WATER POLLUTION CONTROL RESEARCH SERIES
12010 DPF 11/71
Brass Wire Mill
Process Changes
and Waste Abatement,
Recovery and Reuse
U.S. ENVIRONMENTAL PROTECTION AGENCY
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WATER POLLUTION CONTROL RESEARCH SERIES
The Water Pollution Control Research Series describes the
results and progress in the control and abatement of pollution
in our Nation's waters. They provide a central source of
information on the research, development and demonstration
activities in the Environmental Protection Agency, through
inhouse research and grants and contracts with Federal, State,
and local agencies, research institutions, and industrial
organizations.
Inquiries pertaining to Water Pollution Control Research
Reports should be directed to the Chief, Publications Branch
(Water), Research Information Division, R&M, Environmental
Protection Agency, Washington, B.C. 20460.
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BRASS WIRE MILL PROCESS CHANGES AND WASTE
ABATEMENT, RECOVERY AND REUSE
by
Volco Brass and Copper Company
Kenilworth, New Jersey 07033
for the
OFFICE OF RESEARCH AND MONITORING
ENVIRONMENTAL PROTECTION AGENCY
Project No. 12010 DPF
November, 1971
For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402 - Price 55 cents
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EPA Review Notice
This report has been reviewed by the Environmental
Protection Agency and approved for publication.
Approval does not signify that the contents necessarily
reflect the views and policies of the Environmental
Protection Agency, nor does mention of tradenames or
commercial products constitute endorsement or recom-
mendation for use.
ii
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Abstract
This report describes process changes and waste treat-
ment, recovery, and reuse facilities installed by Volco
Brass and Copper Company, Kenilworth, New Jersey. The
plant produces 75 tons of wire per day.
An electrolytic system was installed to recover copper
from the spent primary pickle solution and to regenerate
the sulfuric acid for reuse. A hydrogen peroxide bright
pickle replaced the chromate and fluoride bright pickles
previously used. Copper from the bright pickle is also
recovered in the electrolytic system. The electrolytic
copper is reused on location in casting. An integrated
copper treatment system was installed to treat bright
pickle drag-out. Sludge from the integrated system is
recovered for sale. Rinse water consumption was reduced
from 150 gpm to 10 gpm. Former discharges of chromium,
ammonium, and fluoride ions have been eliminated. Cost
and operating data and effluent analyses are presented.
This report was submitted in fulfillment of Project No.
12010 DPP under the partial sponsorship of the Industrial
Pollution Control Section, 0 R & M, of the Environmental
Protection Agency.
Key Words: Peroxide pickling, chromate pickling, bright
pickle, oxidizing pickle, brass mill wastes, wire pick-
ling, copper treatment, chemical rinsing, copper recovery,
copper sludge salvage, water reuse, pickle regeneration,
electrolytic recovery, by-product recovery.
iii
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CONTENTS
Section
I Conclusions 1
II Recommendations 3
III Introduction 5
IV Discussion 9
V Acknowledgements 15
VI References 17
VII Appendices 19
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FIGURES
Page
1 Pickling Operations and Waste Disposal 37
Previous to this Project
2 Conventional Pickling Waste Treatment Design 38
3 Pickling Operations, Copper Recovery, 39
Waste Treatment, and Water Reuse System
Currently in use at Volco Brass & Copper Co.
4 Overall View of Volco Brass & Copper 40
Pickling Line
5 Heavy Wire Drawing 40
6 Intermediate Wire Following Peroxide 4l
Bright Pickling
7 Fine Wire Following Bright Pickling 4l
8 Copper Recovery and Waste Treatment Equipment 42
9 50% Caustic Soda Storage Tank and Deionizer 42
10 Peroxide Pickle Reservoir Tank (Left) 43
Floor Spill Neutralization Tank (Right),
Steam Condensate Monitor and Pump (Center
Foreground)
11 Chemical Supply Tank (Left), Gravity Sludge 43
Filter (Center), and Automatic pH Controller
(Right)
12 Electrolytic Copper Recovery Cell 44
13 Reuse Water Pump Installed in Rinse Water 44
Settling Tank
vi
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TABLES
Ncu Page
I Primary Pickle Bath Composition and 21
Operating Conditions
IA Primary Pickle Acid Purchases and Costs 21
IB Primary Pickle Spent Acid Dumping Cost 22
2 Secondary or Bright Pickle Bath Composition 22
and Operating Conditions
2A Secondary Pickle Purchased Acid Cost 23
2B Secondary Pickle Spent Acid Dumping Cost 24
3 Solution Composition and Operating Conditions 25
for the Integrated Copper Treatment Solution
3A Treatment Chemical Cost 25
Integrated Copper Treatment System
4 Processing Cost Comparison
Daily Average Basis 26
5 Disposal, Chemical Waste Treatment and
Recovery Cost Comparison 27
6 Copper Recovery from Primary Pickle 28
6A Copper Recovery from Secondary Pickle 28
6B Copper Sludge Recovery from Copper 29
Treatment System
7 Detailed Comparison of Processing, Disposal, 30
Waste Treatment, and Recovery Costs
8 Summary Comparison of Processing, Disposal,^ 31
Waste Treatment and Recovery Costs
9 Comparison of Amortized Costs per Unit of 31
Wire Products; Daily Average Finished Wire
Production of 75 Tons
10 Pickling Effluent Quality and Quantity 32
Comparison
11 Capital Equipment Cost 33
vii
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SECTION I
CONCLUSIONS
1. Continuous electrolysis of the brass primary pick-
ling solution regenerates the sulfuric acid pickle
and recovers copper as high-purity metallic copper.
2. A peroxide bright (secondary) pickle has been success-
fully substituted for the conventional dichromate and
dichromate-bifluoride bright pickles previously used
for copper and copper alloy pickling.
3. Elimination of "lubricant shedding" chromate films
has resulted in a 50$ increase in die life in the
first draw following pickling.
4. Installation of a non-dichromate bright pickle permits
the economic recovery of metallic copper from the
bright pickle and the recovery of a salable cuprous
oxide sludge from the integrated waste treatment
system.
5. Metallic copper can be recovered from the primary
pickle and from the peroxide bright pickle in one
common electrolytic copper recovery unit.
6. The integrated copper treatment (chemical rinsing)
system to treat bright pickle drag-out also eliminates
lubricant breakdown resulting from acid drag-in and
reduces the number of coils requiring re-pickling
due to staining.
