment Standards
The Agency is proposing PSES and PSNS that are equal to BAT
limitations because BAT provides better removal of copper, nickel
and selenium than is achieved by a well operated POTW with
secondary treatment installed and therefore these pollutants
would pass through the POTW in the absence of pretreatment. The
promulgated PSES and PSNS for copper sulfate are also based on
the BAT technology. Pollutants regulated under PSES and PSNS are
copper, nickel, and selenium.
Using the summary data presented in Table 13-6, the Agency has
estimated the percent removal for copper and nickel by comparing
the untreated waste concentrations for those two toxic metals
with the treated waste concentrations for the selected BAT
technology for those same two pollutants. The untreated waste
274
-------
concentrations presented in Table 13-6 are an average of the
concentrations found for copper sulfate during Phase I and for
those copper salts plants sampled in Phase II. This is a
reasonable approach since many plants make copper sulfate and
other copper salts and combine the wastewater streams for
treatment. The calculation of the percent removals for copper
and nickel is as follows:
Copper;
Raw Waste
BAT
1175
0.89
mg/1
mg/1
Percent Removal
Nickel:
Raw Waste
BAT
PercentRemoval
[(1175 -
99.9%
51.2 mg/1
1.8 mg/1
[(51.2 - 1.8)
96.5%
0.89) t (1175)] (100)
t (51.2)] (100)
The percent removals are greater than the removals achieved for
copper (58%) and nickel (19%) by 25% of the POTWs in the "40
Cities" study (Fate of Priority Pollutants in Publicly Owned
Treatment Works,, Final Report, EPA 440/1-82/303, September,
1982). Therefore, since the BAT technology achieves a greater
percent removal of copper and nickel than is achieved by a
well-operated POTW with secondary treatment, those two toxic
metals would pass through a POTW in the absence of pretreatment .
Selenium has also been selected for regulation under PSES for the
reasons previously given for its selection for regulation under
Existing Sources
There are currently five indirect discharging copper salts plants
in the subcategory. There is also one indirect discharge copper
sulfate plant. For Pretreatment Standards for Existing Sources
(PSES), the Agency is proposing limitations based on BAT
described above. The pollutants to be limited are copper,
nickel, and selenium as presented in Table 13-8 and 13-9.
New Sources
For Pretreatment Standards for New Sources (PSNS), the Agency is
setting limitations based on NSPS. Since NSPS is equal to BAT
Tables 13-8 and. 13-9 summarize the limitations for the toxic
pollutants copper, nickel, and selenium.
275
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SECTION 13
REFERENCES
U.S. Environmental Protection Agency, "Development Document
for Effluent Limitations Guidelines and Standards for the
Inorganic Chemicals Manufacturing Point Source Category,"
EPA Report No. 440/1-79-007, June 1980.
JRB Associates, Inc., "An Assessment of pH Control of
Process Waters in Selected Plants," Draft Report to the
Office of Water Programs, U.S. Environmental Protection
Agency, 1979.
276
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SECTION 14
NICKEL SALTS INDUSTRY
INDUSTRY PROFILE
General Description
The nickel salts covered under this subcategory are nickel
sulfate, nickel carbonate, nickel chloride, nickel nitrate, and
nickel fluoborate. A process description and discussion of the
nickel sulfate industry can be found in the Phase I Development
Document: Development Document for Effluent Limitations
Guidelines and Standards for the Inorganic Chemicals
Manufacturing Point Source Category, EPA 440/1-82/007, June,
1982. —
Briefly, nickel sulfate is produced by reaction of nickel, nickel
oxide or waste nickel (such as spent plating bath) with sulfuric
acid:
Ni, + H2S04 » NiS04 + H2
The nickel sulfate may be sold in solution as produced, or may be
purified and crystallized before sale as the solid. Detailed
process information and the results of screening and verification
sampling are provided in the Phase I Development Document.
Therefore, the following discussion will cover the other nickel
salts covered in this subcategory.
These salts, produced for both captive use and merchant markets,
are primarily used in electroplating and catalysts. The chloride
salt is most widely used in electroplating, while the carbonate
and fluoborate salts are used to a lesser extent. Nickel
carbonate is produced from other nickel salts, particularly from
nickel sulfate. Upon reduction with hydrogen, nickel carbonate
yields a finely divided nickel with good catalytic activity.
Nickel nitrate is used in nickel plating, preparation of nickel
catalysts, and in manufacture of brown ceramic colors. Tables
l(a) and l(b) are profile data summaries for the nickel salts
subcategory.
There are 12 known facilities manufacturing nickel salts. Two
plants have no process wastewater discharge, while six plants
discharge directly and four discharge indirectly.
Total annual production of nickel salts is estimated to be in
excess of 5,000 metric tons per year and total daily flow is
277
-------
TABLE 14-1. SUBCATEGORY PROFILE DATA FOR NICKEL SALTS
(a) NICKEL SALTS EXCLUSIVE OF NICKEL SULFATE
Number of Plants in Subcategory
Total Subcategory Production Rate
Minimum (3 plants)
Maximum
12
>5000 kkg/yr
<4.5 kkg/yr
1550 kkg/yr
Total Subcategory Wastewater Discharge
Minimum
Maximum
600 m /day
0
195 m3/day
Types of Wastewater Discharge
Direct
Indirect
Zero
6
4
2
278
-------
TABLE 14-1.
(b)
SUBCATEGORY PROFILE DATA SUMMARY FOR NICKEL SALTS
NICKEL SULFATE^
Total Subcategory Capacity
Total Subcategory Production
Number of Plants in this Subcategory
308 Data on File for
With total capacity of
With total production of
Representing capacity
Representing production
Plant production range:
Minimum
Maximum
Average production
Medium production
Average capacity utilization
Plant age range:
Minimum
Maximum
Waste water flow range
Minimum
Maximum
Volume per unit product:
Minimum
Maximum
Indeterminant
6,350 kkg/year
11
6
17,700 kkg/year
12,650 kkg/year
NA
NA
NA
45 kkg/year
5,900 kkg/year
2,100 kkg/year
1,600 kkg/year
71.5
3
48
1.5 cubic meters/day
17.0 cubic meters/day
0.42 cubic meters/kkg
0.72 cubic meters/kkg
(1) Source: page 674 of Draft Development Document for Effluent
Limitations Guidelines and Standards for the Inorganic Chemicals
Manufacturing Point Source Category, EPA 440/1-82/007; June 1982
(2) "Economic Analysis of Proposed Revised Effluent Guidelines and
Standards for the Inorganic Chemicals Industry," March, 1980.
(3)
Sources of data are Stanford Research Institute, Directory of
Chemical Producers, U.S.A., 1977.
NA Not Available
279
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estimated at greater than 600 cubic meters per day for all plants
combined Based upon available data, it is estimated that over
90 percent of the wastewater flow in the category is generated
from nickel carbonate production alone.
General Process Descriptions and Raw Materials
Nickel carbonate is produced by reacting any of several nickel
salts with sodium carbonate (soda ash). The general reaction is:
NiSO4 + Na2C03 = NiC03 + Na2S04
Two different types of raw materials may be used to produce
•nickel carbonate: pure nickel salts or impure materials such as
spent"plating solutions. When pure salts are used, the resultant
nickel carbonate precipitate is filtered, dried, ground and
packaged. When impure sources of nickel are used as raw
materials, additional rinsing of the precipitate is necessary to
remove impurities. Figure 14-1 presents a general process flow
diagram for the manufacture of nickel carbonate.
Other nickel salts, nickel chloride, nickel nitrate, and nickel
fluoborate, are produced by reaction of pure nickel or nickel
oxides -With hydrochloric acid, nitric acid, or fluoboric acid.
The general reactions for nickel oxide are:
NiO
NiO
2HC1 = NiClj
H,0
2HN03 = Ni(N03)2 + H20
NiO + 2HBF4 = Ni(BF4)2 + H20
The resulting solutions are filtered to remove impurities,
crystallized and centrifuged. The pure crystals are then dried,
ground and packaged. The products may also be sold as
concentrated solutions. Figure 14-2 presents a general P^cess
diagram for the manufacture of nickel chloride, nickel nitrate
and nickel fluoborate.
WATER USE AND WASTEWATER SOURCES
Water Use
Noncontact cooling water used in the reactors and crystallizers
constitutes one of the major water uses in the production of
nickel salts. Water is also used in direct process contact as a
reaction component and for washing precipitated products. A
portion of the reaction water occurs in the product concentrate
or in the dry product as its water of hydration, but much of it
282
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is evaporated to the atmosphere. Small amounts of water are used
for maintenance purposes, and several plants use water in
scrubbers for dust or fume control. Table 14-2 presents a
summary of available plant data on water use.
Wastewater Sources
Noncontact Cooling Water
Noncontact cooling is one of the major sources of discharged
water. This stream is usually not contaminated and is not
treated before discharge.
Direct Process Contact
Plants which use impure nickel raw materials generate filter
sludges or wash wastes which must be treated before discharge.
Filter sludges and decants from processes using pure raw
materials are often recycled back to the process. In nickel
carbonate production, direct contact process wastewater from
washing impurities from the nickel carbonate is the major source
of process wastewater.
Maintenance
Equipment and area cleaning wastes, and indirect contact
wastewater such as spills and sump leaks are periodic streams
that account for a small amount of wastewater generated by the
production of nickel salts. For most nickel salts, including
nickel sulfate but not including nickel carbonate, this is the
major source-of process wastewater.
Air Pollution Control
Wet scrubbers are frequently used to control the discharge of
fumes from reaction tanks and evaporators or concentrators.
Slowdown from these' scrubbers may be intermittent or continuous.
The available data concerning wastewater flows at nickel salts
facilities is summarized in Table 14-3. It is observed that the
nickel carbonate processes produce substantially more process
wastewater than do other nickel salts processes. This difference
is attributable to the greater quantities of wash water required
for removal of product impurities in the nickel carbonate
production process.
DESCRIPTIONS OF PLANTS VISITED AND SAMPLED
285
-------
Six plants producing nickel salts were visited during this study.
In addition, wastewater sampling was conducted at three of these
plants. This section presents summary descriptions of facilities
visited and sampled during this program.
Plants Sampled
Plant F113 produces nickel carbonate, nickel chloride, nickel
nitrate and other inorganic salts. During the sampling visit,
only the nickel carbonate process was operating. Nickel
carbonate is produced on a batch basis by reacting a spent
plating solution with soda ash. After reaction, the precipitate
is rinsed to remove impurities, then dried and packaged. The
decanted rinse water passes through two filter presses. The
filter cake is recovered and returned to the process and the
filtrate is discharged. Other sources of wastewater include
washdown, pump seal leaks, and spills. All wastewater from this
plant is discharged to a POTW without pretreatment. Figure 14-3
is a diagram of the process showing sampling points. Table 14-4
presents data on the major pollutant concentrations and loads for
the sampled streams.
Plant F117 produces nickel carbonate, nickel chloride, nickel
nitrate, nickel fluoborate, and a variety of other metal salts.
During the plant visit, only the nickel carbonate process was
sampled. Nickel carbonate is produced by reacting nickel sulfate^
with soda ash. The resultant slurry is passed through a vacuum
filter. The filter cake is washed with water to remove
impurities, then dried, milled and packaged. The washwater is
treated in a nickel recovery system which uses caustic addition
to pH 10, sand filtration, with final pH adjustment with sulfuric
acid addition before discharge to surface waters. Solids
captured in the sand filter are subjected to filter press
filtration for nickel recovery. Fluoride-containing wastewater
from nickel fluoborate production, when it occurs, is combined
with other process wastewater for treatment by lime
neutralization, flocculant addition, clarification, and final pH
adjustment. Figure 14-4 is a diagram of the process and
treatment system showing sampling points. Table 14-4 presents
data on the major pollutant concentrations and loads for the
sampled streams.
Plant F107 produces nickel carbonate, nickel nitrate and several
other inorganic salts. Both nickel carbonate and nickel nitrate
processes were operating during the sampling visit. Nickel
carbonate is produced by a proprietary batch process. Washdown
wastes, spills and filter backwash from this process are
collected in a trench with other process wastewaters and are
discharged to a POTW without treatment. Nickel nitrate is
286
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s ss a 1" ®fc
I 5s " -1
85 r! o 2 2OT
CO
289
-------
produced at this plant by a process similar to that described
previously. Figure 14-5 is a diagram of the two processes
showing sampling points. Table 14-4 presents data on the major
pollutant concentrations and loads for the sampled streams.
Other Plants Visited
Plant F145 produces nickel carbonate, nickel chloride, and nickel
nitrate salts in addition to many other chemicals. Manufacturing
processes for the nickel salts are similar to those previously
described. Scrubber wastes, washings, filtrates, tank cleanouts,
and leaks or spills which cannot be recycled are sent to a
central treatment system where all plant wastewaters are treated.
Treatment consists of equalization, lime precipitation,
clarification and sludge dewatering. Overflow from this system
is then treated by biological treatment prior to discharge.
Plant F119 produces nickel carbonate and nickel nitrate in
addition to numerous other inorganic salts. Processes for the
nickel salts are similar to those previously described. Off-
gases from the nitrate production are exhausted through a
condenser to recover nitric aci'd, and the gases are then
incinerated to destroy nitrogen oxides before release to the
atmosphere. Process wastewaters from all products manufactured
are directed to a central treatment system consisting of pH
adjustment, settling, flocculation, clarification, and sludge
dewatering. The clarifier overflow is discharged to a POTW.
Plant F118 produces nickel carbonate and nickel chloride in
addition to many other inorganic compounds. Wastewater streams
from all chemical processes are combined and passed, through a
treatment system consisting of equalization, alkaline
precipitation, clarification and final pH adjustment before
discharge.
Plants F113, F117, F145, and F118 also produce nickel sulfate.
The nickel sulfate process wastewaters are combined with other
nickel process wastewaters for treatment and discharge.
Summary of_ Toxic Pollutant Data
Nine toxic metals were found at detectable concentrations in the
total raw wastewater at the three sampled plants. The table
below presents the maximum daily concentrations observed for
these pollutants found in the total process raw wastewater:
290
-------
Q
W
W
K
CQ
a
%*
o!
.
Is
j
s
f
•V
tH
H
n
3
o
.0
CO
•H
z
CO
to
Stream
Description
g
n •
0) O
*j z
CO
l>
H 1
0 1
• |
O
•^
1 s
Z 0 t
Z. . |
0 1
PI
•H
to
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c *^
ig o J
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• 1
H |
Supply Water
•
H
CM
f 1
0 1
0
o
0 1
. f
H 1
f)
0 1
t~ 1
O 1
* 1
0 1
Rinse Decant
,
CM
in
en H in H
HO CMO
o o o o
o o o o
in
PI p-
ov t^v
voo vo o
oo o o
vo
r» i1 oo
PI O VO H
_^
0 0
oo en PI in
• • • •
a
Ni Nitrate Wastew
CM
VO 1
CM |
• 1
O
V 1
in i
o
V
1
O 1
vo
** (
,
0 1
r-
PI
u
01
a
S
Ni Carbonate Wast
PI
.
c
o
•4-4
ufficient informa
to
c
M
1
1
1
XI
Q.
0)
o
X
01
to
a
•o
«
0)
u
n)
CO
01
3
(0
C
o
w and concentratil
re noted.
-day sampling.
O 01 O
H .C S
En S E-I
_ __
H N
•-^ ^^
291
-------
Pollutant
Antimony
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Thallium
Zinc
Maximum Concentration
Observed (uq/1)
1,545
1 ,513
170
877
170
1,513,000
82
300
698
Section 5 of this report describes the methodology of the
sampling program. In the Nickel Salts Subcategory, a total of
nine days of sampling were conducted at these plants. Seven
different process wastewater streams were sampled and analyzed.
The evaluation of toxic pollutants in these streams was based on
260 data points for toxic metals and 791 data points for toxic
organics. In Table 14-5, toxic pollutant raw waste data are
presented as average daily concentrations and loads for the three
sampled plants.
POLLUTION ABATEMENT OPTIONS
Toxic Pollutants of Concern
The toxic pollutants of concern in the Nickel Salts Subcategory
are nickel and copper. Other toxic metals found in significant
concentrations in process wastewaters are related to the purity
of the raw materials used. Antimony and thallium occurred in
process wastewater at concentrations greater than 100 ug/1 from
two of the sampled plants, while cadmium and zinc were found at
significant concentrations at only one plant. No toxic organics
were found, in significant concentrations. Nickel, copper,
antimony, cadmium, and zinc were also found in untreated process
wastewater during the Phase I screening and verification sampling
at three nickel sulfate plants.
When impure raw materials are used, toxic metal impurities will
be removed in the purification process through filtration or
washing of the product. These pollutants can then occur in
wastewater or solid wastes. Using pure raw materials, which are
not always available or economical, however, can often allow
recycle of the process water.
Existing Wastewater Control and Treatment Practices
292
-------
TABLE 14-5,
TOXIC POLLUTANT RAW WASTE DATA FOR SAMPLED
NICKEL SALTS FACILITIES
Average Daily Pollutant Concentrations and Loads
rog/1
Pollutant
Antimony
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Thallium
Zinc
F113
0.673
0.0477
<0.010
<0.0007
0.073
0.0052
0.025
0.00177
0.007
0.0005
16.6
1.18
0.029
0.0021
0 . 118
0.00837
0.037
0.00262
kg/kkg
Plant
F117
0.057
0.014
0.013
0.0033
0.025
0.0063
0.024
0.0061
0.060
0,0152
41.0
10.4
0.008
0.002
0.217
0.0549
0.023
0.0058
Designati
F107d)
<0.531
<0.850
0.047
0.460
<0.003
540.3
<0.001
<0.003
0.387
on
Overall
Average
<0.420
0.0309
<0.291
<0.002
0.048
0.00575
0.170
0.00394
<0.023
0.00785
199.3
5.79
<0.013
0.0021
<0 113
0.0316
0.149
0.00421
Insufficient information.
(1) Flow-proportioned averages from two nickel product
wastewater streams.
293
-------
producing nickel salts.
prior to discharge.
Plant
produces nickel chloride and nickel fluoborate in
^^
technology.
Pl»t
to discharge.
prior to discharge.
there is no discharge.
nickel fluoborate in small quantities along
fluoborate and therefore there is no discharge.
other Applicable Control and Treatment Technologies
effluent for further solids and metals removal.
Process Modifications and Technology Transfer Options
294
-------
y
C°ntaCt »«tew.ter generated
°f
1 '
2.
S!S^iing alJ direct Process contact wastewater or use
possible; ^ aS make"UP f°r Pr°duct solutions, wherl
Minimizing product changes by careful oroduct
scheduling and by increasing the number of realtors
This can result in reducing the volume of wlshdown
water required by minimizing product changeover
JK39^^ pe£°9ative sV3ect to customer demand? ConseqCIntfy
Best Management Practices
trea^e"t of scrubber wastewater from
recycle, where technically
odi-nn
production
cta
Ieaa9e' spillage of raw materials or
295
-------
All other contact wastewater including leaks, spills, and
washdowns should be contained and treated.
treatment.
Plant F117 which produces a variety of inorganic chemicals
(including all four Phase II nickel salts), practices segregation
anS commingling of various wastewater Breams depending upon
rhemical characteristics. Some wastewater, particularly tnat
orfg noting from nickel carbonate and nickel sulfate Potion,
is combined and treated in the same wastewater treatment facility
sludges.
Advanced Technology
For facilities using impure raw materials such as Plating
solutions, etc., significant concentrations of « variety °| toxic
metals may be present in wastewater, .particularly in dissolved
form Careful control of pH to reduce the solubility of the
metais followed by clarification and filtration may be necessary
for optimum treatment.
Selection of. Appropriate Technology and Equipment
Technologies for Different Treatment Levels
A. Level 1
Level 1 treatment consists of alkaline precipitation,
?J the event of treatment system shutdown. The treatment
technology is illustrated in Figure 10-10.
The initial treatment step is the addition of caustic soda This
is followed by clarification/settling (if the wastewater
characteristics are suitable, a tube settler may be substituted
296
-------
for a clarifier to conserve space). Sludge is removed from the
clarifier and directed to a filter press for dewatering. Pits
are provided at the filter press for the temporary storage of
•sludge. The sludge is periodically transported to a hazardous
material landfill. Filter press filtrate is returned to the head
of the treatment system.
The pH of the treated wastewater stream is adjusted to an
acceptable level by acid addition prior to discharge if
necessary. A monitoring system is installed at the discharge
point. The objective of Level 1 technology is to remove heavy
metals and suspended solids.
B.
Level 2
Level 2 treatment consists of granular media filtration for
further removal .of metal hydroxide precipitates and other solids
from the wastewater. This technology is portrayed in Figure 10-
11. In practice, when Level 2 technology is added to Level 1,
final pH adjustment would occur after filtration not prior to it.
The objective of Level 2 treatment technology in this subcategory
is to achieve, at a reasonable cost, more effective removal of
toxic metals than provided by Level 1. Filtration will both
increase treatment system solids removal and decrease the
variation in solids removal exhibited by typical clarifier
performance. Four facilities in this subcategory have Level 2 or
its equivalent, including four of the six direct dischargers.
Level 2 technology was the basis for the promulgated BPT, BCT,
and BAT effluent limitations and NSPS, PSES, and PSNS for the
nickel sulfate subcategory.
As discussed under "Process Modifications and Technology Transfer
Options" in this section, nickel carbonate wastewater may be
amenable to Level 2 treatment without first practicing Level 1
treatment. The benefits to this approach would include increased
recovery of nickel carbonate product and a reduction in treatment
costs.
Equipment for Different Treatment Levels
A. Equipment Functions
Conventional sludge dewatering by a filter press is used for
sludge generated by the clarification/settling system. In some
cases, the sludge may be amenable to nickel recovery, however,
off-site disposal in a hazardous material landfill is generally
assumed. If a tube settler is used instead of a clarifier,
backwash from the settler is returned to the influent holding
basin. Solids resulting from Level 2 filter backwash would be
297
-------
handled as discussed in item C (Solids Handling) below. All
equipment is conventional and readily available.
B. Chemical Handling
Caustic soda (50 percent NaOH) is used to precipitate heavy
metals in Level 1. At all levels of treatment, sulfuric acid
(concentrated) may be used to reduce the pH of the wastewater
prior to discharge.
C. Solids Handling
Treatment sludges generated by Level 1 are dewatered in a filter
press. The solids may be disposed of off-site in a hazardous
material landfill or processed for nickel recovery. Level 2
filter backwash may be sent to the head of the plant or, if the
solids concentration is sufficiently high, may be sent directly
to the filter press.
Treatment Cost Estimates
Based upon Nickel Salt Subcategory profile characteristics, two
model plants were selected for costing of Level 1 and Level 2
treatment systems. The overall ranges of production and
wastewater flow have been discussed earlier in this section and
summarized in Table 14-1. Since nickel carbonate production
accounts for a large portion (>90 percent) of the process
wastewater generated in the subcategory, one set of model plant
wastewater flow characteristics are based upon flow attributable
to this product, and a second model plant has been established
for the other nickel salts.
Flow data for nickel salts producers is presented in Table 14-3.
The flow for nickel salts plants exclusive of nickel carbonate is
very close to the flow from nickel sulfate plants (See the Phase
I Development Document). The pollutants are the same, and are at
similar levels. - Therefore, the Agency has combined the nickel
salts subcategory with the nickel sulfate subcategory.
The model plant for all nickel salts exclusive of nickel
carbonate has an annual production of 429 metric tons (the
average of the plants reporting production in Phase II) and a
daily wastewater flow of 1.67 cubic meters calculated from the
daily production and the unit flow of 0.68 mVkkg (as found at
nickel sulfate plants) with an operating schedule of 175 days per
year. These characteristics were used as the basis for treatment
cost estimates at all levels.
298
-------
TABLE 14-6. WATER EFFLUENT TREATMENT COSTS AND RESULTING
WASTE-LOAD CHARACTERISTICS FOR MODEL PLANT
SUBCATEGORY: Nickel Salts Subgroup
ANNUAL PRODUCTION:
DAILY FLOW:
PLANT AGE:
429
METRIC TONS
1.67
NA
______ CUBIC METERS
YEARS PLANT LOCATION:
NA
a. COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS
COST CATEGORY
Facilities
Installed Equipment
(Including Instrumentation)
Engineering
Contractor Overhead and Profit
Contingency
Land
Total Invested Capital
Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Waste Disposal) 7.4
Residual Waste Disposal
COSTS ($1,000) TO ATTAIN LEVEL
12345
1.1
12.2
2.7
2.4
1.8
20.2
3.3
7.4
0.5
0.4
0.1
0.1
0.1
0.7
0.1
0.2
Negl
Total Annual Cost
b,,
11.2
0.3
RESULTING WASTE-LOAD CHARACTERISTICS
• ' Long-Term Avg.,
Avg. Cone. Concentration (mg/1)
ft\ After Treatment To Level
Parameter Untreated (mg/1) ^ J l_ _2_ _3_ _4_ _5_
6-9 6-9
.* 39.2
2.4 0.3
0.62 0.3
PH
TSS
Cu
Ni
4.0
148.7
27
343
c. TREATMENT DESCRIPTION
LEVEL 1: Alkaline precipitation, clarification, pH adjustment
LEVEL 2:- Filtration
*No data available for TSS in this subcategory with Level 1 technology.
(1) Untreated wastewater characteristics are average of Phase I
nickel sulfate and Phase II nickel salts plants.
299
-------
TABLE 14-7 WATER EFFLUENT TREATMENT COSTS AND RESULTING
WASTE-LOAD CHARACTERISTICS FOR MODEL PLANT
SUBCATEGORY: Nickel Carbonate Subgroup
ANNUAL PRODUCTION:
DAILY FLOW:
PLANT AGE: .
. 142
METRIC TONS
94.8
NA
CUBIC METERS
YEARS PLANT LOCATION:
NA
a. COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS
COST CATEGORY
Facilities
Installed Equipment
(Including Instrumentation)
Engineering
Contractor Overhead and Profit
Contingency
Land
Total Invested Capital
COSTS ($1,000) TO ATTAIN LEVEL
12345
11.7
122.9
26.9
24.2
18.6
22.5
4.5
4.1
3.1
204.3 34.2
33.2
Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Waste Disposal) 56.8
Residual Waste Disposal 0.3
5.6
7.5
Negl.
Total Annual Cost 90.3 13.1
b. RESULTING WASTE-LOAD CHARACTERISTICS
Avg. Cone.
Parameter Untreated (mg/1) __L.
Long-Term Avg.
Concentration (mg/1)
After Treatment To Level
-4- -^-
pH
TSS
Cu
Ni
4.0
148.7
27
343
6-9
*
6-9
39.2
2.4 0.3
0.62 0.3
c.
TREATMENT DESCRIPTION
LEVEL 1: Alkaline precipitation, clarification, sludge dewatering,
pH adjustment
LEVEL 2: Filtration
*No data available for TSS in this subcategory with Level 1 technology.
300
-------
For the nickel carbonate industry, the average production rate
and operating days for the plants reporting these data are used
for the model plant. Therefore, the model plant has an annual
production of 142 metric tons and a daily wastewater flow of 94.8
cubic meters. The unit flow is 120 mVkkg with an operating
schedule of 179 days per year. These characteristics were used
as the basis for treatment costs at all levels. The unit flow is
the average (to two significant figures) of Plants F113 and F117.
Plant F107 was not included because nickel carbonate is produced
for captive used and the additional cleaning water use at F113
and F117 is not done at Plant F107. Plant F145 was not used
because the plant uses pure raw materials to produce a reagent
grade product, and it also does not have the additional cleaning
steps necessary at the average plant.
Estimates of material usages for both treatment
nickel salts segment are listed below:
Chemical
NaOH (50 percent sol.)
H2S04 (100 percent)
Amount
2.34 kg/day
0.17 kg/day
levels for the
Level
Level 1
Level 1
Estimates of solid waste generated for all treatment
levels for the nickel salts segment are provided below;
Waste Source
Level 1 sludge
Level 2 sludge
Amount
0.012 mVday
0.001 mVday
Estimates of material usage for all three treatment levels in the
nickel carbonate segment are listed below:
Chemical
NaOH (50 percent sol.)
H2S04 (100 percent)
Amount
53.0 kg/day
9.8 kg/day
Estimates of solid waste generated for all treatment levels are
provided below:
Waste Source
Level 1 sludge
Level 2 sludge
Amount
0.019 mVday
0.0019 mVday
301
-------
Model Plant Treatment Costs
rs 'ass -ss
incremental to Level 1 .
Basis for Regulations
Basis for BPT Limitations
A. Technology Basis
the Aaencv is setting
ss sre
-s
based upon alkaline
e
r rtssti ib-
p?lmul,a?ed eflfuen? limitations guidelines and standards for the
nickel sulfate subcategory.
B. Flow Basis
representaive of the group. This flow rate was derived as
described above under model plant treatment costs.
the nickel carbonate segment of the Nickel Salts Subcategory,
^^
model plant treatment costs.
C. Selection of Pollutants to be Regulated
The selection of pollutants for which specific e"l"ent
limitations are being established is based on an evaluation of
I
discharge permit applications, and the treatability of the toxic
pollutants.
Tables 8-1 through 8-14 summarize the achievable concentrations
of toxic metal pollutants from the literature using available
technology options, information from other industries, and
302
-------
treatability studies. Water use and discharge data are presented
earlier in this section together with generalized process
characteristics. Pollutant concentrations of raw wastewater
streams and a summary of maximum concentrations observed of toxic
pollutants detected during sampling at several plants are also
presented earlier in this section. Data from Appendix A on the
performance of in-place industry treatment systems were also
utilized in developing the list of pollutants to be regulated.
