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ACID PICKLING SUBCATEGORY
SECTION VI
SELECTION OF POLLUTANTS
The final selection of pollutants for the acid pickling subcategory
was based on the analysis of wastewater samples collected during this
study. A number of pollutants originally limited by the 1976
regulation were considered, because they characterize the wastes from
the pickling operation. The pollutants limited by this regulation
include some of those limited in the 1976 regulation plus certain
toxic pollutants found during extensive monitoring conducted for this
study. This section describes the pollutants considered for
regulation, presents the rationale for selecting those pollutants, and
the process sources of those pollutants.
Pollutant Selection
Conventional Pollutants
In the original regulation, three conventional pollutants were limited
for all types of acid pickling operations: total suspended solids,
oil and grease, and pH. However, the limitations for the oil and
grease were applicable only when pickling wastewaters were treated
jointly with cold rolling wastewaters. Wastewater characteristics for
operations involving all product types are similar, so that the same
limited pollutants can apply to all types of operations in each acid
subdivision.
Based upon the information gathered during this study, the Agency
decided to retain oil and grease as a limited pollutant in certain
instances. Cold rolling wastewaters and pickling wastewaters are
often co-treated to take advantage of emulsion breaking properties of
the acid wastes. Since this is a common practice, and since the
pickling wastewaters can contain moderate amounts of oils, an
allowance for oil and grease is included in the limitations and
standards.
High levels of suspended solids and low pH are also characteristic of
acid pickling wastewaters. Suspended solids are generated in the
pickling process and are carried away in either the rinse or fume
scrubber waters or in the spent pickle liquor. pH was limited in the
original regulation and in this regulation. The pH of the raw
wastewaters from pickling operations is always acidic, with' typical
values ranging from <1 to 4 standard units. Wastewaters with low pH
can have detrimental effects if discharged without treatment.
Neutralization is required to bring the pH to within the regulated
levels of 6.0 to 9.0 standard units.
243
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Other Pollutants
In the original regulation, several nonconventional nontoxic
pollutants were limited. Dissolved iron was limited for all three
acid pickling operations. In addition, dissolved chromium, fluoride,
and dissolved nickel were all limited for combination acid pickling
operations. (The fluoride limitation applied only to those lines
using hydrofluoric acid). Limitations for these four pollutants are
not being retained in the present regulation. However, chromium and
nickel are now limited on a total rather than a dissolved basis for
the combination acid pickling subdivision. These limitations will
control the discharge of dissolved chromium and nickel.
Limitations for dissolved iron and fluoride have not been promulgated.
Toxic metals are, however, limited for each segment. The Agency
believes that the limitations for the toxic metals will effectively
control the discharge of these pollutants. Treatment for dissolved
iron and fluoride is the same as the treatment for toxic metals, i.e.,
chemical precipitation. The limitations for the toxic metals require
efficient operation of the treatment system, and, therefore, will
result in effective removal of dissolved iron and fluoride as well as
toxic metals.
Toxic Pollutants
The Agency found that toxic pollutants are present at significant
levels in the discharges from acid pickling operations. During the
sampling phase of this study, the Agency conducted additional
monitoring for the pollutants limited in the 1976 regulation, toxic
pollutants, and other pollutants. Based upon this sampling and
information provided by the industry, the Agency developed a list of
toxic pollutants known to be present in pickling wastewaters, (Table
VI-1).
The Agency tabulated and calculated a composite concentration value
for each pollutant in the raw wastewater. A net value was used to
describe the contribution of pollutants from the pickling process. If
a pollutant was found in the raw wastewater at an average
concentration (net) of 0.010 mg/1 or greater, it was considered to be
characteristic of acid pickling wastewater and is addressed
accordingly throughout this report. Also shown in Table VI-2 are the
other pollutants for which limitations have been considered.
Several organic pollutants were detected at concentrations greater
than 0.010 mg/1, but none were considered for regulation, as indicated
by their absence from Table VI-2. The three possible situations
leading to the omission of these toxic organic pollutants are: the
pollutant's presence is not due to acid pickling operations; the
pollutant is uniquely occurring in the wastewater; or the pollutant is
present at or near its limit of treatability. Methylene chloride was
omitted, because it was a solvent used as a cleaning agent for
sampling equipment which was in the laboratory when toxic organic
pollutant monitoring was conducted. Its presence is ascribed to these
244
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uses and not to acid pickling operations. Also, some phthalate
compounds were detected at levels greater than 0.010 mg/1, but they
are not believed to be characteristic of acid pickling wastewaters.