7. "Chemical rinsing" plus water reuse were combined to
reduce water consumption from the previous 150 GPM
to 10 GPM.
8. The plant produces an effluent containing approxi-
mately one mg/1 of copper or zinc ions and about 10 mg/1
of suspended solids.
9. "Complete treatment" resulting from chemical rinsing,
plus elimination of chromate and ammonium bifluoride
usage, permits discharge to a storm sewer, thereby
avoiding sanitary sewer rental charges.
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10. Costs for current pickling, waste treatment, and
recovery processes are $156 per day (operating) or
$194 per day (operation plus amortization of capital
investment in waste treatment and recovery facili-
ties), as compared to $195 per day for the pickling
processes and waste disposal methods formerly used
(no waste treatment).
11. Estimated costs for the former pickling processes
and an assumed treatment system (conventional) to
treat spent solutions and dilute rinses would have
averaged $386 per day (operating) or $5^0 per day
(operating plus amortization).
12. Current pickling plus waste treatment and recovery
costs are the same cost per ton of wire ($2.59) as
the processes and waste disposal methods formerly
used and compare with $7.20 per ton based on a con-
ventional waste treatment design.
13. Current waste treatment and recovery costs (Including
amortization) amount to $46.72 per day or $0.62 per
ton of wire product.
14. Based on an average "value added" by the manufacturing
process of $800 per ton of copper or copper alloy
wire, the current waste treatment and recovery costs
(operating plus amortization) amount to 7.8 cents
per hundred dollars of value added, or .078 percent
of "value added."
15. The primary pickle bath (1,000 gal.) which was for-
merly disposed of monthly because of contamination,
is no longer dumped with the installation of the new
system.
16. The bright pickle bath (1,000 gal.), which was for-
merly disposed of weekly, is also no longer dumped
with the installation of the new system.
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SECTION II
RECOMMENDATIONS
Copper is recovered from both the primary and secondary
pickles in its most valuable form, i.e. as electrolytic
copper metal, whereas by-product copper recovery from
waste treatment practices is in the form of a wet cuprous
oxide sludge.
In view of the greater economic value of metallic copper,
refiner apathy toward purchasing and refining copper sludge,
and sludge shipping charges, it is felt that additional
laboratory and pilot work is warranted. This work would be
thus directed at the recovery of copper contained in the
sludge in its ultimate form, as high-purity electrolytic
copper.
One approach to consider would be the solubilization of
cuprous oxide (insoluble in sulfuric acid) in muriatic
acid, followed by the addition of sulfuric acid for the
crystalization of the dissolved copper as cupric sulfate.
The existing crystal filter and electrolytic copper re-
covery system would then be used for the ultimate recovery
of the copper as metallic copper.
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SECTION III
INTRODUCTION
The Voice Brass and Copper Company in Kenilworth, New
Jersey, is a typical copper and cuprous alloy wire mill.
Some of the products may be considered unique, but in
general, the operation is typical. The plant processes
copper and alloys of copper, such as various brasses,
phosphor bronze, and German silver (an alloy of copper,
nickel, and zinc). Approximately 75 tons of wire are pro-
duced per day, but since all materials go through the
pickling process at least three or four times before the
manufacturing is completed, the pickling process handles
at least 250 tons per day of various wire gauges. The
thinner the wire, the larger the surface area per ton
of metal processed.
Production Operations
Copper and cuprous-alloy wire is produced in a wire-drawing
operation where basically the wire is pulled through a
succession of smaller diameter dies to provide the desired
final gauge. The starting point in the case of copper is
hot-rolled rod which the company purchases. The rod is
produced by successive reductions from a metal billet,
which is maintained hot enough through the rolling opera-
tion to allow plastic deformation to occur. The hot roll-
ing results in a continuous coil of metal rod rolled to
a uniform round dimension. After the hot rolling is com-
pleted, the continuous rod, which may be from 5/8" to 1/4"
in diameter, is allowed to slowly cool to room temperature.
This slow cooling effectively anneals the wire to a soft
condition suitable for cold forming. The high tempera-
tures required for hot rolling and/or extrusion, as is the
case for alloy rod, causes the formation of oxide coatings
or "scale" on the surface during the rolling, and/or extru-
sion, and cooling. Before the rod is further processed
in cold rolling or drawing, it is necessary to remove the
adherent scale in a pickling operation such as is shown
in Figures 1 and 4. The pickling acids dissolve and re-
move the oxide coatings.
A soap-type lubricant is then applied to the surface and the
rod is drawn through dies to reduce the rod to wire (Figure
5). Depending on the alloy, the cold forming develops a
metallurgical condition recognized as hardness and embrittle-
ment so that usually the drawing operation cannot be carried
further than 50-80% reduction of the original diameter. At
this stage, the wire has to be annealed to relax the strains
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developed in the body of the metal. Annealing causes the
metal crystals to go through a transformation, called
re-crystalization, which makes the metal soft and malleable
again and allows further cold drawing. During the anneal-
ing state, the surface of the metal may again oxidize even
though the atmosphere during the heat treatment is con-
trolled by excluding oxygen or maintaining a reducing
atmosphere. Some of the oxidation may be due to the vapor-
ization of the lubricant oils that were left on the sur-
face after the drawing operation. As a practical result,
it is necessary to pass the coils of wire through the same
acid treatment again to remove the oxides formed during
the annealing operation. In this manner then, the same
metal may be acid pickled three to four times before a
finished wire product is produced. The number of pickling
steps will depend on the extent of gauge reduction; i.e.,
the finer the wire, the more often the cleaning steps will
be repeated.
The conventional pickling system uses a hot sulfuric acid
solution of about 10-25$ sulfuric acid by volume. This
acid is capable of dissolving the cupric oxide and the
oxides of the various alloying elements in a uniform manner
and without undue attack on the basis metal. One serious
shortcoming of this conventional pickling is that the black,
cupric oxide scale is reduced during the reaction to the
cuprous oxide state which is not soluble in sulfuric acid.
As a result, the pickled rod is covered with an adherent
cuprous oxide dust film called in practice "red copper
dust." Any oxide dust remaining on the surface may become
drawn into the body of the wire in the subsequent wire-
drawing operation and thereby reduce the conductivity and
the tensile strength of the wire. Also, some of the
cuprous oxide dust falls into the lubricant that is applied
and causes dust contamination of the lubricant oil and
subsequent deterioration due to metal soap formation in
the lubricant. To remove this cuprous oxide dust, many
of the wire mills use a subsequent oxidizing acid cleaning
system which will dissolve and remove the cuprous oxide.
