-------
ORGANIZATION OF THIS DOCUMENT
This development document for the nonferrous metals manufacturing
category consists of a general development document which
considers the general and overall aspects of the regulation and
31 subcategory specific supplements. These parts are organized
into 10 volumes as listed below.
The information in the general document and in the supplements is
organized by sections with the same type of information reported
in the same section of each part. Hence to find information on
any specific aspect of the category one would need only look in
the same section of the general document and the specific
supplements of interest.
The ten volumes contain contain the following subjects:
General Development Document
Bauxite Refining
Primary Aluminum Smelting
Secondary Aluminum Smelting
Primary Copper Smelting
Primary Electrolytic Copper Refining
Secondary Copper Refining
Metallurgical Acid Plants
Primary Zinc
Primary Lead
Secondary Lead
Primary Antimony
Primary Precious Metals and Mercury
Secondary Precious Metals
Secondary Silver
Secondary Mercury
Primary Tungsten
Secondary Tungsten and Cobalt
Primary Molybdenum and Rhenium
Secondary Molybdenum and Vanadium
Primary Beryllium
Primary Nickel and Cobalt
Secondary Nickel
Secondary Tin
Volume VIII Primary Columbium and Tantalum
Secondary Tantalum
Secondary Uranium
Volume IX Primary and Secondary Titanium
Primary Zirconium and Hafnium
Volume X Primary and Secondary Germanium and Gallium
Primary Rare Earth Metals
Secondary Indium
Volume I
Volume II
Volume III
Volume IV
Volume V
Volume VI
Volume VII
-------
DEVELOPMENT DOCUMENT
for
EFFLUENT LIMITATIONS GUIDELINES AND STANDARDS
for the
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
VOLUME III
Primary Copper Smelting
Primary Electrolytic Copper Refining
Secondary Copper Refining
Metallurgical Acid Plants
William K. Reilly
Administrator
Rebecca Hanmer, Acting
Assistant Administrator for Water
Martha Prothro, Director
Office of Water Regulations and Standards
Thomas P. O'Farrell-, Director
Industrial Technology Division
Ernst P. Hall, P.E., Chief
Metals Industry Branch
and
Technical Project Officer
May 1989 •
U.S. Environmental Protection Agency
Office of Water
Office of Water Regulations and Standards
Industrial Technology Division
Washington, D. C. 20460
-------
-------
ORGANIZATION OF THIS DOCUMENT
This development document for the nonferrous metals manufacturing
category consists of a general development document which
considers the general and overall aspects of the regulation and
31 subcategory specific supplements. These parts are organized
into 10 volumes as listed below.
The information in the general document and in the supplements is
organized by sections with the same type of information reported
in the same section of each part. Hence to find information on
any specific aspect of the category one would need only look in
the same section of the general document and the specific
supplements of interest.
The ten volumes contain contain the following subjects:
Volume I
Volume II
Volume III
Volume IV
Volume V
Volume VI
Volume VII
General Development Document
Bauxite Refining
Primary Aluminum Smelting
Secondary Aluminum Smelting
Primary Copper Smelting
Primary Electrolytic Copper Refining
Secondary Copper Refining
Metallurgical Acid Plants
Primary Zinc
Primary Lead
Secondary Lead
Primary Antimony
Primary Precious Metals and Mercury
Secondary Precious Metals
Secondary Silver
Secondary Mercury
Primary Tungsten
Secondary Tungsten and Cobalt
Primary Molybdenum and Rhenium
Secondary Molybdenum and Vanadium
Primary Beryllium
Primary Nickel and Cobalt
Secondary Nickel
Secondary Tin
Volume VIII Primary Columbium and Tantalum
Secondary Tantalum
Secondary Uranium
Volume IX
Volume X
Primary and Secondary Titanium
Primary Zirconium and Hafnium
Primary and Secondary Germanium and Gallium
Primary Rare Earth Metals
Secondary Indium
-------
11
-------
TABLE OF CONTENTS
Supplement
Primary Copper Smelting
Primary Electrolytic Copper Refining
Secondary Copper Refining
Metallurgical Acid Plants
Page
1027
1089
1209
1337
For detailed contents see detailed contents list in
individual supplement.
111
-------
iv
-------
NONFERROUS METALS,MANUFACTURING POINT SOURCE CATEGORY
DEVELOPMENT DOCUMENT SUPPLEMENT
for the
Primary Copper Smelting Subcategory
William K. Reilly
Administrator
Rebecca Hanmer
Acting Assistant Administrator for Water
Martha Prothro, Director
Office of Water Regulations and Standards
Thomas P. O'Farrell, Director
Industrial Technology Division
Ernst P. Hall, P.E., Chief
Metals Industry Branch
and
Technical Project Officer
May 1989
U.S. Environmental Protection Agency
Office of Water
Office of Water Regulations and Standards
Industrial Technology Division
Washington, D. C. 20460
1027
-------
1028
-------
PRIMARY COPPER SMELTING SUBCATEGORY
Section
TABLE OF CONTENTS
SUMMARY
Page
1033
II
CONCLUSIONS
1035
III
IV
V
VI
SUBCATEGORY PROFILE
Description of Primary Copper Production
Raw Materials
Roasting
Smelting
Converting
Fire Refining
Casting
Summary of Wastewater Sources
Age, Production, and Process Profile
SUBCATEGORIZATION
Factors Considered in Subcategorization
Production Normalizing Parameters
WATER USE AND WASTEWATER CHARACTERISTICS
Wastewater Sources, Discharge Rates, and
Characteristics
Copper Smelting Wastewater Sources and
Characteristics
Smelting Wet Air Pollution Control
Slag Granulation
SELECTION OF POLLUTANT PARAMETERS
1037
1037
1037
1037
1037
1039
1040
1040
1040
1041
1047
1047
1048
1049
1050
1052
1052
1052
1067
1029
-------
PRIMARY COPPER SMELTING SUBCATEGORY
Section
VII
VIII
IX
X
XI
XII
XIII
TABLE OF CONTENTS (Continued)
Page
CONTROL AND TREATMENT TECHNOLOGIES 1069
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS 1071
BEST PRACTICABLE TECHNOLOGY CURRENTLY AVAILABLE 1073
Effluent Limitations 1073
BEST AVAILABLE TECHNOLOGY ECONOMICALLY 1074
ACHIEVABLE
Technical Approach to BAT 1075
Storm Water and Precipitation Allowances 1075
Effluent Limitations 1076
NEW SOURCE PERFORMANCE STANDARDS 1077
TECHNICAL APPROACH TO BDT 1077
. ' •" • '"' : ' ,
Storm Water and Precipitation Allowances 1077
New Source Performance Standards 1077
PRETREATMENT STANDARDS 1079
Technical Approach to Pretreatment 1079
Storm Water and Precipitation Allowances 1079
Pretreatment Standards for New Sources 1079
Best Conventional Pollution Control Technology 1081
1030
-------
PRIMARY COPPER SMELTING SUBCATEGORY
LIST OF TABLES
Section
III-l Initial Operating Years (Range) Summary
of Plants in the Primary Copper Smelting
Subcategory by Discharge Type
III-2 Production Ranges for the Primary Copper
Smelting Subcategory
III-3 Primary Copper Smelting Subcategory Summary
of Processes and Associated Waste Streams
V-l Indicated Presence or Absence of Toxic Metal
Pollutants - DCP Data
V-2 Water Use and Discharge Rates for Slag
Granulation
V-3 Primary Copper Sampling Data, Fire Refined
Copper Casting Contact Cooling Water Raw
Wastewater
V-4 Primary Copper Sampling Data, Slag Granulation,
Contact, and Non-Contact Cooling Water Raw ,.