The Agency believes the presence of phthalates is probably related to
plasticizers in the tubing used in collecting the samples. The other
toxic organic pollutants, except for chloroform, were present in the
acid rinsewaters at or near treatable levels and were found in no more
than one of the samples taken for each acid subdivision. Chloroform
was found in the rinsewaters at two plants in the hydrochloric acid
pickling subdivision at 0.011 mg/1 and 0.014 mg/1. These
concentrations cannot be effectively reduced with additional
treatment, including adsorption on activated carbon. For these
reasons, the Agency did not limit toxic organic pollutants in this
subcategory.
As noted in Table VI-2, many toxic metal pollutants were detected at
concentrations greater than 0.010 mg/1. These pollutants and the
pollutants limited in the 1976 regulation are present in the
wastewater because of the extreme chemical action that occurs during
the pickling process. The acids remove the surface scale from the
steel products which contain the toxic metals. While these pollutants
may vary in concentration from line to line, they are characteristic
of the process. The Agency has established effluent limitations and
standards to regulate the discharge of these pollutants.
245
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ACID PICKLING SUBCATEGORY
SECTION VII
CONTROL AND TREATMENT TECHNOLOGY
Introduction
This section reviews existing wastewater treatment practices for the
acid pickling subcategory and presents those technologies which were
considered by the Agency in. developing this regulation. The sampling
data gathered at the acid pickling operations visited during this
study and a description of the treatment practiced at each are also
presented..
As a first step, it was necessary for the Agency to determine the
level of existing wastewater treatment in the acid pickling
subcategory. The Agency then developed BPT, BAT, BCT, and PSES
alternative treatment systems in an "add-on" fashion to this base
level. The NSPS and PSNS alternative treatment systems, however, were
not developed in this manner. Since NSPS and PSNS apply to new acid
pickling operations, the Agency did not consider the add-°n,
approach. The alternative treatment systems (levels of treatment) and
their corresponding effluent characteristics are summarized in
Sections IX through XIII. •
Summary of Treatment Practices Currently Employed
Because there is the potential for three different wastewater sources,
the treatment systems used on each source are discussed in detail
below, prior to a discusion of the general treatment scheme.
Treatment of Spent Pickle Liquor
Spent pickle liquor is presently classified as a hazardous waste under
the Resource Conservation and Recovery Act (RCRA) except where it is
reused as a wastewater treatment chemical. There are several
different methods for handling spent pickle liquor, including off-site
disposal, treatment processes, or recovery/regeneration processes.
A. Disposal Methods
The disposal methods, including contract hauling and deep well
injection, may not be ideal solutions for handling the spent acid
concentrates. Hauling and deep well injection may result in
relocation of a pollution problem. However, if properly
performed, these disposal methods can result in negligible
environmental impacts. Contract hauling is commonly used in the
industry, and several plants use deep well injection.
249
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B. Treatment Processes
Treatment processes include chemical neutralization and
precipitation. A detailed discussion of this process is provided
under treatment of acid rinsewaters. Treatment may be performed
separately or jointly with the other wastewaters from the
pickling operation. These methods are commonly employed
throughout the industry. y
C. Acid Recovery and Regeneration
The ideal method for handling spent pickle liquor is to recycle
the wastes through recovery/regeneration processes. These
processes minimize handling costs and either reduce or eliminate
the discharge of pollutants. In addition, the pickling operation
itself may be made more efficient, since the acid bath can be
kept at a relatively constant strength.