Such acid processes are based on chromic acid-sulfuric
acid formulations; chromic acid-ammonium bifluoride mix-
tures; or nitric acid solutions as an oxidizing bath to
remove the tenaciously adhering cuprous oxide film. The
Volco Brass and Copper Company chose instead a new approach
to solving this problem.
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Past Practice
Prior to this project, the company utilized either of two
types of secondary pickles following the hot sulfuric acid
primary pickle. These secondary pickles consisted of the
sulfuric-chromic acid or the ammonium bifluoride-chromic
acid formulations. Since the surface area processed was
large, the rinsing requirements between the various pro-
cess steps was important. The waste water carried, in a
dilute form, the constituents of the concentrated process
solutions, such as sulfuric acid, chromic 'acid, ammonium
bifluoride, and the salts of copper, zinc, tin, nickel,
phosphorous, etc. The total flow rate was approximately
150 gallons per minute.
Waste disposal requirements arose from the necessity to
dispose of spent pickling solutions and the rinse waters
from the rinsing operations which followed the various
cleaning steps. Disposal practice consisted of contract
hauling of spent pickle concentrates at a fee of eight
cents per gallon plus labor charges and disposal of rinse
waters to the sanitary sewer for a fee of $0.25 per thousand
gallons. The latter practice, however, had to be stopped
when the company was advised that their effluent had been
independently sampled, analyzed, and considered unaccept-
able by the Rahway Valley Sewerage Authority because of
possible adverse effects to their Secondary Treatment
Plant and processes.
It is noteworthy that prior to this sanitary discharge, the
company had depended on cooling water dilution for treat-
ment of their pickle rinses prior to discharge to the
storm sewer. This prior practice was stopped after con-
sultation with the New Jersey Health Department.
Having been excluded from both the storm and sanitary sewers,
a new solution was now sought from outside professional
help in order to protect community interests and to avoid
court action and possible closure.
The Pollution Problem
Chemical treatment of high-volume, low-concentration rinse
waters can be used to precipitate copper and to neutralize
acids (1+5). However, chemical treatment following the
use of the ammonium bifluoride-chromic acid pickling system
would be only partially effective. Fluorides cannot be
precipitated in a conventional manner to yield an effluent
containing less than 12-15 ppm fluoride. In addition, the
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ammonia complexes the copper to form copper ammonium sul-
fate which cannot be easily precipitated. Two additional
problems encountered in chemical treatment of rinse waters
from metal finishing operations are effluent clarification
and sludge handling. It is difficult to clarify the
effluent to meet aesthetical requirements and to maintain
low levels of suspended solids of metallic origin. The
second problem is related to the volume of sludge gene-
rated, its drying, and its disposal (6). Precipitated
metal hydroxides and the chromic hydroxide, which would
result from the chromic acid type pickling system, yield
very thin slurries containing not more than 0.5$ dry
weight of solids. Thus sludge concentration would require
an excessive investment in equipment, maintenance, and
labor costs to handle such low density sludges. Moreover,
since the plant is located in a relatively congested area
in Kenilworth, New Jersey, large tracts of land are not
available for waste treatment purposes, such as are re-
quired for sedimentation basins and sludge drying beds
when using a conventional waste treatment design.
Current Practice
To avoid these processing and waste treatment problems,
the company installed a hydrogen peroxide bright pickle,
an integrated system for drag-out treatment before dilution,
and water and waste recovery systems. These facilities and
the reasoning behind this selection are described in the
following section.
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SECTION IV
DISCUSSION
The cost of chemical treatment of dilute rinses, as origi-
nally proposed by Volco, could easily have been the most
costly operation in the entire manufacturing process. The
voluminous waste sludges that would have been generated
would not have been amenable to economical recovery.
Experience with metal finishing waste treatment in various
phases of plating and cleaning operations has shown that
process modifications can sometimes be made to reduce the
waste treatment problem to a reasonable level (7). Labora-
tory investigations and pilot plant studies in this plant
indicated an opportunity to reduce costs by making process
changes and by providing more extensive water treatment,
reuse, and recovery facilities. The costs to be incurred
by using more expensive chemicals for the cleaning process
and for waste treatment could be off-set by recovering
the significant quantities of metals that were previously
lost in plant wastes. An additional objective to be con-
sidered to accomplish further cost reductions was the
reduction of water consumption to 10% of what it had pre-
viously been to allow reduction in the size of the final
treatment equipment and to reduce the water bill.
The process changes selected were far reaching and had to
aim first for an improvement in the quality of the material
in process and under no circumstances a reduction in quality.
The innovations had to be accepted by the operating per-
sonnel which may be the greatest difficulty in view of the
fact that most of the processes previously in use were based
on unchanged practices going back to the turn of the cen-
tury. Operators typically dislike change, especially if
it requires closer analytical control of the processes to
be utilized as compared to a minimum of control that is
the usual practice throughout the country in such pickling
operations.
Schematic flow diagrams are used to permit a rapid* compari-
son of the installed system design (Figure 3) with a typical
conventional pickling waste treatment design (Figure 2). A
schematic of the previous pickling operation, having no
waste treatment or recovery operations is shown in Figure 1.
Pictures of the present recovery and waste treatment installa-
tion and equipment are shown in Figures 8 through 13.
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Primary Pickling Process Improvements
The hot sulfuric acid pickling system as used on copper
and copper alloys is basically a good, fast, and economi-
cal solvent for the various oxides to be removed. It has
the advantage of not attacking the unoxidized base metal
to any significant extent, even if the work is allowed
to be left in the pickling solution for hours. The re-
moval of cupric oxide is based on the following reaction:
CuO + H2S01+ * CuSOi, + H20
Cupric Oxide Sulfuric Copper Water
Acid Sulfate
The only disadvantage, as was mentioned earlier, is the
fact that cuprous oxide is generated during the pickling
process when the sulfuric acid as an electrolyte does
not hinder the electrochemical reaction occurring between
the metallic copper surface and the cupric oxide, the
result being the formation of an insoluble cuprous oxide
dust on the metal surface, which is not removed by the
sulfuric acid.