The following parameters were selected initially as candidate
toxic pollutants for BPT regulations: cadmium, copper, chromium,
nickel, and zinc. These pollutants were observed at least once
during screening and verification sampling at concentrations
considered treatable in raw wastewater. However all of the
toxics except for nickel were observed at relatively low
concentrations in nickel carbonate wastewater. One facility,
which was sampled for nickel nitrate wastewater, accounted for
numerous observations of significant concentrations of cadmium,
copper, chromium and zinc. Nickel concentrations were found at
treatable levels at all facilities sampled. A number of other
priority pollutant metals were detected during sampling, however,
concentrations were generally less than 0.3 mg/1.
Consideration of the raw wastewater concentrations presented
earlier in this section, wastewater information obtained from
industry in both Phase I and Phase II, and information presented
in Section 8 related to the effectiveness of hydroxide
precipitation, clarification, and filtration in reducing the
amounts of all toxic metals discharged suggested a reduction in
the number of parameters to be regulated. Copper and nickel were
finally selected as the toxic pollutants to be regulated.
Cadmium, chromium, and zinc may occur in some cases at nickel
salts facilities (probably associated with some raw material
use). However, their occurrence does not appear to be consistent
enough to warrant adoption as control parameters for the whole
subcategory. In addition, the technology necessary to control
copper and nickel will also result in the control of other toxic
metals.
D. Basis of BPT Pollutant Limitations
Limitations are presented as both concentrations (mg/1) and loads
(kg/kkg), and the relationship between the two is based on the
unit flow rates of 0.68 m* for nickel salts and 120 mVkkg for
nickel carbonate. BPT limitations which apply to all process
wasteswater discharged, are presented in Tables 14-8 and 14-9..
1. Conventional Pollutants
303
-------
a. pH
The treated effluent is to be controlled within
the range of 6.0 - 9.0. This limitation is based
upon the data presented in Appendix B of the
Development Document for Proposed Effluent
Guidelines for Phase I Inorganic Chemicals and the
JRB study.
b. TSS
The BPT limitations for TSS are based upon the BPT
limitations promulgated in Phase I for nickel
sulfate manufacture. The long-term average of
39.2 mg/1 was used to develop discharge
limitations. Variability factors of 1.2 for a
monthly average and 3.6 for a 24-hour maximum were
used yielding TSS concentration limitations of 47
mg/1 and 141 mg/1 respectively. Thus, utilizing
these values, one obtains TSS mass limitations for
the Nickel Salts Subcategory of:
t
1. Nickel Salts Segment
30-day average;
(47 mg/1) (0.68 mmVkkg) (kg/10* mg)(1000 l/m')
= 0.032 kg/kkg
24-hour maximum;
(141 mg/1) (0.68 mVkkg) (kg/1 0« mg)(1000 l/m*)
= 0.096 kg/kkg
2. Nickel Carbonate Segment
30-day average
(47 mg/1) (120 mVkkg)(kg/10«)(1000 1/m')
=5.6 kg/kkg
24-hour maximum
(141 mg/1) (120 mVkkgHkg/10* mg)(1000 1/m')
- 17 kg/kkg
2. Toxic Pollutants
a. Nickel
304
-------
TABLE 14-8. BPT EFFLUENT LIMITATIONS FOR NICKEL SALTS
Conventional
Pollutants
Long-Term
Avg.(mg/l)
CD
VFR
Cone. Basis
(mg/1
-d
Effluent Limit
__ (kg/kkg)
30-day 24-hr. 30-day 24-hr.
avg. max. avg. max.
TSS
Toxic
Pollutants
Nickel
39.2
2.5
1.2/3.6
1.2/3.6
47
3.0
141
0.032 0.096
9.0 0.002 0.006
VFR - Variability Factor Ratio
(1) Based upon limitations promulgated for the nickel sulfate sub-
category in Phase I.
305
-------
TABLE 14-9. BPT EFFLUENT LIMITATIONS FOR NICKEL CARBONATE
Coventional Long-Term
Pollutants Avg"Cmg/lJ
CD
VFR
Cone. Basis' Effluent Limit
(mg/1) Ckg/kkg)
30-day 24-hr.,30-day 24-hr.
avg. max. avg. max.
TSS
Toxic
Pollutants
Nickel
39.2
2.5
1.2/3.6
1.2/3.6
47
3.0
141 5.6
17
9.0 0.36 1.1
VFR - Variability Factor Ratio
(1) Based upon limitations promulgated for the nickel sulfate sub-
category in Phase I.
306
-------
n™ B?T limitations for nickel are based on the
S,,i>»ilinitation? Promul9ated in Phase I for nickel
sulfate manufacture. Concentration limitations of
3 0 mg/1 (on a monthly basis) and 9.0 mg/1 (on a
daily basis) were obtained by use of the
^fi1^ 5a^°rs of 1-2 for a monthly averagl
and 3.6 for daily maximum computations. Utilizing
InlS sub™?5' maSS iimitati°ns for the NickSl
Salts Subcategory may be obtained as follows:
1 • Nickel Salts Segment
30-day averae;
mgMlOOO
mg)(1000
x
Kg/Rkg
24-hour maximumi
2- Nickel Carbonate Segment
30-dav averae
nig) (1000
24-hour maximum
(9.0 mg/1) (120 m.3/kkg)(kg/lO« mg)(lOOO l/m»)
= i.i Kg/Kkg
Basis for BCT Effluent Limitations
S ilnST.rgEr&SSflSS' ITSSE 'S&SSss;
5s^«ti?-jnrttfjr1sftss!Bs'^sp
Basis for BAT Effluent Limitations
Application of Advanced Level Treatment
=1
307
-------
as
significant additional amounts of pollutants. Toxic pollutants
limited by the proposed BAT regulation are copper and nickel.
A. Technology Basis
Granular media filtration (Level 2) added to Level 1 has been
selected as the basis of BAT (same as BPT).
B. Flow Basis
Unit wastewater flow rates of 0.68 mVkkg of nickelnf?ltfca^
mVkkg for nickel carbonate has been selected for BAT (same
for BPT).
C. Selection of Pollutants to be Regulated
Toxic Pollutants
The toxic pollutants copper and nickel have been selected for BAT
limitation. Tables 14-10 and 14-11 present the BAT limitations
for the Nickel Salts Subcategory.
D. Basis of Pollutant Limitations
As in BPT, the BAT limitations are presented as both
concentrations (mg/1) and loadings (kg/kkg). Loadings were
derived from the calculated concentrations using the model Plant
flow rates of 0.68 m'/kkg for nickel salts and 120 m3/kkg for
nickel carbonate.
The BPT effluent limitations for the nickel sulfate subcategory
were promulgated May 22, 1975 (40 FR 22402) .. These effluent
limitations were based on Level 2 technology, but there was
Sited data available to estimate the performance of the
technology. Since 1975, long-term treatment system performance
data from nickel sulfate manufacturing plants ( including one
plant manufacturing another Phase II nickel product and treating
the" combined nickel sulfate and Phase II nickel product Process
wastewater in the same Level 2 wastewater treatment system) and
the agency's treatability study (Treatability Studies for th|
Inorganic Chemicals Manufacturing Point Source Category, EPA
440/1-80/103, July 1980) shows that the Level 2 technology
performs much better than anticipated in 1975. The promulgated
BAT effluent limitations for nickel sulfate are based on this
better performance. Since the same technology is used at Phase
II nickel salts plants to treat nickel salts wastewaters
(including nickel sulfate wastewater in several cases , and since
the same pollutants are found at similar levels for nickel salts
products the BAT limitations for the nickel salts subcategory
308
-------
are based on the demonstrated achievable performance of the Level
2 technology.
Toxic Pollutants
a. Copper
The BAT limitations for copper are based on the BAT
limitations promulgated in Phase I for nickel sulfate.
The long-term average value for copper was 0.3 mg/1 and
variability factors used were 1.2 for a 30-day average
and 3.6 for a 24-hour maximum.
The concentration values that are derived 0.36 mg/1
(30-day average) and 1.1 mg/1 (24-hour maximum). Mass
limitations are computed as follows:
1.
Nickel Salts Segment
30-day average;
(0.36 mg/l)(0.68 m'/kkg)(kg/10* mg) (1000 1/m')
= 0.00024 kg/kkg
24-hour maximum;
(1.1 mg/l)(Q.68 n^/kkg) (kg/10* ing) (1000 1/m')
= 0.00074 kg/kkg
2. Nickel Carbonate Segment
30-day average
(0.36 mg/1) (120 mVkkg) (kb/1 0« mg)(1000 1/m*)
= 0.042 kg/kkg
24-hour maximum
(1.1 mg/1)(120 m3/kkg)(kg/10* ing) (1000 l/m»)
=0.13 kg/kkg
b. Nickel
The BAT limitations for nickel are based upon the BAT
limitations promulgated in Phase I for nickel sulfate.
The long-term average value for nickel was 0.3 mg/1 and
the variability factors used were 1.2 for a 30-day
309
-------
TABLE 14-10. BAT EFFLUENT LIMITATIONS FOR NICKEL SALTS
Cone. Basis
Qng/1)
Effluent Limit
.(kg/kkg)
Toxic
Pollutants
Copper
Nickel
Long- Term1 J
Avg. (mg/1)
0.3
0.3
1.
1.
VFRc
2/3.
2/3.
1)
6
6
30-day
avg.
0.36
0.36
24-hr.
max.
1.1
1.1
30-day
avg.
0.00024
0.00024
24-hr.
max.
0.00074
0.00074
VFR - Variability Factor Ratio
(1) Based upon limitations promulgated for the nickel sulfate sub-
category in Phase I.
310
-------
TABLE 14-11. BAT EFFLUENT LIMITATIONS FOR NICKEL CARBONATE
Toxic
Pollutants
Long-Term (1)
Avg .(ing/11
VFR
CD
Cone. Basis( ^ Effluent Limit
Ong/1) fkg/kkgl
60-day 24-hr.
avg. max.
30-dayZ4-hr
avg. max.
Copper
Nickel
0.3
0.3
1.2/3.6 0.36 1.1 0.042 0.13
1.2/3.6 0.36 1.1 0.042 0.13
VFR - Variability Factor Ratio
(1) Based upon limitations promulgated for the nickel sulfate sub-
category in Phase I.
311
-------
average and 3.6 for a 24-hour maximum. The
concentrations that are derived using these values are
0.36 mg/1 and 1.1 mg/1 respectively. Mass limitations
are computed as follows:
1. Nickel Salts Segment
30-day average:
(0.36 mg/l)(0.68 mVkkg) (kg/10« mg)(1000 1/m3)
= 0.00024 kg/kkg
24-hour maximum;
(1.1 mg/1)(0.68 m3/kkg)(kg/1 0* mg)(1000 1/m3)
~ 0.00074 kg/kkg
2. Nickel Carbonate Segment
30-day average
(0.36 mg/1) (120 mVkkg) (kg/1 0' ing) (1000 1/m3)
= 0.042 kg/kkg
24-hour maximum
(1.1 mg/1) (120 mVkkg) (kg/106 mg)(1000 1/m3)
* 0.13 kg/kkg
Basis for NSPS Effluent Limitations
For NSPS, the Agency is proposing limitations equal to BAT since
no additional technology which would remove significant
additional amounts of pollutants is known to the Administrator.
The pollutants limited include pH, TSS, copper and nickel, and
the limitations are presented in Tables 14-10 and 14-11.
Basis for Pretreatment Standards
The Agency is proposing PSES and PSNS that are equal to BAT
limitations because BAT provides better removal of copper and
nickel than is achieved by a well operated POTW with secondary
treatment installed and, therefore, these toxic pollutants would
pass through a POTW in the absence of pretreatment. Pollutants
regulated under PSES and PSNS are copper and nickel.
Using the summary data presented in Table 14-6, the Agency has
estimated the percent removals of copper and nickel by comparing
the untreated waste concentrations for those two toxic metals
312
-------
with the treated waste concentrations for the selected BAT
technology for those same two pollutants. The untreated waste
concentrations are the average of the raw waste concentrations
found for nickel sulfate in Phase I and the raw waste
concentrations found at nickel salts plants in Phase II. This
approach is reasonable because many plants produce nickel sulfate
and other nickel salts and treat the combined wastewaters from
those products in the same wastewater treatment system. The
calculation of the percent removals is as follows:
Copper;
Raw Waste =
BAT «
PercentRemoval
27 mg/1
0.3 mg/1
= [(27 -
= 98.8%
0.3) T (27)](100)
Nickel:
Raw Waste
BAT
PercentRemoval
343 mg/1
0.3 mg/1
[(343 - 0.3)
99.9%
? (343)] (100)
The percent removals are greater than the removals achieved for
copper (58%) and nickel (19%) by 25% of the POTWs in the "40
Cities" study, (Fate of Priority Pollutants in Publicly Owned
TReatment WOrks, Final Report, EPA 440/1-82/303, September,
1982). Therefore, since the BAT technology achieves a greather
percent removal of copper and nickel than is achieved by a well
operated POTW with secondary treatment, those two toxic metals
would pass through a POTW in the absence of pretreatment.
Existing Sources
There are currently four indirect dischargers in the nickel salts
subcategory. For Pretreatment Standards for Existing Sources
(PSES), the Agency is proposing limitations based on BAT
described above. The pollutants to be limited are copper and
nickel as presented in Tables 14-10 and 14-11.
New Sources
For Pretreatment Standards for New Sources (PSNS), the Agency is
setting limitations based on NSPS. Since NSPS is equal to BAT,
Tables 14-10 and 14-11 summarize the limitations for the toxic
pollutants copper and nickel.
313
-------
SECTION 14
REFERENCES
U.S. Environmental Protection Agency, "Development Document
for Effluent Limitations Guidelines and Standards for the
Inorganic Chemicals Manufacturing Point Source Category,"
EPA Report No. 440/1-79-007, June 1980.
JRB Associates, Inc., "An Assessment of pH Control of
Process Waters in Selected Plants," Draft Report to the
Office of Water Programs, U.S. Environmental Protection
Agency, 1979.
314
-------
SECTION 15
SODIUM CHLORATE INDUSTRY
INDUSTRIAL PROFILE
General Description
Most of the sodium chlorate produced (approximately 82 percent)
is marketed for use in the conversion to chlorine dioxide bleach
in the pulp and paper industry. Sodium chlorate is also used as
a chemical intermediate in the production of other chlorates and
of perchlorates (7 percent). Agricultural uses (4 percent) of
sodium chlorate are as an herbicide, as a defoliant for cotton
and as a dessicant in soybean harvesting. Sodium chlorate is
used to a lesser extent in the processing of ore (5 percent), the
preparation of certain dyes and the processing of textiles, furs
r fd d .manufacture of Pyrotechnics. Industry profile data are
Facilities producing sodium chlorate are usually located at the
same site as other facilities such as pulp mills, chlor- alkali
plants, and large chemical manufacturing complexes. None of the
other Phase II inorganic chemicals are produced at sodium
chlorate facilities. Seven of the 13 sodium chlorate plants are
facilities th€ Sam& SUe aS cnlor-alkali manufacturing
There are 13 known facilities producing sodium chlorate. Nine
facilities are direct dischargers while four facilities achieve
zero discharge of process water. There are no indirect
dischargers in this subcategory.
The total annual production of sodium chlorate is estimated to be
between 250^000 and 300,000 metric tons. In 1981 sodium chlorate
production was estimated to be about 274,000 metric tons by the
Bureau of the Census.
Total daily discharge from sodium chlorate production is
estimated at greater than 17,000 cubic meters (four facilities
achieve zero discharge).
General Process Description and Raw Materials
rhrH« /I5 .Pr?duced by the electrolysis of sodium
chloride solution (brine) in diaphragmless electrochemical cells.
in older plants, cells with graphite anodes are used while the
newer plants are using titanium anodes. Steel cathodes are used
315
-------
TABLE 15-1. SUBCATEGORY PROFILE DATA FOR
SODIUM CHLORATE
Number of Plants in Subcategory
Total Subcategory Production Rate
Minimum
Maximum
13
250,000-300,000 kkg/yr
2,300 kkg/yr
54,000 kkg/yr
Total Subcategory Wastewater Discharge >17,000 m3/day
Minimum 0 m3/day
Maximum 8,180 m3/day
Types of Wastewater Discharge
Direct
Indirect
Zero
9
0
4
316
-------
uniformly
follows:
across the industry. The overall reaction is as
NaCl + 3H20 = NaC103
The brine for the electrolysis may be obtained from natural
brines, or rock salt (NaCl) or pure salt may be dissolved in
water to produce a brine. The brine is then purified by using
sodium carbonate (Na2C03) and sodium hydroxide (NaOH) to
precipitate calcium carbonate and magnesium hydroxide (1). At
some facilities, barium chloride (BaCl2) is also added to remove
sulfate. The total concentration of calcium plus magnesium
should be less than 10 mg/1 to prevent fouling of the cathode
(1). The brine is filtered to remove the calcium and magnesium
precipitates prior to introduction into the cell (1). Sufficient
hydrochloric acid is added to maintain the pH of the cell liquor
at approximately 6.5. At a higher pH, oxygen evolution
increases. At a lower pH, chlorine evolution increases, and both
effects are undesirable (1). Noncontact cooling water is used to
maintain the temperature of the electrolytic cells between 55°C
and 90°C, depending upon the process technology used (1).
Sodium dichromate is added to the electrolytic cells to form a
layer of hydrated chromium oxide on the cathode to prevent the
following undesirable reactions (1):
CIO- + H20 + 2e~ = Cl- + 2 OH~
C103- + 3 H20 + 6e- = Cl- + 6 OH-
The dichromate also acts as a buffer to maintain the pH of the
cell at a near optimum value by the following equilibrium
reaction (1):
Cr207 — + H20 = 2 CrO«. —
2H+
The sodium dichromate also acts to reduce corrosion of steel
surfaces and inhibit the reduction of chlorate and hypochlorite
(1). The cell concentration of sodium dichromate ranges from 900
to 5,000 mg/1 and approximately 0.5 to 5 kg (1 to 10 Ib/ton) of
sodium dichromate are consumed per metric ton of product (1,2).
Sodium dichromate is added to the electrolytic cells regardless
of the type of anode used (graphite or titanium).
Hydrogen and chlorine gas are evolved in the manufacture of
sodium chlorate. The chlorine gas is often scrubbed with a
sodium hydroxide solution to remove hydrochloric acid and
chlorine gas ( 1 ) . The hydrogen gas is either vented or
recovered.
317
-------
318
-------
After electrolysis, the sodium chlorate liquor is fed into
dehypo tanks to destroy residual hypochlorite
(dehypochlonnation) (1). The hypochlorite is destroyed by a
combination of heat (live steam) and chemical reduction (sodium
formate, urea, or sodium sulfite). Barium chloride often is
added to precipitate the chromate as barium chromate (2) The
liquor is then filtered. The filtered liquor may be sold as is
or, if the customer prefers solid sodium chlorate, the filtered
liquor is concentrated in an evaporator for crystallization of
the product. Soda ash is added to control the pH of the liquor
in the evaporator. In the evaporator, the solution is
concentrated to precipitate sodium chloride. The vapors are
condensed and may become a source of wastewater dependinq uoon
the type of condenser used. The liquor is then filtered or
allowed to settle to remove sodium chloride from the product.
The sodium chloride is returned to the salt dissolver for reuse.
The liquor is cooled to produce sodium chlorate crystals in the
crystallizer. The crystals are centrifuged and dried to produce
solid sodium chlorate. The centrate is recycled to the
evaporator for reuse.
The product is either marketed as a solid or as a solution.
Figure 15-1 shows a general process flow diagram for the
manufacture of sodium chlorate.
WATER USE AND WASTEWATER SOURCE CHARACTERISTICS
Water Use
Noncontact cooling water is the single largest use of water in
the production of sodium chlorate. In addition, water is used in
direct process contact as a reaction medium with a portion going
into the dry product as its water of crystallization. Plants-
producing solution-grade sodium chlorate incorporate much of the
direct contact process water as the solution water in the product
shipped. Small amounts of water are used for maintenance
purposes, washdowns, cleanups,-filtration, backwashing, etc., and
the majority of plants use water in wet scrubbers. Water uses
tor plants producing sodium chlorate are summarized from industry
responses to the Agency's request for information under section
JUB o£ the Act and engineering visit reports in Table 15-2
Table 15-2(a) shows the relationships between type of raw
materials, type of product, water use, and discharge status for
,U™ «-• th? 13 •?1u?ts. in the ind"stry. (Little detailed
information is available for the other two plants, as one was
being rebuilt, and the other did not have data. Both plants are
associated with paper mills).
319
-------
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Wastewater Sources
Table 15-3 summarizes flow volumes from wastewater streams in the
sodium chlorate industry. Noncontact cooling water which is used
to maintain the temperature of the electrolytic cells is the main
source of wastewater. This stream is frequently comingled with
process wastewater and may or may not be treated prior to
discharge. One source of process water stems from P««f i^0"
of the brine fed to the electrolytic cells. Purification of this
brine is accomplished by the addition of caustic soda and soda
ash to precipitate metal impurities. This purification .Process
Ssults in wastewater produced with the sludge (precipitated
metal hydroxides). The purified brine is then electrolyzed in
the cells. The cell liquor from the electrolytic cells is
S* "JHf '.^2- £"*
remove HC1 and Cl« from cell off-gases. Other process wastewater
is generated from cell washdown, filter bag wash, leaks and
snills This liquor and the scrubber water may be recycled or
discharged Generally with neutralization and sedimentation as
thS oSly treatment. Barometric condenser water is a major source
of S?o?e£ wastewater at one plant. Table 15-3 (a) shows the
derivation of the model plant for the sodium chlorate
subcategory.
DESCRIPTION OF PLANTS VISITED AND SAMPLED
Six of the 13 plants which produce sodium chlorate were visited
during the study program. Of these, four plants were sampled for
toxic and conventional pollutants. All four Campled plants
(F122 F149 F146 and F112) produce sodium chlorate (NaC10?) by
the electrolysis of brine similar to the process shown in Figure
15-1 .
Plants Sampled
At Plant F122, rock salt is dissolved in recycled water from the
barometric condenser and river water to make up the brine for the
nrocess The brine is purified to remove calcium carbonate and
SlciSm' sulfate, passSd through a sand filter and then further
Seated to inhibit corrosion. The feed solution then undergoes
chlorination and electrolysis at the cells and the cell liquor is
322
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evaporated to produce sodium chlorate
product is sold as solid sodium chlorate.
crystals. Almost all
i« USS? as make-uP for the cooling water.
Slowdown from the cooling tower collects in the cooling water
supply sump and is discharged. The cooling water is treated with
a corrosion inhibitor. All of the barometric condensate in the
process area is recycled to the salt dissolving pit. Contact
wastewater from spills, washdown, roof and floor drains is
collected in the sumps. Part of this sump liquor is recycled and
the rest is discharged. Wastewater from the chlorate process in
S?nS!n? fc£at re^cled iS discharged to an on-site lagoon
Effluents from other product processes also flow into the laaoon
from where they are discharged to surface water. Figure 15-2
presents the sodium chlorate process and sampling points at Plant
3? I Purified brine obtained from another on-site
operation The brine undergoes further treatment and filtration
to remove impurities. Chlorine is added to the brine prior to
Jf JS !SJyS1S* f°£v, pHu 9ontro1 in the cell. Sodium dichromate is
also added to the brine. The cell liquor produced during
electrolysis is resaturated with sodium chloride, treated with
urea to remove hypoch lor it es, and filtered to produce a sodium
cniorate solution.
325
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The contact wastewater sources consist of a strong and weak
liquor. The strong liquor results from drainage from the cell
pad sump and is recycled internally to the brine purification
resaturator. The weak liquor consists of overflow from the brine
purification filter, and drainage from the overflow filtrate
receiver and clarified water, and is recycled to the brine pond.
Hence, most brine purification wastes are attributed to the other
on-site process, and little to sodium chlorate production at this
plant. Noncontact cooling water (treated for corrosion and pH
control) is recycled to a cooling tower, and tower blowdown may
be discharged either manually or automatically to a rainwater
sump. Plant effluent consists primarily of pump seal and tank
seal water but also contains the overflow from the strong and
weak liquor sumps, rainwater and blowdown from the cooling tower.
The effluent is discharged to another plant downstream from the
chlorate process and undergoes neutralization and sedimentation
before discharge into the river. Figure 15-4 presents the
wastewater sampling points and process steps at Plant F146.
Plant F112 obtains salt from an off-site source. A brine is
produced, treated with sodium carbonate and caustic, and filtered
before being fed to the electrolytic cells. The solution then
undergoes dehypochlorination and resaturation. The product
solution also undergoes final adjustment with water and brine
before being marketed either as solid sodium chlorate or as a
sodium chlorate solution. The filter residue from brine
purification is dried to 80-90 percent solids and disposed as
solid waste. There is no wastewater from the brine purification
process at this plant. The plant does not filter the product
solution and has no product filter backwash water.
Noncontact cooling water blowdown is the only wastewater stream
generated at the facility and is discharged to a river. The
cooling water is treated for corrosion control and also undergoes
chlorination with C12 gas and pH adjustment with HZS04 before
final discharge. All water from the process area sumps is
recycled to the salt feed tanks. Figure 15-5 shows the process
steps and sampling points at Plant F112.
Table 15-4 shows the wastewater stream flow and pollutant
concentrations for the four sampled plants.
Other Plants Visited
The production of sodium chlorate at Plant F103 begins with the
dissolution of rock salt in water and treatment of the resulting
brine to remove impurities. The solution is adjusted for pH and
electrolyzed. Caustic and urea are then added to reduce
hypochlorite concentrations, the pH is adjusted and the liquor
330
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ufficient information
w and concentration values
Id tests were conducted i
ept at F122 where laborato
-day sampling.
oratory testing for total
oratory testing indicated
icated the presence of chl
-day sampling.
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332
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filtered. The filtrate is evaporated and the hot solution
primarily of noncontact cooling
"o r • f-s- »-da2rat p^srf
the
Summary of Toxic Pollutant Data
333
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TABLE 15-5. TOXIC POLLUTANT RAW WASTEWATER DATA FOR SAMPLED
SODIUM CHLORATE FACILITIES
Pollutant
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Silver
Thallium
Zinc
Average
F149
1.933
0.00052
0.210
0.00006
<0.010
<0. 000003
17.000
0.00455
1.227
0.00033
1.033
0.00028
0.0057
0.000002
0.640
0.00017
0.357
0.0001
0.577
0.00015
0.540
0.00014
Daily Pollutant Concentrations and Loads
mq/1
F146
<0.106
<0. 00083
<0.005
<0. 00004
<0.010
<0. 00008
0.246
0.00193
0.090
0.00071
0.022
0.00017
<0.002
<0. 00002
0.039
0.00031
<0.001
<0. 00001
<0.068
<0. 00053
0.140
0.0011
1. Cooling Tower Blowdown only
2. Includes only those plants
kg/kkg
F122
0.459
0.121
<0.0027
<0. 00071
<0.0043
<0. 00113
1.300
0.342
0.021
0.00553
<0.0041
<0. 00108
0.145
0.0382
0.149
0.0392
0.013
0.00342
<0.031
<0. 00816
0.012
0.00316
with process
F112(D
0.333
0.00084
<0.004
<0. 00001
<0.023
<0. 00006
oleooso
0.357
OaOOOSO
• 0.215
0.0Q054
<0.008
<0. 00002
-------
Pollutant
Maximum Concentration Observed
(ug/1)
Antimony
Arsenic
Chromium
Copper
Lead
Mercury
Nickel
Silver
Thallium
Zinc
Benzene
Chloroform
1,2-Dichloroethane
Dichlorobromoethane
Chlorod i bromoethane
Carbon Tetrachloride
Methyl Chloride
Methylene Chloride
Trichlorofluoromethane
2,000
610
20,000
2,800
1,300
220
690
500
1,100
1,100
83
220
4,710
95
27
19
183
12
27
mhi« ? .uhlS report describes the sampling program
methodology. In the sodium chlorate industry, twelve davs of
sampling were conducted. Twenty-one streams we?e lampled and
™v™i. tOXiC metal P°H«tants was SasJd on
analytical data points while toxic organics evaluation
consisted of 2,280 analytical data points. Table ?5- 5 presents
the toxic pollutant raw waste data as the averaae dailS
rai0n8f°nd in the combin^ raw wSltewale?9 at tie
averages for the
POLLUTION ABATEMENT OPTIONS
Toxic Pollutants of_ Concern
high concentrations in the wastewaters
WaS
Toxic metals found in
res~u??s S|±in?heH- ,
results trom the addition of sodium dichromate to inhibif
corrosion and to reduce the formation of hypochlorite ion Other
metals detected in the wastewaters may be con?ainld in'the rlw
^ (br^6S °C r°Ck salt) whic^' in some cases? may be
»« °m u°ther Product Process wastewater streams . ThesI
impurities may be released to sodium chlorate wastewater streaml
335
-------
during purification processes. The extensive use of recycling in
this industry would tend to build up the concentration of toxic
pollutants in the mother liquor and in purges, leaks and
washdowns.
While nine toxic organics were found above 10 ug/1 in the raw
wastewater streams, only one pollutant, 1,2-Dichloroethane was
fSSfSt significantly higher "concentrations. This pollutant was
nresent in all wastewater streams sampled at one facility. Its
lourceis considered to be the river water which is used to
Tislolve the feed salt. The 1,2-Dichloroethane concentration in
the sampled river water was 13,700 ug/1 as opposed to 4,710 ug/1
found in the total raw waste of the plant. s^n£e *ne
1 2-Dichloroethane was found at only one plant and is related to
its presence in the intake water at that plant the Agency
proposes to exclude that pollutant under Paragraph 8(a) (in) of
the Settlement Agreement.
During a visit to one sodium chlorate facility, plant Personnel
indicated that chlorinated organics are generated by the use of
graphite anodes; however, they also indicated that they had no
data to demonstrate which chlorinated organics are generated or
the amount generated.