Wastewater
V-5 Primary Copper Sampling Data, Treated
Wastewater
1042
1043
1044
1053
1054
1055
1056
1058
1031
-------
PRIMARY COPPER SMELTING SUBCATEGQRY
Section
III-l
III-2
V-l
V-2
V-3
LIST OP FIGURES
Primary Copper Smelting Process
Geographic Locations of Primary Copper
Smelting Plants
Sampling Sites at Primary Copper Smelter
Plant B
Sampling Sites at Primary Copper Smelting and
Refining Plant C
Sampling Site at Primary Copper Smelter
Plant D
Page
1045
1046
1063
1064
1065
1032
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - I
SECTION I
SUMMARY
On February 27, 1975 (40 FR 8514), EPA promulgated interim
technology-based effluent limitations for existing sources and
proposed new source performance and pretreatment standards for
the primary copper subcategory of the nonferrous metals
manufacturing point source category. These effluent guidelines
and standards limited the quantities of total suspended solids,
copper, cadmium, lead, zinc, and pH in primary copper subcategory
wastewaters.
The 1975 BPT limitations for primary copper smelters, and primary
copper refiners located on-site with smelters, required no
discharge of process wastewater pollutants with two rainfall
related exceptions. When a 10-year, 24-hour rainfall event
occurred, primary copper smelters were allowed to discharge a
volume of water equal to that resulting from the 10-year, 24-hour
rainfall event falling within a smelter's wastewater impoundment.
Additionally, smelters were allowed to discharge a volume of
water equal to that resulting from the difference between monthly
evaporation and precipitation. This discharge was subject to
concentration-based limitations.
The 1975 BAT regulation for primary copper smelters allowed a
discharge of water equal to the 25-year, 24-hour rainfall event
falling within a smelter's wastewater impoundment. This
discharge was subject to no effluent standards. Additionally,
smelters were allowed to discharge a volume of water equal to
that resulting from the difference between the net monthly
evaporation and net monthly precipitation. This discharge was
subject to concentration-based limitations.
Revised BPT limitations were issued for the primary copper
subcategory on July 2, 1980 (45 FR 44926). The Agency retained
the no discharge of process wastewater pollutants requirement for
primary copper smelters and the 10-year, 24-hour storm event
discharge provision. The monthly discharge allowance for
smelters when the net precipitation was greater than the net
evaporation was deleted.
in the March 8, 1984 rulemaking (49 FR 8742), EPA promulgated
modifications to BAT, NSPS, and PSNS for this subcategory
pursuant to the provisions of Sections 301, 304, 306, and 307 of
the Clean Water Act, as amended. This supplement provides a
compilation and analysis of the background material used to
develop these effluent limitations and standards. The BPT
limitations promulgated in 1980 remain unchanged and are
discussed later for information purposes only.
1033
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - I
The primary copper smelting subcategory is comprised of 19
plants. Of the 19 plants, one discharges directly to rivers,
lakes, or streams; none discharge indirectly through publicly
owned treatment works (POTW); and 18 achieve zero discharge of
process wastewater.
For the primary copper smelting subcategory, promulgated BAT
effluent limitations do not allow a discharge of process
wastewater pollutants except for the 25-year, 24-hour rainfall
event exemption. NSPS and PSNS also do not allow a discharge of
process wastewater pollutants. There are no storm water
discharge exemptions provided for new sources.
1034
-------
PRIMARY COPPER SMELTING SUBCATEGORY
SECT - II
SECTION II
CONCLUSIONS •.-i
In the 1980 rulemaking, EPA divided primary copper. production
into two subcategories: the primary copper smelting subcategory
and the primary electrolytic copper refining subcategory. This
subcategorization has been retained for the primary production of
copper arid the primary copper smelting subcategory has not been
further subdivided into segments or building blocks for the
purpose of regulation.
EPA promulgated BPT effluent limitations for the primary coppe-r
smelting subcategory on July 2, 1980 as Subpart D of 40 CFR Part
421. No modifications are promulgated for the 1980 BPT. The
promulgated BPT for the primary copper smelting subcategory is no
discharge of process wastewater pollutants, subject to an
uncontrolled discharge equal to the volume in excess of
storm water from a 10-year, 24-hour storm falling on a cooling
impoundment.
EPA has amended BAT effluent limitations for the primary copper
smelting subcategory. EPA promulgated BAT for the primary copper
smelting subcategory be no discharge of process wastewater
pollutants, subject to an uncontrolled discharge equal to the
volume of storm water in excess of a 25-year, 24-hour storm
falling on a cooling impoundment.
EPA promulgated NSPS for the primary copper smelting subcategory
be no discharge of process wastewater pollutants with no
provision for a storm water discharge allowance.
EPA did not promulgate pretreatment standards for existing
sources (PSES) for the primary copper smelting subcategory,
because there are no existing indirect dischargers in this
subcategory.
EPA promulgated PSNS for the primary copper smelting subcategory
be no discharge of process wastewater pollutants with no
provision for a storm water discharge allowance.
1035
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - II
THIS PAGE INTENTIONALLY LEFT BLANK
1036
-------
PRIMARY COPPER SMELTING SUBCATEGORY
SECT - III
SECTION III
SUBCATEGORY PROFILE
This section of the primary copper smelting supplement describes
the raw materials and processes used in smelting pure copper from
copper bearing ores to pure copper and presents a profile of the
primary copper smelting plants identified in this study.
DESCRIPTION OF PRIMARY COPPER PRODUCTION
The manufacturing of copper from copper sulfides
pyrometallurgical processes may consist of seven steps:
through
1. Roasting,
2. Smelting,
3. Leaching, if preceded by a pyrometallurgical step,
4. Converting,
5. Fire refining,
6. Slag granulation and dumping, and
7. Casting of products from these operations.
In actual practice, however, not all of these operations are
practiced at all smelters and they may be combined in several
ways with other processes such as electrolytic refining and
metallurgical acid production. Figure III-l (page 1°?5)
illustrates the copper smelting process. Electrolytic refining
and product casting, as well as recovery of precious metals from
anode slimes, are discussed in the Primary Electrolytic Copper
Refining Subcategory Supplement.