Frequent dumping of the sulfuric acid pickle is usually
necessary due to the increase in copper content, causing
another electrochemical reaction on the brass surface
that results in a metallic copper deposition, while the
zinc from the brass is going into solution. It was thought
that a continuous electrolytic removal of the copper would
solve this problem and at the same time maintain a low
copper concentration in the pickle acid and permit the
most economical recovery of copper that is accumulating.
Similar electrolytic copper recovery systems were used
earlier, but only in systems where only pure copper mate-
rial was processed. In view of the harmful effects of the
copper content of the pickling solution on brasses, most
such pickling acids are dumped too frequently to allow
the recovery of metallic copper by electrolysis. Another
objection by the Trade to electrolytic recovery of copper
from such pickling systems was that the zinc, tin, nickel,
lead, etc., metallic content would interfere with the
successful operation of an electrolytic recovery system.
Our investigation has shown that electrolytic recovery of
copper in an economical manner is possible, provided the
cathode current density for electrolysis is kept within
the range of 5 to 10 Amps/ft2. Experience indicates that
the copper concentration can be maintained at a constant
low level of 15 gm/1 so that the electrochemical plating-out
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of copper can be avoided on brass surfaces. It is there-
fore possible to avoid frequent dumping of the simple and
economical sulfuric acid pickling solution. More import-
antly, it is possible to recover economically the copper
that is accumulating and it is assumed that dumping may
not be required, except at very infrequent intervals,
such as two to three years, when the accumulation of zinc,
nickel, tin, lead, etc., could be detrimental. The elec-
trolytic copper recovery cell used to accomplish these
objectives is shown in Figures 8 and 12.
Secondary or Peroxide Bright Pickling
The so-called "red copper dust," cuprous oxide, that cannot
be removed in the sulfuric acid pickle, and which is to
some extent formed during the pickling operation, has to
be removed for efficient operation and for the best quality
of product. Since the chromic-acid-type oxidizing acids
can be harmful for wire drawing, create excessive die wear,
form chromate salts which contaminate the copper values to
be recovered, and on the other hand, nitric acid would
create an air pollution problem, a new pickling process
has been developed in which the oxidizing conditions are
provided by inclusion of hydrogen peroxide in the make-up.
The sulfuric acid bright pickle following the pre-pickle
contains only sulfuric acid, 2-5$ hydrogen peroxide, and
stabilizing agents. The breakdown product of hydrogen
peroxide is water; therefore this solution does not ever
require dumping. The dissolution of the "red copper dust"
in the peroxide pickle is based upon the following reaction:
Cu20 + H202 + 2H2SQi* * 2CuSOu + 3H20
Cuprous Hydrogen Sulfuric Cupric Water
Oxide Peroxide Acid Sulfate
The cupric sulfate that is formed in the pickling process
can be periodically removed by simple crystalization and
the cupric sulfate crystals can be added to the electro-
lytic copper recovery system or can be sold separately
as a by-product.
The hydrogen-peroxide-containing bright pickle met all the
requirements with regard to appearance of the finished
product and it is yielding the cleanest copper or copper
alloy metal surface that we have encountered. The cost
of the hydrogen peroxide, which is consumed as cuprous
oxide is dissolved, is offset by:
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(a) Recovery of the copper;
(b) Elimination of the need to purchase
chromic acid;
(c) Saving of the waste treatment costs with
chromic acid and sludge handling that it
would entail;
(d) Elimination of the frequent dumping of the
process solution, thereby simplifying
scheduling needs; and
(e) A surface far better for wire drawing,
avoiding the detrimental after-effects
of the chromic acid.
Production work loads of wire pickled in the peroxide
bright pickle are shown for both intermediate wire
(Figure 6) and fine wire (Figure 7).
Integrated Copper Treatment System (10)
The bright pickle is followed by a chemical treatment rinse
that precipitates the copper and other metal salts dragged
out of the pickling solution. The treatment solution is
recirculated between the treatment wash tank and a reser-
voir tank. The reservoir tank serves the purpose of pro-
viding a larger solution reserve to avoid fluctuation of
chemical concentration and as a settling basin for the pre-
cipitated copper and metals (8). The copper is precipi-
tated in this system as cuprous oxide, a dense, reddish-
brown powder with no occluded water. The sludge contains
5Q% dry weight in comparison to the standard neutraliza-
tion systems where cupric hydroxide is precipitated with
a sludge containing a dry solids weight of not more than
.5$. The sludge volume actually compared to the standard
neutralization system is less than 1%.
A high sludge density results from two mechanisms at work
in the integrated treatment system. The first mechanism
is chemical, wherein the drag-out is neutralized under
the most desirable chemical conditions; that is, only con-
centrated acid drag-out is treated in the chemical rinse.
In this manner, no dilution occurs prior to neutraliza-
tion and thus the formation of light, hydrated floccu-
lent metal hydroxides is avoided. Secondly, beneficial
sludge compaction and aging are gained in the treatment
reservoir as a result of new sludge contacting old sludge
in the recirculated treatment system. The dense cuprous
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oxide resulting from this integrated treatment can be
returned to the refiners without even filtration, just
as the by-product of wet sludge. The dry weight of this
sludge contains 86% copper.
The chemical rinse making up the integrated waste treat-
ment system solution is a simple solution of caustic soda,
soda ash, and a reducing agent, with no expensive chemi-
cal content. The pH controller automatically adds fresh
chemicals whenever required.
The neutralization of the sulfuric acid drag-out is based
upon the following reaction:
H2SC\ + Na2C03 » Na2S(\ + C02* + H20
The reaction between the reducing agent and the cupric
ions at the pH involved is best represented by the follow-
ing reaction:
4Cu+2 + N2Hi, + 40H" -» N2t + 4Cu+ + 4H20
Since the cuprous (Cu*1) ions are insoluble at a pH between
8 and 9> the reaction goes to completion with the complete
removal of copper.
As sodium sulfate accumulates in this solution, some solu-
tion has to be periodically dumped, and to avoid batch
dumps, a small volume of sodium sulfate solution is con-
tinuously discharged with the rinse water effluent. The
sodium sulfate concentration is maintained in the range
of 100-120 g/1.
Water Reuse
The chemical rinse accomplishes the main function of the
water rinse, which is neutralization and elimination of
acid on the wire. Therefore the following water rinse
has to only remove excess alkalinity; no acid, and only
minimal quantities of copper, enter this system. A
rinse water effluent with less than 1 ppm copper content
is easily achieved (9). If necessary, the copper Concen-
tration in the effluent can be maintained at one-tenth
of this value.