Existing Wastewater Control and Treatment Practices
Control and treatment technologies at the plants which were
visited and sampled were discussed previously. Control and
treatment practices at the remaining sodium chlorate plants
(FU1? F114? F131, Fill, F136, F105 and F135) are discussed
briefly below.
Plant F141 does not discharge any process wastewater. Two lined
evaporation ponds allow for solar evaporation and total recycle
of the process wastewater streams. The plant is located in an
arid region of the country. Approximately 15,000 mVday of
noncontact cooling water is discharged to surface water during
the summer months only. The plant uses pure salt as the raw
material and has minimal brine purification wastewater. The
product is sold as solid sodium chlorate.
Process wastewater streams in Plant F114 are recycled and blended
with a brine solution obtained from an adjacent plant. In 1980,
tne p?ant was in the process of installing a liquid ring hydrogen
compressor which would allow reuse of the gas as a boiler fuel.
Seal water from the installed compressor would be the only
process wastewater discharged from the plant. Brine purification
wastes are attributed to the adjacent plant which provides the
purified brine. The product is sold as the solution only.
336
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Plant Fi 31 does not discharge any wastewater streams to either
i£ S?SrE 5 °^ treatment facilities. Noncontact cooling wat«
controf ThJ t i t- ^ in~Plant holding pond for use in dust
m?n«m i' K * Pla"t uses a pure salt as the raw material, with
SJriSSir.: S P^ification wastes. The plant does not have air
nrnHnS 4 ^ Produces ?nly solution grade sodium chlorate. The
product is not filtered before shipment.
Plant Fill discharges all wastewater streams to surface water
waLr Sn™J°Ur?e °f wastewater flow is noncontact cooling
water. Sources of process contact wastewater include brine
PK°dUCt /ilter bac^ashes, chlorate trench and
streams' barometric condensate, and water used to
from cell off -gases. No information on any
bu mf treatment including in-plant treatment, is available
levels Tn ?he filr^ data, indicate that chlorine and chromium
levels in the discharge are low. The plant uses an impure brine
m C1 M°St °f the Pr°duCt is Sold as s°lid
At Plant F136, the source of raw material is purified brine from
an ad3acent chlor-alkali plant. Most wastewater is recycled but
washf aandSCr±nr «as^*j > washwater (cell wash and tank car
wash) and pump seal water is combined with chlor-alkali
n°ncontact cooling water before PH adjustment and
At Plant FT 05, wastewater streams consisting of equipment wash
water and cooling water are combined with pulp mill wastewater
aaaa
Plant F135 combines wastewater streams from sodium chlorate
production with pulp mill effluent. No information is availablJ
2?fi!!2!Je?at?' treatment technologies at this plant. The final
effluent is discharged to surface water.
other Applicable Control/Treatment Technologies
ron«== technol°gy ^ the sodium chlorate industry
consists of pH adjustment and sedimentation as the result of
combination with wastewater streams from other products. Many
facilities combine process wastewater with large volumes of
noncontact cooling water for discharge. Of the plants which do
discharge, only one case is known whe?e treatment effects the
removal of toxic metals and chlorine. Over half of the plants in
the industry also practice either complete or extensive ?ecycliiS
?LhP ?°e?S wa»tewater. Other identified control or treatment
technologies which might be applicable include hexavalent
337
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chromium reduction, dual-media filtration, and chlorine
reduction.
The Zero Discharge Option
barometric condenser water, to dissolve the salt; plants using
brines cannot recycle much water for this purpose. Plants using
Durilied brine or purified salt generate minimal amounts x>f brine
nurif ication process wastewater whereas plants using natural
brines or ?ockPsalt must purify the brine before electrolysis,
thus generating a significant ^ount of wastewater Plants that
produce a considerable portion of product as the water solution
Eliminate a significant amount of water that would otherwise be
process wastewater with the product shipped. All four existing
Slants that have achieved zero discharge use a purified salt as
raw material and three of the four ship a considerable Portion of
the product in solution (the one plant of these four that ships
primarily solid sodium chlorate is located in an arid region of
the country and recycles process water through an evaporation
pond) .
One other zero discharge plant is also located in an arid region.
A third plant uses a very pure salt from an adjacent plant and
generates no brine purification wastewater, which allows complete
Recycle of the remaining process wastewater. The fourth plant
evaporates the water from the residue from brine purification
(there is little water generated from purification of the brine
from a purified salt9 anyhow), and does not filter its product
solution, thus eliminating that source of wastewater also. The
customers for the fourth plant apparently do not "quire
filtration of the product solution. Since the four plants
achieve zero discharge through special circumstances (access to
an economic source of purified salt, customer preference for
solution grade product, and/or location in an arid region of the
country), the le?o discharge option is not technically feasible
for the average plant.
Process Modifications and Technology Transfer Options
Process modifications which have been implemented at sodium
chlorate plants reduce the amount of process wastewater
discharged include the following:
338
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5.
Recycle of scrubber wastewater within the
improve reagent utilization.
scrubber to
Use of sodium hydroxide as the alkali in the scrubbers
so that the water is amenable to reuse in the plant.
Calci urn-based alkalies reduce the efficiency of
electrodes by forming a coating on the electrode
Use of noncontact evaporators and crystallizers in the
production of solid sodium chlorate. Noncontact water
would thus be used which would reduce the amount of
process contact water. Plants practicing contact
cooling through the use of barometric condensers
generate large amounts of slightly contaminated
wastewater. Two plants use the contact cooling water
to dissolve the raw salt to make the brine.
Operations using rock salt use the recycled wastewater
in dissolving the salt.
Use of a coated titanium anode instead of a graphite
electrode. Graphite electrodes may contain lead
dioxide and are also consumed more rapidly in the
process. The elimination of a source of lead, reduced
generation of solid waste (graphite), and elimination
of a source of chlorinated organics can be obtained
using coated titanium anodes. However, the primary
reason many manufacturers are switching to coated
titanium anodes is increased electrical efficiency.
procesf modifications or technology options which would
reduce the amount of wastewater discharged were identified.
Best Management Practices
Recycle of some wastewater streams is already extensively
practiced in this industry. Collection and recycle of pump seal
water and spills is employed at several facilities. Rain water
to the extent possible, should be diverted around salt storaae
pads and other contact areas. The use of high purity brine or
salt can minimize pretreatment of the salt and generation of
wastewater; however, the purity of the salt used is usually an
economic decision. In combination with recycle the use of hiah
purity salt may enable the attainment of zero discharge.
The use of chromate and its concentration in the cell should be
reduced to the lowest concentration feasible for cell use to
339
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reduce the cost of production and reduce the cost of wastewater
treatment.
Advanced Treatment Technology
In some case, additional treatment may be required to reduce
chromium and antimony to lower concentrations. Level 2 treatment
technology may be needed to accomplish adequate removal.
Selection of_ Appropriate Technology and Equipment
Technologies for Different Treatment Levels
A. Level 1
Level 1 treatment consists of hexavalent chromium and chlorine
reduction, alkaline precipitation, settling, pH adjustment and
sludge dewatering. This technology is illustrated in Figure 10-
16. A holding basin for equalization sized to retain 4-6 hours
of flow is provided.
The pH of wastewater leaving the holding basin must be reduced by
the addition of concentrated sulfuric acid to a pH range of 2 to
3. This pH is necessary to reduce hexavalent chromium to
trivalent chromium. A reducing agent such as sodium bisulfite is
then added to the wastewater (sulfur dioxide, sodium
metabisulfite, or ferrous iron are alternative reagents which
could also be used to reduce hexavalent chromium). Hydrated lime
is then added to the wastewater to elevate the pH to
approximately 8.5 to produce a chromium (trivalent) hydroxide
precipitate. The chromium hydroxide and other, solids are allowed
to settle in a clarifier. The overflow from the clarifier is
aerated and neutralized (if necessary) before discharge. A
monitoring system is installed at the discharge point. The
reducing agent, sodium bisulfite, is also effective as a means of
total residual chlorine reduction.
Sludge collected in the clarifier is directed to a filter press
for dewatering. Pits are provided at the filter press for the
temporary storage of sludge. The sludge is periodically
transported off-site to a hazardous material landfill. The
objective of Level 1 is to reduce the chlorine residual and to
reduce hexavalent chromium to trivalent chromium, and then to
precipitate chromium, antimony, other heavy metals and suspended
solids.
Level 1 treatment was selected as the basis of BPT because it
represents a viable industry practice for the control of
hexavalent and total chromium, antimony, total residual chlorine,
340
-------
and suspended solids. Currently, one of nine direct dischargers
in the sodium chlorate industry has the technology or its
equivalent installed. Four facilities achieve zero discharge and
thus would not be affected. In addition, two of the direct
dischargers direct their wastewater to a paper or pulp mill for
use or treatment.
B. Level 2
Level 2 treatment consists of granular media filtration for the
additional removal of suspended solids containing precipitated
chromium hydroxide and antimony from the effluent. Sludges from
brine purification and chromium hydroxide precipitates would be
removed by filtration. Dual-media filtration is preferred
because it overcomes the limitations on loadings normally
encountered with sand filters due to the high flow rates
encountered in this subcategory. Level 2 was selected as BAT
because it provides significant additional removal of antimonv
and chromium.
Equipment for Different Treatment Levels
A. Equipment functions
A conventional type clarifier is used to remove the suspended
solids. A plate and frame filter press is used for sludqe
dewatering and the filtrate from the filter is returned to the
lime mixing tank. Level 2 requires the addition of a granular
media filter, typically anthracite and sand, to handle a higher
loading. All. equipment is conventional and readily available.
B. Chemical Handling
Concentrated sulfuric acid is added to lower the pH using
conventional acid handling equipment. Sodium bisulfite is
manually added to a chemical feed system which is fed into a
mixing reaction tank. A conventional hydrated lime storage and
feed system is used to proportionally add the proper amount of
lime.
C. Solids Handling
Treatment sludges produced by Levels 1 and 2 are directed to a
sludge holding basin from which it is fed to the filter press.
The solids produced by the filter are assumed to be dewatered to
50 percent solids by volume and disposed of in an off-site
hazardous materials landfill. The sludge was assumed to be
hazardous because of its high metal content.
341
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Treatment Cost Estimates
In the sodium chlorate industry, costs were developed for one
model plant representing the average production and flow. The
Agency in developing the proposed regulations considered data
from all plants in the subcategory. The Agency used flow data
from the seven dischargers which provided sufficient flow data in
developing the model plant unit flow (See Table 15-3(a). (Two
dischargers did not provide flow data; those plants are pulp and
paper mills using the typical production process and would be
expected to produce solution grade product for internal use.
Therefore, the flow from those two plants is believed to be
within the range of flows observed at other plants). The unit
flow does not include barometric condenser wastewater because one
of the three plants using barometric condensers completely
recycles the barometric condenser wastewater and a second
recycles most of it. The barometric condenser wastewater is
considered process wastewater, and the proposed limitations would
include pollutants discharged with the barometric condenser
wastewater. The barometric condenser wastewater is high in
volume but low in pollutant concentrations, and those plants
where the barometric condenser wastewater is discharged
separately from the rest of the process wastewater should have no
difficulty in achieving the proposed limitations since treatment
of the low volume concentrated wastewaters should be sufficient.
However, plants that mix barometric condenser wastewater with
other process wastewater before discharge will be at a distinct
disadvantage because the resulting wastestream will be high in
volume (thus increasing treatment plant size and costs) and lower
in concentration of pollutants (thus reducing the efficiency of
the treatment). In developing the proposed limitations and model
plant, the Agency assumed that plants that mixed barometric
condenser wastewater with other process wastewater could
economically separate the other process wastewater from the
barometric condenser wastewater for treatment. However, since
the costs for such a separation are highly site specific, the
Agency has been unable to quantify those costs, and they are not
included in the treatment system costs.
General
Production ranges and wastewater flow characteristics have been
presented earlier in this section and are summarized in Table 15-
1. There are nine direct dischargers and four plants which
achieve zero discharge. No plants in this subcategory discharge
to a POTW.
A. Sodium Chlorate
342
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The model plant for the sodium chlorate subcategorv has a
production rate of 32,000 metric tons per year and a daily flow
Sofof ZuCU^lc meters Per day- These figures were used as the
Figure ?5-3U)atment CO8t .. ^iinates at both levels. See
Material usage for both levels is estimated as follows:
Chemical
Amount
Treatment Level
H2S04 (100 percent)
NaOH (50 percent sol.)
Sodium Bisulfite
59.25 kg/day
152.6 kg/day
33.2 kg/day
(1)
(1)
(1)
Total solid waste generated is estimated at 0.021 mVdav for
Level 1 and an additional 0.002 mVday for Level 2.
M2de3, Plant Treatment Costs. On the basis of the model nlant
specifications and design concepts presented earlier £A ?„
fwo^LL?' the estimated c°sts °f treatmeTfor one moLl witS
increment? t^Lev^T " ™* ^6' ^e cost of Level T^
Basis for Regulations
Basis for BPT Limitations
A. Technology Basis
For BPT, the Agency is setting limitations based upon hexavalent
t
.
discharge and thus would not be affected.
B. Flow Basis
zero
sodium chlorate subcategory, a unit flow rate of 2 7
-''b *
343
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„-,.
s™gs,jgSSgS«S9iS
SUBCATEGORY: Sodium Chlorate
ANNUAL PRODUCTION: 32,000
DAILY FLOW:
PLANT AGE:
237
CUBIC METERS
NA
YEARS PLANT LOCATION:'
J2A.
COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS
COST CATEGORY
Facilities
Installed Equipment
(Including Instrumentation)
Engineering
Contractor Overhead and Profit
Contingency
Land
Total Invested Capital
Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Waste Disposal)
Residual Waste Disposal
Total Annual Cost
b. RESULTING WASTE-
COSTS ($1,000) TO ATTAIN LEVEL
1 2
21.2
191.1
42.5
38.2
29.3
322.3
52.4
109.0
0.4
27.4
5.5
4.9
3.8
41.6
6.8
9.8
Negl.
Parameter
Avg. Cone.
Untreated(mg/1)
pH 7.0
TSS 50
Cr (Total) 4.7
.Chlorine 20
(Total Residual)
c.
161.8 16.6
LOAD CHARACTERISTICS
Long-Term Avg.
Concentration (mg/1)
After Treatment To Level
_L -L
6-9 6-9 ,
13 9.3
0.25 0.16
0.64 0.64
TREATMENT DESCRIPTION
LEVEL l: Hexava^t^roMu^duction, ^lorine^eductlon,
LEVEL 2: Filtration
344
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c.
Selection of Pollutants to be Regulated
u P°llutants for which specific effluent
are being established is based on an evaluation of
the raw wastewater data from screening and verification
consideration of the raw materials used in the pS'
ii£2[?ture data historical discharge monitoring reports
poUutantsPP °nS' ^ the treatability of the
8:,14 ST13^26 the achievable concentrations
h« P°llutants from the literature using available
technology options, other industries, and treatability studies
™
are
,
screening and verification sampling at several
f11^ J" tMs Se^ti0"- Data f?o xon e
S tn"?lac?u l"dustry treatment systems was also
developing the list of pollutants to be regulated.
me UP°?- the occurrence of treatable levels of specific toxic
metals, antimony and chromium were selected as candidate toxic
bv
un c..
ml™.,.and Chlorine will be reduced slmultLieouIly
UttnChaS *1S° SSl "
antimony and chromium as the toxic pollutants to be regulated.
D. Basis of BPT Pollutant Limitations
concentrations <»g/D and loads
th€ tW° iS based on a unit
flow rte o
-
mVkkg"°nShlP
BPT limitations, which apply to all
discharged, are presented in Table 15-8.
process wastewater
345
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1. Conventional Pollutants
a. pH
The treated effluent is to be controlled within
the range of 6.0 - 9.0. This limitation is based
upon the data presented in Appendix B of the
Development Document for Proposed Effluent
Guidelines for Phase I Inorganic Chemicals (Ref.
3) and the JRB study (Ref. 4).
b. TSS
Three Phase II plants (F125, F115 and F140)
considered to be efficiently operating their
wastewater treatment facilities provided long-term
Level 1 treatment system performance data for TSS.
Since no other data from well-operated Level 1
treatment systems was available, and since the
clarification provided at plants FT25, FITS and
F140 for TSS removal would be similar to that
necessary for TSS removal at sodium chlorate
plants, the BPT limitations*for TSS are based upon
a summary of long-term data from Plants F125, F115
and F140. The long-term average of 13 mg/1 was
used to develop discharge limitations.
Variability factors of 1.9 for a monthly average
and 3.3 for a 24 hour maximum were used yielding
TSS concentration limits of 25 mg/1 and 43 mg/1,
respectively. The monthly average variability
factor was obtained from the variability factors
from all three plants with long-term data
employing Level 1 type treatment. Since the data
from all three plants was not in a form which
could be used to develop daily maximum variability
factors, the daily maximum variability factor of
3.0 for filters was adjusted upward by 10% to
account for the higher variability experienced
with clarification only. Thus, utilizing these
values, one obtains TSS mass limitations for the
sodium chlorate subcategory of:
30-day average:
(25 mg/1) (2.7 mVkkg)(kg/10« mg)(1000 1/m3)
- 0.068 kg/kkg
24-hour maximum:
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(43 mg/l)(2.7 mVkkg) (kg/10« mgHlOOO 1/m')
= 0.12 kg/kkg
2. Toxic Pollutants
a. Chromium (Total)
Since there is no long-term performance data for
this subcategory, the long-term average
concentration for chromium is based on industrial
wastewater system performance data found in Table
8-12 and the promulgated total chromium
limitations for the sodium dichromate subcategory,
which uses a similar wastewater treatment system
for chromium control. The variability factor
ratio is based on those used for the Sodium
Dichromate subcategory. The long-term average
used was 0.25 mg/1. Variability factors of 2.0
for the 30-day average and 4.0 for the 24- hour
maximum from the Sodium Dichromate subcategory
were used, yielding chromium limitations of 0.5
mg/1 and 1.0 mg/1 respectively. Thus utilizing
these values, mass limitations for the sodium
chlorate subcategory may be obtained as follows:
30-day average; " •
(0.5 mg/1) (2.7 mVkkg) (kg/10* mgMlOOO 1/m')
= 0.0014 kg/kkg
24-hour maximum;
(1.0 mg/1) (2.7 mVkkg)(kg/10« mgMlOOO 1/m*)
= 0.0027 kg/kkg
Antimony (total)
Since there is no long-term average performance
data for this industry, the long-term average
concentration for antimony is based on industrial
wastewater treatment system data performance data
found in Table 8-11. The lowest reported
achievable concentration for antimony with a lime
precipitation and clarification system (0.8 mg/1)
was used as the long term average. The
variability factors of 2.0 for 30-day average and
4.0 for the 24-hour maximum used for chromium were
used for antimony, yielding antimony effluent
concentrations of 1.6 mg/1 and 3.2 mg/1
347
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respectively. Utilizing these values, mass
limitations for antimony are obtained as follows:
30-day average;
(1.6 mg/l)(2.7 mVkkg) (kg/10«mg) (1000 1/m*)
« 0.0043 kg/kkg
24-hour maximum;
(3.2 mg/l)(2.7 mVkkg) (kg/10«mg) (1000 l/m*)
- 0.0086 kg/kkg
3. Non-conventional Pollutants
a. Chlorine (Total Residual)
Since there is no long-term performance data for
this industry, the. BPT limitations for chlorine
are based on the long-term monitoring data for
chlorine in the chlor-alkali subcategory which
uses a similar wastewater treatment technology for
chlorine control. (See the Phase I Development
Document, Appendix A, Plant A).
factors are based on that same
plant is achieving a long-term
residual chlorine concentration of 0.64 mg/1. The
variability factors for this longterm average are
1.4 for the 30-day average and 2.3 for the 24-hour
• maximum. These variability factors yield effluent
limitations of 0.9 mg/1 and 1.5 mg/1, for the 30-
day average and 24-hour maximum respectively. The
mass limitations for chlorine in the sodium
chlorate subcategory are as follows:
30-day average;
(0.9 mg/l)(2.7 mVkkg) (kg/10« mg)(1000 1/m*)
= 0.0024 kg/kkg
24-hour maximum;
(1.5 mg/1) (2.7 mVkkg) (kg/10« mg)(1000 1/m*)
* 0.0041 kg/kkg
Basis for BCT Effluent Limitations
On October 29, 1982, EPA proposed a new and revised methodology
for determination of BCT for conventional pollutants. In this
The variability
facility. The
average total
348
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TABLE 15-7. BPT EFFLUENT LIMITATIONS FOR SODIUM CHLORATE
Conventional Long-Term
Pollutants Avg-(mg/l)
TSS
Toxic
Pollutants
Antimony
(Total)
Chromium
(Total)
13
0.8*
0.25(2)
Non-Conventional
Pollutants
Chlorine
(Total
Residual) 0.64
(3)
VFR
1.9/3.3
CD
2/4
(2)
2/4(2)
1.4/2.3
(3)
Cone. Basis
(mq/1)
30-day 24-hr,
avg. max.
25-
1.6
0.5
0.9
43
1.0
1.5
Effluent Limit
(kq/kkg)
30-day 24-hr.
avq. max.
0.068 0.12
3.2 0.0043 0.0086
0.0014 0.0027
0.0024 0.0041
LTA = Long-term average achievable level.
VFR - Variability Factor Ratio
(1) Based upon long-term data at Plants F115, F125 and F140.
C2) LTA used as basis for promulgated limitations for Sodium Bichromate
Subcategory - Phase I.
(3) LTA and limitations based upon promulgated total residual chlorine
I - Chlor-Alkali
*From Table 8-11.
See Phase I Inorganic Chemicals Development Document; EPA 440/1-82-007.
349
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subcategory, only two conventional pollutants have been selected
for limitation, pH and total suspended solids (TSS). Two tests
are required according to the revised methodology, a POTW test
and an industry cost-effectiveness test. The POTW test is passed
if the incremental cost per pound of conventional pollutant
removed in going from BPT to BCT is less than $0.46 per pound in
1981 dollars. The industry test is passed if the same
incremental cost per pound is less than 143 percent of the
incremental cost per pound associated with achieving BPT.
The methodology for the first BCT cost test is as follows:
(1) Calculate the amount of additional TSS removed by the
BCT technology.
(a) BPT long-term average =
Level 2 long-term average*
Difference
13 mg/1
9.3 mg/1
3.7 mg/1
*(See Sections 11 and 12 for derivation)
(b) Annual flow for model plant:
(2.7 mVkkg) (32,000 kkg/yr) = 86,400 mVyr
(c) Total annual additional TSS removed for model plants
(3.7 mg/1) (86,000 mVyr) (kg/10«mg)(1000 1/m3)
* 320 kg/yr
= 705 Ibs/yr
(2) Calculate incremental cost, in dollars per pound of TSS
removed, for the model plant.
(a) Incremental annualized cost of Level 2 technology,
from Table 15-6: $16,660 per year.
(b) Divide annualized cost by annual TSS removal:
($16,600 per year) t (705 Lbs per year) = $23.56 per
pound of TSS removed.
This is far above the $0.46 per pound bench mark cost.
Therefore, the candidate BCT technology failed the first BCT cost
test and there is no need to apply the second BCT cost test.
Since the candidate BCT technology failed the BCT cost test, EPA
is not proposing any more stringent limitations for TSS under BCT
since we have identified no other technology which would remove
additional amounts of TSS. As a result, BCT for TSS is equal to
the BPT Limitations.
350
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Basis for BAT Effluent Limitations
Application of Advanced Level Treatment
Utilizing the cost estimates in this report, the Agency has
analyzed the cost of the base level system (BPT = Level 1) and
the advanced level option for toxic pollutant removal. The
economic impacts on the Sodium Chlorate Subcategory have been
evaluated in detail and taken into consideration in the
determination of the BAT regulations.
For BAT, the Agency is proposing limitations based on treatment
°J ^T ] ?JVS i?Yel 2' Level 2 adds 9^™^ media
of the Level 1 efflunet. The toxic pollutants limited
by the proposed BAT regulation are antimony and chromium. The
non-conventional pollutant to be regulated is total residual
chlorine.
A. Technology Basis
The overflow from the clarifier is filtered in a granular media
filter to remove additional antimony and chromium from the waste
stream. The backwash from the filters is returned to the
clarifier or if the solids concentration is sufficiently high the
backwash is directed to the filter press for dewatering! The
filter will not remove additional amounts of chlorine.
B. Flow Basis
A unit flow rate of 2.7 mVkkg of sodium chlorate wastewater has
been selected for BAT (same as BPT).
C.
Selection of Pollutants to be Regulated
Toxic Pollutants
Antimony and chromium have been selected as the toxic pollutants
for control under BAT, as both pollutants have been detected at
sodium chlorate plants at significant, treatable concentrations.
Table 15-9 presents the BAT limitations for the Sodium Chlorate
Subcategory.
a. Chromium
Since there is no long-term treatment system
performance data for this industry, the estimated
achievable long-term average concentration of 0.16
mg/1 for chromium from Table 8-13 is used for the
long-term average. The variability factors of 2.0
351
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for the 30-day average and 4.0 for the 24-hour
limitations' for chromium in the sodium chlorate
subcategory are calculated as follows:
30-day average;
(0.32 mg/l>(2.7 m'/kkgXkg/10* mg)(lOOO l/m»)
= 0.00086 kg/kkg
24-hour maximum;
(0.64 mg/l)(2.7 m'/kkg)(kg/10«)(1000 l/m»)
= 0.0017 kg/kkg
b. Antimony
Since there is no long-term treatment system
performance data for this industry, the estimated
Achievable long-term average concentration is
?SeS from industry performance data in Table
a-il The lowest reported achievable
concentration of 0.4 mg/1 for antimony utilizing
lime addition plus filtration is taken as the
loSa-term average. The variability factors of 2.0
flT 30™ay average and 4.0 for 24-hour maximum
used for chromium are used for antimony, JieWinj
effluent antimony concentrations of 0.8 mg/1 and
1.6 mg/1 respectively. The mass limitations are
calculated as follows;
30-dav average;
(0.80 mg/1) (2.7 m'/kkg)(kg/1 (>•)( 1000 l/m»)
= 0.0022 kg/kkg
24-hour maximum;
(1.6 mg/1)(2.7 m3/kkg)(kg/lO« mg)(1000
= 0.0044 kg/kkg
Non-Conventional Pollutants
Total residual chlorine has been selected for controller
concentra?!onraanld ,SdiSTSc4«?Sr BA^a.e the sane as £or
BPT for this parameter.
352
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TABLE 15-8. BAT EFFLUENT LIMITATIONS FOR SODIUM CHLORATE SUBCATEGORY
Toxic
Pollutants
Long-Term
Avg.(mg/1)
Antimony (T) 0,4*
VFR
2/4
(2)
Cone. Basis
(mg/1)
30-day 24-hr.
avg. max.
Effluent Limit
[kg/kkg)
0.80
30-day24-hr.
avg. max.
1.6 0.0022 0.0043
Chromium (T) 0.16d)
2/4(2)
0.32 0.64 Q-..00086 0.0017
Non-Conventional
Pollutants
Chorine
(Total
Residual) 0.64
(3)
1.4/2.3
(3)
0.9
1.5
0.0024 0.0041
LTA
VFR
Long-term average achievable level.
Variability Factor Ratio; ratio of the 30-day average variability
factor to the 24-hour maximum variability factor.
(1) From Table 8-13.
(2) Phase I Inorganic Chemicals Development Document; EPA 440/1-82/007,
variability factors for Sodium Dichromate.
(3) See Table 15-7.
*From Table 8-11.
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Basis for NSPS Effluent Limitations
For NSPS, the Agency is proposing limitations equal to BAT since
no technology which would remove significant additional amounts
of pollutants is known. The pollutants limited include pH, TSS,
antimony, chromium (total), and chlorine (total residual). The
pH TSS and chlorine limitations are found in Table 15-7, and the
antimony and chromium limitations are found in Table 15-8.
Basis for Pretreatment Standards
Pretreatment is necessary because it provides better removal of
antimony and chromium than is achievable by a well operated POTW
with secondary treatment installed, and thereby prevents pass-
through that would occur in a POTW in the absence of
pretreatment.
Using the summary data presented in Tables 15-6, the Agency has
estimated the percent removals for antimony and chromium by
comparing the treated waste concentration for the selected BAT
technology for those two toxic metals with the average untreated
waste concentrations for those same two pollutants. The
calculation is as follows:
Antimony; Raw Waste = 0.83 mg/1
BAT = 0.4 mg/1
Percent Removal = [(0.833 - 0.4) t (0.8)] (100)
= 52%
Chromium (Total); Raw Waste =6.2 mg/1
BAT = 0-. 1 6 mg/1
Percent Removal =
[(6.2 - 0.16)/(6.2)] (100)
97%
The percent removal for total chromium is greater than the
removals achieved by 25% of the POTWs in the "40 Cities study
(Fate of Priority Pollutants iri Publicly Owned Treatment Works,
Final Report, EPA 440/1-82/303, September, 1982). There is
limited data available on the removal of antimony by a POTW, but
removals for other toxic metals range from 19% to 66% for 25% of
the POTWs in that study. Therefore, the Agency believes it is
prudent to assume that antimony could pass through a POTW. Since
both chromium and antimony pass through a well operated POTW with
secondary treatment, pretreatment is necessary.