The Agency has identified the following recovery and regeneration
systems which are presently operated in this country. These
systems are available and have been proven effective at many
pickling operations. y
1. Sulfuric Acid Recovery
Acid recovery, which is the most common method for
recovering spent sulfuric acid, removes the ferrous sulfate
present in the spent acid through crystallization. Spent
pickle liquor high in iron content is pumped into a
crystallizer, where the iron is precipitated (under
refrigeration or vacuum) as ferrous sulfate heptahydrate
crystals. As the crystals are formed, water is removed with
the crystals, and the free acid content of the solution
increases to a level which is reusable in the picklinq
operation. The crystals are separated from solution, and
the recovered acid solution is pumped back to the pickling
tank. The by-product ferrous sulfate heptahydrate is
commercially marketable. The crystals are dried, bagged,
and marketed, or sold in bulk quantities. Ferrous sulfate
commonly referred to as "copperas," is used in appreciabl4
quantities in numerous industries, including the manufacture
of inks, dyes, paints, fertilizers and magnetic tapes. It
is also used as a coagulant in water and wastewater
treatment. See Figures II1-5 and II1-6 for the two types of
available recovery operations. As an added note, recovery
processes, which produce, ferrous sulfate monohydrate
crystals as a by-product are also available. This process
is usually carried out at elevated temperatures.
2. Hydrochloric Acid Regeneration
The only commercially proven technology to regenerate spent
hydrochloric acid is through thermal decomposition. The
250
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spent pickle liquor contains free hydrochloric acid, ferrous
chloride, and water. The liquor is heated to remove some of
the water through evaporation and to concentrate the
solution. The concentrated solution is then further heated
to 925° to 1,050°C (1,700° to 1,920°F). At this
temperature, water is completely evaporated and the ferrous
chloride decomposes into iron oxide (ferric oxide, Fe2O?)
and hydrogen chloride (HC1) gas. The iron oxide is
separated and removed from the system. The hydrogen
chloride gas is reabsorbed in water (sometimes rinsewater or
scrubber water is used), to produce hydrochloric acid
solution (generally from 15% to 21% HC1) which is reused in
the pickling operation. There are several types of
"roaster" processes in operation. The basic differences
among the processes are the design and operation of the
roaster/reactor and the recovery equipment (see Figures
III-7 through III-9).
3. Combination Acid Pickling
The Agency is unaware of any operating nitric or
hydrofluoric acid recovery process operating in this
country. It has been reported that such a system is
installed and successfully operating in the People s
Republic of China. However, due to the lack of operating
and performance data, the Agency is not basing any of the
limitations or standards on this technology.
A summary of the treatment practices in each subdivision
disposal of spent pickle wastes is listed below:
for the
Acid
Subdivision
Sulfuric
Hydrochloric
Combination
Central
Treatment
38.3%
13.7%
46.0%
Acid
Recovery
2.6%
8.4%
0%
Contract
Hauling
44.5%
53.7%
44.0%
Deep
Well
5.2%
12.6%
0%
POTW
Discharge
9.4%
11.6%
1 0.0%
Treatment of Fume Scrubber Water
Many pickling lines include wet scrubber systems to control the
emission of fumes from the operation. Water is used to^ scrub the
fumes and thus becomes contaminated with the same type of pollutants
which are discharged from the other waste sources. The flow rates
from the scrubbers can be very large and contain high pollutant loads.
One method of controlling the amount of pollutants discharged from
this source is to recycle the fume scrubbing wastewater. Recycle
rates of 100% have been reported for many operations, and recycle
rates ranging between 90-95% of the total wastewater flow are typical.
High recycle rates are achievable because corrosion does not occur.
The scrubbers are usually constructed of fiberglass, which is not
251
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affected by low pH. The degree of recycle is limited by the buildup
of dissolved solids in the recycle loop. At very high levels, the
ability of the scrubber to remove the acid from the fumes could be
reduced.
The discharges from fume scrubbers are subject to varying degrees of
treatment. The systems used to treat these wastewaters are the same
bel w USSd t0 treat rin-sewaters. These systems are described
Treatment for Pickle Rinsewaters
Most of the operations that treat pickle rinsewaters do so in central
•futmenfc .systems. Some of the wastewaters that are often combined
with the pickling wastes are cold rolling wastewaters and wastewaters
from alkaline cleaning, salt bath descaling and hot coating
operations. The pickling wastewaters are often combined with cold
rolling wastewaters, because the acid in the pickling wastewaters
helps break oil emulsions in cold rolling wastewaters. Picklina
?aSJe?aters are, often treated together with alkaline wastewaters so
that they neutralize each other. This can greatly reduce the costs
for chemicals necessary for neutralization. In any event, most
existing treatment systems have components which accomplish the
following: neutralize the acid in the wastes; precipitate dissolved
metals out of solution; promote flocculation of solids; and provide
sufficient sedimentation of the solids and precipitated metals. The
sludge generated in the treatment process is dewatered before final
disposal.