Rinsing of coiled intermediate wire, as shown in Figure
6, had been a serious problem in the past. Hand spray-
ing by the operators by high-pressure hoses using 150 GPM
water was the previous processing method and the rinsing
of each coll of wire consumed about one-half minute of
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time. Since there were 6-10 coils of wire on one loadbar,
each load that was processed through the pickling system
took 3-5 minutes for rinsing. Rinsing of fine wire ("ship-
ping wire"), racked on loadbars as shown in Figure 7, con-
sumed even more time. After the chemical rinse, on the
other hand, a 30-second immersion or dip rinse is all that
is required.
Equally important, the chemical rinse by itself has reduced
water consumption to one-third of the volume of water needed
without the copper treatment system. For even greater
economy, a water reuse system was installed to permit the
reuse of Q0% of the total rinse water flow in recirculation.
In operation, the rinse waters are collected, adjusted in
pH, and are clarified for removal of hard water constitu-
ents prior to pumping back to the pickle line (Figure 13).
From a maintenance standpoint, it is anticipated that the
settling tank will require only annual desludging in view
of the minor sludge load contributed by the hard water
constituents contained in the 10 GPM fresh water input
into the reuse water system.
The combined effect of chemical rinsing, plus water reuse,
results in a spectacular water savings. The total effluent
water discharged is approximately 10 GPM, compared to
150 GPM consumption which was the case previous to waste
treatment. In summary, the waste water is high-quality
water (Table 10) and is suitable for reuse for rinsing
purposes back in the process. The main purpose of the
10 GPM effluent is to serve as "blow-down" of the water
reuse system, thereby maintaining the dissolved solids
level at an optimum value.
Economic Evaluation and Effluent Comparison
The economic data resulting from this study is detailed in
Tables 1 -» 3; "previous costs" before the waste treat-
ment and recovery installation, being based on historical
records over a one-year period, whereas "current costs"
were based upon present-day practices. Estimated costs
associated with a conventional waste treatment design for
the given Volco pickling operation were included in the
tabulated cost comparisons to permit a meaningful compari-
son (Tables 4 * 7). The cost of amortizing these instal-
lations is reflected in the cost comparisons in Table
8 and 9. The final effluent quality, previous and cur-
rent, are compared in Table 10.
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SECTION V
ACKNOWLEDGEMENTS
Supervision of the waste treatment and recovery installa-
tion and operation was provided by Volco Brass and Copper
Company personnel, Mr. Al Izzo, Mr. John Ligenza, and
Mr. Maxwell Gilbert.
Leslie E. Lancy, Ph.D., President of Lancy Laboratories,
Division of Dart Industries, Inc., Chemical Group,
Zelienople, Pennsylvania, supervised the design of the
waste treatment and recovery operation and the prepara-
tion of this report. The report was prepared by Mr.
Charles A. Forbes.
The advice and cooperation of Mr. William Lacy, Mr. Edward
Dulaney, and Mr. John Ciancia, all of the Office of Re-
search and Monitoring of the Environmental Protection
Agency, are acknowledged with sincere thanks.
This report was submitted in fulfillment of 12010 DPF
under the partial sponsorship of the Environmental
Protection Agency.
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SECTION VI
REFERENCES
1. Whistance, D. J. and Mantle, E. C., "Effluent
Treatment in the Copper and Copper Alloy Industries,"
British Non-Perrous Metals Research Association,
2«0 pp (19&5).
2. "Cerro Copper and Brass Waste Treatment Plant,"
Water Pollution Control Association of Pennsylvania,
pp 12-13July-August (1968).
3. McGrath, J. J., "Treatment of Brass Mill Effluents
at Toronto Plant," Proceedings of Ontario Industrial
Waste Conference (1969).
4. Hupfer, M. E., "Metal Finishing and Brass Mill Wastes,"
Sewage and Industrial Wastes 29. No. 1, pp 45-52 (1957).
5. Bethel, J., Sawyer, C., and Hitchcock, C.,
"Copper and Brass Tube Mill Wastes Treatment,"
Public Health Engineering Abstracts. 40. No. 8, pp 30
(I960).
6. Ceresa, M., and Lancy, L. E., "Waste Water Treatment,"
Metal Finishing Guidebook - Directory, pp ?6l (1969).
7. Lancy, L. E., and Pinner, R., "Waste Treatment and Metal
Recovery in Copper and Copper Alloy Pickling Plant,"
Metallurgia. 73. (437) PP 119-122 (1966).
8. Lancy, L. E., "Neutralizing Liquid Wastes in Metal
Finishing." Metal Progress. 90. 4, pp 82-84 (1967).
9. Lancy, L. E., "An Economic Study of Metal Finishing
Waste Treatment." Plating 54. No. 2, pp 157-161 (1967).
10. U. S. Patent 2,725,314.
17
-------
SECTION VII
APPENDICES
Part A
Tables 1 through 11
Part B
Figures 1 through 13
19
-------
TABLE I
Primary Pickle Bath Composition and
Operating Conditions
Item
Sulfuric Acid
Temperature
Previous
10-25% Vol.
125-160° F
Current
lQ-25% Vol.
125-160° F
Alternate Primary Pickle
Sulfamic Acid
Temperature
8-12 oz./gal.
125-160° F
Use discontinued
Use discontinued
TABLE IA
Primary Pickle
Acid Purchases and Costs
Material
HaSO,, 66° Be
Sulfamic Acid
Total
Previous Operations
Tons per
Year
70*
18
Annual
Cost
$2,736*
5,235
$7,971
Avg Daily
Cost
$10.90
18.10
$29.00
Current Opera-
tions Dollar Cost
0 (acid is con-
tinuously re-
generated)
0 (use discon-
tinued)
0
* A detailed breakdown of historical sulfuric acid pur-
chase records is as follows:
25 Ton 66° Be Sulfuric Acid at a purchased cost of $925
plus
45 Ton DuPont "Duclean #1" (Inhibited Sulfuric Acid)
at a purchased cost of $1811
21
-------
TABLE IB
Primary Pickle
Spent Acid Dumping Cost
Item
Haulage charge
($.08/gal.)