Using the summary data presented in Table 15-6, the Agency has
also estimated the percent removals for antimony and total
354
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chromium by comparing the treated waste concentration for the
selected BPT technology for those two toxic metals with the
treated waste concentrations for the selected BAT technology for
those same .two pollutants. The calculation is as follows:
Antimony; BPT = 0.8 mg/1
BAT =0.4 mg/1
Percent Removal =
[(0.8 - 0.4)
50%
f (0.8)] (TOO)
Chromium (Total) BPT =0.25 mg/1
BAT =0.16 mg/1
Percent Removal
[(0.25 - 0.16)
36%
-r (0.25) ] (TOO)
The percent removals for total chromium are less than the
removals achieved by 25% of the POTWs in the "40 Cities" study
for chromium (65%). However, a portion of the total chromium is
hexavalent chromium, which is removed poorly by a POTW. Federal
Guidelines; State and Local Pretreatment Standards. Volume II
EPA 430/9-16-017b, January, 1977, page 6-51^ *t?+ez '.hat the
average hexavalent chromium removal fo»- ^l^nts with biological
treatment (i.e., secondary treatment) is 18%. Hexavalent
chromium could interfere with the operation of the POTW, or be
incorporated into the sludge and thus interfere with the FOTw's
chosen sludge disposal method. Information from the chrome
pigments industry and the sodium dichromate industry indicates
that filtration does remove some additional hexavalent chromium.
Accordingly, since additional hexavalent chromium is removed by
filtration, since the removal of hexavalent chromium by a POTW is
small, and since hexavalent chromium is highly toxic, the Agency
believes it is prudent to regulate the discharge of total
chromium, which includes hexavalent chromium in discharges to
POTW from sodium chlorate plants with pretreatment limitations
based on the application of BAT technology.
There is only very limited data on the removal of antimony by a
POTW available. The removals achieved by 25% of the POTWs in the
"40 Cities" study for other toxic metals range from 19% to 66%.
The removal of antimony by a POTW could be less than 50%.
Therefore, the Agency believes it is prudent to regulate the
discharge of antimony to POTW in the sodium chlorate industry
with pretreatment limitations based on BAT technology.
Existing Sources
355
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Since there are no indirect dischargers in this subcategory,
the
Agreement .
New Sources
The Agency is proposing PSNS that are equal to NSPS because these
standards provide for the removal of antimony and chromium, which
would likely pas! through a well operated POTW with secondary
treatment in the absence of pretreatment. Pollutants regulated
SESSfpSHS are antimony and chromium, Chlorine is not regulated
under PSNS because POTW influent is often chlorinated.
356
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1.
2.
3.
4.
SECTION 15
REFERENCES
*••
357
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SECTION 16
ZINC CHLORIDE INDUSTRY
INDUSTRIAL PROFILE ;
General Description
Zinc chloride is manufactured primarily for market use although
some zinc chloride is used in the captive production of zinc
ammonium chloride. Zinc chloride is used as an ingredient in dry
S3? batteries; oil well completion fluids; tinning; galvanizing
and soldering fluxes;'and for the preservation and flameproofing
of wood. It is also used as a deodorant, and in disinfecting and
embalming fluids. In chemical manufacturing, zinc chloride
serves as a catalyst and as a dehydrating and condensing agent.
Further uses include the manufacture of parchment paper, dyes,
activated carbon and durable press fabrics and the printing and
dyeing of textiles. The industry data profile is presented in
Table 16-1.
There are seven known producers of zinc chloride of which five
plants discharge wastewater directly, while two discharge
indirectly.
Production in this subcategory is more than 25,000 tons per year,
while total daily flow is in excess of 1,500 cubic meters.
General Process Description and Raw Materials
Zinc chloride is produced by reacting zinc metal with
hydrochloric acid and concentrating the zinc chloride solution by
evaporation. The general reaction is:
Zn + 2HC1 = ZnCl2 + H2
Various forms of zinc feed material are used, from pure zinc
metal to galvanizer skimmings. The latter may contain
galvanizing fluxes, iron oxide, cadmium and lead in addition to
the zinc metal. Galvanizing wastes may require milling and
further processing prior to use in the zinc chloride
manufacturing process. A zinc chloride solution is produced by
the dissolution of the zinc feed with hydrochloric acid. The
solution is generally purified by chemical addition to remove
metal salts, then filtered and concentrated. The product is
either marketed as a solution or further concentrated to yield a
solid product. One facility utilizes a zinc chloride-containing
process wastewater containing organic chemicals from an adjacent
358
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TABLE 16-1. SUBCATEGORY PROFILE DATA FOR
ZINC CHLORIDE
Number of Plants in Subcategory
Total Subcategory Production Rate
Minimum
Maximum
Total Subcategory Wastewater Dischargt
Minimum
Maximum
Types of Wastewater Discharge
Direct
Indirect
Zero
>25,000 kkg/yr'
<4.5 kkg/yr
Confidential
>1500 m3/day
26 m3/day
719 m3/day
5
2
0
359
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-p
u
-^ n
Filter
'1
04
t-l
0
en
Concentrator
0 W
•H rH
4J nt
n) u
O -H
••-I E -^
j./
Evaporator
—>
^
Scrubber
•u
•H
l-l
•H
r,.
H
0)
4J
•H
b
0) 0)
•|J Jtff
•HO
b
1
360
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TABLE 16-2. WATER USAGE AT ZINC CHLORIDE FACILITIES(D
WATER USE
Noncontact
Cooling
Direct Process
Contact
Indirect Process
Contact
Maintenance
Air Pollution
Scrubbers
Noncontact
Ancillary
TOTALS
F125
0
0
4.94
NA
NA
NA
4.94
Flow (m3/kkg of zinc
Plant Desianat
F140 F120
0 0
!-6 0.03
13.65 0.69
0.03 0.05
0 1.38
0.32 0.10
15.6 2.25
Chloride)
ion
F144
0
5.67
7.56
0.05
0
NA
13.3
F143
5.73
0
1.62
0.42
3.33
1.39
12.5
NA Flow volume not available.
1. Values indicated only for those plants that reported
separate and complete information.
Source: Section 308 Questionnaires and Plant Visit Reports
361
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TABLE 16-3. WASTEWATER AT ZINC CHLORIDE FACILITIES
WASTEWATER SOURCE F125
Direct Process
Contact 0
Indirect Process
Contact 4.94
Maintenance NA
Air Pollution
Scrubbers NA
TOTALS 4.94
Noncontact
Cooling 0
Noncontact
Ancillary NA
Storm Water NA
Flow (m3/kkg of Zinc Chloride)
Plant Designation
F140 F120 F144 F14J
1.6 0 1.89 0
13.65 0.69(2) 7.56 1.62
0 NA(2) 0.05 0.42
0 1.24(2) 0 3.33
15.3 1.93 9.5 5.37
00 0 5.73
0.032 0.01 NA 1.39
NA ^ 7.14 0.53 2.67
NA Flow volume not available.
1. Values indicated only for those plants that reported
separate and complete information.
2. Wastewater recycled within plant.
3. Stormwater unknown but not zero.
Source: Section 308 Questionnaires and Plant Visit Reports
362
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facility as a raw material for zinc chloride production. The
organic chemicals are removed from that wastewater before the
zinc chloride solution is processed. Figure 16-1 shows a general
process flow diagram for the manufacture of zinc chloride.
WATER USE AND WASTEWATER SOURCE CHARACTERIZATION
Water Use
Water is used primarily for air pollution control, in barometric
condensers, equipment washdowns, pump seal maintenance, and as a
reaction medium for the hydrochloric acid. Table 16-2 summarizes
plant water use in the subcategory as determined from industry
responses to the Agency's request for information under 8308 of
the Act and engineering visit reports.
Wastewater Sources
Generally, condensate from the evaporators used to concentrate
the zinc chloride product solution and blowdown from the cooling
of the barometric condenser water constitute the major wastewater
streams. These streams are combined with wastewater from air
pollution scrubbers, equipment washdowns, pump seal leaks and, in
some cases, other product processes and treated before discharge
or recycle. Table 16-3 identifies the various wastewater streams
and related daily flows for those zinc chloride plants which
supplied complete data. Storm water can contribute significant
additional water flow to the treatment facility at several
plants.
DESCRIPTION OF PLANTS VISITED AND SAMPLED
Five plants (F118, F120, F140, F144 and F145) producing zinc
C5i?f^de were visited during the course of the program. In
addition, wastewater sampling was conducted at Plants F120 and
F144. One of these plants, plant F120, no longer produces zinc
chloride and is therefore not counted as one of the existina
seven plants. =>*-iny
Plants Sampled
Plant F120 produced zinc chloride and a number of other inorganic
products, but has since discontinued zinc chloride production.
At the time of sampling, the plant produced a zinc chloride
solution by the reaction of zinc-containing waste materials
(galvanizer skimmings) with hydrochloric acid. A wet scrubber
used to minimize hydrochloric acid emissions generated a dilute
acid waste. Solids from the batch reactor were hauled to an
approved landfill site. The zinc chloride solution was then
363
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o 33
364
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ZnCl., Other Product Process Wastewater
»2
<—® Supply Water
O//3
Limestone
Neutralization
Clarifier
(Underflow)
(Centrate) L
Centrifuge
Solids
Stormwater, Process Upsets
-Other Product Process Wastewater
Storm Water
Reservoir
-Caustic Addition
#4
Discharge
Sampling Points
FIGURE 16-3. WASTEWATER TREATMENT PROCESS AND SAMPLING LOCATIONS FOR PLANT F144.
365
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purification/evaporation stage.
So!rP?ocesf »^e a? -fst S| , I one ana a hal£ yea..
5iSS£i: InloThe S' n^rtnffact that there
has been no discharge.
-In -iS.t2t ^s 'Si.
rlSovI?"r?ir to recycle o? discharge (optional
asociae sa.pl in,
locations at Plant F120
sold as a solution or as a solid product.
366
-------
and the centrate is recycled to the beginning of the process.
Plant Fl44 also has a large wastewater impoundment facility to
contain excess runoff during storms, process upsets, and other
wastewater flows during preventive maintenance at the treatment
facility. The water in the holding pond is discharged through
the treatment plant when process wastewater flows are reduced.
Streams sampled at Plant F144 included the intake water, plant
raw wastewater (which contained the zinc chloride process
wastewater), combined plant raw wastewater with raw wastewater
from other products produced at the facility, and treated
clarifier effluent. Figure 16-3 presents a schematic of the
wastewater treatment process and the sampling points.
Table 16-4 presents flow data, total suspended solids (TSS),
zinc, arsenic, lead and antimony concentrations for the sampled
wastewater streams.
Other Plants Visited
Plant F118 combines zinc metal with hydrochloric acid to yield a
zinc chloride solution. The solution is diluted with water to
the desired concentration for sale. Wastewater generated in this
process consists of spills and maintenance washdowns. The zinc
chloride wastewater is combined with wastewaters from all other
products and treated with alkaline precipitation and
clarification before discharge to a receiving stream.
Plant F140 receives process wastewater from an adjacent facility
as a raw material for zinc chloride production. The wastewater
contains zinc chloride along with other metal impurities and
organic wastes. The process water is treated to remove organics.
Metal impurities are then removed by pH adjustment using zinc
carbonate, and filtration. The process water may be strengthened
first by addition of zinc and hydrochloric acid and then
purified. The solution is then concentrated by evaporation to
the desired strength.
All wastewater streams (blowdown resulting from cooling of
barometric condenser water, precipitation run-off, leaks, spills,
and pump seal water) are collected and pumped to a holding tank
where the pH is raised to about 7. The neutralized wastewater is
allow to settle before discharge to a river and the settled
sludge is recycled to the production process.
Plant F145 produces a variety of inorganic and organic chemicals.
Zinc chloride is produced by combining zinc metal or zinc oxide
with hydrochloric acid. All zinc chloride wastewater, including
scrubber water and any process water which cannot be recycled, is
367
-------
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368
-------
sent to the wastewater treatment facility which receives both
organic and inorganic streams from all plant production
processes. The wastewater is equalized, subjected to lime
precipitation at pH 9.5-10.2, agitated and clarified. The sludge
from the clarifiers is dewatered and disposed as solid waste
Ko?™VS • loVfrom the clarifiers receives biological treatment
before being discharged directly to a receiving stream.
Summary of Toxic Pollutant Data
Eleven toxic metals were found at detectable concentrations in
vi faw *astewater at the two sampled plants. Two toxic organic
pollutants were found in untreated wastewater at concentration
levels greater than 0.010 mg/1 (10 ug/1). One of these
methylene chloride, was found in high concentrations in the raw
wastewater of Plant F144. There is no known source for the
methylene chloride at the plant and its presence in the
wastewater was not be confirmed by resampling. The most probable
explanation is contamination of sampling equipment or containers
or an erroneous laboratory determination.
The maximum concentrations observed in the raw wastewater at
two sampled plants are presented below:
the
Pollutant
Maximum Concentration Observed*
(ug/1)
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Nickel
Selenium
Silver
Thallium
Zinc
Chloroform
Methylene Chloride
1,869
14,170
95
640
350
2,100
1,205
6
165
485
490,000
521
430,000
*Maximum daily observed concentrations for antimony, arsenic,
525l"m«1c
-------
TABLE 16-5. TOXIC POLLUTANT RAW WASTE DATA FOR SAMPLED
ZINC CHLORIDE FACILITIES
Average
Daily Pollutant Concentrations and Loads
mg/1
kg/kkg
Pollutant
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Thallium
Zinc
F120
1.435
0.00396
5.605
0.0155
0.069
0.00019
0.146
0.00040
0.279
0.00077
1.834
0.00506
1.049
0.00289
0.142
0.00039
0.325
0.00090
111.724
0.308
Plant
Designation
F144
0.
0.
<0.
tf.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
<0.
0.
<0.
0.
184.
4.
045
00104
006
00014
032
00074
520
0121
067
00155
107
00248
017
00039
001
00002
100
00232
700
29
Overall
Average
0 .74
o!o0250
<2.81
0.00782
0.05
0.00047
0.333
0.00625
0.173
0.00116
0.854
0.00377
0.533
0.00164
<0.071
0.00021
<0.213
0.00161
148.200
2.3
370
-------
Section 5 of this report describes the methodology of the
sampling program. In the zinc chloride industry, a totll of six
days of sampling were conducted at Plants FT 20 and F144? Five
^ samPled and analyzed. The evaluation of
ti a
POLLUTION ABATEMENT OPTIONS
Toxic Pollutants of Concern
The principal pollutant of concern is zinc. Other pollutants
found in significant concentrations in the process wastewaterl
so^ef^lhelox'^ ^^ PUrU? °f the ZinC Stll ^T SSd
nickel fonrJ H,,^n ? arsenic, antimony, lead, chromium and
«if«?«af during screening and verification sampling likely
?aw9 zinc aLt^tUeStSH0Vhe 9alvanizer skimmings usld as the
f~ n* ? material. Highest concentrations of these metals were
found primarily in the scrubber wastewater streams from PlSt
in 5L.;C?UbSr St?P Preceeds the heavy metals removal stSp
J eve^al other plant processes. Therefore, such high
°f the above-mentioned heavy metals would not be expected
actor gfses! ^ °perations included scrubbing of the Zn/HCl
Existing Wastewater Control and Treatment Practices
Pfa£ticef.at the visited plants were presented earlier
presented .belSl! °" ^ treatment Practices at other plants Ire
consisting of
sedimentation
— •" — ~»»-»* wj. J.O.JICVJ
before discharge to a receiving stream.
to a chemical landfill.
is
and unlined impoundments
Solid wastes are hauled
a hr*« Produces zinc chloride using zinc oxide, zinc powder
and brass skimmings as raw materials. Wastewater from the
process is neutralized before discharge to a POTW
Plant F126 produces zinc chloride in small quantities. Process
^ equallzed and neutralized prior to discharge tS 5
otner Applicable Control/Treatment Technologies
371
-------
Although some plants only neutralize their wastes before
discharge, the primary method of wastewater treatment in the zinc
chloride industry is precipitation and clarification or
sedimentation of process wastes. Another technology which would
be applicable to this industry is filtration for further solids
and toxic metal removal.
Process Modifications and Technology Transfer Options
A reduction in the volume of process contact wastewater generated
might be achieved by recycling all direct process contact
wastewater where possible. For example, several facilities
employ recycle of scrubber water with only a small volume of
blowdown necessary. Condensate from product concentration and
crystallization appears to be another wastewater source with
potential for recycle. The principle difference between plants
with high water use and those with low water use is that the
latter use pure raw materials and sell solution grade zinc
chloride only. This is an economic decision not a technology per
se. None of the existing zinc chloride manufacturers has
achieved zero discharge.
Sludge volumes may be reduced by the use of caustic soda instead
of lime for wastewater treatment. This practice offers other
advantages including reduced scale formation and faster reaction
times.
Best Management Practices
If contact is possible with leakage, spillage of raw materials,
or product,, all stornu water and plant site runoff must be
collected and directed to the plant treatment facility. This
contamination can be minimized by indoor storage of chemicals and
proper air pollution, control.
If solids from the wastewater treatment plant are disposed or
stored on-site, provision must be made to control leachates and
permeates. Leachates and permeates which contain toxic
pollutants should be directed to the treatment system for further
treatment.
Advanced Treatment Technology
Zinc-containing residues such as galvanizing wastes and zinc
dusts are often used as raw materials for zinc chloride
production. These materials contain a variety of toxic and non-
toxic metals such as lead, zinc, cadmium, iron and manganese.
The manufacturing process removes much of these metals from the
zinc chloride product in the form of filter cake. Other
372
-------
constituents can be transmitted to the wastewater. Further
reduction of metals would require treatment by granular media
filtration.
One facility producing zinc chloride from an organic wastewater
stream generated at a nearby chemical manufacturing complex may
require treatment technology in addition to the levels considered
here. The water is treated to remove organics as part of the
manufacturing process, but no data is available on the amount of
toxic organics in the wastewater. Elevated COD and the presence
of toxic organics would be pollutants which could occur at this
facility. The presence of these additional pollutants are not
expected to affect the effectiveness Of treatment for metals
removals, as a similar situation occurs at Plant F145 which
provides effective treatment for removal of metals.
Selection of Appropriate Technology and Equipment
Technologies for Different Treatment Levels
A.
Level 1
Level 1 treatment consists of alkaline precipitation,
clarification or settling, dewatering of the sludge in a filter
press, and pH adjustment if necessary. This technology is
illustrated in Figure 10-10. A holding basin sized to retain 4-6
hours of flow is provided.
The initial treatment step is the addition of lime or caustic
soda. This is followed by clarification/settling (if the
wastewater characteristics are suitable, a tube settler may be
substituted for a clarifier to save space). Sludge is removed
from the clarifier and directed to a filter press for dewatering.
Pits are provided at the filter press for the temporary storage
of sludge. The sludge is periodically transported to a hazardous
material landfill. The pH of the treated wastewater stream is
adjusted to an acceptable level by acid addition prior to
discharge if necessary. A monitoring system is installed at the
discharge point. The objective of Level 1 technology is to
remove heavy metals and suspended solids.
Level 1 treatment was selected as the basis for BPT because it
represents a typical and viable industry practice for the control
of suspended solids, arsenic, lead and zinc. All of the direct
dischargers have Level 1 treatment or equivalent already
installed.
B. Level 2
373
-------
plants have equivalent treatment installed.
Equipment for Different Treatment Levels
A Equipment Functions
readily available.
B. Chemical Handling
-^..
Ssed tS reduce the pH of the wastewater prior to discharge.
C. Solids Handling
high, may be sent directly to the, filter press.
Treatment Cost Estimates
374
-------
TABLE 16-6. WATER EFFLUENT TREATMENT COSTS AND RESULTING
WASTE-LOAD CHARACTERISTICS FOR MODEL PLANT
SUBCATEGORY: Zinc Chloride
ANNUAL PRODUCTION:
DAILY FLOW: I.QQQ
PLANT AGE: NA
26.000
METRIC TONS
CUBIC METERS
YEARS PLANT LOCATION:
NA
a. COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS
COST CATEGORY
Facilities
Installed Equipment
Concluding Instrumentation)
Engineering
Contractor Overhead and Profit
Contingency
Land
Total Invested Capital
Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Waste Disposal)120.8 22.5
Residual Waste Disposal 5.9* 0.2
216.6 43.0
COSTS ($1,000) TO ATTAIN LEVEL
1234 5
59.0
305.0 82.2
72.'8 16.4
65.5 14.8
50.2 11.3
552.5 124.7
89.9 20.3
Total Annual Cost
Parameter
pH
TSS
As
Pb
Zn
b . RES
Avg . Cone .
Untreated (
2.6
300
2.8
0.86
150
RESULTING WASTE-LOAD CHARACTERISTICS
Long-Term Avg.
Concentration (mg/1)
After Treatment To Level
rl) 12345
6-9
13
0.5
0.3
0.93
6-9
9.3
0.5
0.035
0.23
LEVEL 2:
c. TREATMENT DESCRIPTION
LEVEL 1: Alkaline precipitation, clarification, sludge dewatering,
inirei 9. c-PS adjustment
ration
375
-------
TABLE 16-7. WATER EFFLUENT TREATMENT COSTS AND RESULTING
WASTE-LOAD CHARACTERISTICS FOR MODEL PLANT
SUBCATEGORY: '' Zinc Chloride
ANNUAL PRODUCTION: 5,700
DAILY FLOW:
PLANT AGE:
METRIC TONS
260
N/A
CUBIC METERS
YEARS PLANT LOCATION:
N/A
a. COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS
COST CATEGORY
Facilities
Installed Equipment
(Including Instrumentation)
Engineering
Contractor Overhead and Profit
Contingency
Land
Total Invested Capital
Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Waste Disposal) 95.7
Residual Waste Disposal
COSTS ($1,000) TO ATTAIN LEVEL
12345
21.6
156.8
35.7
32.1
24.6
270.8
44.1
95.7
2.1
29.4
5.9
5.3
4.1
44.7
7.3
8.9
0.1
Total Annual Cost
Parameter
pH
TSS
As
Pb
Zn
b. RES
Avg. Cone.
Untreated (
2.6
300
2.8
1.6
185
141.9 16.3
RESULTING WASTE-LOAD CHARACTERISTICS
Long-Term Ayg.
Concentration (mg/1)
After Treatment To Level
Ml 12345
6-9
13
0.5
0.3
0.93
6-9
9.3
0.5
0.035
0.23
c. TREATMENT DESCRIPTION
LEVEL 1: Alkaline precipitation, clarification, sludge dewatering, pH
adjustment.
LEVEL 2: Filtration
376
-------
several larger plants which produce over 90 percent of the zinc
chloride in the U.S.
Costs for two model plants were developed because of the wide
variation of plant sizes in this subcategory. The annual
production rates used were 26,000 kkg and 5,700 kkg. The
wastewater flows used were 1000 mVday and 260 mVday
respectively. Costs for the smaller plant were developed on the
basis of the same wastewater characteristics as for the large
plant to represent many plants which produce smaller quantities
of the chemical. Chemical usage and sludge production were
proportioned based upon flow but the small plant was assumed to
use caustic soda while the large plant was assumed to use lime.
Lime is cheaper but produces considerably more sludge, which
cannot economically be reclaimed for zinc. Caustic produces less
sludge and, when pure zinc is used (as is often the case for
small plants), the sludge can be recovered for reclamation of the
zinc.
Chemical reagent usage for wastewater treatment at the two model
plants are estimated as follows:
Large Plant Small Plant
Ca(OH)2
H2S04 (100 percent)
400 kg/day
100 kg/day
88 kg/day (1)
22 kg/day (1)
Total solid waste generated is estimated as follows (Level 2
listings are incremental amounts):
Level
(1)
(2)
Solid Waste
Large Plant
0.39 mVday
0.011 m»/day
Small Plant
0.086 mVday
0.0024 m'/day
Model Plant Treatment Costs. On the basis of model plant
specifications and design concepts presented earlier and in
Section 10, the estimated costs of treatment for two models with
two levels are shown in Tables 16-6 and 16-7. The cost of Level
2 is incremental to Level 1.
Basis for Regulations
Basis for BPT Limitations
A. Technology Basis
377
-------
For BPT, the Agency is setting limitations based upon alkaline
precipitation and clarification, followed by pH adjustment (if
necessary), and dewatering of the sludge in a filter press. Of
the five direct dischargers in this subcategory, all have this
technology or equivalent installed.
B. Flow Basis
For the Zinc Chloride Subcategory, a unit flow rate of 13.5
mVkkg was selected as being representative of the group for the
reasons given above under treatment cost estimates.
C. Selection of Pollutants to be Regulated
The selection of pollutants for which specific effluent
limitations are being established is based on an evaluation of
the raw wastewater data from screening and verification,
consideration of the raw materials used in the process,
literature data, historical discharge monitoring reports and
permit applications, and the treatability of the toxic
pollutants.
Tables 8-1 through 8-14 summarize the achievable concentrations
of toxic metal pollutants from the literature using available
technology options, data from other industries, and treatability
studies. Water use and discharge data are presented earlier in
this section together with generalized process characteristics.
Pollutant concentrations of raw wastewater streams and a summary
of maximum concentrations observed of toxic pollutants detected
during screening and verification sampling at several plants are
also presented earlier in this section. Data from Appendix A on.
the performance of in-place industry treatment systems was also
utilized in developing the list of pollutants to be regulated.
Based upon the occurrence of treatable levels of specific toxic
metals, arsenic, lead, and zinc were selected as candidate toxic
pollutants for BPT regulations. Antimony, cadmium, chromium,
copper, nickel, selenium, silver, and thallium were detected but
at less than treatable levels.
Consideration of the raw wastewater concentrations presented
earlier, industry data, and information in Section 8 related to
the effectiveness of hydroxide precipitation, and clarification
leads to the selection of arsenic, lead, and zinc as toxic
pollutants to be regulated.
D. Basis of BPT Pollutant Limitations
378
-------
^i x£f i°ns are Presented as both concentrations (mg/1) and loads
(kg/kkg), and the relationship between the two is based on the
unit flow rate of 13.5 mVkkg.
BPT limitations, which apply to all
discharged, are presented in Table 16-8.
1. Conventional Pollutants
process wastewater
a. pH
The treated effluent is to be controlled within
the range of 6.0 - 9.0. This limitation is based
upon the data presented in Appendix B of the
Development Document for Proposed Effluent
Guidelines for Phase I Inorganic Chemicals (Ref
1) and the JRB study {Ref. 2).
b. TSS
Three Phase II plants (F125, F115 and F140)
considered to be efficently operating their
wastewater treatment facilities provided long-term
Level 1 treatment system performance data for TSS.
Since no other data from well-operated Level 1
treatment systems was available, and since the
clarification provided at Plants F125, F115 and
F140 for TSS removal would be similar to that
necessary for TSS removal at zinc chloride plants
(Plants F125 and F140 are zinc chloride plants),
the BPT limitations for TSS are based upon the
average of long-term averages calculated from data
collected at Plants F125, F115 and F140. The
long-term average of 13 mg/1 was used to develop
discharge limitations. Variability factors of 1.9
for a monthly average and 3.3 for a 24-hour
maximum were used yielding TSS concentration
limitations of 25 mg/1 and 43 mg/1 respectively.
(See Section 15, BPT Limitations, for derivation
of the variability factors.) Thus, utilizing
these values, one obtains TSS mass limitations for
the zinc chloride subcategory of:
30-day average;
(25 mg/l){13.5 mVkkg) (kg/1 0« mgMlOOO 1/m3)
= 0.34 kg/kkg
379
-------
24-hour maximum;
(43 mg/l)(13.5 mVkkg) (kg/10* mg)(1000
=0.58 kg/kkg
2. Toxic Pollutants
a. Arsenic
The BPT limitations for arsenic are based on
estimated maximum 30-day averages achievable with
Level 1 treatment taken from Table 8-11, and
variability factors computed from long-term data
for zinc at Plant F144 presented in Appendix A.
Using a value of 0.5 mg/1 as a long-term average/
2.0 as a variability factor for 30-day average
computations, and 6.0 as a variability factor for
24-hour maximum computations, concentration
limitations of 1.0 mg/1 (30-day avarage) and 3.0
mg/1 (24-hour maximum) are obtained. Mass
limitations are computed as follows:
30-day average;
(1.0 mg/1) (13.5 m-Vkkg)(kg/10« mg)
= 0.014 kg/kkg
24-hour maximum:
(1000 l/m')
(3.0 mg/1) (13.5 mVkkg) (kg/1 0® mg) (1000 1/m')
= 0.041 kg/kkg
b. Lead
Because there are no long-term performance data
for lead from any zinc chloride plant with Level 1
treatment, the BPT limitations for lead are based
on estimated 30-day averages achievable with Level
1 treatment taken from Table 8-11, and variability
factors for zinc computed from long-term data at
Plant F144 presented in Appendix A. Using a value
of 0.3 mg/1 as a long-term average, 2.0 as a
variability factor for 30-day average
computations, and 6.0 as a variability factor for
24-hour maximum computations, concentration limits
of 0.6 mg/1 (30-day average) and 1.8 (24-hour
maximum) are obtained. Using these values, mass
limitations for lead are calculated as follows:
380
-------
(0.6 mg/l)(l3.5 mVkkg) (kg/10* mg)(1000
= 0.0081 kg/kkg
24-hour maximum;
(1.8 mg/l)O3.5 mVkkg) (kg/1 0«) (1000 l/m»)
= 0.024 kg/kkg
c. Zinc
The BPT limitations for zinc are based on long-
term monitoring data from Plant F118 presented in
Appendix A. The plant has a Level 1 treatment
system. The plant is achieving a long-term
average concentration for zinc of 0.93 mg/1
Variability factors for zinc developed at Plant
F144, and presented in Appendix A, were used
because the data from Plant F118 was not in a form
that could be used to develop variability factors.