Control and Treatment Technologies
Considered for Toxic Pollutant Removal
Since the Agency found.toxic metal pollutants at significant levels in
the discharges from acid pickling operations, it evaluated treatment
systems designed primarily to remove these pollutants.
The alternative treatment systems considered by the Agency for acid
pickling operations are described below. These systems have been
demonstrated to varying degrees in the pickling subcategory and in
other industrial applications for wastewaters with similar
characteristics.
A. Lime Precipitation
Chemical treatment of acid pickling wastewaters with lime and
polymer flocculation is well demonstrated at many pickling
operations in the industry. Lime precipitation is an effective
method for removing toxic metal pollutants from the wastewater
Lime precipitation involves the.addition of lime, either in the
muy *?* hYdrated slurry form, to the wastewater in a mixing tank.
The dissolved metals in the wastewater precipitate as metal
hydroxides. These precipitates, along with other suspended
252
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solids in the wastewater,
sedimentation or filtration.
are subsequently removed by
B.
Lime is commonly used to neutralize acidic wastes because of
economic considerations. Other chemicals such as caustic are
available, but are considerably more expensive. In certain
applications, caustic or other neutralizing agents could,
however, offer advantages over lime. High removal efficiencies
of metals with lime precipitation are well demonstrated in this
subcategory. Low effluent levels have also been demonstrated in
other steelmaking subcategories where lime precipitation is used
for wastewater treatment.
A. final consideration relating to lime precipitation systems is
the generation of solid wastes resulting from its use. The large
amounts of sludge generated can be safely disposed of by
landfilling. This is the most common disposal method practiced
in the industry.
The amount of sludge produced during treatment of pickling
wastewaters can be minimized through recycling of the sludge
within the treatment process. In conventional lime precipitation
systems, the entire volume of sludge produced is discharged for
disposal. Alternatively, a portion of the sludge may be recycled
to the head of the treatment plant to act as seed for the-
treatment process. The sludges produced in this system are
considerably denser than the sludge produced by the conventional
process. The sludge volume can be reduced by over 95%. This
method is becoming common practice in the industry.
Flow Reduction
The discharge of rinsewaters can be minimized through the use of
cascade or high pressure/high temperature spray rinse systems.
In cascade rinsing, the conventional rinse systems, which
generally involve immersion or spraying (low pressure) in one or
more large tanks, are replaced by a series of smaller tanks. The
fresh water makeup is added to the last rinse tank and cascades
to the first rinse tank. The product moves in the opposite
direction to the water flow, so that it is rinsed by
progressively cleaner water. The product is sequentially
immersed in each of the tanks, or is rinsed by sprays located
over each of the tanks. Cascade rinsing can reduce the discharge
by over 90%. ,
The Agency has only recently become aware of a high
pressure/high temperature rinse system, which has been applied
in the industry over the last few years. In this system, the
temperature of the rinsewater ;is elevated by contact with steam.
The heated rinsewater is accelerated through a venturi and
applied to the product through a series of sprays located on both
sides of the product. The elevated temperature and pressure of
the rinsewater improves the efficiency of rinsing. The
253
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rinsewater volume is also reduced. At this time, the Agency has
only limited data for this system and is, therefore, unable to
develop limitations and standards based upon this technology.
Since the use of this technology will result in lower wastewater
volumes than those used by the Agency in developing the
limitations and standards for existng sources, the Agency
believes that plants with this technology will not have problems
in achieving the appropriate limitations and standards. In fact,
these plants will probably have an advantage because of lower
water use rates.
C. Vapor Compression Distillation (Evaporation)
Vapor compression distillation is typically used to concentrate a
high dissolved solids waste stream (3,000 - 10,000 mg/1) to a
slurry consistency (approximately 100,000 mg/1). The slurry
discharge can be dried in a mechanical drier or allowed to
crystallize in a small solar or steam-heated pond prior to final
disposal. The distillate quality water generated by this system
can be recycled back to the acid pickling operation thereby
eliminating all discharges. One desirable feature of this system
is its relative freedom from scaling. Because of the unique
design of the system, calcium sulfate and silicate crystals grow
in solution as opposed to depositing on heat transfer surfaces.
Economic operation of this system requires a high calcium to
sodium ratio (hard water).