RAW MATERIALS
There are approximately 160 known copper minerals, about a dozen
of which are commercially important. The most important copper
ores in the United States are chalcopyrite, chalcocite,
covellite, chrysocolla, bornite, cuprite, and malachite. These
are either sulfide, silicate, or oxide ores. Most of the copper
ore processed in the United States is a copper sulfide. At the
mine site, copper bearing ore is concentrated into copper sulfide
which forms the main raw material for copper smelting.
ROASTING
Roasting, the first step in producing copper from copper sulfide
concentrates, oxidizes the iron sulfide present in the _copper
concentrate to iron oxide and S02 gas. During this oxidation
process, the amount of air added is limited so as not to oxidize
the copper sulfide.
1037
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - III
Keeping the copper sulfide unoxidized allows for easy removal of
the iron oxide during smelting because of specific gravity
differences between iron oxide and copper sulfide.
Depending on the raw material and the type of smelting furnace,
copper sulfide concentrates may be roasted in one of three ways:
multiple-hearth roasters, fluidized bed roasters, and sintering
machines. Multiple-hearth roasters, as the name suggests,
contain several hearths where the concentrate is roasted. A
fluidized bed roaster suspends concentrate in air while the
roasting takes place. The fluidized bed roaster has replaced
many multiple-hearth roasters because its capacity is roughly
eight times greater than a multiple-hearth roaster. A third
method of roasting, known as sintering, actually melts the
surface of the concentrate. After the calcine (the roasted
product) cools, the concentrate has become agglomerated and is
fed to a blast furnace. Currently there are no blast furnaces
used in the United States primary copper smelting plants.
The SO2 gasses and particulate matter produced during roasting
are collected in a centralized flue. Of the seven primary copper
smelters who reported sufficient information about roasting, one
uses a dry control method, one uses a wet scrubber, and five have
no roasting air pollution control for particulate matter.
Traditionally, control of SO2 emissions are accomplished with an
acid plant. By definition this waste stream becomes part of the
metallurgical acid plant subcategory, and is further considered
xn the Metallurgical Acid Plant Supplement.
SMELTING
The calcine produced from roasting is composed primarily of
copper sulfide and iron oxide. With the aid of a fluxing agent,
the calcine is melted in a smelting furnace. Through gravity
separation, the copper sulfide is separated from the iron oxide.
The iron oxide and fluxing agents float to the top of the bath,
forming slag, which is continuously tapped from the furnace. The
copper sulfide and other heavy metals settle to the bottom of the
furnace and are periodically tapped. The matte, or molten metal
from the furnace bottom, is composed of copper, nickel, iron,
cobalt, sulfur, and small amounts of precious metals. The purity
of the matte can be improved by altering both the roasting and
smelting processes. However, optimum conditions dictate that the
matte contain approximately 35 percent iron because, as iron
oxide concentrations are reduced, more copper is removed with the
slag.
Three types of furnaces may be used to smelt roasted calcines:
reverberatory, electric, and blast furnaces. The most widely
used of the three, the reverberatory furnace, was designed to
process fine concentrate. A reverberatory furnace is
characterized by a low roof with heat added by burning fuel oil,
natural gas, or pulverized coal between the charge and the roof.
An electric furnace send an electric current through the charge
melting it with the heat liberated through electrical resistance.
1038
-------
PRIMARY COPPER SMELTING SUBCATEGORY
SECT - III
The major advantage of an electric furnace over a reverberatory
furnace is that the volume of off-gases is reduced. With a
smaller volume of gas, the SO2 content is higher, thus the SO2 is
more readily recoverable in an acid plant.
Several variations of the preceding smelting process description
have been developed; they include the Mitsubishi and Noranda
processes and the smelting of unrpasted calcines. Continuous
matte smelting and converting furnaces, known as the Mitsubishi
process, incorporate three furnaces to combine roasting,
smelting, and converting, (oxidation of copper sulfide) into one
continuous process. By combining these three processes, smelting
rates and heating costs are greatly reduced. The Noranda
process, sometimes referred to as Smelt ing-Convert ing Reactions,
combines the smelting and converting processes together. The
reactions that take place within the reactor are similar to those
that occur during a normal two-stage smelting and converting
process. Iron contained within the charge is first oxidized
followed by oxidation of the copper sulfide.
Wastewater generated from smelting is attributable to control of
air pollution and slag granulation. Of the 19 copper smelters in
the United States reporting data, one plant controls air
pollution with a wet scrubber, five use dry control methods, and
six report no control of air pollution.
Slag tapped from the smelting furnace is granulated with water
jets to ease handling and disposal problems. An alternative to
slag granulation is slag dumping. With slag dumping, the molten
slag is dumped onto the ground (slag pile) and allowed to air
cool. This process is also termed "pancaking." In granulation,
the slag is taken to the slag disposal area in its molten form
and is impacted by a high velocity jet of water. The resultant
waste material is finely divided and is either stored as waste or
sold as road bedding or concrete agglomerate. With only three
plants reporting slag granulation, it is apparent the preferred
method of slag disposal is slag dumping. There are three copper
smelters who reported practicing slag granulation.
CONVERTING
The composition of the matte from the smelting process is
primarily copper sulfide and iron sulfide. To form blister
copper (98 percent pure copper), the matte undergoes a two-stage
process. Compressed air is blown into the matte converting the
remaining iron sulfide to iron oxide. Silica is added to form
iron silicate which floats to the top as slag:
2FeS + 3O2
2FeO
2SO2
After skimming the slag, additional compressed air is added
oxidize the copper sulfide to copper and 802:
CU2S + 02 ---- > 2Cu + SO2
to
1039
-------
PRIMARY COPPER SMELTING SOBCATEGORY SECT - III
The remaining metal is now 98 percent pure copper. This product
is commonly referred to by industry as "blister copper."
The SC-2 emissions and particulate matter leaving the furnace are
captured with air scrubbers and the particulate returned to the
smelter. The slag removed during conversion contains a
relatively large amount of copper and is returned to the smelter.
Of the 19 copper smelters, 13 use a conversion process. Two of
these plants use wet scrubbers, eight use dry air pollution
control methods and four reported no control (one plant did not
provide this data). The two plants that use wet air pollution
control use it as a method for pretreatment before the gas enters
an acid plant. The scrubber liquor cools and humidifies the gas
along with removing particulate matter. Wastewater from these
scrubbers, therefore, is considered a' part of the metallurgical
acid plant subcategory.