These are 2.0 for a 30-day average and 6.0 for a
24-hour maximum. From these values, limitations
or 1.9 mg/1, 30-day average and 5.6 mg/1, 24-hour
maximum, were derived. Utilizing these values
mass limitations for the Zinc Chloride Subcategory
may be obtained as follows:
M-day average;
,
- 0.026 kg/kkg
24-hour maximum;
m3/kkg)( kg/10* mg) (1000 l/m»)
(5.6 mg/1) (13.5 mVkkg) (kg/10« mg) (1000 I/in*)
* 0.076 kg/kkg
Basis for BCT Effluent Limitations
a,.1?
are required according to the revised methodology, a POTW test
and an industry cost effectiveness test. The POTW test is passed
theinren>ental cost per pound of conventional pollutant
dolrTh0m-B?T ^° BCT iS less than $°'46 Per Pound ?n
dollars. The industry test is passed if this
incremental cost per pound is less than 143 percent of
incremental cost per pound associated with achieving I3PT
381
-------
TABLE 16-8. BPT EFFLUENT LIMITATIONS FOR ZINC CHLORIDE
Coventional
Pollutants
Long-Term
Avg-Cmg/1)
VFR
Cone. Basis Effluent Limit
Cmg/1J (kg/kkg) '
3TF~day 24-hr.30-day 24-hr.
max. avg.
max.
TSS
Toxic
Pollutants
Arsenic
Zinc
Lead
13.0
0.93
(4)
0.3
^
1.9/3.3
2/6
2/6
2/6
(3)
(3)
(3)
25
1.0
1.9
0.6
43
0.34
0.58
3.0 0.014 0.041
5.6 0.026 0.076
1.8 0.0081 0.024
VFR - Variability Factor Ratio
(1) Based upon long-term data at Plants F115, F125 and F140,
(2) Based upon Table 8^-11.
(3) Based upon long-term data at Plant F144.
(4) Based upon long-term data at Plant F118.
382
-------
The methodology for the first BCT cost test is as follows:
(1)
Calculate that amount of additional TSS removed by the BCT technology,
(a) BPT long-term average =' 13 mg/i
Level 2 long-term average * = 9.3 mg/1
*(See Sections 11 and 12 for derivation)
(b)
Difference « 3<7 mg/1
Annual flow for model plant:
(13.5 mVkkg)(5,700 kkg/yr)
(13.5 m3/kkg)(26,000 kkg/yr)
76,950 m'/vr "Small
351,000 mVyr "
(0 Total annual additional TSS removed for model plant:
Small Plant:
(3;LmE/:l)(76/950 m3/yr)(kg/10« ing) (1000 l/m3)
= 2B5 kg/yr
= 628 Ibs/yr
Large Plant:
l^Lj^k1/*351'000 m3/yr)(k9/10«mg)(1000 l/m')
* 2864 Ibs/yr
of TSS
Cost'
cost for Levei 2
$16,300 "Small", and $43,000 "Large"
(b) Divide annual ized cost by annual additional TSS removals:
($16,300 per yr) * (628 Ibs/yr) = $25.96 per Ib of TSS
removed for small model plant.
($43,000 per year) t (2864 Ibs/yr) = $15.01 per Ib of TSS
removed for the large
model plant.
383
-------
the first BCT cost test there is no need to apply the second BCT
cost test.
Since the candidate BCT technology failed the BCT - POTW cost
test, EPA is not proposing any more stringent limitations for TSS
under BCT since we have identified no other technology which
would remove additional amounts of TSS. As a result, BCT for TSS
is equal to the BPT limitations.
Basis for BAT Effluent Limitations
Application of Advanced Level Treatment
Utilizing the cost estimates in this report, the Agency has
analyzed the cost of the base level systems (BPT - Level 1) and
an additional advanced level option for toxic pollutant removal.
impacts on the Zinc Chloride Subcategory have been
detail and taken into consideration in the
The economic
evaluated in
determination of the BAT regulations.
For BAT, the Agency is proposing limitations based on treatment
consisting of Level 1 plus Level 2 technology. Toxic pollutants
limited by the proposed BAT regulation are arsenic, lead, and
zinc.
A. Technology Basis
Alkaline precipitation followed by clarification, dewatering of
the sludge in a filter press, and filtration of the clarifier
effluent followed by pH adjustment if necessary form the selected
BAT technology basis.
B.
Flow Basis
A unit wastewater flow rate of 13.5 m3/kkg of zinc chloride has
been selected for BAT (same as BPT).
C. Selection of Pollutants to be Regulated
Toxic Pollutants
The toxic pollutants arsenic, lead, and zinc have been selected
for BAT limitation. Table 16-9 presents the BAT limitations for
the Zinc Chloride Subcategory.
D.
Basis of BAT Pollutant Limitations
As in BPT, the BAT limitations are presented as both
concentrations (mg/1) and loads (kg/kkg). Loadings were derived
384
-------
USing
model plant flow
Toxic Pollutants
a. Arsenic
Because there is no. long-term monitoring data for
?n /AT limitati°ns for arsenic are based on
ron 2~?ay avera9es achievable with Level 2
treatment taken from Table 8-11, and variability
factors computed from long-term data for zinc at Plant
ma/t Presented *n Appendix A. Using a value of 0 5
factor ?nr ?n9^term average' 2'° ™ a variability
lac?°F.1for 30~day average concentrations, and 6 0 as a
m-» maximum) are
imitations are computed as follows:
30-day average;
obtined. Mass
24-hour maximum;
mg)(1000 l/m')
b.
Lead
The BAT limitations for lead are based
lan x
plant achieves a long-term average effluent
lead concentration of 0.035 mg/1. Variability factors
d at Plant/144 were used. These are K25 fo? 1
average and 4.8 for a 24-hour maximum. F?om
values, limitations of 0.044 ma/1
mg/1' 24-hour ^aximum we?e '
are computed as follows;
30-day averae;
tk
these
™
Mass
24-hour maximuma
385
-------
(0.17 mg/l)(13.5 mVkkg) (kg/10« mg)(1000 1/m*)
= 0.0023 kg/kkg
c.
Zinc
The BAT limitations for zinc are based upon long-term
monitoring data from Plant F144, presented in Appendix
A. This plant achieves a long-term average effluent
zinc concentration of 0.225 mg/1. Variability factors
developed for zinc at Plant F144, and presented in
Appendix A, were used. These are 2.0 for a 30-day
average and 6.0 for a 24-hour maximum. From these
values, limitations of 0.45 mg/1, 30-day average, and
1.35 mg/1, 24-hour maximum, are obtained. Mass
limitations are computed as follows:
30-day average;
(0.45 mg/1) (13.5 mVkkg) (kg/10« mg)(1000 1/m')
« 0.0061 kg/kkg
24-hour maximum;
(1.35 mg/l)(13.5 mVkkgH kg/10* mgMlOOO 1/m')
- 0.018 kg/kkg
Basis for NSPS Effluent Limitations
For NSPS, the Agency is proposing limitations equal to BAT for
toxic pollutants and BPT for conventional pollutants since no
additional technology which removes significant additional
quantities of pollutants is known. The pollutants limited
include pH, TSS, arsenic, lead, .and zinc. The NSPS effluent
limitations are listed in Tables 16-8 and 16-9.
Basis for Pretreatment Standards
Existing Sources
The Agency is proposing PSES equal to BAT limitations
because BAT provides better removal of arsenic, lead, and zinc
than is achieved by a POTW and, therefore, these toxic pollutants
would pass through a POTW in the absence of pretreatment.
Pollutants regulated under PSES are arsenic, lead, and zinc.
Table 16-9 contains these limitations.
Using the summary data presented in Table 16-6, the Agency has
estimated that percent removals for arsenic, lead, and zinc by
comparing the untreated waste concentrations for those three
386
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TABLE 16-9. BAT EFFLUENT LIMITATIONS FOR ZINC CHLORIDE
Cone. Basis Effluent Limit
Pollutants
Arsenic
Zinc
Lead
jjong-Term
Ave. (mg/1)
0.5(D
0.225(2)
0.035C2)
VFR
2/6(2)
2/6(2)
1.25/4.79(2:>
30-day
avg.
1.0
0.45
0.044
24-hr,
max.
3.0
1.35
0.17
30-day
avo
0.014
0.0061
0. 00060
24-hr.
0.041
0.018
0.0023
VFR - Variability Factor Ratio
(1) Based upon Table 8-11.
(2) Based upon long-term data at Plant F144
387
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metals with the concentrations of those same three pollutants in
effluent from the selected BAT technology. The calculations are
as follows:
Arsenic; Raw Waste = 2.8 mg/1
BAT =0.5 mg/1
Percent Removal = [(2.8 - 0.5) t (2.8)1(100)
= 82%
Lead:
Raw Waste =0.86 mg/1
BAT = 0.035 mg/1
Percent Removal = [(0.86 - 0.035)/(0.86)](100)
= 96%
Zinc:
Raw Waste = 150 mg/1
BAT =0.23 mg/1
Percent Removal = [(150 - 0.23)7(150)] (100)
= 99.8%
The percent removals are greater than the removals for lead (48%)
and zinc (65%) achieved by 25% of the POTWs in the "40 Cities"
study (Fate of Priority Pollutants in Publicly Owned Treatment
Works,Final Report, EPA 440/1-82/303, September , 1982). Only
limited data is available on removal of arsenic by POTWs, but the
removals for other toxic metals by 25% of the POTWs in that study
ranged from 19% to 65%. We assume that the POTW removals of
arsenic are in that range. Therefore, since the BAT technology
achieves a greater percent removal of arsenic, lead, and zinc
than is achieved by a well operated POTW with secondary
treatment, those three toxic metals would pass-through the POTW
in the absence of pretreatment.
Using the summary data presented in Table 16-6, the Agency has
also estimated the percent removals for lead and zinc by
comparing the concentrations of those two toxic metals in
effluent from BAT treatment with the concentrations of the same
two pollutants in effluent from BAT treatment. Since the
concentrations of arsenic are the same from BPT and BAT
technology, the Agency compared the untreated waste
concentrations for arsenic with the effluent concentration from
BAT treatment for that metal. The calculations are as follows:
Arsenic; Raw Waste =2.8 mg/1
BAT =0.5 mg/1
Percent Removal - [(2.8 - 0.5) t (2.8)](100)
388
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82%
Lead;
BPT
BAT
Percent Removal = [(0.3 -
Zinc;
BPT
BAT
Percent Removal • [(o 93
= 75%
=0.3 mg/1
: 0.035 mg/1
0.035) t (0.3)] (100)
3 0.93 mg/1
s 0.23 mg/1
- 0.23) ^ (0.93)[(100)
toxic metals ranged from
in the absence of pretreatment
New Sources
s
zinc and are listed in Table 1^9
°f
in that study *°r other
the POTW
*>r to.ic
arsenic, lead, and
389
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SECTION 16 REFERENCES
1. U.S. Environmental Protection Agency, "Development Document
for Effluent Limitations Guidelines and Standards for the
Inorganic Chemicals Manufacturing Point Source Category,
EPA Report No. 440/1-79-007, June 1980.
2. ORB Associates, Inc., "An Assessment of pH Control of
Process Waters in Selected Plants," Draft Report to the
Office of Water Programs, U.S. Environmental Protection
Agency, 1979.
390
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SECTION 17
BAT REVISIONS
BACKGROUND
nd are stn n Pc°<™lgated on March 12 1974
' If
''Ihe19lli
- Ins"tute Petitioned the Agency to
o y
°s water
391
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calcium chloride subcategory. The remainder of this section sets
forth the background, rationale for the amendments, and
recommendations concerning each subcategory.
SODIUM CHLORIDE (Solution Brine-Mining Process)
General
The sodium chloride (solution brine-mining process-) subcategory
includes 22 plants (1), none of which are indirect dischargers.
The annual production was estimated at about 3,175,000 metric
tons (3,500,000 short tons) per year in 1981 (3.36 million metric
tons in 1979). The estimated daily discharge is 24,224 mVday
(6.4 million gallons per day) of barometric condensate
wastewater.1 The plants are located in inland rural areas where
the annual precipitation is too high to permit solar evaporation
of the water from the brine to be used to recover the sodium
chloride product. It should be noted that the 1974 rulemaking
considered only the handling of condensate alone rather than
total flow of condensate plus cooling water (see note below).
Process Description
In the production of sodium chloride by the solution brine-mining
process, underground salt deposits are mined by pumping water
into the salt deposit where the water dissolves the salt and
forms a concentrated solution or brine. The brine is then pumped
back to the surface where it is chemically treated to remove
impurities and then evaporated to recover the sodium chloride
(table salt). The chemical treatment varies from plant to plant,
but a typical process will first aerate the brine to remove
dissolved hydrogen sulfide and oxidize any iron salts present to
the ferric state. The brine is then treated with soda ash and
caustic soda to convert most of the calcium, magnesium, iron, and
other metal impurities present to insoluble precipitates (as
hydroxides or carbonates) which are removed by clarification.
The brine is then evaporated using multiple-effect evaporators.
As the water Is removed, the salt crystals form and are removed
as a slurry. The solids are screened to remove lumps, washed
with fresh brine to remove calcium sulfate crystals (which are
returned to the evaporator), filtered, dried, and screened.
amount represents only the actual amount of condensate
before mixture with contact cooling water in the barometric
condenser. The actual total amount of discharged process water
(condensate plus cooling water) is estimated to be 1,454,000
mVday (384 MGD).
392
-------
Water Use and Wastewater Characteristics
rnm wastewater discharged consists essentially of the
barometric condenser water used to condense the steam and
CatSrabCbbLSVab^T ^ /he multiple-effect evaporators As ?h2
carried ovJr' ft ?A evaporates, some salt crystals are
•. v. uthe escaPin9 vapor (become entrained) and are
the barometric condenser water and subsequently
be oesn .f^11^! ties such as toxic pollutants, that may
Pni-r^nS i ! evaporating solution, could also become
?K Si3f2 ? contami«?ate the barometric condenser wastewater
The order of concentration of contaminants in the wastewatJr
from highest to lowest, will be the same as the orde? of thJir
concentrations in the evaporating solution. The residue after
JontamTnan? in^-h^H Pr°^Ct S°^' Acc°rdingly, the most Ukefy
itself barometric condenser wastewater is the product
The technology used as a model for the zero discharge BAT
promulgated in 1974 assumed replacement of barometric cSndlnsers
by surface condensers (e.g., shell and tube condensers ). The
S£ JS?
-------
studies which directly bear on the issue of pollutant
entrapment. These data include the analytical data on
barometric condenser discharge water from two sodium chloride
facilities as well as several plants from other industries.
In the sodium chloride (solution brine-mining) manufacturing
process, the source of the wastewater is barometric condenser
wastewater. Accordingly, we also reviewed data for similar
processes in other inorganic chemicals industries. Relevant data
are available for the chlor-alkali (diaphragm cell), sodium
thiosulfate, sodium chlorate, and ammonium bromide subcategories.
The chlor-alkali (diaphragm cell) data are contained in the
"Development Document for Effluent Limitations Guidelines, New
Source Performance Standards, and Pretreatment Standards for the
Inorganic Chemicals Manufacturing Point Source Category EPA
440/1-82/007 (July, 1982) (3). The data for the sodium
thiosulfate and ammonium bromide subcategories includes both
screening and verification data acquired in 1978 (sodium
thiosulfate) and 1980 (ammonium bromide) and data submitted to
EPA in 1976 and 1980, respectively, in response to our requests
for data under Section 308 of the Act. The data for the sodium
chlorate subcategory were developed under Phase II and are
summarized elsewhere in this document (Section 15 and Appendix
A) The 1974 data included results of analyses for only a few
metals; the more recent data included results of analyses for all
toxic metal and toxic organic pollutants. In all cases, the
products are being recovered from solution by evaporating the
water and condensing the escaping steam using barometric
condensers. Also, in all cases, the existence of toxic organic
pollutants is highly unlikely because organic substances are
neither used in the production process nor likely contaminants of
the raw materials. In any event, no toxic organic pollutants are
likely to be added to wastewater. as the result of the NaCl
process because the process raw material is salt (formed millions
of years ago) and no organic chemicals are added in the process.
Essentially then, we have a purely inorganic process in the case
of sodium chloride produced in the manner described previously.
The data acquired in 1973 for barometric condenser water from
sodium chloride production are presented in the following table
(from Table 22, page 143 of the 1974 Development Document,
Reference 2):
Concentration (mq/1)
Stream
Intake
Effluent
TSS
0
0
DH
8.0
8.1
Ca Cl S
128 65
147 120
0^ Fe
13
37
0
0
394
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Tables
Because
in the
These data show that the barometric condenser discharge contains
some net addition of calcium, sulfate, and chloride, but
essentially no iron. The sodium chloride addition to the
discharge averages 2 pounds per ton of product or 0.1 percent
(page 141 of the 1974 Development Document, Reference 2). The
calcium and sulfate carried over are from the small amount left
after purification of the brine. The absence of any net increase
in iron (Fe) indicates that no toxic metals are carried over
either, because the iron is present in the treated brine at
higher concentrations than any of the toxic metals. Treatment of
the brine to remove iron by precipitation as the hydroxide or
carbonate will also reduce the amount of toxic metals as has been
demonstrated throughout the inorganic chemicals and other
industries. Precipitation of toxic metals (and iron) as the
metal hydroxide is the technology basis for the promulgated BPT
limitations for most of the subcategories of the Inorganic
Chemicals Manufacturing industry. This treatment generally
reduces toxic metal concentrations to less than 1 milligram per
liter and iron concentrations to less than 10 ppm (see the
Development Document for the Inorganic Chemicals Effluent
Guidelines and Standards, EPA 440/1-82/007, July 1982
14-17, 14-18, 14-33b, 14-34, and 14-37, Reference 3).
the toxic metal, iron, sodium and calcium compounds ,.„ ,.„,=
purified brine do not evaporate with the boiling water, the only
way these substances can enter the barometric condenser
wastewater is by entrainment. The most likely substance to be
entrained is the substance present in the purified brine in the
greatest amount, which is the sodium chloride product. Of toxic
metals and iron, the most likely pollutant to be entrained is the
iron since the treated brine contains more iron than any of the
toxic metals. The data above show that the discharge contains
less than 60 ppm chloride (a measure of the amount of sodium
chloride entrained) and no net addition of iron. Treatment of
the brine produces a product that is 99.8 percent pure sodium
chloride, and the data above indicate that much of the impurities
are calcium and sodium sulfates and calcium chloride.
The conclusion to be drawn from the data described above is that
the barometric condenser water discharged from plants in the
solution brine-mining process for sodium chloride production does
not contain toxic metals at significant levels.
The toxic metal discharges in barometric condenser wastewater for
S?««,?5i?r"a}S?li*. > (Plants A-E), sodium
thiosulfate (Plant F), and ammonium bromide (Plant G)
subcategories are shown in Table 17-1.
As shown in Table 17-1, none of the toxic metals are present at
significant levels and most metals are below the detectable
395
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TABLE 17-1
DISCHARGES
Pollutant
Sb
As
Be
Cd
Cr
Cu
Pb
Hg
Ni
Se
Ag
Tl
zn
<20
<2
<50
<50
18
<20
30
B
<20
<25
<50
<50
<0.4
<50 <50
50
<2
:75
BAROMETRIC
Concentration (ug/l(ppb))(D
TOXIC METAL
CONDENSER WASTEWATER
<20
<2
<50
<50
Plant
<20
28
<2
<50
^50
<0.4
<50
<2
<50
<0.4
65
<2
135
E
<3
<0.2
0.3
6.5
6.5
10
20
<2
<50
0.7
1.1
18
28
13
1.6
10
<9
0.9
270
<2
<2
<2
24
22
<3
<5
49
33
25
< = less than
Plants A to E = Chlor-Alkali (Diaphragm Cell)
Plant F = Sodium Thiosulfate
Plant G = Ammonium Bromide
(1) All values are maximum daily values observed from three 24-
hour composite samples obtained during verification sampling
at plants B, Cf Df and G. Values reported for Plants Af E,
and P are the values observed during screen sampling (72-
hour composites).
396
-------
iCtiSns^bein' Ivl Seated"" concentrations of toxic metals
Plant
A
B,C,D
E
F
G
Cu
1,700
600
530
140
Cr
1,900
940
260
•»
Pb
2,000
160
260
220
Ni
22,000
-
-
Zn
1,600
500
240
550
650
?upKrt the conclusions that the
avfilabje from an ammonium bromide
carry-over °
Ammonia
3.2 mg/1 •
Bromide 6.0 mg/1
is the product, and would be
397
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TABLE 17-2,
CHEMICAL COMPOSITION OF BAROMETRIC CONDENSATE
FROM PLANT F122 CALL VALUES ARE AVERAGE OF
THREE DAILY MEASUREMENTS).
Pollutant
Sb
As
Be
Cd
Cr
Cu
Pb
Hg
Ni
Se
Ag
Tl
Zn
Barometric
Condensate
<0.007
<0.002
<0.0002
<0.0037
0.22*
0.022
<0.0016
<0.0013
2.87**
<0.007
0.00027
<0.003
,<0.0025
*Added to the process as sodium dichromate,
**Evaporators are made of a nickel alloy.
398
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"^orators.
beCaUSe
te.1 is used in the
significant'levefs
COntain
data submitted by two
permitting authrites ,3 art oT"^1"9 P^ocess) Plar*s to the
permits for those plant! That SJt- a^ticati°™ for NPDES
pollutants are below Iiqni?ican? ?L0fata !hows a11 toxic metal
detection limit. Si^^iCant levels, and most are below the
Treatment Cost Estimates
sCrfacfcondenser^in'the £diu£°Jhl"?i ^^ °f installati- «£
brine-mining process) a subcategory (solution
"
.
Utilized
the cost
asrss
installation of the solace condanS^S °" Occurrln9 while the
utilized in preparation o^theSe estimates. proceedin9 «»• "een
Saner"! °™
1A C°ndenser
399
-------
120
CS = Cold Steel
SS304 = Stainless
Steel 304
roo
200 300 400 500 600 800 1000
Surface Area in Square Meters
Figure 17.1. SURFACE CONDENSER COST (SOURCE: REFERENCE 4).
400
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TABLE.17-3. WATER EFFLUENT TREATMENT COSTS AND RESULTTNr
WASTE-LOAD CHARACTERISTICS FOR MODEL P LA Si
SUBCATEGORY: Sodium Chi or*A*
ANNUAL PRODUCTION: 397.266
DAILY FLOW:
PLANT AGE:
45.420
METRIC TONS (438,000 short tons)
N/A
CUBIC METERS (total flow); 757 ri* cpndensate
YEARS PLANT LOCATION: N/A
a.
COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS
COST CATEGORY
COSTS ($1,.000) TO ATTAIN LEVEL
1A
IB
Facilities
Installed Equipment
30.0 150.0
Contractor Overhead and Profit
Contingency
Land
Total Invested Capital
Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Waste Disposal)
Residual Waste Disposal v»"*±)
172.3
40.5
861.3
202.3
36.4 182.6
27.9 139.6
307.1 1,535.2
50'. 0 249.8
58.2 245.2
Total Annual Cost 108.2 495.0
b. RESULTING WASTE-LOAD CHARACTERISTICS
Ave. Cone n Long-Term Avg.
*vg. uonc. Concentration (mg/1)
Pollutant Untreated fBg/n 1A Afj£r Tre2atment J° Level
TSS
27
LEVEL 1A:
LEVEL IB:
c.
TREATMENT DESCRIPTION
Surface condenser'- loss of 10% capacity during sununer months
Surface condenser - no loss of capacity
401
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loss of capacity is approximately 10 percent.2 The Level IB
condenser is sized such that there would be no loss in
productivity during such a period. In both cases, the amount of
condensate to be handled was assumed to be the same.
In both cases, a building is provided for the housing of the
condensers.
Facilities
Building
Equipment
Level 1A
85 m2
Surface Condenser
(cold steel) 920
(See Figure 17-1)
Level IB
5 - 85 m2
5 - 920 m2
Operating Personnel 2 m.h./day 5 m.h./day
Level IB condensers are 5 times the size of the level 1A condensers.
Since the available information indicates that the model plant is
a typical plant for the industry, it is estimated that
replacement of barometric condensers with surface condensers
would require a total capital and annual investment as follows
(1982 dollars):
Total Capital Costs
Total Annual Costs
Level 1A
$7,277,600
$2,514,600
Level IB*
$36,388,000
$11,613,800
* Sized for no loss of capacity during summer months
The level 1A costs do not include the costs associated with the
loss of 10% of the production capacity. Because available data
lead to the conclusion that the barometric condenser wastewater
in this subcategory does not contain toxic pollutants at
significant levels, the Agency does not believe these costs are
justified. Therefore, we propose to withdraw the currently
effective BAT regulation for this subcategory.
2If the temperature of the incoming cooling water is greater than
25°C (77°F), a greater loss of capacity would result.
402
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Sf.1. 5r°£™ to exclude tne subcategory from further national
BAT and PSES regulation development because based on the
available data it is concluded that the wastewater does not
contain toxic or nonconventional pollutants at significant levels
and because there are no indirect dischargers in this
subcategory. For new sources, the cost of surface condensers is
about the same as the cost for barometric condensers. Therefore
a new plant can install surface condensers from the start, and
there is no need to change the currently effective NSPS or PSNS
for this subcategory.
Basis for BCT Effluent Limitations
On October 29, 1982 EPA proposed a new and revised methodology
,?? termination of BCT for conventional pollutants (47 FR
76). The methodology has been described in detail in several
C
Two candidate BCT technologies have been tested in this
subcategory, namely, the use of surface condensers in place of
barometric condensers to eliminate the discharge of total
suspended solids (TSS), and the use of filters to reduce the
discharge of TSS (TSS is the only conventional pollutant in the
A. Option 1 - Surface Condensers
The use of surface condensers at 22 plants is estimated to be
"SSc »i« ?T removin9 approximately 540,000 kg (1,188,000 Ib) of
TSS annually at a cost of $2,514,600 (for the Level 1A, or
smaller condenser). The annual cost for the industry using the
larger condenser with no loss of capacity would be $11,613,800.
Therefore, the computation of TSS removed would be as follows:
(BPT limitation) (ann. production) » TSS removed/yr.
(0.17 kg/kkg) (3,175,000 kkg/yr) = 539,750 kg/yr
For the surface condenser option as BCT:
$2,514,600/vr
540,000 kg/yr
$4.66/kg (1 kg = 2.2 Ibs.)
$2.12/lb. TSS removed (1982)
As a result of the above computation, the candidate BCT
technology failed the BCT - POTW cost test. Since the LevJl 1A
option failed the BCT cost test, inclusion of costs due to loss
of production and production capacity, or applying the BCT cost-
403
-------
test to the more expensive Level IB would also fail the test
because the amount of TSS removed would not change with these
more expensive options.
B. Option 2 - Granular Media Filtration
The use of granular media filtration at 22 plants is estimated to
be capable of removing 300,000 kg (660,000 Ib.) of additional TSS
(over BPT) annually at a cost of $5,500,000. The TSS removals.
were estimated by assuming the filter would remove 50% of the
TSS. This removal is better than that normally expected from a
filter, and tends to minimize the cost per pound of TSS removed.
The cost of the filter has been estimated using the cost tables
in Chapter 10.
(Additional TSS removed) (Ann. prod.) - Add. TSS removed/yr.
(0.09 kg/kkg) (3,175,000 kkg/yr) = 300,000 kg/yr.
For the granular media filtration option as BCT:
$18.33/kg (1 kg = 2.2 Ibs.)
$8.33/lb. TSS removed (1982)
$5,500,000/vr
300,000 kg/yr
As a result of the above computations, the candidate BCT
technology failed the BCT-POTW test ($0.43 per poundJ1982)).
Since both candidate BCT technologies failed the cost test, and
no other less expensive technology options have been identified
which would remove additional amounts of TSS and pass the test,
EPA proposes to establish BCT limitations for the sodium chloride
(solution brine-mining process) subcategory equal to the
currently effective BPT.
CALCIUM CHLORIDE (Brine Extraction Process)
General
The calcium chloride subcategory (brine extraction process)
includes seven plants, none of which are indirect dischargers.
Three of these facilities are known to achieve zero discharge by
reinjection of the brine, and none of the seven have a process
water discharge. Four plants are located in desert areas of
California, and three are located in Michigan. All seven use
natural brines as raw material. The annual production capacity
of calcium chloride from all processes is 1,047,585 metric tons
(1,155,00 short tons) per year(5). The U.S. Bureau of Mines
reported actual total production of 735,700 metric tons (811,135
short tons) in 1980, however, 526,978 metric tons (581,012 short
404
-------
tons) or 71.6 percent were produced from natural sources (brines)
Cacf ''aT" elther 3S Solid
^
grocess Description
'
A typical concentration of the brine is (2):
CaCla 19.3% Bromides n •>**
Nlcl2 I'll gther Minerals o.ll*
NaCl 4.9% water 70.8%
Water Use and Wastewater Characteristic
405
-------
In 1974, one plant was visited and used as the basis of BPT
limitations. At this plant, process wastewater resulted from
process blowdown and from several partial evaporation steps. The
effluent from this plant contained approximately 2,860 cubic
meters/day (0.755 MGD) of washdown and washout water.
At this plant, the wastewater from all chemical manufacturing
processes located at the site was treated in an activated sludge
treatment plant to remove organic substances, and then passed to
a settling basin to remove suspended matter. The pH was then
adjusted and the water passed to a second pond to further settle
suspended matter, and finally discharged. In 1974, the plant
planned on making a change in the evaporators to reduce or
eliminate calcium chloride discharges and eliminate ammonia.
More recycling of spent brines was also planned.
During a follow-up study in 1976, considerable changes had been
made in the usage of water at this plant. Average total
wastewater discharge (including noncontact cooling water) was
reduced from 31,600 cubic meters per day (8.35 MGD) in 1974 to
11,550 cubic meters per day (3.05 MGD) in 1976. Currently (1983)
the discharge consists solely of noncontact cooling water. A
surface condenser was installed to eliminate discharges from a
barometric condenser. The condensate from the surface condenser
is now recycled and is estimated at approximately 1458 cubic
meters per day (385,000 gpd). Approximately 955 mVday (252,000
gpd) of concentrated brine is returned to the formation.