Associated
Labor Charge
Total
Previous Operations
Annual
Cost
$960
290
$1250
Avg. Daily
Cost
$3.84
1.15
$4.99
Current Opera-
tions Dollar Cost
0 (not dumped)
0 (not dumped)
0
TABLE 2
Secondary or Bright Pickle Bath Composition and
Operating Conditions
Pickling Chemical
Previous Operations
Current Opera-
tions
Sulfuric Acid
Sodium Dichromate
Ammonium Bifluoride*
Temperature
Hydrogen Peroxide (35%)
Stabilizer "BPX"**
Inhibitor "CPXI"**
Inhibitor "CPXII"**
5-10* by Volume
4-8 oz./gal.
4 oz./gal.
Room
None
None
None
None
10-15% by Vol.
None
None
115-120° P
2-5* by Vol.
2% by Vol.
2 oz./gal.
.4 oz./gal.
* In order to meet brightness requirements on certain cus-
tomers' orders, an occasional addition of 4 oz./gal. of
ammonium bifluoride was added to the conventional sulfuric
dichromate bright pickle bath.
**Manufactured by Electrochemicalsf Inc., Subsidiary of
Dart Industries Inc., Chemical Group. Cleveland, Ohio.
44114. '
22
-------
TABLE 2 A
Secondary Pickle
Purchased Acid Cost
Pickling
Chemical
Na2Cr20-7«2H20
NHltHP2
H202
"BPX"
"CPXI"
"CPXII"
H2S04**
Total
Previous Operations
#/yr.
46,000
1,250
Annual
Cost
$7,820
312
$8,132
Avg.
Daily Cost
$31.30
1.25
32.55
Current Operations
Unit
Cost
0*
0*
$1.6?/gal.
9.60/gal.
.80/0
.80/0
.02/#
Avg.
Daily
Cost
0*
0*
$100.00
14.40
8.00
8.00
13.50
143.90
*Both the dichromate and dichromate ammonium bifluoride
secondary pickles were eliminated.
**A sulfurlc acid cost breakdown between primary and
secondary pickles in previous operations is not avail-
able; therefore sulfuric acid cost for both purposes
is included in Table IA.
23
-------
TABLE 2B
Secondary Pickle
Spent Acid Dumping Cost
Item
Haulage Charge
($.08/gal.)
Associated Labor
Cost
Total
Previous Operations
Annual Cost
$3,840
1,200
5,040
Avg.
Daily Cost
$15.30
4.80
20.10
Current Operations
Dollar Cost
0 (not dumped)
0
0
Note: All data in Tables 1, 1A, IB, 2, 2A, and 2B were
based on pickling operations run on a 3 shifts/day
5 days/week, 50 weeks/yr. common basis.
24
-------
TABLE 3
Solution Composition and Operating Conditions
For the Integrated Copper Treatment Solution
Copper Treatment Solution Composition
pH 9.5-10.51.
Hydrazine (^H^) 500 ppm2.
Temperature Room
Chemical Feed Solution Make-up per 100 Gallons of Stock
Solution:
Soda Ash 200#
Caustic Soda 25#
Hydrazine Hydrate, 85%. . . . 2-1/2 gal.
Notes:
1. Maintained in this range by automatic control
instrumentation;
2. Hydrazine concentration may range from
300-700 ppm;
3. Daily sludge withdrawals are made for the by-
product recovery of copper sludge as cuprous
oxide.
TABLE 3A
Treatment Chemical Cost
Integrated Copper Treatment System
Treatment
Chemical*
Caustic Soda ($.055/lb.)
Soda Ash ($.033/lb.)
Hydrazine Hydrate, 85#
($.95/lb.)
Treatment Chemical Cost/Day
Daily
Consumption
315 Ibs.
68 Ibs.
34.4 Ibs.
Chemical
Cost
$17-30
2.25
32.72
52.30
*The chemical feed solution contains caustic soda, soda ash,
and hydrazine hydrate, and is fed "on demand" from an auto-
matic pH controller for control of the copper treatment
solution. (See Figure 11)
25
-------
TABLE 4
Processing Cost Comparison
Daily Average Basis
Description
Primary Pickling:
Sulfuric and
Sulfamic Acid
Secondary or Bright
Pickling:
Dichromate Pickle
Peroxide Bright
Pickle
Process Rinse Water
Total Processing
Cost
Previous
Cost
$29. OO1
32. 552
54. OO3
115.55
Based On
Conventional
Waste
Treatment
Design
$29.00
32.. 55
54. OO3
115.55
Current
Cost
Installed
System
Design
None
Dichromate
Pickle
Eliminated
$143. 902
3.60"
147.50
Notes:
1. See Table 1A
2. See Table 2A
3. Previous rinse water consumption was 150 GPM
or 216,000 gal./day. At a use cost of
$.25/1000 gal., this represented a daily pur-
chased water cost of $54/day.
4. Current rinse water consumption is 10 GPM or
14,400 gal./day, representing a purchased
water cost of $3.60/day.
26
-------
TABLE 5
Disposal, Chemical Waste Treatment and
Recovery Cost Comparison
Daily Average Basis
Cost Item
Hauling Costs for Spent
Acid Dumps
Treatment Chemicals:
NaOH, Na2C03, N2H4
Ca(OH)2t Na2S205, H2S04
Polyelectrolyte
Labor: Waste Treatment
Operator and Sludge
Handling Cost
Sanitary Sewer Cost
Copper Recovery or Sav'g
(See Table 6 following) '
Total
Previous
Cost
$25. 091
2
2
None2
54.006
s 0
$79.09
Based On
Conventional
Waste
Treatment
Design
None
$130.00
(est.)
86. 50"
5^.006
0
$270.50
Current
Cost
Installed
System
Design
None
$52.303
29.005
07
($72.58)
$ 8.72
Notes:
1,
2,
3
4,
See Table IB, 2B
No waste treatment provided previously, except
that waste acid dumps were hauled from the plant
by an Industrial Waste Hauler.
See Table 3A.
Includes three operators per day or an annual
operator cost of $21,600.
One waste treatment operator controls the 24-hour
per day operation on the day shift, annual
operator cost = $7,200.
Sanitary sewer rental charge is the same as the
purchased water cost or $.25/1000 gal., or
$54/day. (See Table 4)
Sanitary sewer rental charges are by-passed; com-
pletely treated effluent is discharged to the
storm sewer.