The installation of this system may be the only possible way to
achieve zero discharge of. process water at all acid pickling
operations. However, the high cost and energy intensive nature
of this system makes it unattractive.
Summary of Monitoring Data
Table VII-1 provides a key for the control and treatment technology
abbreviations used in the tables throughout this report. Raw
wastewater and effluent monitoring data for the acid pickling
operations visited are presented by subdivision in Tables VI1-2
through VII-9. The concentration values presented in the tables
represent, except where footnoted, averages of gross measured values.
In many cases these data were obtained from central treatment systems.
These central treatment data are used since pickling wastewaters are
commonly co-treated with wastewaters from other finishing operations.
Additionally, these data are representative of the pollutant levels
that can be achieved with separate treatment of pickling wastewaters.
Spent concentrates, fume scrubber wastewaters, and absorber vent
scrubber wastewaters are listed in the raw form only. No effluent
values are given, since these wastewaters are universally treated
jointly with the other pickling wastewaters. In several instances,
the effluent waste loads (lbs/1000 Ibs) for certain central treatment
operations indicated on the data tables represent apportioned loads
In these central treatment systems, the percentage contribution of an
individual operation to the total treatment system influent load is
254
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determined and subsequently applied to the total effluent load. This
procedure was repeated for each pollutant. By using this procedure,
the Agency estimated the effects of treatment on the pollutant loads
from individual processes with discharges to a central treatment
facility. Following the determination of the raw and effluent waste
loads, the pollutant load reductions accomplished by each operation
for each pollutant were then determined.
Summary of. Long-Term Analytical Data
As a supplement to the sampled plant monitoring data, long-term
effluent analytical data from operations responding to the D-DCPs are
presented in Volume I.
Plant Visits
Brief descriptions of the visited plants follow. Treatment system
flow schematics are provided at the end of this section.
Plant A (0900) - See Plant 121
Plant C (0424) - Figure VII-1 (Combination)
This plant recently completed the installation of a new central
treatment facility. At the time of the sampling inspection, the
rinsewaters from bar and plate pickling lines were combined prior to
entering an equalization tank. From the equalization tank, the
wastewaters were transferred to a mixing tank where lime and coagulant
aids were added. The neutralized wastes then were settled in a
sedimentation tank. The discharge was sent to a receiving stream.
The spent pickle liquors from the bar and plate lines are discharged
to a holding tank, and then are hauled away by a contractor,
Plant D (0248B) - Figure VII-2 (Combination)
At the time of the sampling visit, the acid rinsewaters generated by
the continuous strip pickling operation were discharged to a receiving
stream without treatment. However, a central treatment system which
treats wastewaters from this line was completed in 1978 and is now in
operation.
Plant F (0856H) - Figure VII-3 (Combination)
Pickle rinsewater and fume scrubber water are combined prior to
entering an equalization tank. After equalization, lime is added and
the pickling wastewaters are combined with hot forming wastewaters in
a scale pit. From the scale pit, the combined wastewaters are settled
in a settling basin. The spent pickle liquor at this'operation is
hauled away to a company owned disposal site.
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Plant H-2 (0432A) - Figure VII-4 (Sulfuric)
Dunk rinses are cascaded to minimize flow; spray and other rinses are
blended with other plant wastewaters for treatment by gas flotation,
neutralization with lime or caustic, flocculation with polymers, and
clarification with thickening and vacuum filtration of clarifier
underflows. Spent concentrates are hauled off-site by a contractor.
Plant I. (0432K) - Figure VII-5 (Combination)
This plant employs lime neutralization of the spent pickling
solutions,mixing with the acid rinses, and sedimentation in a lagoon
to treat this wastewater generated by the strip pickling process.
Plant 1-2 (0856P) - Figure VII-6 (Sulfuric)
Waste pickle liquor is hauled away by a private contractor. All
rinses are combined with other plant wastes in a terminal lagoon and
discharged to a canal.
Plant 1-2 (0856P) - Figure VII-6 (Hydrochloric)
This plant dilutes pickle liquor and rinses together with other plant
wastes in a terminal lagoon and then discharges to a canal.
Plant L (0440A) - Figure VII-7 (Combination)
This • plant discharges rinsewaters generated by the batch bar pickling
operation to a POTW. Waste pickle liquors are treated at the plant
employing lime neutralization.