In late 1982 and early 1983, a survey of all seven plants in this
subcategory was conducted to determine the discharge status of
all seven plants. The results of this survey and data gathered
previously are listed below:
Plants
Zero Discharge3
Indirect Discharge4
This survey was conducted by consulting the 1982 SRI Directory of
Chemical Producers (7), by telephone contact with each of the
plants, review of the 1974 Development Document and the Phase I
rulemaking record and a previous contractor's report (8).
3Includes three plants known to be zero discharge and three
others located in inland, arid and areas; these facilities
reinject waste brine because of a scarcity of process water
available.
4A11 plants confirmed that they were not indirect dischargers or
were located in rural areas with no POTW.
406
-------
There are no known dischargers in this industry.
Recommendations
Chan9es
the
"- -ass
are no
existing
•3-r^ . Effluent Limitations. Since there
dischargers, there is no need for a BCT.
SODIUM SULFITE
General
.«
407
-------
per year and a total average daily discharge of 568 cubic meters
(0.15 MGD). However, as stated above, there are now only three
plants included in the sodium sulfite subcategory, with a
substantial decrease in capacity.
After receiving the petition from the Salt Institute to review
the sodium chloride subcategory, EPA decided to reconsider the
BAT for the sodium sulfite subcategory {soda ash -sulfur dioxide
process). BAT for this subcategory requires no discharge of
"process wastewater pollutants" except for excess water
discharged from wastewater impoundments designed to contain the
25-year - 24-hour storm. BPT, however, allows a continuous
discharge.
Process Description
In the soda ash-sulfur dioxide reaction process, sulfur dioxide
gas is passed into a solution of sodium carbonate until the
product is acidic. At this point the solution consists
primilarly of sodium bisulfite which is converted to sodium
sulfite by the further addition of soda ash and heat until all
the carbon dioxide is released.
The crude sulfite formed from this reaction is purified, filtered
to remove insolubles from the purification steps, crystallized,
dried and shipped.
Water Use and Wastewater Characteristics
The process water generated in this subcategory consists
primarily of evaporator/crystallizer condensate, condensed dryer
vapor, filter'washwater, and process cleanout water. Wastewater
volumes are generally low, and for the three plants in this
subcategory are as follows;
Plant
Capacity* Direct/Indirect
B
C
27,210 kkg
33,560 kkg
9,070 kkg
69,840 kkg/yr
Direct
Direct
Indirect
Flow
16.4 m'
330.0 m*
70.0 m*
Treatment
pH adjust,
oxidation,
filtration
pH adjust, oxidation,
settling
None
416.4 mVday
Treatment technologies in use by the direct dischargers are
equal to or better than those used in the sodium bisulfite
subcategory.
408
-------
follows:
f°r devel°Pment of the BPT limitations were as
Process condensate
Dryer ejector and
filter wash
m Vkko
0.17
0.29 - 0.63
based upon the wastewater stream from the
range (63mVkKg) ?*** "*** °*erations * the high end of Si
ash*- su?furbi?nv?Lthe t^'ee remaining P^nts utilizing the soda
of 2 2 m3fvka*i f«? rea^ion process yield an average unit flow
ot 2.2 m^ kkg** (581 gal/ton) for all wastewater discharged.
/ TT~ Ltnis subcategory is oxidation of the sulfite to sulfate
(usually by aeration) and filtration of the wastewater to removl
suspended solids. BPT effluent limitations in effect are:
Parameter
PH
TSS
COD
Limitations
(30 day average)
6-9
0.016 kg/kkg
1.7 kg/kkg
(24-hr Maximum)
0.032 kg/kkg
3.4 kg/kkg
*Reference 7
**Range: 0.22 mVkkg to 3.6 m'/kkg
409
-------
The treatment technology used as a basis for the zero discharge
BAT limitations, NSPS, and PSNS was evaporation of the treated
process wastewater. This technology was believed to be
economically achievable based on 1971 fuel costs and the sale of
the residue (sodium sulfate) from the evaporation. Those plants
located in areas of the country where evaporation exceeded
precipitation could use solar evaporation to achieve no discharge
of process wastewater pollutants. However, for plants that
cannot use solar evaporation, the cost of fuel has quadrupled
since 1971, whereas the selling price of sodium sulfate has
increased only slightly.
Review of_ Available Data
Data specific to the sodium sulfite industry are contained in the
1974 Development Document (Reference 2), and we also have data
from sodium sulfite plants submitted to EPA in 1976-77 in
response to our request for data under Section 308 of the Act.
The data specific to sodium sulfite contain limited information
about the amount of toxic pollutants in the wastewater. However,
the sodium sulfite production process is very similar to the
production process for sodium bisulfite (compare the 1974
Development Document, pp. 154-8, with the 1982 Development
Document, page 711). The major differences are that sodium
sulfite is collected from the reaction mixture at a higher pH and
that purification of the sodium sulfite, at least at one plant,
includes the addition of small amounts of copper.
Since the raw materials are the same for sodium sulfite and
sodium bisulfite, and since the unit flows are nearly the same
(2.2 mVkkg for sodium sulfite and 1.5 mVkkg for sodium
bisulfite), we estimated the total toxic pollutant load for the
sodium sulfite industry based on the observed total toxic
pollutant loads found at sodium bisulfite plants, with allowance
for a slightly higher flow for sodium sulfite and for the use of
copper during purification of sodium sulfite (these factors
increased estimated raw waste loads above those observed at
sodium bisulfite plants). We also considered the fact that both
direct discharge plants reported in their responses to our 1976
request for data that the plants have treatment systems identical
to those used in the sodium bisulfite industry. Those treatment
systems do control discharges of toxic metals and chemical oxygen
demand (COD). In addition, sodium sulfite and sodium bisulfite
wastewaters are commingled for treatment in common treatment
plants at both of those facilities.
Table 17-4 summarizes
observed in treated
the toxic pollutant concentration data
effluent during verification sampling from
410
-------
TABLE 17-4. TOXIC POLLUTANT CONCENTRATIONS OBSERVED IN
TREATMENT EFFLUENT DURING VERIFICATION SAMPLING
Pollutant
Arsenic
Copper
Zinc
Cadmium
Chromium
Lead
Mercury
Nickel
Antimony
Thallium
Silver
Concentration fmg/1)
PliHtPlant
.1987 |586
ND
0.27
0.010
ND
0.11
0,15
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.010
0.050
0.020
ND
ND
ND - Not Detected
411
-------
the two sodium bisulfite plants visited during Phase I. Both
plants employ hydroxide precipitation, aeration, and settling.
All toxic metal levels are below detection levels or are
marginally treatable by the technologies examined elsewhere in
this document for metal salts production. All concentrations
listed in the table are below the proposed BPT and BAT
limitations for the same parameters listed in Sections 11 through
16.
Comparison of_ Sodium Sulfite and Sodium Bisulfite Subcateqories
The discussion above points out the similarity between the Sodium
Sulfite and Sodium Bisulfite Subcategories. Our review of both
subcategories has shown that the processes and raw materials for
the two chemicals are the same. In the case of sodium sulfite
the process is taken further to completion. Examination of the
wastewater flows shows that the unit flows for the two processes
were nearly identical (1.5 mVkkg vs. 2.2 mVkkg), and the
wastewater treatment technology in use at the plants was
identical. In addition, both of the direct discharge sodium
sulfite plants also produce sodium bisulfite and the wastewaters
are commingled in a -common treatment system. Table 17-5 is a
summary and comparison of the two subcategories pointing out the
similarities between them.
Treatment Cost Estimates
Based upon last quarter 1982 costs, treatment cost estimates were
prepared for the, three existing plants. The only technology
considered was evaporation because the existing BAT was based
upon this technology. Table 17-6 summarizes, the cost data
developed.
Based upon these estimates, installation of the existing BAT
technology at all three plants would require the following
investment:
Total Capital Costs
Total Annual Costs
$1,916,200
$2,817,100*
Based on these costs, our Economic Impact Analysis for this
subcategory predicts at least two plant closures and severe
impacts for the other plant assuming the one indirect discharger
had to comply with the currently effective BAT. Considering that
5Annual costs include energy costs which are very high
BAT technology (evaporation).
for the
412
-------
TABLE 17-5. COMPARISON OF SODIUM SULPITE
AND SODIUM BISULFITE SUBCATEGORIES
Plants
Unit Flow
Process
Raw Materials
Treatment Tech.
In Place
BAT
Sodium Sulfite
3
2.2 m3/kkg
Soda Ash - S02
NaC03, S02
OH Pptn., Aeration,
Filt. or Settling
Zero Discharged)
Sodium Bisulfite
7
1.5 m3/kkg
Soda Ash - S02
OH Pptn., Aeration
Settling
Discharge subject
to 40 CFR 415.542
(1) Currently in effect. To be modified by this proposal
413
-------
JABLE 17-6..WATER EFFLUENT TREATMENT COSTS AND RESULTING
WASTP.-I.OAD CHARACTERISTICS FOR MODEL PLANT
SUBCATEGORY: Sodium Sulfite
ANNUAL PRODUCTIONS-27.210:6-33.560:0-9, METRIC TONS
oTo
.DAILY FLOW: A-16.4;B-550;C-70 CUBIC METERS
PLANT AGE:
N/A
YEARS PLANT LOCATION: DE. VA. CA
a. COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS
COST CATEGORY
Facilities
Installed Equipment
(Including Instrumentation)
Engineering
Contractor Overhead and Profit
Contingency
Land
Total Invested Capital
Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Wast6 Disposal)
Residual Waste Disposal
Total Annual Cost
COSTS ($1,000) TO ATTAIN LEVEL 1
Plant A Plant B Plant C
$152.6 $1,012.8 $373.8
30.5 202.6 74.8
27.5 182.3 67.3
21.1 139.8 51.6
$231.7 $1,537.5 $567,5
37.7
180.4
32.9
$251.0
250.2
1,622.2
92.3
399.7
674.5 144.5
$2,546.9 $636.5
Parameter
TSS
COD
TDS
b. RESULTING WASTE-LOAD CHARACTERISTICS
Avg. Cone.
BPT
Effluent Loading kg/kkg
After Treatment To Level
B C
0.016 kgAkg
1.7 kg/kkg
70,000-90,000 mg/1
0
0
0
0
0
0
0
0
0
c. TREATMENT DESCRIPTION
PLANT A: Evaporation - Agitated Falling-Film Evaporator (to dryness)
PLANT B: Evaporation - Multiple Effect Evaporator plus Agitated Falling-
Film Evaporator
PLANT C: Evaporation - Multiple Effect Evaporator plus Agitated Falling
Film Evaporator
414
-------
£33
Basis for ProEosed BCT Effluent Limitations
«»I76>. The
has
-thodology
<47 *
wastewater and contained
metals. TSS is the only
wastewater. Filtration was ..w
because the BPT limitations were
precipitation, aeration, and filtration.
this
all
so ids COD and
,„ thfBPrUmf?atiLsh;ndandiHat?.teChn°10^ ma* be
the- subcategory: limitations and production capacity for
(0.016 kg/kkg) (69,840 kkg/yr) . 1,117.4
Therefore:
**''}7'.l°%%r. " $2'512-'2/*9 TSS removed , 2.2 Ib/kg
= $l,141.87/lb TSS removed (1982)
ssr ssssr
Basis for Proposed. BAT Effluent Limitations
415
-------
TABLE 17-7. BAT AND BCT EFFLUENT LIMITATIONS FOR SODIUM SULFITE
Conventional*- '
Pollutants
PH
TSS
30-day avg.
0.016
Effluent Limitations
_
24-hour max.
0.032
Non-Conventional
Pollutants
COD
1.7(2)
3.4(2)
Toxic Pollutants
Chromium (T)
Zinc (T)
0.00063(3)
0.0015(3)
0,0020(3)
0,0051(3)
(1) Within the range 6.0 to 9.0
(2) Based upon BPT promulgated for Sodium Sulfite Subcategory
(40 CFR Sec. 415.202).
(3) Based upon BAT promulgated for Sodium Bisulfite Subcategory
(40 CFR Sec. 415.542).
(4) BCT only.
416
-------
e " s- a
ft* y'ss^^ -S.»E
discharge for this subcategory should be withdrawn
to.ic-i.tS'a nonfcSioLf p^L^^ed ^isr &
w1sa-th^aiJi?s:iioSc^jrs'1»sssoss!:'2g.«i;f;1siioS:
already in effect for the sodium bisulfite subcategory. Jm tl°ns
subcategory. Su""narlzes the limitations being proposed for this
-SB
the BAT limitations are based upon the BPT technology
Basis for NSPS Effluent Limitations
. —^ ~~,,..^ TIWWJ.U we: me same as
technology basis for BAT is the same as for BPT.
Basis for Pretreatment Standards
facility adds small amounts of copper in the
S Parameter will be effectively controlled bv
1 the limitations f- the other
417
-------
The Agency does not have raw waste load data for sodium sulfite
manufacturing but does have such data for sodium bisulfite
manufacturing. Because of the similarities in the processes and
wastewater sources, the sodium bisulfite raw waste load data for
COD chromium, and zinc have been used as the raw waste loads
expected from sodium sulfite manufacturing. These concentrations
are compared to the treated effluent long-term average
concentrations for the selected BAT technology for sodium sulfite
to estimate the percent removals for COD, chromium, and zinc.
The calculations are as follows:
COD:
Raw Waste = 1960 ppm
BAT = 550 ppm
Percent Removal = [(1960-550)t{1960)](100)
= 71.9%
Chromium;
Raw Waste =1.95 ppm
BAT =0.22 ppm
Percent Removal =
[(1.95-0.22)*(1.95)1(100)
88 = 7%
Zincs
Raw Waste * 1.81 ppm
BAT =0.52 ppm
Percent Removal
- [(1.81-0.52)*(1.81)1(100)
= 71.3%
The percent removals of chromium, zinc, and COD are greater than
the- removals for chromium (65%), zinc. (65%), and COD (72-s)
achieved by 25% of the POTWs in the "40 Cities" study (see Fate
of Priority Pollutants in Publicly Owned Treatment Works, Final
Report, Volume I, EPA-440/1-82-303, September 1982). - Therefore,
chromium, zinc, and COD would pass through a POTW in the absence
of pretreatment.
Existing Sources
There is one indirect discharger in this subcategory which
discharges 70 cubic meters per day (18,500 gpd) to a POTW. Total
toxic metal pollutant loading for this single facility are
estimated to be 0.053 kg/day (0.12 Ib/day). This estimate is
based on the COD data provided by the Plant. That data shows
that the average COD discharge is less than the long-term average
COD used to develop the COD effluent limitations. Since the
toxic metals are in the wastewater with the COD, the toxic metals
are also estimated to be low in concentration and about equal to
their long-term average concentrations. On the basis of flow and
418
-------
low toxic pollutant loading, we propose to exclude this
subcategory from further PSES development under Paragraph
8(b)(n) of the EPA-NRDC Settlement Agreement. -yrapn
New Sources
The Agency is proposing PSNS that are equal to NSPS because these
standards provide for the removal of toxic metals which may Sals
through a well operated POTW with secondary treatment in ?he
Pretreatment The pollutants regulated under PSNS
419
-------
SECTION 17
REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
U.S. Bureau of Mines, "Directory of Companies Producing Salt
in the United States - 1981," Mineral Industry Surveys,
prepared in the Division of Industrial Materials.
U.S. Environmental Protection Agency, "Development Document
for Effluent Limitations Guidelines and New Source
Performance Standards for the Major Inorganic Products
segment of the Inorganic Chemicals Manufacturing Point
Source Category," EPA-440/l-74-007a, March 1974.
U.S. Environmental Protection Agency, "Development Document
for the Inorganic Chemicals Effluent Guidelines and
Standards," EPA 440/1-82-007, July, 1982.
Peters, M.S. and Timmerhaus, K.D., "Plant Design and
Economics for Chemical Engineers," Third edition, McGrawHill
Book Co., 1980.
Chemical Marketing Reporter, "Chemical Profile - Calcium
Chloride," December 25, 1978.
U.S. Bureau of Mines, "Minerals Yearbook - 1980," Vol.
Meals and Minerals.
Stanford Research
Producers - 1982".
Institute, "Directory of
I,
Chemical
"Supplement for Pretreatment to the Development Document for
the Inorganic Chemicals Manufacturing Point Source
Category," EPA 440/1-77/087.
Terlecky, P.M. and Harty D.M^, "Status of Group II Chemical
Subcategories of the Inorganic Chemicals Manufacturing
Industry of {Phase ID," Frontier Technical Associates, Inc.
Report No. FTA-82-E-2/03 Revised January 14, 1983.
420
-------
SECTION 18
PRETREATMENT STANDARDS
FOR DEFERRED SUBCATEGOR I ES
INTRODUCTION
General
stlnlardHSre
, t ,o
Subcateqor i es Surveyed
The 23 subcategories surveyed are as follows:
Borax
Bromine
Calcium Carbide**
Calcium Chloride**
Chromic Acid
Fluorine
Hydrogen***
Iodine
Calcium Oxide**
Calcium Hydroxide
Potassium Chloride
12. Potassium (metal)**
1
2
3
4,
5.
6,
7.
8,
9.
10.
11 .
13. Potassium Sulfate**
14. Sodium Bicarbonate**
15. Sodium Chloride**
16. Sodium Sulfite**
17. Stannic Oxide
18. Zinc Sulfate
19. Aluminum Sulfate*,**
20. Ferric Chloride*
21. Lead Monoxide*
22. Potassium Dichromate*,**
23. Sodium Fluoride*
*Subcategories with existing PSES.
**Subcategories with existing PSNS.
Category.
421
-------
An accurate and up-to-date list of all companies and plants which
manufacture the products in the 23 subcategories was developed.
Sources utilized in compiling that list included: the Stanford
Research Institute's "Directory of Chemical Producers - 1982" (1)
the OPD Chemical Buyers Directory (2), the Salt Institute's
membership list, the U.S. Bureau of Mines (3), the Lime
Association, the Thomas Register, in-house files at EPA and the
contractor, and a previous EPA survey. All plants identified
from the above sources were contacted to determine which plants
and facilities in each subcategory were indirect dischargers.
Some of the plants initially identified were subsequently
determined to be distributors or repackagers and were not
producing the chemical.
The several sources listed above identified 304 plants in 22
subcategories (all except the Hydrogen subcategory). Information
on 302 of those plants was provided through telephone or written
contacts with the plants, by Regional and State NPDES permit
authorities, and from local POTW authorities. The two plants
which could not be contacted are located in remote, rural areas
where there are no POTW's. For the hydrogen subcategory
(refinery by-product), there are 137 plants listed in addition to
those above. However, any discharges to POTW's are controlled
under existing PSES and PSNS for the Petroleum Refining
Subcategory (40 CFR 419).
Basis for PSES Exclusions
Paragraph 8(a)(i) of the Settlement Agreement authorizes the
Administrator to exclude from regulation industrial categories or
subcategories for which equal or more stringent, limitations are
already provided by existing effluent limitations and standards
(in this case, the Hydrogen Subcategory). Paragraph 8(b) of the
Settlement Agreement authorizes the Administrator to exclude from
regulation under the pretreatment standard a subcategory if (i)
95 percent or more of all point sources in the subcategory
introduce into POTWs only pollutants which are susceptible to
treatment by the POTW and which do not interfere with, do not
pass through, or are not otherwise incompatible with such
treatment works; or (ii) the toxicity and amount of the
incompatible pollutants introduced by such point sources into
POTWs is so insignificant as not to justify developing a
pretreatment regulation.
SURVEY RESULTS BY SUBCATEGORY
This section summarizes the results obtained for the 23
subcategories surveyed. Subcategories 1 through 18 have no
422
-------
Subcateqories _N-]_8
1. Borax
2. Bromine
e
3. Calcium Carbide
uncovered6
subcategory. Calcium
under the Lrroa!^
4. Calcium Chloride
in this subcategory.
5. Chromic Acid
Carblde
s in this
£
chloride by the brine
or indirect dischargers
6. Fluorine
h!^5%1are- tw° known Producers
hydrofluoric acid electrolysis
dischargers in this subcategory.
7. Hydrogen
423
-------
subcategory is subject to effluent limitations for the
Refining Point Source Category (40 CF1 Pt. 419).
Petroleum
8.
Iodine
There are three known producers of iodine but only one plant
discharges to a POTW. That one plant discharges approximately
200 gpd to a POTW.
9. Calcium Oxide (Lime)
There are 50 known facilities producing calcium toxide. ,(lime^;
There are no indirect dischargers. One plant could not be
contacted but is located in a remote, rural area far from a POTW.
10. Calcium Hydroxide (Hvdrated Lime)
There are 37 known producers of hydrated lime. One_ of these
discharges to a POTW, and two discharge directly. A total of 33
facilities achieve zero discharge because they are dry
operations, by recycle, and by impoundment and eyfP?"^0"; ,Th®
discharge status of one facility is unknown, but it is located in
a remote, rural area far from a POTW. The single indirect
discharger discharges only 200 gallons/day (10 gpm for 20 mm.)
to a POTW.
11. Potassium Chloride
There are eight known producers of potassium chloride by the
Trona process and by the mining process (40 CFR 415.500) at
present. There are no indirect dischargers in this subcategory.
12. Potassium (Metal)
There is one known producer in this subcategory which does not
discharge process wastewater from potassium metal manufacturing
to a POTW.
13. Potassium Sulfate
There are six known producers of potassium sulfate none of which
discharge to POTWs.
14. Sodium Bicarbonate
There are four known plants producing sodium bicarbonate. Three
plants do not discharge process wastewater while one plant
commingles wastewater from sodium bicarbonate production with
424
-------
?OTWC Pr°CeSS wastewater, treats it and then discharges to a
Parameter
Average Concentration (mg/1)
<0.029 <0.0011
15. Sodium Chloride
employing both processes are included here!
a.
which
bringing ana
Sy °f plants
b.
.
None of these plants discharge to POTWs
Solar Evaporation Process. There are 39 known
producers of sodium chloride by the solar evaporation
process. There are no indirect discha?ge?s. P
Both processes (a and b) are employed at some facilities.
16. Sodium Sulf ite
felt on °" o£etntsl?eo1rt eth2££Sati°n.and a"alyS?S PrSe"ted5?°
this subcatlgory frol^SK. ' Cy 1S Pr°P°sin9 'o exclude
17. Stannic Oxide
425
-------
with air or oxygen. No wastewater is produced and there is no
discharge.
18. Zinc Sulfate
There are 12 known producers of zinc sulfate. There are two
indirect dischargers. One of these discharges an average of 4000
gpd to the POTW. Flows are less than 1 percent of plant flow.
The zinc sulfate process discharge at the second plant amounts to
less than 350 gpd, which is less than 1 percent of total plant
discharge to the POTW.
Subcateqories 19-23
Thi's group of five categories represents chemicals for which PSES
are already in effect. The purpose of this review was to
determine if the current regulatons are adequate for control of
toxic pollutants.
19. Aluminum Sulfate
There are 70 known producers of aluminum sulfate at present. Of
these, only two discharge indirectly. One of these two plants
discharges less than 1000 gallons per year to the POTW, while the
discharge to a POTW from the second is in compliance with the
currently effective PSES.
PSES
follows:
In Effect. Current PSES in this subcategory are as
Parameter
Zinc (Total)
PSES (30-day avg./24-hr, max.)
2.5/5.-0 mg/1
Since these concentrations are similar to those promulgated for
other subcategories in Phase I, the existing PSES are believed to
be adequate.
20. Ferric Chloride
There are eight known producers of ferric chloride from pickle
liquor. Only one plant in this subcategory currently discharges
indirectly while four achieve zero discharge.
PSES in Effect. Current PSES in this subcategory are as follows:
Parameter PSES (30-day avq./24-hr, max.)
Cr (Total)
Cr (VI)
1.0/3.0 mg/1
0.09/0,25 mg/1
426
-------
Cu (Total)
Ni (Total)
Zn (Total)
0.5/1.0 mg/1
1.0/2.0 mg/1
2.5/5.0 mg/1
believed to be adequate
2 1 . Lead Monoxide
for other
, the existing PSES are
-
dr^els and"
£SES in Effect, current PSES in this subcategory are as follow,
Parameter DQPC iir* j
- — L PSES (30-day avn. /74-hr. ma».
(TOtal)
. for other
the existing PSES are
believed to be adequate.
22 • Potassium Dj.chr ornate
ESHS in Effect, current PSES in thl. subcategory are as follow,
PSES
Cr (VI)
Cr (Total)
0.090/0.25 mg/1
• 0/3.0 mg/1
Se.ner h for other
believed to be adequate. ^nerefore, the existng PSES are
23. Sodium Fluoride
There are four known producers of which two discharge indirectly
IB Mfect. current PSES in this subcategory are as follows:
PSES
427
-------
Fluoride
25/50 mg/1
One plant is known to produce less than 1000 pounds per year of
sodium fluoride, which would generate an insignificant flow.
Control of fluoride, as required by the PSES, involves lime
precipitation and clarification. This technology not only
removes fluoride from the wastewater but also effects the removal
of any toxic metal pollutants that may be present in the
untreated wastewater. Therefore, the existing PSES are believed
to be adequate.
PROPOSED EXCLUSIONS
The Agency proposes to exclude from national PSES regulation
development the twelve subcategories listed below under Paragraph
8 b(ii) of the Settlement Agreement because there are no indirect
dischargers in the subcategory:
No Indirect Dischargers
Borax
Bromine
Calcium Carbide
Calcium Chloride
Chromic Acid
Fluorine
Calcium Oxide (Lime)
Potassium Chloride
Potassium Metal
Potassium Sulfate
Sodium Chloride
Stannic Oxide
jl^j L X 11^— *^ w»*»* •» * *• ^* ^f •• •• —• —
The Agency proposes to exclude the following subcategories from
PSES development under Paragraph 8 (b)(ii) because the discharge
to POTW from the one indirect discharger in each subcategory is
so insignificant due to low flow or low quantities of toxic
pollutants: •
One Indirect Discharger
Iodine
Hydrated Lime
Sodium Bicarbonate
Sodium Sulfite (See also Section 17)
The zinc sulfate subcategory has two indirect dischargers.
However, the total flow of both plants is very low (15.9 cubic
meters per day (4200 gallons per day)) and in each case is less
than 1 percent of the plant total daily flow to the POTW. The
Agency proposes to exclude this subcategory from categorical PSES
for zinc sulfate under Paragraph 8 b(ii).
The Hydrogen (By-product from Petroleum Refining) subcategory is
included under the promulgated PSES for the Petroleum Refining
Point Source Category.
428
-------
TABLE 18-1. SUMMARY OP THE DISCHARGE STATUS OF ALL
PSES SUBCATEGORIES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
Borax
Bromine
Calcium Carbide
Calcium Chloride
Chromic Acid
Fluorine
Hydrogen
Iodine
Lime
Hydrated Lime
Potassium Chloride
Potassium (Metal)
Potassium Sulfate
Sodium Bicarbonate
Sodium Chloride (brine)
Sodium Chloride (evap.)
Sodium Sulfite
Stannic Oxide
Zinc Sulfate
Aluminum Sulfate(3)
Ferric Chloride(3)
Lead Monoxide(3)
Potassium Dichromate(3)
Sodium Fluoride(3)
Discharge Method
Plants
4
8
3
7
2
2
*(137)
3
50
37
8
1
6
4
22
39
3
1
12
70
8
9
1
4
Other**
4
8
3
7
2
2
*
2
49
35
8
1
6
3
22
39
2
1
10
68
7
9
1
2
Indirect
0
0
0
0
0
0
*
1
0
1
0
0
0
1
0
0
1
0
2(2)
2
1
0
0
2
Unknown
0
0
0
0
0
0
*
0
id)
Id)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
(1) One plant unable to be contacted, thought to be zero or direct.
(2) Plow at both plants Is 1OM, and iess than 1, of plant flow to POTW.
(3) PSES currently in effect.
429
-------
Subcategories with PSES In Effect
Information was developed during the survey to show that the PSES
in effect are adequate, therefore, no change is proposed for the
PSES following five subcategories:
Aluminium Sulfate
Ferric Chloride
Lead Monoxide
Potassium Bichromate
Sodium Fluoride
PROPOSED PSNS
The 12 subcategories for which no PSNS are currently in effect
are:
Borax
Bromine
Chromic Acid
Fluorine
Iodine
Calcium Hydroxide
Potassium Chloride
Stannic Oxide
Zinc Sulfate
Ferric Chloride
Lead Monoxide
Sodium Fluoride
Each of the above subcategories is currently subject to a zero
discharge requirement under BPT. Therefore, a PSNS equal to BPT
would not be a barrier to entry since existing plants are
required to achieve zero discharge of process wastewater
pollutants and meet that requirement.
The Agency proposes PSNS for each subcategory based upon the
currently effective BPT, which for each subcategory requires zero
discharge of process wastewater pollutants.
There are also no New Source Performance Standards (NSPS) for
these 12 subcategories. However, none are needed since, in the
absence of an NSPS, a new plant is subject to the currently
effective BPT effluent limitations of zero discharge of process
wastewater pollutants.
430
-------
SECTION 18
REFERENCES
3.
4.
Minerals, Mineral Intry Suveys, JVp
°£
Salt
for
t
the inorganic Chemials M«nSf J'1?p"ent
Category, " Calspan Selort No ND-B^wV ^ ?°Urce
(Survey conducted in 1 976 ) . 5782-M-85, 17 March 1977
5.
6.
Industry -
Report So.
»
Manufacturing
. Inc?
pM,
by the New York DEC, Region 7? ' SU"""ary °f data
Dr. T.