27
-------
Tables Showing Basis for
Copper and Copper Sludge Recovery Values
TABLE 6
Copper Recovery from Primary Pickle
Recovered
Material
Electrolytic
Copper2
Previous
0
Conven-
tional
Waste
Treat
Design
0
Current Operations
#/day
40#
Value
$.50/0
Recov-
ery
Cost1
$1.20/
day
Net
Value
Re-
covered
$18. 80/
day
TABLE 6A
Copper Recovery from Secondary Pickle
Recovered
Material
Ele'ctrolytic
Copper2
Previous
0
Conven-
tional
W. Tr.
Design
0
Current Operations
#/day
<6I
Value
$.50/#
Recov-
ery
Cost1
day
Net
Value
Re-
covered
$21.60/
day
Notes:
1. The electrolytic recovery coat is based on a power
cost of $.02/Kw hr.
2. The electrolytic copper is reused on Icrcation
in casting operations.
28
-------
TABLE 6B
Copper Sludge Recovery from Copper Treatment System
Recovered
Material
Copper Sludge
Previous
0
Conven-
tional
W. Tr.
Design
0
Current Operations
#/day
585
Value
$.055/#1
Net Value
Recovered
$32. 182
Notes:
1, Based on a recent sale of 40,000 Ibs. of copper
sludge.
2. Future plans are based on ultimate recovery of
copper in the sludge as electrolytic copper for
use on location as a source of metallic copper
in casting operations.
29
-------
TABLE 7
Detailed Comparison of Processing, Disposal,
Waste Treatment, and Recovery Costs
Primary Pickle Chemicals
Disposal by Hauling
Bright Pickle Chemicals
Disposal by Hauling
Process Rinse Water- WafcgtV
Sanitary Sewer Cost
Integrated Copper Treatment
Chemicals
Labor
Recovered Values
Cu El. Primary Pickle
Cu El. Bright Pickle
Cu Sludge - Int. Treat.
Conventional Tr. Costs
Chemicals
Labor
Total
Amortization Costs (15 yrs)
Total
Daily Average Basis - In Dollars
Previous
29.00
4.99
32.55
20.10
5^,00
54.00
0
0
0
0
0
0
0
0
194.64
0
194.64
Conventional
29.00
0
32.55
0
54.00
54.00
0
0
0
0
0
0
130.00
86.50
386.05
154. OO1
540.05
Current
0
0
143.90
0
3.60
0
52.30
29.00
(18.80)
(21.60)
(32.18)
0
0
156.22
38. OO2
194.22
Notes:
1,
The cost of a conventional waste treatment installa-
tion was calculated to be $598,000. This total
includes a waste treatment equipment cost of
$248,000, an installation cost of $250,000, a
new waste treatment building (80' x 50') cost
of $60,000, and engineering fees of $40,000.
The installed system cost was $141,000. This total
included waste treatment and recovery equipment
($42,000); installation, $61,000; engineering fees
($20,000); and a new waste treatment building cost of
($18,000).
30
-------
TABLE 8
Summary Comparison of Processing, Disposal,
Waste Treatment and Recovery Costs
Cost Item
Processing Costs
(Table 4)
Disposal/Treatment/
Recovery Costs (Table 5)
Amortization Costs
(Table 7)
Total
Daily Average Basis - In Dollars
Previous
115.55
79.09
0
194.64
Conventional
115.55
270.50
15^.00
540.05
Current
147.50
8.72
38.00
194.22
TABLE 9
Comparison of Amortized Costs per Unit of Wire Product
Daily Average Finished Wire Production of 75 Ton
A. Unit Cost Based on Processing, Disposal, Waste
Treatment and Recovery Costs, Including Amortization
Cost Item
Processing, Disposal, Waste
Treatment and Recovery
Costs, Including Amorti-
zation (Table 7)
Cost/Ton
Previous
$194.64
$ 2.59
Conventional
$540.05
$ 7.20
Current
$194,22
$ 2.59
B. Unit Cost Based on Disposal, Waste Treatment and
Recovery Costs. Including Amortization
Cost Item
Disposal, Waste Treatment
and Recovery Costs, In-
cluding Amortization
(Tables 5, 7)
Cost/Ton
Previous
$79.09
$ 1.05
Conventional
$424.50
$ 5.66
Current
$ 46.72
$ .62
31
-------
TABLE 10
Pickling Effluent Quality and Quantity Comparison
Item
(ppm, ex-
cept pH)
PH
Cr+6 as
Cr03
Cr+3
Cu+2
Zn+2
Ni+2
Sn+2
Solids:
Suspended, ppm
Dissolved, ppm
Flow, GPM2
Previous
1/23/6?1
3.81
70
27
124
374
71.5
1551
150
7/7/67
3.83
96.9
75
36
2.4
150
Current
1/25-2/5/71
Composite
8.0
No such proc
No such proc
.65
.08
None
10
2/8-2/17/71
Composite
8.09
3ss used
3ss used
.50
None
None
10
2/17/71
7.9
No sue]
No sue!
.3
None
None
None
10
10
5/12/71
8.0
i process
i process
.25
1.60
< .05
None
3.4
760
10
5/13/71
8.7
. used
. used
.85
.30
<.05
None
33.2
814
10
U)
fU
Notes: 1. United States Testing Company Report #90314 dated 2/10/67; all other
results by Lancy Laboratories.
2. The 10 GPM, current effluent flow rate, corresponds to the freshening
water input of 10 GPM into the Water Reuse System.
-------
TABLE 11
Capital Equipment Cost
Summary - Copper Recovery, Bright Pickle, and Waste
Treatment Equipment Cost
Integrated Copper Treatment System. . . .$ 10,370
Bright Pickle System 8,720
Electrolytic Copper Recovery System . . . 5,830
Deionized Water System 2,880
Batch Waste Treatment System 1,920
Final pH Adjustment and Water
Reuse System 3>330
Auxiliary Equipment 4,900
Integrated Copper Treatment System
(Flat Wire Mill) 4.165
$ 42,115
33
-------
APPENDICES
Part B
35
-------
SPENT ACID COLLECTION LINE
CITY WATER
ISO 0PM
WORK
HOT
SULFURIC
KID
PICKLE
/ SEE \
\ TABLE I /
DICHROMATE
PICKLE
/ SEE N
\ TABLE 2 /
Z 0PM
TO RAHWAY VALLEY
MUNICIPAL SANITARY
SEWER SYSTEM.