Plant O (0176) - Figure VII-8 (Combination)
This plant treats its pickle rinsewaters and wastes from other
processes in a central treatment system. The pickling wastes comprise
50-o of the total flow to the central treatment system. Central
treatment consists of equalization, sodium hydroxide neutralization,
aeration, and clarification. Sludges are dewatered in a sludge
lagoon. Spent pickle liquors at this operation are hauled off-site by
a private contractor.
Plant 0-2 (0590) - Figure VII-9 (Sulfuric)
This plant employs batch evaporative crystallization of spent sulfuric
acid. Acid is recovered and ferrous sulfate heptahydrate is produced
as a by-product. Rinses are recycled to the process as makeup to the
pickle tank. Zero discharge is achieved.
Plant P-2 (0312) - Figures VTI-J_0 and V_n-n_ (Sulfuric)
This plant recovers waste pickle liquor by a batch vacuum
crystallization recovery system. Rinses are metered to the sewer.
256
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Plant Q-2 (0894) - Figure VII-12 (Sulfuric)
This plant practices batch pickle liquor recovery through the cooling
of spent pickle liquor and crystallization of ferrous sulfate
heptahydrate. Rinses and mists from the fume filter are recycled back
to the pickle tank. Zero discharge is achieved, '
Plant R (0240A) - Figure VII-13 (Sulfuric)
This plant neutralizes spent concentrates and rinses from batch
specialty steel pickling operations with lime. The neutralized
wastewaters are discharged to a sludge lagoon. There is no discharge
from the sludge lagoon.
Plant R-2 (0240B) - Figure VI1-14 (Sulfuric)
Pickle liquor and rinses are combined in an equalization tank, mixed
and treated with acetylene sludge, lagooned, and discharged to a
receiving stream.
Plant S-2 (0256G) - Figure VI1-15 (Sulfuric)
Concentrated pickle liquor 'is contract hauled. Standing rinse is
reused as makeup to the pickle tank. Running rinse is treated with
lime and lagooned. The lagoon overflow is recycled, and the sludge is
contract hauled.
Plant T--2 (0792B) - Figure VII-16 (Sulfuric)
Sulfuric acid is recovered from spent pickle liquor by evaporative
concentration. Rinses are cascaded and used as pickle tank makeup.
Steam condensate is used as a final product rinse. There is no
discharge of wastewaters from this operation.
Plant U (0748) - Figure VII-17 (Combination)
This plant employs batch lime neutralization of the acid rinses after
combining the rinses, with wastes from a degreasing line. This
operation also neutralizes its spent pickle liquor prior to
evaporating this waste stream to extinction. The effluent from the
batch treatment system is discharged to a receiving stream.
Plant U-2 (0480A) - Figure VII-18 (Hydrochloric)
The waste pickle liquors and rinsewaters from the batch pickling
operations are neutralized in a batch treatment tank by sodium
carbonate prior to discharge to a municipal sewerage system.
Plant V-2 (0936) - Figure VII-19 (Hydrochloric)
The spent pickle liquor from the batch pickling operations is contract
hauled. Rinses are neutralized with sodium hydroxide prior to
discharge to a municipal sewerage system.
257
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Plant W-2 - Figure VII-20 (Hydrochloric)
Waste pickle liquor is treated by pyrolytic regeneration of
hydrochloric acid. Rinses and fume scrubber wastes are diluted and
metered to a sewer. Absorber vent scrubber wastes are neutralized
with caustic solution prior to discharge to a receiving stream.
Plant X^2 (0060B) - Figures VII-21 and VII-22 (Hydrochloric)
This plant practices spent acid recovery by hydrochloric acid
regeneration. Rinses are diluted and discharged to a receiving
stream. Absorber vent scrubber wastes are treated in a clarifier
along with other plant wastes.
Plant Yj-2 - Figures VII-23 and VII-24 (Hydrochloric)
,_ Pickle acid is recovered by pyrolytic regeneration of
hydrochloric acid. Rinses and absorber vent scrubber wastes are
diluted and discharged to a receiving stream.
Plant 2-2 (0396D) - Figure VII-25 (Hydrochloric)
Refer to Plant 093.
Plant AA-2 (0384A) ^ Figure VII-26 (Hydrochloric)
Refer to Plant TOO.