431
-------
SECTION 19
EXCLUDED SUBCATEGORIES
INTRODUCTION
The Inorganic Chemicals Manufacturing Point Source Category has
been divided into 184 subcategories for regulatory purposes. On
June 29, 1982 the Agency promulgated effluent limitations
guidelines and standards for 60 of those subcategories (the Phase
I guidelines). The Agency is now proposing effluent limitations
guidelines and standards for 17 additional subcategories (the
Phase II guidelines). The Agency is proposing to exclude 104 of
•the remaining 107 subcategories from national regulation
development. One subcategory is deferred for regulation under
another, more appropriate guideline. The Agency also proposes to
amend the applicability section of one promulgated inorganic
chemical subcategory to include an additional product
representing two subcategories.
The determinations in this section complete the examination
required by the Settlement Agreement of all remaining
subcategories covering the chemical products listed under SIC
Codes 2812, 2813, 2816, and 2819. The methods used, sources
examined, a summary of the determinations, and the rationale for
the proposed exclusions are provided in this section.
Subcateqories Surveyed
The 1-07 subcateogries surveyed are listed in Table 19-1.
Methods Employed
An accurate and up-to-date list of all companies and plants which
manufactured the products in the subcategories was compiled.
Sources utilized include: The Stanford Research Institute s
"Directory of Chemical Producers - 1982", (2) The OPD Chemical
Buyers Directory (3), the Thomas Register, in-house files at EPA
and the contractor and previous surveys for EPA. The purpose of
this survey was to identify which plants and facilities were
producing the individual chemicals, and to determine the
discharge status of the plants in each subcategory. Some of the
plants identified from the above sources were subsequently
determined to be distributors or repackagers, and were not
producing the chemical.
Information was obtained through telephone contacts with
knowledgeable personnel at 269 plants. Additional information
432
-------
Table 19-1. Inorganic Chemical Subcategories Surveyed
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.
46.
47.
48.
49.
50.
Aluminum Chloride
Aluminum Compounds
Aluminum Hydroxide (Hydrated Alumina)
Aluminum Oxide (Alumina)
Alums (also 6, 55, 77)
Ammonia Alum (also 5)
Ammonia Compounds
Ammonia Molybdate
Ammonia Perchlorate
Ammonia Thiosulfate
Barium Compounds
Barium Sulfate
Barytes Pigments
Beryllium Oxide
Bleaching Powder (Calcium Hypochlorite, No. 20)
Boron Compounds (not produced at mines)
Borosilicate
Brine Chemicals
Calcium Compounds (Inorganic)
Calcium Hypochlorite (Bleaching Powder. No. 15)
Cerium Salts ' '
Chlorosulfonic Acid
Chrome Oxide (Chrome Pigments)
Chromium Sulfate
Deuterium Oxide (Heavy Water)
Hydrated Alumina Silicate Powder
Hydrogen Sulfide
Hydrophosphites
Indium Chloride
Industrial Gases
Inorganic Acids (except nitric and phosphoric acid)
Iodides
Iron Colors
Iron Oxide (Black) (iron Oxide Pigments)
Iron Oxide (Magnetic) (Iron Oxide Pigments)
Iron Oxide (Yellow) (iron Oxide Pigments)
Lead Arsenate
Lead Dioxide, Brown
Lead Dioxide, Red
Lead Silicate
Lithium Compounds
Magnesium Compounds, Inorganic
Manganese Dioxide (Powdered Synthetic)
Mercury Chloride
Mercury Oxide
Nickel Ammonium Sulfate
Nitrous Oxide
Ochers (Iron Oxide Pigments, No. 34-36)
Oleum (Sulfuric Acid)
Oxidation Catalyst made from Porcelain
433
-------
Table 19-1. (continued)
51. Pechloric Acid
52. Peroxides (Inorganic)
53. Potash Alum (Potassium Aluminum Sulfate, also 5)
54. Potash Magnesia
55. Potassium Aluminum Sulfate (also 5, 53)
56. Potassium Bromide
57. Potassium Carbonate
58. Potassium Chlorate
59. Potassium Compounds, Inorganic
60. Potassium Cyanide
61. Potassium Hypochlorate
62. Potassium Nitrate and Sulfate
63. Rare Earth Metal Salts (Salts of Rare Earth Metals, No.
65)
64. Reagent Grade Chemicals
65. Salts of Rare Earth Metals (Rare Earth Metal Salts, No,
63)
66. Satin White Pigment
67. Siennas (Iron Oxide Pigments, No. 34-36)
68. Silica, Amorphous
69. Silica Gel
70. Silver Bromide
71. Silver Carbonate
72. Silver Chloride
73. Silver Cyanide
74. Silver Iodide
75. Silver Nitrate
76. Silver Oxide
77. Soda Alum (also 5)
78. Sodium Antimonate
79. Sodium Compounds, Inorganic
80. Sodium Cyanide
81. Sodium Hydrosulfite (Zinc Process)
82. Sodium Silicofluoride
83. Stannic and Stannous Chloride
84. Strontium Carbonate
85. Stronium Nitrate
86. Sulfide and Sulfites
87. Sulfocyanides (Thiocyanates also 91)
88. Sulfur
89. Sulfur Chloride
90. Sulfur Hexafluoride
91. Thiocyanates (also 87)
92. Tin Compounds
93. Ultramarine Pigments
94. Umbers (Iron Oxide Pigments, No. 34-36)
95. White Lead Pigment
96. Whiting (Calcium Carbonate)
97. Zinc Sulfide
434
-------
Table 19-1. (continued)
Radioactive Materials.
98.
99.
100.
101.
102.
103.
104.
105.
106.
107.
Cobalt 60
Fissionable Materials
Isotopes, Radioactive (also 98)
ES
Radium Chloride (also 101, 106)
Radium Luminous Compounds (also 101
Uranium Slugs, Radioactive
10S)
<-•»
435
-------
was gathered from 69 of those 269 plants through industry
responses to EPA's requests for information under S308 of the
Act. Engineering visits were made to 16 of the plants, and 14 of
the 16 were sampled. Supplemental information was provided by
NPDES permit authorities and by POTW authorities. The proposed
exclusions and other actions described in this section are based
on the data acquired by the Agency through this survey.
EXCLUDED SUBCATEGORIES
Miscellaneous Inorganic Chemicals
1. Aluminum Chloride (Anhydrous). There are presently five
plants in this subcategory. Two plants achieve zero
discharge while two plants are direct dischargers and there
is one indirect discharger. The two direct discharging
plants discharge a total of less than 37.9 cubic meters per
day (<10,000 gpd) of wastewater. Because of this low
volume, the Agency does not expect significant amounts of
toxic or nonconventional pollutants to be discharged and
therefore proposes to exclude the subcategory under the
provisions of Paragraph 8 (a)(iv) because the amount and
toxicity of each pollutant does not justify developing
national regulations. PSES are currently in effect for this
subcategory.
2. Aluminum Compounds. Specific aluminum compounds not
addressed elsewhere are:
a. Aluminum Nitrate - Three plants, low production (<4.5
kkg/yr (<10,000 Ib/yr each)).
b. Aluminum Silicate - There is one plant which has no
discharge.
The Agency proposes to exclude the above chemicals under
Paragraphs 8(a)(iv) and 8(b) of the Settlement Agreement because
(1) the low production results in low flow and thus loading; and
(2) there is no discharge of process wastewater from the plant
making the chemical.
3. Aluminum Hydroxide (Hydrated Alumina). The promulgated BPT
and BAT limitations, NSPS and PSNS for hydrated alumina are
contained in 40 CFR 421.10 (Subpart A - Bauxite Refining
Subcategory of the Nonferrous Metals Manufacturing Point
Source Category). Under the provisions of Paragraph 8
(a)(i), this subcategory is proposed for exclusion from any
further regulation development under the inorganic chemicals
point source category because the wastewater from the plants
436
-------
4.
5.
6.
7.
in the subcategory is controlled
limitations guidelines and standards.
by other effluent
Aluminum Oxide (Alumina). BPT, BAT, NSPS, and PSNS
limitations and standards have been promulgated {40 CFR
421.10 Subpart A - Bauxite Refining Subcategory of the
Nonferrous Metals Manufacturing Point Source Category).
Under the provisions of Paragraph 8 (a)(i), this subcategory
is proposed for exclusion from any further regulation
development as part of the inorganic chemicals manufacturing
point source category because the wastewater from the plants
in the subcategory is controlled by other effluent
limitations guidelines and standards. The current effluent
limitations would continue to apply.
"Alums". This subcategory represents the consolidation of
four subcategories as originally listed in Table 19-1:
ammonia alum (No. 6), potash alum (No. 53), potassium
aluminum sulfate (No. 55), and soda alum (No. 77). The
subcategories were consolidated because production methods
and probable pollutants are expected to be the same. There
is only one producer of alums and that one plant does not
discharge process wastewater.
Therefore the Agency proposes to exclude this subcategory
under Paragraphs 8 (a)(iv) and 8(b)(ii) because there are no
known dischargers.
Ammonia Alum. (See subcategory No. 5 above)
ammonium compounds, not
Ammonia Compounds. Specific
addressed~elsewhere are:
Ammonium Bisulfite - There are three plants in this
subcategory. Two plants achieve zero discharge. The
remaining plant discharges about 10,000 gallons per
year to a POTW. The Agency proposes to exclude this
chemical-from national BAT regulation under Paragraph
8(a)(iv) of the Settlement Agreement. In addition, the
single indirect discharger is proposed for exclusion
from categorical PSES under Paragraph 8(b)(ii) because
the low flow is too insignificant to justify a national
regulation.
Ammonium Dichromate - There is only one plant in this
subcategory. This plant, a direct discharger, also
produces sodium dichromate and combines the wastewater
for treatment and discharge. This chemical is proposed
for exclusion from national BAT and PSES regulation
437
-------
development under Paragraphs 8(a) (iv) and 8(b)(ii) of
the Settlement Agreement based upon the fact that there
is only one plant and there are no indirect
dischargers.
c. Ammonium Fluoride - There is only one plant producing
this chemical in quantity. This plant does not
discharge process wastewater. Two other plants produce
a very pure product (reagent grade) in very low
quantities (<4.5 kkg/yr). Both of these plants achieve
zero discharge. This chemical is proposed for
exclusion because there are no dischargers (Paragraphs
8(a)(iv) and 8(b)(ii)).
d. Ammonium Fluoborate - There is only one plant producing
this chemical and that plant does not discharge process
wastewater. This chemical is proposed for exclusion
under Paragraphs 8(a)(iv) and 8(b)(i) of the Settlement
Agreement because there are no dischargers.
e. Ammonium Sulfide. - There are two plants producing this
chemical, but the product is produced in solution form
only and no effluent is produced because all water used
is incorporated into the product. This chemical is
proposed for exclusion under Paragraphs 8(a)(iv) and
8(b)(ii) of the Settlement Agreement because there is
no discharge of process wastewater.
f. Ammonium Tungstate - There are two plants producing
this chemical each employing a different production
process. One of the facilities disposes of wastewater
in an evaporation pond and achieves zero discharge.
Therefore, there is only one discharging facility which
is a direct discharger.
This chemical product is proposed for exclusion based
upon Paragraphs 8(a)(iv) and 8(b)(ii) of the Settlement
Agreement because there is only one discharger.
8. Ammonium Molybdate. There are two plants producing this
chemical. One plant has no discharge, while the second
plants produces a reagent grade product in small amounts
(<4.5 kkg/yr (<5 tons/yr)). This chemical is produced only
intermittently. All plant wastewater is commingled with all
other product wastewaters and treated in a treatment system
equivalent to BAT technology prior to discharge. The Agency
proposes to exclude this subcategory Paragraphs 8(a)(iv) and
8{b)(ii) of the Settlement Agreement because there is only
one discharger.
438
-------
°
'"•
£*?* deE^eY'V^re^a-bl N°, ^ ' °^"Jc SlS?^S
SBi^^™^8:iffl«£SBas
11• Barium Compounds. Inorganic
at a limited number of
addressed elsewhere are:
arb,
Barium
these
c.
d.
Barium Hydroxide - This chemical is produced at (•„,.,-
e.
produce reagent grade chemicals
439
-------
12,13.
nroduction One of these plants is known to achieve
lert SiscKarge The other three plants (two direct and
one indirect) are estimated to discharge a total of
less than 10,000 gallons per year.
Barium Perchlorate - There are two plants producing
this chJmical. One achieves no discharge by recycle
whi?e tnS second discharges to a POTW. Production at
the second plant is less than 2.3 kkg/yr (5000 Ib/yr).
BecauS! of the very low production, discharges of toxic
pollutants would be insignificant.
The Aaency proposes to exclude all of the above
chemict! VodScts under Paragraphs 8 a)(iv) and
8(b)(ii) of the Settlement Agreement (low loading
because of low flow) .
Barium Sulfate,. Barvtes Pigments. In each
subcateqory there is only one plant which produces the
chemfcH In bulk, and toother plants that have very
low production rates. None of the small producers
d?schlrges process wastewater. The Agency proposes to
exclude each subcategory under Paragraphs 8(a) iv) and
8(b)(ii) because there is only one discharger in eacn
subcategory. The Agency considered combining the
Jubcategories because the products «"e^nSi
the production processes, raw materials, and
pollutants are significantly different for each plant .
Hence combining the subcategories was not technically
feasible.
15.
=Non-Ferrous"Metals Category (40 CFR Part ._...
new stud? of ?hls category by EPA is currently underway
(proposal expected February, 1984).
Calcium Hypochlorite, No. 20). See
jte that sodium perborate is sometimes
also "referred to"as" bleaching powder. Sodium perborate is
addressed under Sodium Compounds (Subcategory No. 79).
16. Boron Compounds (Not produced at Mines).
compounds not addressed elsewhere are:
Inorganic boron
a. Boron Trifluoride - Two plants produce this chemical on
a specialty basis with very low production. Generally,
440
-------
e.
f.
17.
Produced two or three times per
lon,
gallons per year.
etimated to be
Plant Produces this chemical
ha™ an evaP°ration pond to achieve no
discharge of process wastewater.
chemicaldondf ," ^f ^ °nly one Plant Producing this
chemical on a specialty basis with very low production.
Boron Nitride - There are three' plants producing this
chemical at present. All three discharge to a POTW bit
flows are low (two plants discharge less than 3 8 cubic
Tfnn* Per day.each <<1000 gpd). The third plant Sow
is unknown but is expected to be similar (and low) to
known toC h£r°dUCeiS beCaUSS Pr°cess technologies are
known to be similar. Hence, the total flow is
estimated to be about 3,000 gallons per day.
nnn ' The Prod"ction of this chemical is
non-aqueous process with no discharge of process
wastewater. There are two plants
but there
two
No
its
of
to
to
produced in small
So waStewa?er
Lithium Metaborate - This chemical is produced at
Drforfi-v0" i? .sPfcialty ba^is with lo5 production.
priority pollutants are known to be involved in
production. One plant achieves zero discharge
process wastewater. The other plant is estimated
All of the above chemicals are
fHtlfcihS aat few Plants with
441
-------
18,
19,
Brine Chemicals. Brine refers to strong salt solutions.
This subcategory has been interpreted to mean chemicals
produced from brine. Most of these chemicals have been
considered separately (e.g., calcium chloride, sodium
chloride). Four salts which have not been considered
separately are sodium, calcium, potassium and ammonium
bromide.
There are five plants producing these four products.
However, only two plants (direct dischargers) have a
discharge of process wastewater. Screening and verification
sampling at one of those two plants show that no toxic or
nonconventional pollutants were found at treatable levels.
Relevant data are presented in Table 19-2b. Most plants
return spent brines to their source without addition of
toxic materials, because the process is primarily an
extractive one.
The Agency proposes to exclude this subcategory under
Paragraphs 8(a)(iii), 8(a)(iv) and 8(b)ii) because no toxic
or nonconventional -pollutants were detected at treatable
levels.
Calcium Compounds (Inorganic).
not addressed elsewhere are:
Inorganic calcium compounds
Calcium lodate - There are four plants producing this
chemical but only one is a bulk producer. This plant
does not discharge process wastewater from this
product. The other three produce a reagent grade
product in very low quantities and one of the three
small plants does not discharge. The two dischargers
(one direct and one indirect) are estimated to
discharge a total of less than 5,000 galIons'per year.
Calcium Nitrate - This chemical is produced only as a
reagent grade material 'at three locations, therefore
production quantities are low with little wastewater
generated. Only one of those three plants discharges
process wastewater. Since the raw materials are lime
or calcium carbonate and nitric acid, chemical grade
raw materials would be used producing little toxic
pollutants.
Calcium Stannate - There are three plants producing
this chemical with only two dischargers, one direct and
one indirect. The two plants produce limited
quantities of the chemical as a specialty product and
442
-------
is
and loading).
, low
20.
21.
are chlor-alkali plants
ion, low flow
«• four
' and the other
siar
•»"»«•* the
.111 (an
8(b)(ii).
tor exclusion under
EPA proposes to
the
*
process wastewaters are ?n«
standards for chlor-Ilkal? n?
presented in Tabfe l!4c "Jlant
• these
exifting guidelines and
Relev^t data are
443
-------
22,
earth hydroxides imported from France (7). The second
plant, an indirect discharger, obtains rare earth oxides and
treats them with various acids to produce the salts. Little
effluent is produced by this process (about 40 gallons per
day) Consideration was given to combining this subcategory
with rare earth metal salts, but this was rejected because
the processes employed in this subcategory are substantially
different as are the raw materials used.
Since there are only one direct and one indirect discharger,
and since the indirect discharger has such a low flow, the
Agency proposes to exclude this subcategory from further
regulation development under Paragraph 8(a)(iv) and 8
(b)(ii) of the Settlement Agreement.
Chlorosulfonic Acid. No toxic pollutants were detected at
treatablelevels during screening and verification sampling
at one plant of the three plants producing this chemical.
Effluent wastewater discharged at this plant was the same as
influent water quality. Relevant data are presented in
Table 19-2d. This subcategory is proposed for exclusion
under the provisions of Paragraphs 8(a)(iii), 8(a)(iv) and
8(b), because toxic pollutants were not detected at
treatable levels during screening and verification sampling,
hence the toxic pollutant discharges were too insignificant
to justify developing a national regulation.
Chromium Oxide (a. Chrome Pigment). Chromium oxide is
defined as a chrome pigment in the promulgated guidelines
for the Chrome Pigments subcategory. The promulgated BPT,
BAT, and BCT limitations and NSPS, PSES, and PSNS for the
Chrome Pigments Subcategory are at 40 CFR 415.340.
Therefore, the Agency proposes to exclude this subcategory
from further consideration (Paragraph 8(a)(i)>. The current
effluent limitations would continue to apply.
Chromium Sulfate. There is only one plant producing this
chemical, therefore the Agency proposes to exclude this
subcategory under Paragraphs 8(a)(iv) and 8(b)(ii).
Heavy Water (Deuterium Oxide). There are no producers of
deuterium oxide (heavy water) in the U.S. today. Therefore
the Agency Proposes to exclude this subcategory under
Paragraphs 8(a)(iv) and 8{b)(ii).
26. Hvdrated Alumina Silicate Powder. There is one plant
currently producing this chemical, and this plant has no
discharge of process wastewater. Therefore, the Agency
23
24.
25.
444
-------
27,
28,
29,
30,
31
proposes to exclude
8(a)(iv) and 8(b)(ii).
this subcategory under Paragraphs
Hydrogen Sulfide. There are four plants producing hydrogen
sulfide essentially as a by-product. Three of the plants
are petroleum refineries and one is an organic chemicals
plant. Wastewater for the three plants producing hydrogen
sulfide at petroleum refineries is subject to effluent
limitations for the Petroleum Refining Point Source Category
(40 CFR 419). These limitations are applicable to all
discharges from any facility producing petroleum products by
the use of topping, catalytic reforming, cracking,
petrochemical operations, and lube oil manufacturing whether
or not the facility includes any process in addition to
those listed above. There is .only one other plant.
Therefore, the Agency proposes to exclude this subcategory
from national regulation development under Paragraph
8(a)(i), 8(a)(iv), and 8(b).
Hydrophosphites. This chemical is no longer produced in
this country. Therefore, the Agency proposes to exclude
this subcategory under the provisions of Paragraphs 8(a)(iv)
and 8(b)(ii) because there are no k'nown producers.
Indium Chloride. There are three plants in this subcategory
but only one has a discharge. All plants produce small
quantities as a specialty product. The Agency proposes to
exclude this subcategory under Paragraphs 8(a)(iv) and
8(b)(n) because there is only one discharger.
Industrial Gases. Specific industrial gases not addressed
elsewhere are the "rare" or "inert" gases produced in
conjunction with oxygen and nitrogen from liquefaction of
air (e.g., neon and argon). In Phase I, oxygen and nitrogen
were excluded under Paragraph 8(a)(iv) because the amount
and toxicity of each pollutant observed in samples collected
from plants in the subcategory did not justify developing
national regulations (see the Phase I Development Document,
p. 806). Since the inert gases are produced simultaneously
with oxygen and nitrogen from the same liquid air, and the
wastewaters were included in the samples collected in Phase
I, the Agency proposes to exclude these products also under
the provisions of Paragraph 8(a)(iv) and 8(b)(ii).
Inorganic Acids (except nitric and phosphoric acid). The
only common inorganic acids not addressed elsewhere are:
a. Hydrobromic Acid - There is no discharge of
wastewater from production of this chemical.
process
445
-------
b.
33.
34,
Hydriodic Acid - There is no discharge of process
wastewater from production of this chemical.
Since there is no process wastewater discharged from
this subcategory, the Agency proposes to exclude it
under the provisions of Paragraphs 8(a)(iv) and
32. Iodides. Specific iodides not addressed elsewhere are:
a. Calcium Iodide - There is only one plant producing this
chemical and that plant has no discharge of process
wastewater from calcium iodide production.
b. Lithium Iodide - There are two plants producing this
chemical, but neither has a discharge of lithium iodide
process wastewater.
c. Sodium Iodide - There are two plants producing this
chemical in bulk form, but only one has a discharge.
That plant discharges an estimated 1000 gallons per
year directly to a receiving stream.
Since there is only one discharger, with a discharge of
only 1000 gallons per year, this subcategory is
proposed for exclusion under the provisions of
Paragraphs 8(a)(iv) and 8(b)(ii).
Iron Colors. Iron colors can be broadly subdivided into two
groups: those colors based upon various iron oxides (see
No. 34-36 below), and those colors, generally blue, based on
iron- cyanide complexes. The products based upon iron oxides
are considered below under iron oxides (iron oxide
pigments). There is only one plant (a direct discharger)
producing iron cyanide-based pigments. The Agency proposes
to exclude this subcategory under Paragraphs 8(a)(iv) and
8(b)(ii) because there is only one plant.
35, 36, 48, 67, and 94. Iron Oxide(s) (Iron Oxide Pigments) .
These subcategories include the Iron Oxides (Black, Yellow,
and Magnetic) and the Ochers, Siennas, and Umbers
Subcategories. Four plants, one direct and three indirect
dischargers, produce iron oxide pigments by an inorganic
chemical process. One other plant produces iron oxide
pigments by an organic chemical process. Most iron oxide
pigments producers use a mechanical (grinding) process.
Based upon screening and verification sampling at two of the
four inorganic chemical plants, there^. are no toxic
pollutants at treatable levels discharged from any of these
446
-------
42.
f?Vr ?Jants: Relevant data are presented in Table IQ ?f
"•
41 '
Lead Wfl-nt,,' subcategory
- SPficific "">!•» compounds not addressed
tt
three
b.
^
Magnesium Compounds (Inorganic)
compounds not addressed elsewhere are
Specific magnesium
a.
447
-------
d.
e.
f.
four plants produce the product from magnesium
hydroxide and hydrochloric acid by a process which
generates no wastewater. Hence there are no
dischargers.
Maanesium Fluoride - This chemical is produced from
Sonuoric acid and magnesium hydroxide on a
specialty basis at two plants. The total Auction is
less than ten tons per year, which results in an
insignificant discharge.
Maanesium Nitrate - There are five plants producing
2h?S chSnical, however, the two large plants have no
discharge of process wastewater from this product. The
othSr three Pplants (one direct and two indirect
dischargers) produce specialty or reagent grades only
in small quantities. The total flow is estimated to be
less than 20,000 gallons per year.
Magnesium Silicate - There are only two plants, and one
has no discharge.
Maanesium Sulfate - There are five plants producing
this cSical, but none of the plants have a discharge.
Magnesium Carbonate - There are four Plants (three
direct and one indirect) producing magnesium carbonate
but each uses a different raw material source and
production process (ore, by chemical process, from
ocean brine, and solution mining). Since each plant
usSs an entirely different process and raw material
sou?ce? thl identity and quantity of pollutants would
be different for each process. Hence, this chemical
would require different subcategories each with one
p?ant. The one indirect discharger is estimated to
discharge less than 5,000 gallons per year because of
its very low production rate.
The Agency proposes to exclude this subcategory under
Paragraphs 8(a)(Iv) and 8(b). For magnesium carbonate two
of the four plants are producing small quantities, while all
four of the plants produces by a different process.
43. Magnesium
and 8(b)(ti), because there is only one discharging
plant
448
-------
44'
46
47.
§iiriSiSllsiRis-nJh?re-lsonly.05e plant pacing this
cnemical. The plant is an indirect discharger and is
required by the POTW to control its discharge9 using an
add-on*! Jevei technology. That technology inv?lve£
?h?i ?? 1 treatment beyond that used as the basis for the
chlor-alkali BAT limitations and therefore toxic pollutant
are expected to be insigSif {£££?
-bcategory
45. Mercury Oxides. There is only one plant producing this
S^r^'hi T^ /Pla2fc is the sameP PlantP that^oduces
S«S ryf.chlorjde (Product No. 44 above) and combines the
wastewaters from boch products for treatment. For the
S?SSS2Lpr!8ented,f2r excludin9 mercury chloride, the Agency
proposes to exclude this chemical subcategory under
Paragraphs 8(a)(iv) and 8(b). • unaer
Nicel Ammonium Sulfate. There are two plants producing
has n° discharge of process wastewate?
-The second P^duces reagent and
h« . chemicals along with hundreds of other
chemicals in small quantities. All combined wastewater is
treated in an advanced level treatment system prior to
discharge. Monitoring data confirms the absence of toxi?
pollutants at treatable levels at this plant. Therefor^
under
Nitrous Oxide There are six plants in this subcategory,
all of which are indirect dischargers. Total process
wastewater discharge at all six plants is only 30 000
gallons per day Screening and verification sampling of'all
the process wastewater sources at two plants showed that no
Sli? K?r nonc9nventional pollutants are discharged at
treatable levels in process wastewater from plants in this
f?nJ?te??^' <-Th? ^!ening and v^ification sampling of tne
levSL i!J? «?fc b°th PJant? detected ammonia at excessive
levels, but at very low levels in all process wastewater
sources contributing to that final effluent. Relevant data
fh6 Pre?ented in Table 19-2e. At one plant, the water in
the discharge trench was so low that the trench had II be
2S5fS ^ ™ai!S the water level so samples could be
obtained The dam was constructed of ceramic clay wrapped
in an old burlap sack found at the plant. This could have
introduced pollutants into the sample causing the hiah
thatenlan?Und' ^ ^T^ C°Uld n°? be *™c*ss related 2
Sm«iS because all process wastewater sources were
sampled and. no ammonia was found at treatable levels in
449
-------
those sources. At the second plant, the source of the
ammonia is believed to be fugitive ammonium nitrate dust
(the raw material for nitrous oxide production). Proper
control of dust emissions to the air could correct this
problem. The Agency proposes to exclude this subcategory
under Paragraphs 8(a)(iv) and 8 b(ii).
48. Ochers (Iron Oxide Pigments). See Iron Oxide Pigments,
Subcategories No. 34, 35 and 36.
49,
50,
51
52.
Oleum (Sulfuric Acid). Oleum is sulfuric acid. Sulfuric
acid has been excluded from further national BAT regulation
in Phase I because no toxic pollutants were found at
treatable levels during screening sampling (see the Phase I
Development Document, pages 830, 832).
Oxidation Catalysts Made from Porcelain. There are no
plantsproducing this material in the U.S. The Agency
proposes to exclude this subcategory under Paragraphs
8(a)(iv) and 8(b)(ii).
Perchloric Acid. There is only one plant which produces
thischemical. The Agency proposes to exclude this
subcategory under Paragraphs 8(a)(iv) and 8(b)(ii).
Peroxides (Inorganic). Specific peroxides not addressed
elsewhere are:
Sodium Peroxide - There is only one plant producing
this chemical by a dry process. Therefore there is no
discharge of process wastewater.
Potassium Peroxide - There are no producers of this
chemical in the United States today.
The Agency proposes to exclude this subcategory under
Paragraphs 8(a)(iv) and 8(b)(ii) because there are no
discharging facilities.-
53. Potash Alum. This subcategory has been addressed under the
"Alums" Subcategory, No. 5.
54. Potash Magnesia. There are two plants producing this
chemical from ore. These plants are located in an arid area
and dispose of all aqueous wastewater in evaporation ponds
with no discharge.
a.
b.
450
-------
-><-
"•
56.
57. Potassium
chemical ^ produced at only one
58,
59
and the discharge is insignificant.
Potassium Chlorate - There is only one pro*
onlyndne
direct
a-
8.ot
f ^chargers. One plant produces less than 45
/7 °f Pr°dUCt and all wastewaterrm
hundreds
Hundreds
uction
chemicals produced at that <5it-« =.
' dvanced ^astewater treatment
0*5 c^«^
to be less than 5/000 gllons pe? yelr S
h , is produced on a
basis (i.e., low production quantities) at
drhKnS-u EaCh Plant (one direct and SS5 iSdlreSt
discharger) makes numerous other reagent and SDerialfG
oe j.ess tnan 10,000 gallons per year.