FIRE REPINING
After the converting process is completed, further purification
of the copper is required to improve certain physical properties
such as ductility and conductivity. The first stage of the
refining process is commonly called fire refining and is normally
conducted at the smelting site. Impurities within the copper
other than precious metals have a higher affinity for oxygen than
copper. Compressed air is blown into the molten bath to oxidize
the impurities which are removed as slag with the help of a
fluxing agent and returned to the smelter. After several cycles
of oxidation and slag removal, the bath becomes saturated with
copper oxide. The molten bath is then converted back to copper
by adding reducing agents such as green wood poles, natural gas,
or ammonia. Copper leaving this process usually contains 0.1 to
0.3 percent oxygen.
Currently in the United States, there is no wastewater generated
from any fire refining process. There were seven facilities that
reported using fire refining methods.. Of these seven smelters,
three reported using dry methods to control air emissions.
CASTING
The final step in the smelting process is casting the fire
refined or blister copper into solid shapes. Most usually this is
into the shape of an anode for further refining in an
electrolytic process. The casting of blister copper was found,
during the study for the 1980 rulemaking to be accomplished
without the generation and discharge of process wastewater.
SUMMARY OP WASTEWATER SOURCES
In summary, the principal uses of water in the primary copper
smelting subcategory are due to smelting wet air pollution
control and slag granulation. There are other minor wastewater
streams associated with primary copper smelting. These
1040
-------
PRIMARY COPPER SMELTING SUBCATEGORY
SECT - III
wastewater streams include, but are not limited to, maintenance
and cleanup water and storm water runoff. These wastewater
streams are not considered as a part of this rulemaking. EPA
believes the flows and pollutant loadings associated with these
waste streams are insignificant relative to the waste streams
selected and are best handled by the appropriate permit authority
on a case-by-case basis under the authority of Section 402 of the
Clean Water Act.
AGE, PRODUCTION, AND PROCESS PROFILE
The primary copper smelting subcategory consists of 19
operations. The location and discharge status of the primary
copper smelters in the United States at the time of the survey is
shown in Figure III-2 (page 1046). In some cases both smelting
and refining operations are found at or near the same site. As a
rule, however, smelters are located near copper mines and mills
in the Southwest, and electrolytic refineries are either found
near smelters or near maritime centers.
Table III-l (page 1042) shows the average age of the smelters 'as
approximately 40 years. As seen in Table III-2 (page 1043), the
average smelter plant production is approximately 200,000 tons
per year of smelted copper.
As shown in Table III-l, only one of the 19 copper smelters
discharges wastewater. This facility is a direct discharger
Table III-3 (page 1044) presents a summary of the number of
facilities with a reported process and the number of facilities
generating wastewater within that process.
1041
-------
PRIMARY COPPER SMELTING SUBCATEGORY
SECT - III
LE III-l
ATING YEARS (RANGE)
IMARY COPPER SMELTING SUBCATEGORY
SCHARGE TYPE
ting Plant Age Range (Years)
1947- 1937- 1917- Before
1938 1918 1903 1903
35-45 45-65 65-80 80- + NR Tota
§03 K H rH 1 in
pa CM Q CD P~ CO ro
EH P4 6 m <* I
O Pa >H W cncn in
EC CQ rH rH CM
H !3 ft i m
EH H ft t^- 00 CM
H o vo in i
25 to O en en in
H EH rH rH rH
<> *H
i~3 n5 i m
(It S CM 00 rH
•H r-- vo i
[V| JH en en o
O CM rH rH rH
>H
2 ro co o
S 00 t^ rH
S cr> en i
5 rH rH O
CO
a)
o»
^
a)
& Q)
O ft
w S
•H EH
P
rH oo en
rH rH
1 1 O
rH in VO
1 rH rH
1 1 O
1 *f ^l1
1 CM CM
1 rH rH
1 rH rH
4J
0 rH
(D O «J
Jj Jj 1 i
•H a) o
Q N EH
1042
-------
PRIMARY COPPER SMELTING SUBCATEGORY
SECT'--III
TABLE III-2
PRODUCTION RANGES FOR PRIMARY COPPER SMELTING PLANTS
(tons/yr)
Production (1976)
Range
0 - 50000
50000 - 100000
100000 - 150000
150000 - 200000
200000 - Above
NR
TOTAL PLANTS
Number of
Copper Smelters
5
3
4.
2
3
2
19
1043
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - III
TABLE II1-3
PRIMARY COPPER SMELTING SUBCATEGORY
SUMMARY OP PROCESSES AND ASSSOCIATED WASTE STREAMS
No. of Plants
No. of Plants Reporting Generating
Process With Process Wastewater*
Roasting 8 1
Smelting 15 4
Converting 14 1
Fire Refining 7 0
• \
* Through reuse or evaporation practices, a plant may generate a
wastewater from a particular process but not discharge it.
1044
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - III
Copper Conc«ner«t«»
Solid* eo •
f
j\
1. '
StUB
Povar P
'
iiMt*
Boil
t
vm
Prteoadi
To Sal
Acid P
CO-
l*Bt
t
B*AC
•r
r
clonifit
fude
last
Eki««
4
bina
Ml
1
ioos
SUg
ctr ^
1
RoMdat
Caleia*
i •tiring
,»
CoBverciag
Bllsur
Copper
Fir* lUf inlag
Cooling
g.
SUg
0
< 1 1
>
Onroa*c*d Coaceacrsca
Solids to Diseoaal _
Ct m*»
Sl«g
k - - •
I
i
Air
'C.rto..
k
ttecar
Aaod* or*Pir* H«fin«d
Copper to El«ctroly«i«
or tterkcc
FIGURE III-l
PRIMARY COPPER SMELTING PROCESS
1045
-------
PRIMARY COPPER SMELTING SUBCATEGORY
SECT - III
CM U
H .>•
H
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - IV
SECTION IV
SUBCATEGORIZATION
This section summarizes the factors considered during the
designation of the primary copper smelting subcategory.
Primary electrolytic copper refiners located onsite with primary
copper smelters were considered as a single subcategory during
the previous 1975 rulemaking. Primary copper refiners not
located on site with smelters were considered as a separate
subcategory. The 1975 rulemaking established interim BPT and BAT
limitations, along with NSPS and PSNS for primary copper. In
1980, a modified BPT regulation was promulgated for primary
copper operations that divided primary copper into smelting and
refining operations regardless of location or association with
other operations.
FACTORS CONSIDERED IN DESIGNATING THE PRIMARY COPPER SMELTING
SUBCATEGORY
The factors listed for general subcategorization were each
evaluated when considering subdivision of the primary copper
smelting subcategory. Three factors were particularly important
in establishing the primary copper smelting subcategory; the type
of metal produced, the nature of the raw materials used, and the
manufacturing processes employed. Analysis of these three
factors, along with other considerations discussed below,
resulted in the designation of the primary copper smelting
subcategory.