Plant BB-2 (0060) ^ Figure VII-27 (Hydrochloric)
Concentrated pickle liquor is disposed of by off-site contract hauling
to a regeneration system owned by the same company or in an on-site
deep well. Rinses are equalized; mixed with cold rolling wastewaters-
neutralized; aerated; treated with polymers; clarified; lagooned; and
discharged to a receiving stream. Sludge from the clarifiers is
dewatered by vacuum filters prior to transport to a dump.
Plant QQ-2 (0584E) z Figure VII-28 (Sulfuric)
Spent concentrates and fume scrubber blowdowns are collected
equalized, filtered, and discharged to a deep well. Rinsewaters are
blended with other plant wastewaters and treated by chromium
reduction; emulsion breaking; polymer addition; neutralization with
lime; clarification; and discharge through a settling lagoon with
surface skimming for oil removal.
Plant SS-2 (01 12A) - Figure VII-29 (Sulfuric)
Spent concentrates are collected, equalized, and discharged to a
receiving stream. Fume scrubber blowdowns and rinsewaters are
combined with all other plant wastes; blended; skimmed; neutralized
with lime; aerated; flocculated with polymers; and transferred to a
258
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settling lagoon; from which sludges are treated by cyclones and
thickeners.
Plant TT-2 (0856D) - Figure VII-30 (Sulfuric)
Waste pickle liquors are collected, neutralized, and transferred to
off-site evaporation ponds. Rinses are cascaded, blended with fume
scrubber blowdowns, and discharged without treatment. A treatment
facility is under construction.
Plant WW-2 (0868A) - Figure VII-31 (Sulfuric)
Spent concentrates are filtered and injected into deep wells.
Rinsewaters are blended with other plant wastewaters, flocculated with
polymers and alum, neutralized with lime, clarified, skimmed and
discharged through a terminal settling lagoon.
Plant 090 .(0476A) - Figure VI1-32 (Sulfuric)
This plant treats rinses from batch pipe and tube pickling in a
central treatment facility that includes equalization, oil skimming,
aeration, neutralization with lime, polymer addition, clarification,
and finally, discharge to a receiving stream. Spent concentrates are
recovered by a vacuum crystallization acid recovery system.
Plant 091 (0612) ^ Figure VII-33 (Sulfuric)
Concentrates from a batch rod pickling operation are hauled off-site
for disposal. Rinses are blended and equalized with hydrochloric acid
pickling and galvanizing wastewaters; aerated; neutralized with lime;
clarified; and, filtered prior to discharge.
Plant 091 (0612) - Figure VII-33 (Hydrochloric)
Spent pickle liquor and rinses are neutralized with lime, oxidized,
clarified, and filtered through pressure sand filters prior to
discharge to a receiving stream. Clarifier sludge is dewatered by
vacuum filters prior to disposal.
Plant 092 (0088A) - Figure VII-34 (Sulfuric and Hydrochloric)
Refer to Plant 123.
Plant 093 (0396D) - (Hydrochloric)
Spent pickle liquor and rinses are mixed with galvanizing and cold
rolling wastewaters, neutralized and clarified with polymer addition
prior to discharge to a municipal sewerage system. Sludges from the
clarifier are dewatered by vacuum filtration prior to transport to a
landfill. Cold rolling and galvanizing lines also contribute
wastewaters to this treatment system in such a way that the pickling
wastewaters can not be isolated. Therefore the Agency did not rely on
data from this plant in establishing limitations and standards.
259
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Plant 094 (0948C) - Figure VII-35 (Sulfuric)
Spent concentrates are hauled off-site. Rinses are combined with all
other finishing mill wastewaters, equalized, skimmed, treated with
lime and polymer, and clarified via a thickener. Underflows are
centrifuged and discharged.
Plant 095 (0584F) - Figures VII-36 and VII-37 (Hydrochloric)
This plant practices spent acid recovery by hydrochloric acid
regeneration. Some rinsewater is recycled to fume scrubbers and
absorber vent scrubbers. The remaining rinsewater and scrubber wastes
are sent to waste lagoons.
Plant 096 (01121) - Figure VII-38 (Sulfuric)
Batch fastener pickling wastes are blended with galvanizing,
aluminizing, and electroplating wastes; aerated and neutralized with
lime; thickened; and filtered. Filtrates are discharged to a holding
lagoon for plant-wide reuse or discharge.