SEE TABLE 10 FOR TYPICAL
"PREVIOUS" EFFLUENT ANALYSIS.
Pick/ing Operations
Figure /
and Waste Disposal
Previous to this Project
Volco Brass & Copper Company
-------
POLYELECTROLYTE
^MIXING TANK
CHROMIUM CONTAMINATED
RINSE WATER
FROM PICKLING PLANT-^
NON-CHROMATE ACID RINSES
FROM PICKLING PLANT,
EXHAUST
FAN
ACID FLOOR SPILL
SPENT ACID DUMPS
FROM PICKLING PLANT
SODIUM
SODIUM ,
BISULFITE J
CHROMIUM
TREATMENT
TANK
HYDRATED
LIME
STORAGE
BIN
pH ADJUSTMENT
TANK
1
ACID CO
ANI
CHROME 1
TANK
D
1
LLECTION
)
tEDUCTION
D
L*^
rs
ROTARY VACUUM FILTERS
SLUDGE HOPPER-jl
/ HAUL TO LAND N \
\ FILL SITE /
TO RAHWAY VALLEY MUNICIPAL
SANITARY SEWER SYSTEM ~
CONVENTIONAL PICKLING WASTE TREATMENT DESIGN
SCHEMATIC FLOW DIAGRAM
FIGURE 2
VOLCO BRASS AND COPPER
KENILMtORTH, NEW JERSEY
38
-------
REUSE WATER UNE
.STABILIZER, INHIBITOR
CITY WATER
* 10 «PM
_FL
HOT
SULFURIC
PICKLE
SEE
FABLE
,)
i
»
... , . , .
I I 1
1
'
\\ ,
PEROXIDE
BRIGHT
(
PICKLE
SLE2)
>*
A
r
L
i
v * . »
-
1
3O 0PM
i
COPPER
TREATM.
(ft
^»),
' '
FROM
AIR
BLOWER
PEROXIDE
FICKLE
RESERVOIR
'L_.
1
1
^
i'<
> r !* .
COLD HOT
RINSE 0. X.
RINSE
PLUS
* I--"-
rnoM uti
~~| SC
LUB
|
X-
NaOH
Na;C03
*2H4^ *£, AUTO
~n _r ^ " p
'^ 4
4 L
COPPER
TREATM.
RESERVOIR
~1
TO
FLOOR
SPILL
ELECTROLYTIC
COPPER
RECOVERY
CELL
IO 0PM
TO
STORM SEWER
SETTLINfi TANK
SEE TABLE 10 FOR
TYPICAL CURRENT
EFFLUENT QUALITY
FINAL pH ADJUSTMENT
TANK
Pickling Operations , Copper Recovery ,
Waste Treatment, &_ Water Reuse System
Currently in use at
Volco Brass & Copper Co.
-------
OVERALL VIEW OF VOLCO BRASS & POPPER PICKLING LINE
FIGURE 4
HEAVY WIRE DRAWING (.620" dia. to .400" dia. .
5 Reductions)
FIGURE 5
-------
INTERMEDIATE WIRE FOLLOWING PEROXIDE BRIGHT PICKLING
FIGURE 6
FINE WIRE FOLLOWING BRIGHT PICKLING
FIGURE 7
41
-------
POPPER RECOVERY' AMD WASTE TREATMENT EQUIPMENT
(Right to Left: Crystal Filter, Electrolytic Copper Re-
covery Cell, Copper Treatment Reservoir, 50$ Caustic
Soda Supply Tank) FIGURE 8
50$ Caustic Soda
Storage Tank and
Deionizer
FIGURE 9
42
-------
PEROXEDE PICKLE RESERVOIR TANK (LEFT), FLOOR SPILL
NEUTRALIZATION TANK (RIGHT), STEAM OONDENSATE
MDNITOR AND PUMP (CENTER FOREGROUND)
FIGURE 10
CHEMICAL SUPPLY TANK (LEFT, GRAVITY SLUDGE
FILTER (CENTER) AND AUTOMATIC pH CONTROLLER (RIGHT)
FIGURE 11
43
-------
ELECTROLYTIC POPPER
(Cathode of Flattened
Scrap Copper Tubing
Being Removed for
Inspection)
FIGURE 12
REUSE WATER PUMP INSTALLED IN RINSE WATER
SETTLING TANK
FIGURE 13
44
-------
1
Accession Number
w
5
2
Subject Field & Group
SELECTED WATER RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
Organization
Volco Brass and Copper Company, Kenilworth, New Jersey 07033
Title
Brass Wire Mill Process Changes and Waste Abatement, Recovery and Reuse
10
Authors)
Leslie E. Lancy
Charles A. Forbes
16
Project Designation
12010 DPF 11/71
21
Note
22
Citation
Lancy Laboratories, Inc., Zelienople, PA. 16063
Descriptors (Starred First)
25
Identifiers (Starred First)
Brass wire mill wastes, wire pickling, pickle regeneration, electrolytic
copper recovery, chemical rinsing, copper sludge salvage, water reuse, by-product
recovery.
27 Abstract Tj.£s rep0rt describes process changes and waste treatment, recovery, and reuse
facilities installed by Volco Brass and Copper Company, Kenilworth, New Jersey. The plant
produces 75 tons of wire per day-
An electrolytic system was installed to recover copper from the spent primary pickle
solution and to regenerate the sulfuric acid for reuse. A hydrogen peroxide bright pickle
replaced the chromate and fluoride bright pickles previously used. Copper from the bright
pickle is also recovered in the electrolytic system. The electrolytic copper is reused on
location in casting. An integrated copper treatment system was installed to treat bright
pickle drag-out. Sludge from the integrated system is recovered for sale. Rinse water
consumption was reduced from 150 gpm to 10 gpm. Former discharges of chromium, ammonium,
and fluoride ions have been eliminated. Cost and operating data and effluent analyses
are presented.
This report was submitted in fulfillment of Project No. 12010 DPF under the partial
sponsorship of the Industrial Pollution Control Section, OR&M, of the Environmental
Protection Agency.
Abstractor.
Edward L. Dulaney
Institution
n tut ion
Industrial Pollution Control Section, ORM, EPA
WR:102 (REV. JULY 1969)
WRSIC
SEND. WITH COPY OF DOCUMENT, TO: WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON. D. C. 20240
* GPO: 1 970-389-930
------- |