Raw Materials
The raw materials usually used for primary copper smelting are
copper ores and in the United States sulfide ores are used
exclusively for smelting. The raw materials for electrolytic
refining are either blister copper produced by fire refining or
extracted copper from leaching and related mining. These raw
materials are obviously quite different and do not appear to
permit continued consolidation of smelting and refining.
Type of Metal Produced
Copper smelting with fire refining produces a somewhat impure
copper (98+% Copper) which must be further refined for most uses
while electrolytic refining produces a high purity copper (99.9+%
copper) which can be used for most purposes without further
refining or alloying. Hence there is no indication from the
products manufactured that the segments should be co-regulated.
1047
-------
PRIMARY COPPER SMELTING SUBCATEGORY
SECT - IV
Manufacturing Processes Employed
The operations involved in copper smelting genera;y produce off-
gasses which are rich in sulfur dioxide (SO2) and which must be
further treated before release to the atmosphere. This is usually
accomplished by the installation of a sulfuric acid plant on the
exhaust gas system from the smelter. Off-gasses from the
electrolytic refining operations are not as rich in sulfur
compounds and cannot be treated to control air pollution in a
sulfuric acid plant. This difference in the waste products from
the smelting and the electrolytic refining operations is quite
significant and forms a rational basis for separating the
operations into separate subcategories.
During the study for the 1980 BPT rulemaking, the ability of the
primary copper smelting processes to consume water and not
require a discharge was extensively studied. This study concluded
that the principal sources of wastewater in the subcategory are
smelting, slag granulation and casting and that all of these
wastewaters can be totally recycled and reused.
By definition, the gas conditioning and cleansing which must be
done on smelter gasses before injecting them into the sulfuric
acid plant is part of the acid plant subcategory operations.
Because of this separation the primary smelting operations can be
operated without the need to discharge wastewater from the
operations. The electrolytic refining operations on the other
hand cannot be operated without the discharge of water from the
processes.
PRODUCTION NORMALIZING PARAMETERS
Effluent limitations and standards for primary copper smelting
operations are based on no discharge of process wastewater
pollutants. No subdivisions or building blocks are being
provided for discharge allowances in. this subcategory.
Therefore, no production normalizing parameters (PNP) are
presented for this category.
1048
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - V
SECTION V
WATER USE AND WASTEWATER CHARACTERISTICS
This section describes the characteristics of wastewater
associated with the primary copper smelting subcategory. Data
used to quantify wastewater flow and pollutant concentrations are
presented, summarized, and discussed. The contribution of
specific production processes to the overall wastewater discharge
from primary copper smelting plants is identified whenever
possible.
Two principal data sources were used in the development of
effluent limitations and standards for this subcategory: data
collection portfolios and field sampling results. Data
collection portfolios, completed for the primary copper smelting
subcategory, contain information regarding wastewater flows and
production levels.
Since .the data collection portfolios were collected, the Agency
received updated and revised flow and production for some waste
streams through comments on the proposed regulation and through
special requests. These data are also included in this section.
In order to quantify the pollutant discharge from primary copper
smelting plants, a field sampling program was conducted.
.Wastewater samples were collected in two phases: screening and
verification. The first phase, screen sampling, was to identify
which toxic pollutants were present in the wastewaters from
production of the various metals. Screening samples were
analyzed for 125 of the 126 toxic pollutants and other pollutants
deemed appropriate. Because the analytical standard for TCDD was
judged to be too hazardous to be made generally available,
samples were never analyzed for this pollutant. There is no
reason to expect that TCDD would be present in primary copper
smelting wastewater. A total of 10 plants was selected for
screen sampling in the nonferrous metals manufacturing category.
A complete list of the pollutants considered and a summary of the
techniques used in sampling and laboratory analyses are included
in Section V of Vol. I. In general, the samples were analyzed for
three classes of pollutants: toxic organic pollutants, toxic
metal pollutants, and criteria pollutants (which includes both
conventional and nonconventional pollutants).
As described in Section IV of this supplement, primary copper
smelting has been further categorized into three subdivisions.
This regulation contains zero discharge limitations and standards
for three unit processes generating process wastewater.
Differences in the wastewater characteristics associated with
these subdivisions are to be expected. For this reason,
wastewater streams corresponding to each subdivision are
1049
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - V
addressed separately in the discussions that follow.
WASTEWATER SOURCES, DISCHARGE RATES, AND CHARACTERISTICS
Tne wastewater data presented in this section were evaluated in
light of production process information compiled during this
study. As a result, it was possible to identify the principle
wastewater sources in the primary copper smelting subcategory:
1. Smelting wet air pollution control,
2. Slag granulation, and
3. Anode casting contact cooling.
Data supplied by dcp responses were used to calculate the amount
of water used per metric ton of production. Water use
(application rate) is defined as the volume of water or other
fluid required for a given process per mass of copper product and
is therefore based on the sum of recycle and make-up flows to a
given process. Wastewater flow discharged after pretreatment or
recycle (if these are present) is used in calculating the
production normalized flow—the volume of wastewater, discharged
from a given process to further treatment, disposal, or discharge
per mass of copper produced. Differences between the water use
and wastewater flows associated with a given stream result from
recycle, evaporation, and carry-over on the product. The
production values used in calculations correspond to the
production normalizing parameter, PNP, assigned to each stream,
as outlined in Section IV. There are no PNPs for the primary
copper smelting subcategory because no discharge allowances have
been provided for any specific process or building block.
Production normalized flows are compiled and statistically
analyzed by stream type. Where appropriate, an attempt is made
to identify factors that could account for variations in water
use. This information is summarized in this section.
Characteristics of wastewater from the previously listed
processes were determined from sampling data collected at primary
cqpper smelters. This data was used to determine the pollutants
.present in each waste stream, and to estimate the yearly mass of
pollutant generated by each waste stream for the entire industry.
There were site visits at three smelters which represents 16
percent of the smelters. Diagrams indicating the sampling sites
and contributing production processes are shown in Figures V-l to
V-3 (pages 1063 - 1065).
In the data collection portfolios, plants were asked to indicate
whether or not any of the toxic pollutants were believed to be
present in their wastewater. Responses for the toxic metals
selected as pollutant parameters are summarized below for those
plants responding to that portion of the questionnaire. The
tally from plants that are solely copper smelters and for plants
that have both smelting and refining is shown in Table V-l (page
1053).
1050
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - V
These data demonstrate that the process wastewater contains
quantifiable concentrations of toxic metal pollutants.