Plant 097 (0760) - Figure VII-39 (Sulfuric)
Spent concentrates are recovered by a two-stage evaporation and
crystallization recovery system designed to produce dry copperas.
Cold water rinses are used as the pickle tank-makeup, while hot rinses
are discharged to a POTW for further treatment.
Plant 098 (0684D) - Figure VII-40 (Sulfuric)
Three lines pickle bar, wire, and special shapes. Rinses are
concentrated and dumped to pickle tanks as makeup. Acid vapors are
collected by a demister and recycled to pickle tanks. All sumps and
foundation drains are collected and transferred to storage. All
liquid wastes are contract hauled off-site.
Plant 099 (0528B) - Figure-41 (Hydrochloric)
The spent pickle liquor is recovered by acid regeneration. Rinses and
fume scrubber wastes are mixed with other plant wastes, neutralized
and settled in ponds prior to discharge to a receiving stream.
Plant 100 (0384A) z Figure VII-42 (Hydrochloric)
This plant utilizes cascade rinse systems with the rinsewater being
used as makeup to a fume scrubber. Spent pickle liquor and fume
scrubber wastes are combined with cold rolling wastewaters and
disposed of by deep well injection.
Plant 121 and A (0900) - Figure VI1-43 (Combination)
This operation was visited on two occasions for this study. The first
time the operation was designated as Plant A, and for the second
260
-------
sampling trip the operation was designated as Plant ,121 . The pickle
rinse and fume scrubber waters are combined with other small volume
waste flows before entering a central treatment system. The pickling
wastes comprise approximately 75% of the total wastewater flow
entering the central treatment system.
The combined wastes are treated by equalization, neutralizaton and
clarification. The underflow from the clarifiers goes to thickeners
and centrifuges. The overflow from the clarifiers goes to a polishing
tank from which approximately 50% of the treated water is discharged
to a receiving stream. The waste pickle liquor is hauled off-site by
private contractors.
Plant 122 (0176) (Combination)
Wastewaters from hot forming, scale removal, alkaline cleaning, and
hot coating operations are combined with pickling wastewaters for
central treatment. The pickling wastewaters can not be isolated from
the other wastewaters, therefore the Agency did not rely on the data
from this plant in establishing limitations and standards.
Plant 123 (0088A) - Figure VII-34 (Combination)
The rinsewaters from this combination acid pickling operation (sample
point D) are combined with other pickling and hot mill wastes prior to
entering a central treatment system. The combined waste stream then
undergoes equalization, neutralization with lime,/ flocculation with
polymers, and clarification. Sludges produced are 3'ewatered in vacuum
filters. Spent acid solutions are hauled off-fsite by private
contractors.
Plant 125 (0884F) - Figure VII-44 (Combination)
This operation treats its pickle rinse and fume scrubber blowdown
water in a three-compartment lime neutralization pit prior to
discharging these wastes to a POTW.
Effect of Make-up Water Quality
Where the mass loading of a limited pollutant in the make-up water to
a process is small in relation to the raw waste loading of that
pollutant, the impact of make-up water quality on wastewater treatment
system performance is not significant, and, in many cases, not
measureable. In these instances, the Agency has determined that the
respective effluent limitations and standards should be developed and
applied on a gross basis.
As shown in Tables VII-10 to VII-12, the impact of make-up water
quality on raw wastewater pollutant loadings for the sampled acid
pickling operations is not significant for any of the toxic metal
pollutants. The suspended solids levels in make-up waters for
hydrochloric acid pickling operations were found to be significant
when compared to raw waste loadings at the sampled plants. Most of
261
-------
the loading in the intake waters can be attributed to one abnormally
high value of 196 mg/1 found at one plant. Notwithstanding the above,
the model treatment technology includes lime or caustic precipitation
which will result in formation of metal hydroxide precipitates and a
hydroxide floe. The suspended solids concentrations after lime or
caustic addition are significantly higher than raw waste
concentrations and the removal of the hydroxide floe will also result
in removal of suspended solids contained in make-up waters. Thus, the
Agency concludes that the impact of make-up water quality on raw waste
loadings for acid pickling operations are not significant, and the
limitations and standards should be applied on a gross basis, except
to the extent provided by 40 CFR 122.63(h).
262
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