451
-------
61
62.
c.
d.
e.
60.
Potassium Thiocyanate - There is one plant producing
this chemical In quantity while two other plants have
very low production rates. The process is essentially
dry and there are no dischargers.
Potassium Silicof luoride - There is one plant Producing
this chemical but no process wastewater is discharged
from this product.
Potassium Silicate - No toxic pollutants Attributable
to potassium silicate production were detected during
screening and verification at on© plant of three
producing the chemical. The process is identical to
the process used to produce sodium silicate except for
the substitution of potassium hydroxide for sodium
hydroxide when the potassium salt is made. Sodium
silicate was excluded in Phase I because no toxic
pollutants were detected at treatable levels in
untreated wastewater at the one plant sampled.
The Aaencv proposes to exclude all of the above chemical
product; in thisPsubcategory under Paragraph 8(a)(iv) and
8(b)(ii) of the 'Settlement Agreement because of low
production resulting in little or no discharge and thus
insignificant discharges of toxic and nonconventional
pollutants.
Potassium Cyanide. There are only two plants producing this
chemical at present. One achieves zero discharge by total
recycle, and the second plant discharges proce *s wastewater
to a POTW after treating for cyanide removal by alkaline
chlorination.
The
to exclude this subcategory under
pretreating wastewater before discharge to the POTW.
Potassium Hvpochlorate. This chemical is no lo"9^ produced
in the United States. The Agency proposes to exclude this
subcategory under the provisions of Paragraphs 8(a)(iv) and
Potassium Nitrate and Sulfate. The potassium sulfate
s^i!e^ry£LlJaT^xcTUdedn^r^hase I BAT development because
the promulgated BPT and BAT for the potassium sulfate
subcategory required that plants achieve no discharge of
process wastewater pollutants. There is one potassium
452
-------
64.
ms-charger^1* in th* U'S' This ^ 1- - Direct
"
23
"' Piff 1SrThi!SsaTS1iai%. There are £ive kn°™ Producers of
mecaj. salts in th& n ^ ^r^or*-i m •
are discussed above in Suhrat-ennr-ii M« -n \ mi. salts
jr • -i ^^-^ tiwwvc in ouocategory wo. 21 ) . Threp nf t-h^
diJcha?iS? !!nSChleV? !er° discha^e' ^d there is one direct
" " one indirect discharoer in i-ho K *•
year (
-------
65.
66.
67.
68.
69,
70,
71.
72.
provisions of Paragraph 8(a)(i) (for chemicals included
under regulated subcategories) and 8(a)(iv) (for chemicals
included under subcategories that have been excluded).
Salts of Rare Earth Metals.
to No. 63 above.
This subcategory is identical
Satin White Pigment. This chemical product is produced at
only one plant. Therefore the Agency proposes to exclude
this subcategory under Paragraphs 8(a)(iv) and 8(b)(ii).
Siennas. (See Iron Oxide Pigments, No. 34-36).
Silica, Amorphous. There are seven plants in the
subcategory. Screening and verification sampling at three
of the seven plants found no toxic pollutants at treatable
levels at any of the three plants. Relevant data are
presented in Table 19-2g (Plants A, B and C). This
subcategory is proposed for exclusion under Paragraphs
8(a)(iii), 8(a)(iv) and 8(b)(ii) (low loading).
Silica Gel. There are three plants in this subcategory.
Screening and verification sampling at one of these plants
found no treatable levels of toxic or nonconventional
pollutants in effluent from that plant. Relevant data are
presented in Table 19-2h. This subcategory is excluded
under Paragraphs 8(a)(iii), 8(a)(iv), and 8(b)(ii).
Silver Bromide. This chemical is produced in very small
quantities for research or other highly specialized uses.
There is only one discharger in this subcategory. That one
plant discharges to a POTW. Minimal wastewater is expected
from such small production volumes and no significant
pollutant loads are anticipated. Therefore, the Agency
proposes to exclude this subcategory under Paragraphs
8(a)(iv) and 8{b).
Silver Carbonate. This chemical is produced in very small
quantities for research or other highly specialized uses.
There is only one discharger in this subcategory. That one
plant discharges to a POTW. Minimal wastewater is expected
from such small production volumes and no significant
pollutant loads are anticipated. Therefore, the Agency
proposes to exclude this subcategory under Paragraphs
8(a)(iv) and 8(b).
Silver Chloride. This chemical is produced in very small
quantities for research or other highly specialized uses.
There is only one discharger in this subcategory. That one
454
-------
74.
75.
76.
suchChsamra9n 'produ^on
pollutant loads a?e aStiUpat
73.
silver recovery and
pretreatment requirements
with the POTW's pret?eS£nJnt
value of the - ?e?ovj?ed si
cost of the treatment Sy?emSth
cease operatino the ?re
Agency propose^to excludJ
8(a)(iv) and 8(b). eXC1Ude
system
*.i,with the POTW's
Plants must comP!y
Since *ie
pant ^l °f the
Plants are unlikely to
Jhe"fore/ the
ory under Paragraphs
Silver Iodide.
quantTtIes~~Tor "research"^ hh p£?auced in
There is only one dischara^r i n +h* higj]1y specialized U»«B.
Plant discharges to a POTW Sin?i iSUbcate9°ry. That one
from such small production voinmL,* fwater 1S exP®cted
pollutant loads are antiri™,^ mu ^ no significant
rara? an^ .s??* saeis£2t^5^S' ssysss
^fSjas -S-.S a-s-^Ba
treatable levels in the^trSaJed^^stewaLr^'1"'3"'8 3t
wastewater discharged at that pi
BPT effluent limitations.
: this subcategory. 40 CF* «I3 ^-«,,
th;-slIver"Stratr:uSca?ego?y.Umitati0nS and standards'for
The Agency
regulatory
discharoe to .a
455
-------
research quantities of silver oxide (only 2 kg (4.4 lb.) in
1981). All wastewater from this process and other plant
process water is treated in a limeprecipitation-alum
coagulation treatment system before discharge. Process
wastewater volume discharged is negligible.
The Agency proposes to exclude this subcategory under
Paragraphs 8(a)(iv) and 8(b).
Note- The Agency considered combining all the silver
product subcategories (No.'s 70 to 76) into a silver
compounds subcategory. However, silver nitrate is soluble
in water whereas the other six products are insoluble, so
' that the production process, raw materials, expected
pollutants and unit flows are significantly different for
silver nitrate production compared to the other six
products. Therefore, the combined subcategory would have to
have two segments, which does not appear to provide
significant regulatory simplification. The Agency also
considered combining six products (No. s 70, 71, 72, /J, /*,
and 76) into one subcategory. There are six plants which
manufacture one or more of those products, but only three
(one direct -and two indirect) dischargers. The direct
discharger produces only a few pounds of silver compounds
each year, and consequently generates minimal wastewater.
That minimal wastewater is treated with an advanced level
treatment technology for silver recovery. The two indirect
dischargers use advanced level treatment systems for silver
recovery and to' comply with the pretreatment requirements
established by the POTWs. Accordingly, the Agency has not
combined the silver products into a new silver comppounds
subcategory, because that new subcategory would also have
been excluded under Paragraph's 8(a)(iv) and 8(b).
77. Soda Alum. This subcategory has been addressed under the
"Alums" Subcategory, No. 5.
78.
79.
Sodium Antimonate. This product is generated at only two
sites by a process releasing no wastewater. Therefore, the
Agency proposes to exclude this subcategory from national
BAT and PSES effluent limitations development under
Paragraphs 8(a)(iv) and 8(b)(ii).
Sodium Compounds (Inorganic). Specific sodium compounds not
addressed elsewhere are:
a. Sodium Molybdate - There are two plants producing this
chemical. One has no discharge, while the second
produces research quantities and is a direct
456
-------
80.
ssar sr
TS
*
°
b.
c.
d.
Sodium Perborate - There is one plant
discharger, producing this chemical.
a direct
a direct
Sodium Perchlorate - There are only two d
producing this chemical and neither Sasa discharge
Sodium Stannate - Three plants (two direct dischargers
TOciSlti ndl^-,diS?hargerLPro^uce this chemical on I
specialty basis along with many other chemicals
Production quantities at each plant are very low The
lels thfn°To
j.ess cnan 10,
n n plants is
gallons per year.
to
wasewatr
" There are three Plants Producing
°f th plants discharge procesl
cemcabrt frc ^° plants Prod"cing this
cnemical, but one plant achieves no discharge of
lesseS?hanSt?Wfer'K- The remaini^ P?«n? dJschlrges
less than 1.9 cubic meters per day (<500 and) nf
process wastewater from this product. 9P
The Agency proposes, to exclude ..the above chemical oroducts
under Paragraphs 8(a)(iv) and 8(b)(ii) because the volume of
wastewater discharged is insignificant.
tw° plants
this
. system and then to a POTW Alkaline
chlorination is used at this plant to destroy cyanide before
'" "SlSSSJ with
under
This plant is also the only potassium cyanide producer with
a discharge. Therefore, the Agencyy did not combine the
457
-------
81
82.
83,
84.
85.
potassium cyanide and sodium '"cyanide
there is only one discharged.
subcategories, since
Sodium tiydrosulfite (Zinc Process). There is one plant
producing this chemical by the zinc process. This plant
achieves no discharge of process wastewater from this
product. Therefore, this subcategory is excluded under
Paragraph 8(a)(iv).
, •*
Sodium Silicofluoride. This chemical is produced as a by-
product ..of wet process phosphoric acid production at six
^grtilizer plants and by one plant which does not produce
wet process phosphoric acid. At phosphate fertilizer plants
there is no discharge of process wastewater from the
production of sodium Silicofluoride. The one plant which
does not produce sodium Silicofluoride as a by-product of
wet process phosphoric acid production uses a different
production process to manufacture sodium s.ilicofluoride.
Thus there is only one discharger in this subcategory.
Therefore, the Agency proposes to exclude
under Paragraphs 8(a)(iv) and 8(b)(ii).
this subcategory
Stannic and Stannous Chloride. There are three plants which
produce tin chlorides, but only two have a discharge. Both
are direct dischargers. Both plants,produce the products
intermittantly at low production rates. The total discharge
is estimated to be less than 5,000 gallons per year.
Therefore, no significant pollutant loads are expected from
these sources, and the Agency proposes to exclude this
subcategory under Paragraphs .8(a)(iv) and 8(b)(ii).
Strontium Carbonate. There are five plants which produce
strontium carbonate but only three plants have a discharge.
of process wastewater (two direct dischargers and one
indirect discharger). All three dischargers also produce
barium carbonate and combine the wastewatecs from both
products "for treatment and discharge.' One of the three
plants was sampled in Phase I and no toxic pollutants were
detected. Therefore, the Agency proposes to exclude this
subcategory under the Paragraphs 8(a)(iv) and 8(b)(ii).
Strontium Nitrate. There are four plants producing this
chemical. One of the producers achieves no discharge of
process wastewater. One of the two indirect dischargers
discharges to a POTW but the flow is low (less than 0.4
cubic meters per day (<100 gpd). The other indirect
discharger produces the chemical in small quantities and is
estimated to discharge less than 5,000 gallons per year to
458
-------
87,
88,
89.
cii -
discharge of about 5,oJS gallon! per yea?!
which
*" estimated
this subcategory under
86.
-Ifites
sulfide or sulfite
barium sulfide/
?romul9ated for
^SUlf ide' and
heref°^e the
weu
such as sodium hydrSsulfite
sodium hydrosulfide? ReJul4tion
sodium sulfite; sodium hydrosSlJ?^
sodium hydrosuifide have been ^c?u '
Agency proposes to excludl thlJauSSJlS Jheref°^e the
8(a)(i), 8(a)(iv) and 8(b)(ii) subcate^^ under Paragraphs
(Potassium Thiocylnate) o? Io
There are no discharges ?S;
exclude the sulfocyanides (fhl
Paragraphs 8(a)(iv) and 8
-------
90,
d. Sulfuryl Chloride - Thetre cfre only two plants, but only
one has a discharge.
The one discharger produces all four chemicals. Therefore,
the Agency proposes to exclude this subcategory under
Paragraphs 8 (a)(iv) and 8(b)(ii) because there is only one
discharger in the subcategory,
Sulfur Hexafluoride. There are two plants in this
subcategory, one a direct discharger and the other does not
discharge from this process. The direct discharger has only
a small volume of process wastewater (1.5 cubic meters per
day (<400 gpd)).
The Agency proposes to exclude this subcategory under
Paragraphs 8(a)(iv) and 8(b)(ii) because there is only one
discharger in the subcategory.
Thiocvanates. (See Subcategory No. 59 (c), 79 (f) and 87).
Tin Compounds. Most tin compounds not addressed elsewhere
are produced, if at all, only infrequently as low volume
special order or research products. The only tin compound
not addressed elsewhere which is produced in quantity is tin
fluoroborate. There are four plants producing tin
fluoborate. However, only one plant has a discharge of 19
cubic meters per year (5000 gallons per year). This flow is
too insignificant to justify developing a national
regulation and therefore the Agency proposes to exclude this
subcategory under Paragraphs 8(a)(iv) and 8(b)(n).
Screening and verification sampling data for the one
discharger are presented in Table 19-2i. •
93;—Ultramarine Pigments. These substances are not produced in
the—U7slat present. Therefore, the Agency proposes to
exclude this subcategory under Paragraphs 8(a)(iv) .and
91
92.
94. Umbers. This subcategory has been addressed under Iron
Oxides - see subcategory No. 34.
95. White Lead Pigments. The white lead pigments subcategory
includesthe production of lead carbonate, lead silicate
(subcategory No. 40), and lead sulfate. There are three
plants producing any of these products, one of which is a
direct discharger and the other two are indirect
dischargers. Both indirect dischargers are required by the
POTWs to treat the wastewater before discharge to the POTWs.
One plant must comply with the POTW's limitation for lead of
460
-------
has
96.
exclude the white
subcategories undlrla.agrhs
97.
a
Calcium Carbonate Subctegov a?e ^9U^elines for
Calcium carbonate has been fxcluded from /?H CFR 415-300.
regulation development in Phfsf ? Kther national BAT
pollutants were found at treatable Kv.? becaVse ™ toxic
provisions of Paragraphs 8?I) Uv)°and I(b) (??)"' Under the
one
r makes «»ny
i
Plant in the subcategory? € XS °nly one Discharging
Radioactive Materials
98. Cobalt 60
104. Nuclear Fuel Scrap
Reprocessing
M. Ftssionable Materials I05. Radium Chloride
-00. isotopes. Radioactive 106. Radtum LumlnQus ^^
101. Luminous Compounds (Radium) ,07. Uranium Slugs,
461
-------
Radioactive
102. Nuclear Cores, Inorganic
103. Nuclear Fuel Reactor Cores,
Inorganic
In many cases two or more of the ten subcategories refer to the
same or similar products. To facilitate the Agency's review, the
similar subcategories were addressed together, as follows:
(a) Cobalt 60 and isotopes, radioactive, since cobalt 60 is
a radioactive isotope.
(b) Luminous compounds (radium), radium chloride, and
radium luminous compounds, since all three
subcategories involve radium.
(c) Fissionable materials, nuclear cores (inorganic),
nuclear fuel reactor cores (inorganic), and uranium
slugs (radioactive), since all four subcategories refer
to the production of the fissionable uranium slugs used
in nuclear reactors.
(d) Nuclear fuel scrap reprocessing.
The rationale for the Agency's proposed actions for each group of
subcategories is presented below.
Cobalt 60 and other radioactive isotopes are produced in
nuclear reactors by inserting the non-radioactive precursor
(such as a non-radioactive isotope of cobalt) into the
reactor, where it is bombarded by neutrons released in the
reactor. The cobalt 60 (or other radioactive isotope)
produced is removed from the reactor and used as produced.
There is no water used in producing the radioactive isotopes
and no wastewater is generated or discharged. Therefore,
the Agency is excluding the cobalt 60 and isotopes,
radioactive subcategories from regulation under Paragraph
8(a)(iv) because there are no dischargers.
A.
B.
No radium chloride or radium luminous compounds (luminous
compounds, radium) are produced in this country nor have any
been produced for over 25 years. Hence, the Agency is
excluding the radium chloride, radium luminous compounds,
and luminous compounds, radium subcategories from regulation
under Paragraph 8(a)(iv) because there are no producers.
462
-------
c.
D.
Fissionable materials production involves the production of
the uranium or uranium oxide slugs used as the fuel in
nuclear reactors. The fuel is loaded into the reactor in
rods. Since, strictly speaking, the nuclear core is an
assembly of fuel rods, moderators, and supporting elements,
and the assembling of the core is a construction process,
the Agency has interpreted the nuclear cores (inorganic)
and nuclear fuel reactor cores (inorganic) subcategories to
mean the production of the fissionable uranium slugs used in
the core fuel rods, as that is the only chemical process.
Fissionable materials (nuclear cores, nuclear fuel reactor
cores, uranium slugs) production is conducted in this
country only under license issued by the Nuclear Regulatory
Commission (NRC). The license controls all aspects of the
production of fissionable materials including wastewater
discharges. Any materials in the wastewater are source
material, by-product material, or special nuclear material,
as these terms are defined at 10 CFR 820.3(a)(3), (15), and
(16). The Supreme Court decided in Train v. Colorado PIRG
426 U.S.I. (1976) that these materials, "at—Ieast~when
regulated by the NRC, are not "pollutants" under the Clean
Water Act.
Spent nuclear fuel may be reprocessed .to recover useful
fissionable .materials that may remain in the spent fuel or
in the case of plutonium 239, have been produced durina the
burn" cycle. All facilities engaged in this process
operate under licenses issued by the NRC. The licenses
control all aspects of the reprocessing, including
wastewater discharges. Any materials in the wastewater are
source material, by-product material, or special nuclear
material, as these terms are defined at 10 CFR 820.3(a)(3)
(15), and (16). The Supreme Court decided, in Train v'
Colorado PIRG, 426 U.S.I. (1976) that these materialsT" at
least when regulated by the NRC, are not "pollutants" under
the Clean Water Act.
463
-------
Table 19-2. SUMMARY OF TOXIC AND NON-CONVENTIONAL POLLUTANT DATA
FOR SCREENING/VERFICATION SAMPLING (Table 19-2a, AMMONIUM
THIOSULFATE).
SUBCATEGORY: 10 - Ammonium Thlosulfate
Pollutant
Sb
As
Be
Cd
Cr
Cu
Pb
Hg
Ni
SI
Ag
Tl
Zn
Ethyl benzene
Tolune
2,4 Dinltro phenol
4,6 Dinitro-o-cresol
Bis (2-ethylhexyl)phthalate
Thiosulfate
Plant A*
0. 88
0.004
0.008
0.084
0.153
2.0
3.6
0. 006
0. 38
0.018
0.002
0.121
1.3
7300
0.019
0.021
0.351
0.054
0.033
23,000
Concentration (mg/1)
Plant B
0.32
0
0
0.016**
0.071
0.01
0.44
0
0 '•
0
0
0.13
0
Not Analyzed
* Samples may have been contaminated by contact with sealing compound
on new floor. Total flow averaged 150 gallons per day.
** Two samples only. Analysis for cadmium in third sample erroneous, as
analysis of the blank for that sample showed high cadmium result.
464
-------
Table 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL POLLUTANT DATA
FOR SCREENING/VERIFICATION SAMPLING (Table 19-2 b., BRINE CHEMICALS)
SUBCATEGORY: 18 - Brine Chemicals
Pollutant
Sb
As
Be
Cd
Cr
Cu
Pb
Hg
N1
Se
Ag
Tl
Zn
Concentration (mg/1)
Plant A
0.003
0.0002
0.0002
0.057
0.091
0.13
0.079
0.0003
0.052
0.014
0.055
0.008
0.55
Flow averaged 700 gallons per day.
465
-------
Table 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL POLLUTANT DATA FOR
SCREENING/VERIFICATION SAMPLING (Table 19-2 £, CALCIUM HYPOCHLORITE),
SUBCATEGORY: 20 - Calcium Hypochlorlte
Pol 1utant Plant A
Sb
As
Be
Cd
Cr
Cu
Pb
Hg
Ni
Se
Ag
Tl
Zn
Chloroform
Methylene Chloride
Di chlorobromomethane
Chiorodibromomethane
0.1
0.004
0.001
0.006
0.039
0.041
0.14
0.002
0.015
0.004
0.0003
0.002
0.085
0.090
0.014
0.025
0.041
Plant B
4.1
0.002
0.011
0.15
0.11
0.17
0.27
0.01
0.6
0.007
0.014
1.1
0.37
0.17
1.1
ND
0.0007
466
-------
Table 19-2. SUMMARY OF TOXIC AND NONC.ONVENTIONAL POLLUTANT DATA FOR
SCREENING/VERIFICATION SAMPLING (Table 19-2 d, CHLOROSULFONIC ACID),
Subcategory: 22 - Chlorosulfonlc Acid
Pollutant
Sb
As
Be
Cd
Cr
Cu
Pb
Hg
Ni
Se
Ag
Tl
Zn
Chloroform
Methylene Chloride
Di-n-octyl phthalate
Concentration (mg/1)
Plant A
0.067
0.017
0.0011
0.0
0.0036
0.0
0.0
0.0
0.022
0.0
0.0
0.01
0.0067
0.017
0.014
0.011
467
-------
Table 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL POLLUTANT DATA
FOR SCREENING/VERIFICATION SAMPLING (TABLE 19-2 e^, NITROUS OXIDE),
SUBCATEGORY: 47- Nitrous Oxide
Concentration (ing/1)
Pollutant Plant A
Sb
As
Be
Cd
Cr
Cu
Pb
Hg
Ni
Se
Ag
Tl
Zn
0.06
0.01
0.002
0.002
0.24
0.021
0.007
0.002
0.035
0.015
0.002
0.01
0.08
360.
Plant B
0.008
0.004
0.001
0.009
0.060
0.075
0.061
0.005
0.009
0.003
0.0007
0.003
0.015
3400.
* See Text.
468
-------
Table 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL POLLUTANT DATA FOR
. SCREENING/VERIFICATION SAMPLING (Table 19-2 f, IRON WIDE PIGMENTS),
SUBCATEGORY: 34.35.36.48.67.94 - Iron Oxide
Pollutant
Sb
As
Be
Cd
Cr
Cu
Pb
Hg
Ni
Se
Ag
Tl
Zn
Fe
Methylene Chloride
**
Concentration (mg/l)
A* Riant B
0.55
0.005
0.005
0.036
0.22
0.12
0.39
0.001
0.74
0.015
0.008
0.14
0.65
83
Not Analyzed
0.13
0.002
0.002
0.002
0.038
0.018
0.13
0.003
0.21
0.009
0.044
0.084
0.015
Not Analyzed
0.015 ,
Plant C**
0.02
0.045
0.04
0.04
9.3
fUnCt1°n1n9 <*«»«"*• Effluent not in co.pliance with
Long-term treatment system performance data.
469
-------
TABLE 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL POLLUTANT DATA .MnDI)llftllO
FOR SCREENING/VERFICATION SAMPLING (Table 19-2 £, SILICA, AMORPHOUS),
SUBCATE60RY: 68 - Silica, Amorphous
Pollutant
Sb
As
Be
Cd
Cr
Cu
Pb
Hg
W
Se
Ag
Tl
Zn
Chloroform
Methylene Chloride
Methyl Chloride
Di chlorobromomethane
2,4 Dinitrophenol
Di-n-octyl phthalate
1,1,1 - Trichloroethane
Plant A*
0.008
0.009
0.0005
0.011
0.09
0.018
0.01
0.002
0.17
0.007
0.007
0.003
0.16 -
0.192
0.065
0.548
0.015
0.064
0.012
ND
Plant B
0.075
0.025
0.002
0.011
0.017
0.011
0.10
0.003
0.037
0.046
0.0012
0.006
0.086
ND
ND
ND
ND
ND
ND
ND
Plant C
0.12
0.0025
0.005
0.016
0.015
0.013
0.20
0.001
0.12
0.015
0.01
0.007
0,031
ND
0.026
ND
0.028
ND
ND
0.086
* Toxic organic pollutants from organic chemical process at same site.
470
-------
Table 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL POLLUTANT DATA
FOR SCREENING/VERIFICATION SAMPLING (Table 19-2 h,SILICA GEL),
SUBCATEGORY: 69 - Silica Gel
Pollutant
Sb
As
Be
Cd
Cr
Cu
Pb
Hg
N1
Se
Ag
Tl
Zn
Chloroform
Methylene Chloride
Concentration (mg/1)
Plant A
0.067
0.023
0.002
0.005
0.024
0.024
0.030
0.0
0.038
0.35
0.015
0.12
0.048
0.040
0.015
471
-------
TABLE 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL POLLUTANT DATA
FOR SCREENING/VERIFICATION SAMPLING (Table 19-21, TIN COMPOUNDS),
SUBCATEGORY: 92 - Tin Compounds (Tin Fluobbrate)
Concentration (mg/1)
Pollutant Plant A
Sb 0.008
As 0.016
Be 0.005
Cd 0.006
Cr 0.007
Cu 0.17
Pb 0.12
Hg 0.0005
Ni 0.22
Se 0.005
Ag 0.0004
Tl 0.045
Zn 0.12
Phenol 0.045
Butyl Benzyl Phthalate 0.043
472
-------
SECTION 19
REFERENCES
5.
6.
1972.
Park, cSTTIoFnlS.
" S- "Standard mistrial
, U.S. Government Printing Office,
*i Chfffiical Producer^
' stanfor<3 Research Institute, Menlo
Chical Marketing Reporter,
cheaical Buyers Directorv
rea tfi ack9""^ ->ata) to
Inorganic Chmiclls ManSf^f el°pment D°=™ents for
Category," Calspan Seport No ND l™^,* P°lnt Source
(Survey conducted in 1976K KD-5782-M-85, 17 March 1977
"» Deluded
Associates, ,c.
7.
8.
Terlecky, P.M. and Frederick v B
Rare Earth Metal Salts' »;R"
Subcategories," Menorfndum
Assoc.ates to Dr. Thomas
»n- u
u?ischarge Status of
Associates, Inc., November 30,
.
Frontier Technical
and
and
473
-------
11 U.S. Bureau of Mines, Minerals Yearbook, vol. 1 (Metals and
Minerals), "Minor Metals" (1976).
12 U.S. Bureau of Mines, Minerals Yearbook, vol. 1 (Metals and
Minerals), "Minor Metals" (1975).
U.S. Bureau of Mines, Minerals Yearbook, vol. 1 (Metals and
Minerals), "Minor Metals" (1974).
U.S. Bureau of Mines, Minerals Yearbook, vol. 1 (Metals and
Minerals), "Minor Metals" (1973).
Personal Communication: R. Call is EPA Eastern Environmental
Radiation Facility, Montgomery, AL to D.M. Harty, Frontier
'Technical Associates, Inc., December 1, 1982.
Personal Communication: Mr. Dan Kaufman, Radium Chemical
Co., Woodside, NY to D.M. Harty, FTA, December 2, 1982.
Stinson, S.C., "Supply Problems Cloud Outlook for
Radioisotopes," Chemical and Engineering News, May 31, 1982.
Personal Communication: George Mayberry Automation
Industries, Phoenixville, PA to D.M. Harty, FTA, December 6,
1982.
Personal Communication: Marvin Turkanis Neutron Products,
Inc., Dickerson, MD to D.M. Harty, FTA, December 7, 1982.
Personal Communication: Bob McNally Technical Operations,
Inc., Boston, MA to D.M. Harty, FTA, December 7, 1982.
Personal Communications X-ray Industries Detroit, MI to
D.M. Harty, FTA, December 7, 1982.
22 U.S. Bureau of Mines, Mineral Facts and Problems, "Depleted
Uranium" by William "sT—KlrkT^UMINES Bull. 671, 1980, p.
997-1003.
13.
14.
15.
16.
17.
18.
19.
20
21
474
-------
Appendix A
Analysis of Long-Term Effluent Monitoring Data
Phase II
A-i
-------
TABLE OF CONTENTS
Section
CADMIUM PIGMENTS AND SALTS
Plant F101
Plant F102
Plant F110
Plant F117
Plant F119
Plant F124
Plant F125
Plant F128
Plant F134
COBALT SALTS
Plant F117
Plant F118
Plant F119
Plant F124
Plant F139
COPPER SALTS
Plant F.115
Plant F118
Plant F119
Plant F127
Plant F133
NICKEL SALTS
Plant F117
Plant F118
Plant F119
Plant F124
Plant F125
Plant F139
SODIUM CHLORATE
Plant F103
Plant F147
Plant F149
ZINC CHLORIDE
Plant F118
Plant F125
Plant F140
Plant F144
A-12
A-13
A-14
A-17
A-19
A-20
A-21
A-22
A-23
A-26
A-28
A-29
A-33
A-34
A-36
A-39
A-41
A-42
A-43
A-44
A-45
A-49
A-S1
A-52
A-53
A-56
A-57
A-58
A-
-------
Treatment Technology Abbreviations Used!
Eq
Neut
Neut (2)
FL(m)
FL(s)
FL(p)
CL
S
Sd
RCL
PH
Floe
Act.
Sludge
AR
Cr-Red
Pep
! Equalization
; Neutralization
Two stage neutralization, if used in sequence
Filtration with multi-media
Filtration with sand filter
Filtration with filter press
Filtration-method unknown
Clarifier
Sulfide addition
Sedimentation (basin, pond, lagoon)
Recycle
pH adjustment
Flocculant addition
Biological activated sludge
Aeration
Hexavalent chromium reduction
Alkaline precipitation
A-iii
-------
-------
CADMIUM PIGMENTS AND SALTS
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