The raw wastewater sampling data for the primary copper smelting
subcategory are presented in Tables V-3 and V-4 (pages 1055 and
1056). The stream codes displayed in Figures V-l through V-3
(pages 1063 - 1065) may be used to identify the location of each
of the samples. Where no data are listed for a specific day of
sampling, the wastewater samples for the stream were not
collected. If the analyses did not detect a pollutant in a waste
stream, the pollutant was omitted from the table.
The data tables included some samples measured at concentrations
considered not quantifiable. The base neutral extractable, acid
extractable, and volatile toxic organics generally are considered
not quantifiable at concentrations equal to or less than 0.010
mg/1. Below this concentration, organic analytical results are
not quantitatively accurate; however, the analyses are useful to
indicate the presence of a particular pollutant. The pesticide
fraction is considered not quantifiable at concentrations equal
to or less than 0.005 mg/1. Nonquantifiable results are
designated in the tables with an asterisk (double asterisk for
pesticides).
These detection limits shown on the data tables are not the same
in all cases as the published detection limits for these
pollutants by the same analytical methods. The detection limits
used were reported with the analytical data and hence are the
appropriate limits to apply to the data. Detection limit
variation can occur as a result of a number of laboratory-
specific, equipment-specific, and daily operator-specific
factors. These factors can include day-to-day differences in
machine calibration, variation in stock solutions, and variation
in operators.
The statistical analysis of data includes some samples measured
at concentrations considered not quantifiable. Data reported as
an asterisk are considered as detected but below quantifiable
concentrations, and a value of zero is used for averaging. Toxic
organic, nonconventional, and conventional pollutant data
reported with a "less than" sign are considered as detected but
not further, quantifiable. A value .of zero is also used for
averaging. If a pollutant is reported as not detected, it is
excluded in calculating the average. Finally, toxic metal values
reported as less than a certain value were considered as not
detected and a value of zero is used in the calculation of the
average. For example, three samples reported as ND, *, and 0.021
mg/1 have an average value of 0.010 mg/1. The averages
calculated are presented with the sampling data. These values
were not used in the selection of pollutant parameters.
In the following discussion, water use and field sampling data
are presented for each operation. Appropriate tubing or
background blank and source water concentrations are presented
1051
-------
PRIMARY COPPER SMELTING SUBCATEGORY
SECT - V
with the summaries of the sampling data. Figures V-l through V-3
show the location of wastewater sampling sites at each facility.
The method by which each sample was collected is indicated by
number, as follows:
1. one-time grab
2. 24-hour manual composite
3. 24-hour automatic composite
4. 48-hour manual composite
5. 48-hour automatic composite
6. 72-hour manual composite
7. 72-hour automatic composite
COPPER SMELTING WASTEWATER SOURCES AND CHARACTERISTICS
Presented below is a discussion of the characteristics of
wastewater from the significant sources attributable to the
smelting of copper concentrates. Wastewater generated from
preconditioning of roasting and converting off-gases is
considered in the Metallurgical Acid Plants Supplement.
Smelting Wet Air Pollution Control
Roasted calcines are charged to a smelting furnace for separation
of copper sulfide and iron oxide. In this process fluxing agents
are added to form an iron silicate slag which floats to the top
of the charge and is removed. Gaseous emissions from this
operation contain low SO2 concentrations but significant amounts
of particulate matter. Consequently, there were five out of six
plants who reported using dry air pollution control devices.
There was one facility that reported using a wet scrubber to
control air emissions from its smelter and the scrubber liquor
was eventually evaporated. This stream was not sampled, but
based on the raw materials used and the products of the smelting
process, this wastewater should contain soluble salts such as
metallic sulfates, chlorides and various metals.
Slag Granulation and Casting
Disposal of smelter furnace slag is normally done through stock
piling. There were three plants that reported using high
pressure water jets to granulate the slag before dumping. The
water usage and discharge rates at these three plants is
presented in Table V-2 (page 1054). Wastewater from this
operation should contain treatable concentrations of total
suspended solids and dissolved toxic metal pollutants (0.40 mg/1
arsenic). Table V-4 (page 1056) presents the sampling data
gathered at primary copper smelters. Copper casting cooling water
data is presented in table V-3 (page 1065) and copper anode
casting water data is included in table V-4.
1052
-------
PRIMARY COPPER SMELTING SUBCATEGORY,
SECT - V
TABLE V-l
INDICATED PRESENCE OR ABSENCE, OF TOXIC METAL POLLUTANTS
DCP DATA
For Smelters only
Antimony
Cadmium
Chromium
Copper
Lead
Nickel
Selenium
Zinc
Known
Present
2
4
2
5
5
4
4
5
Believed
Present
3
2
3
2
1
2
2
1
Believed
Absent
2
1
2
0
1
1
1
1
Known
Absent
0
0
0
0
0
0
0
0
For Smelters and Refiners Combined
Antimony
Cadmium
Chromium
Copper
Lead
Nickel
Selenium
Zinc
4
4
4
7
5
4
4
5
1
1
0
0
1
2
2
2
2
2
3
0
1
1
1
0
0
0
0
0
0
0
0
0
1053
-------
PRIMARY COPPER SMELTING SUBCATEGORY
SECT - V
TABLE V-2
WATER USE AND DISCHARGE RATES FOR SLAG GRANULATION
(1/kkg of copper smelted)
Plant
Code
71*
214
7001
Production
Percent Normalized
Recycle Water Use
0
80
0
(1/kkg)
89930
104407
10056
(gal/ton)
21520
24986
2407
Production
Normalized
Discharge Flow
(1/kkg)
0
20881
10056
(gal/ton)
0
4997
2407
* -
Disposal through solar evaporation.
1054
-------
PRIMARY COPPER SMELTING SUBCATEGORY
SECT - V
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1057
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PRIMARY COPPER SMELTING SUBCATEGORY
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PRIMARY COPPER SMELTING SUBCATEGORY
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1061
-------
PRIMARY COPPER SMELTING SUBCATEGORY
SECT - V
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1062
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - V
(toncontact
Cooling
Hatar
Acid Plant
Baghouae
Spray
VOA Black.
Sourea Hatar
• Diseiaarm
FIGURE V-l
SAMPLING SITES AT PRIMARY COPPER SMELTER PLANT
1063
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - V
FIGURE V-2
SAMPLING SITES AT PRIMARY COPPER SMELTING AND REFINING PLANT C
1064
-------
PRIMARY COPPER SMELTING SUBCATEGORY
SECT - V
A
Ore
Concentration
0.216 MOD
Discharge
FIGURE V-3
SAMPLING SITE AT PRIMARY COPPER SMELTER PLANT D
1065
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - V
THIS PAGE INTENTIONALLY LEFT BLANK
1066
-------
PRIMARY COPPER SMELTING SUBCATEGORY
SECT - VI
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
This section examines chemical analysis data and discusses the
selection or exclusion of pollutants for potential limitation in
the primary copper smelting subcategory. There were no specific
pollutants selected for limitation in the primary copper smelting
subcategory because there was no discharge allowance provided for
this subcategory. Therefore there are no specific pollutants to
review or discuss.
1067
-------
PRIMARY COPPER SMELTING SOBCATEGORY SECT - VI
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1068
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - VII
SECTION VII
CONTROL AND TREATMENT TECHNOLOGIES
The preceding sections of this supplement discussed the waste
water sources, flows, and characteristics of the wastewaters from
primary copper smelting plants. This section summarizes the
description of these wastewaters and indicates the level of
treatment which is currently practiced by the primary copper
smelting industry for each waste stream.
Since the 1980 BPT regulation and the 1984 BAT, NSPS, and PSNS
promulgated for primary copper smelters require no discharge of
process wastewater pollutants, a discussion of the nature of
process water from smelting operations is not pertinent.
1Q69
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - VII
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1070
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - VIII
SECTION VIII
COSTS, ENERGY AND NONWATER QUALITY ASPECTS
The preceding sections of this supplement discussed the waste
water sources, flows, and characteristics of the wastewaters from
primary copper smelting plants. This section summarizes the
description of •these wastewaters and indicates the level of
treatment which is currently practiced by the primary copper
smelting industry for each waste stream.
Since the 1980 BPT limitations required plants to achieve no
discharge of process wastewater pollutants and all existing
plants should have achieved that level of control, there should
be no additional cost for these plants to comply with BAT because
BAT is based on the same requirement.
The nature of the processes in this subcategory is such that they
can be brought to no discharge by recirculation and reuse of
water. These considerations do not have any adverse impact on any
facet of the environment. Therefore there are no nonwater quality
impacts of the regulation.
1071
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - VIII
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1072
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - IX
SECTION IX
BEST PRACTICABLE TECHNOLOGY CURRENTLY AVAILABLE
EPA promulgated BPT effluent limitations for the primary copper
smelting subcategory on July 2, 1980, as Subpart D of 40 CFR Part
421. ' EPA is not modifying these limitations. The provisions of
Subpart D apply to the primary copper smelting subcategory.
Under these limitations, existing point sources may not^discharge
process wastewater pollutants to U.S. waters except as the result
of exceeding a 10-year, 24-hour rainfall event. A process
wastewater impoundment which is designed, constructed and
operated so as to contain the precipitation from the 10-year, 24-
Sour rainfall event as established by the..National Climatic
Center, National Oceanic and Atmospheric Administration, for the
area in which such impoundment is located may discharge that
volume of process wastewater which is equivalent to the volume of
precipitation that falls within the impoundment in excess of that
attributable to the 10-year, 24-hour rainfall event, when such
event occurs.
EFFLUENT LIMITATIONS
The promulgated BPT limitations for the primary copper smelting
subcategory are:
(a) Except as provided in paragraph (b) there shall be no
discharge of process wastewater pollutants to navigable waters.
(b) A process wastewater impoundment which is designed,
constructed and operated so as to contain the precipitation
from the 10-year, 24-hour rainfall event as established by the
National Climatic Center, National Oceanic and Atmospheric
Administration for the area in which such impoundment is located
may discharge that volume of process wastewater which is
equivalent to the volume of precipitation that falls within the
impoundment in excess of that attributable to the 10-year, 24-
hour rainfall event, when such event occurs.
1073
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - IX
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1074
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - X
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
These effluent limitations are based on the best control and
treatment technology used by a specific point source within the
industrial category or subcategory, or by another category where
it is readily transferable. Emphasis is placed on additional
treatment techniques applied at the end of the treatment systems
currently used for BPT, as well as reduction of the amount of
water used and discharged, process control, and treatment
technology optimization.
The factors considered in assessing best available technology
economically achievable (BAT) include the ages of equipment and
facilities involved, the process used, process changes, nonwater
quality environmental impacts (including energy requirements),
and the costs of application of such technology (Section 304 (b)
(2) (B) of the Clean Water Act). At a minimum, BAT represents
the best available technology economically achievable at plants
of various ages, sizes, processes, or other characteristics.
Where the Agency has found the existing performance to be
uniformly inadequate, BAT may be transferred from a different
subcategory or category. BAT may include feasible .process
changes or internal controls, even when not in common industry
practice.
The required assessment of BAT considers costs, but does not
require a balancing of costs against effluent reduction benefits
(see Weyerhaeuser v. Costie, 590 F.2d. 1011 (D.C. Cir. 1978)).
However, in assessing BAT, the Agency has given substantial
weight to the economic achievability of the technology.
TECHNICAL APPROACH TO BAT
The Agency reviewed a wide range of technology options and
evaluated the available possibilities to ensure that the most
effective and beneficial technologies were used as the basis of
BAT. Since no discharge of process wastewater pollutants from
the primary copper smelting subcategory is the basis of
promulgated BAT limitations, (except during a 25-year, 24-hour
storm) it was not necessary to examine treatment options for this
subcategory.
STORM WATER AND PRECIPITATION ALLOWANCES
The interim BAT effluent limitations promulgated on February 27,
1975 included net precipitation and catastrophic storm
allowances. Primary copper smelters were allowed a discharge of
process wastewater which is equivalent to the volume of
precipitation that falls within the wastewater impoundment in
excess of that attributable to the 25-year, 24-hour rainfall
1075
-------
PRIMARY COPPER SMELTING SUBCATEGORY
SECT - X
event, when such event occurs. In addition, smelters were
allowed to discharge a volume of process wastewater on a monthly
basis that is equal to the net difference between the rainfall
falling on the impoundment and the mean evaporation from the pond
water surface. This monthly discharge was subject to
concentration-based standards, whereas the catastrophic storm was
not subject to any effluent limitations.
EPA modified the primary copper smelting and electrolytic
refining precipitation allowances for BPT in the 1980 rulemaking
However, no modifications were made to BAT in that rule. The
Agency is modifying its approach to excess precipitation for BAT
to be consistent with the excess precipitation limitations in the
amended BPT. Wastewater generated at primary copper smelters is
due primarily to slag granulation and anode casting contact
cooling, which can be recycled or reused in other plant
processes. There is no monthly allowance for net precipitation
from cooling impoundments because they require much smaller
surface areas than evaporative impoundments. The Agency is,
however, retaining the catastrophic storm water allowances for
the 25-year, 24-hour storm event for the primary copper smeltinq
subcategory.
• • '''
EFFLUENT LIMITATIONS
The promulgated BAT for the primary copper smelting subcategory
is zero discharge, subject to a discharge allowance for storm
water resulting from a 25-year, 24-hour storm. When such a storm
occurs, primary copper smelters are allowed to discharge a volume
of process water in excess to that attributable to the 25-year,
24-hour storm that falls on the wastewater cooling impoundment.
The effluent quality of this discharge is not controlled.
The promulgated BAT limitations for the primary copper
subcategory are:
smelting
(a) Subject to the provisions of paragraph (b), there shall be no
discharge of process wastewater pollutants into navigable waters.
(b) A process wastewater impoundment which is designed,
constructed and operated so as to contain the precipitation
from the 25-year, 24-hour rainfall event as established" by the
National Climatic Center, National Oceanic and Atmospheric
Administration for the area in which such impoundment is located
may discharge that volume of process wastewater which is
equivalent to the volume of precipitation that falls within the
impoundment in excess of that attributable to the 25-year, 24-
hour rainfall event, when such event occurs.
1076
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - XI
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
The basis for new source performance standards (NSPS) under
Section 306 of the Act is the best available demonstrated
technology (BDT). New plants have the opportunity to design the
best and most efficient production processes and wastewater
treatment technologies without facing the added costs and
restrictions encountered in retrofitting an existing plant.
Therefore, Congress directed EPA to consider the best
demonstrated process changes, in-plant controls, and . ?nd-2:3?ip,S~
treatment technologies which reduce pollution to the maximum
extent feasible. This section describes technologies for
treatment of wastewater from new sources, and Presents mass
discharge standards of regulated pollutants for NSPS based on the
selected treatment technology.
TECHNICAL APPROACH TO BDT
All of the treatment technology options applicable to a new
source were previously considered for BAT. Because no discharge
of process wastewater pollutants is the most rigorous requirement
and that requirement is imposed by the existing BPT limitation,
there are no more stringent requirements which can be made at
this level of regulation.
STORM WATER AND PRECIPITATION ALLOWANCES
Storm water allowances are eliminated under NSPS for the primary
copper smelting subcategory. New plants can be constructed with
demonstrated cooling tower technology rather than cooling
impoundments to cool and recirculate casting contact cooling
water and slag granulation wastewater. The retrofit cost of
adding cooling towers to replace cooling impoundments may be cost
prohibitive for existing sources. However, new sources will not
have this constraint on their operations.
NEW SOURCE PERFORMANCE STANDARDS
The standard of performance for new sources is:
There shall be no discharge of process wastewater pollutants into
navigable waters.
1077
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - XI
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1078
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - XII
SECTION XII
PRETREATMENT STANDARDS
Section 307(b) of the Act requires EPA to promulgate pretreatment
standards for existing sources (PSES), which must be achieved
within three years of promulgation. PSES are designed to prevent
the discharge of pollutants which pass through, interfere with,
or are otherwise incompatible with the operation of publicly
owned treatment works (POTW). The Clean Water Act of 1977
requires pretreatment for pollutants, such as heavy metals, that
limit POTW sludge management alternatives. Section 307(c) of the
Act requires EPA to promulgate pretreatment standards for new
sources (PSNS) at the same time that it promulgates NSPS. New
indirect discharge facilities, like new direct discharge
facilities, have the opportunity to incorporate the best
available demonstrated technologies, including process changes,
in-plant controls, and end-of-pipe treatment technologies, and to
use plant site selection to ensure adequate treatment system
installation. Pretreatment standards are to be technology-based,
analogous to the best available technology for removal of toxic
pollutants.
There are no indirect discharging primary copper smelting plants
in the United States. Consequently, the Agency is not
promulgating pretreatment standards for existing sources.
TECHNICAL APPROACH TO PSNS
All of the treatment technology options applicable as
pretreatment were previously considered for BAT. Because no
discharge of process wastewater pollutants is the most rigorous
requirement and that requirement is imposed by the existing BPT
limitation, there are no more stringent requirements which can be
made at this level of regulation.
STORM WATER AND PRECIPITATION ALLOWANCES
Precipitation allowances are eliminated under PSNS for the
primary copper smelting subcategory. New plants can be
constructed with demonstrated cooling tower technology rather
than cooling impoundments to cool and recirculate casting contact
cooling water and slag granulation wastewater. The retrofit cost
of adding cooling towers to replace cooling impoundments may be
cost prohibitive for existing sources. However, new sources will
not have this constraint on their operations.
PRETREATMENT STANDARDS FOR NEW SOURCES
The pretreatment standard for new sources is: There shall be no
discharge of process wastewater pollutants into navigable waters.
1079
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - XII
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1080
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - XIII
SECTION XIII
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY
EPA is not promulgating best conventional pollutant control
technology (BCT) for the primary copper sme.lting subcategory at
this time.
1081
-------
PRIMARY COPPER SMELTING SUBCATEGORY SECT - XIII
THIS PAGE INTENTIONALLY LEFT BLANK
Pages 1083 through 1088 are omitted.
1082
-------
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
DEVELOPMENT DOCUMENT SUPPLEMENT
for the
Primary Electrolytic Copper Refining Subcategory
William K. Reilly
Administrator
Rebecca Hanmer
Acting Assistant Administrator for Water
Martha Prothro, Director
Office of Water Regulations and Standards
\
Thomas P. O'Farrell, Director
Industrial Technology Division
Ernst P. Hall, P.E., Chief
Metals Industry Branch
and
Technical Project Officer
May 1989
U.S. Environmental Protection Agency
Office of Water
Office of Water Regulations and Standards
Industrial Technology Division
Washington, D. C. 20460
1089
-------
1090
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
Section
I
II
III
IV
TABLE OF CONTENTS
SUMMARY
CONCLUSIONS
SUBCATEGORY PROFILE
Description of Primary Copper Production
Raw Materials
Electrolytic Refining
Electrowinning
Casting
By-Product Recovery
Nickel Sulfate Recovery
Silver Recovery
Gold Recovery
Palladium Recovery
Platinum Recovery
Selenium Recovery
Tellurium Recovery
Summary of Wastewater Sources
Age, Production, And Process Profile
SUBCATEGORIZATION
Factors Considered in Subdividing the Primary
Copper Smelting and Refining Subcategories
Raw Materials
Plant Size
Plant Age
Product
Production Normalizing Parameters
Anode and Cathode Rinsing
Spent Electrolyte
Casting Contact Cooling
Casting Wet Air Pollution Control
By-Product Recovery
Page
1099
1103
1109
1109
1109
1109
1111
1112
1112
1113
1113
1114
1115
1116
1116
1117
1117
1118
1129
1129
1130
1130
1130
1131
1131
1131
1132
1132
1132
1132
1091
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
V
VI
VI
VII
WATER USE AND WASTEWATER CHARACTERISTICS 1133
Wastewater Sources, Discharge Rates, and 1134
Characteristics
Copper Refining Wastewater Sou.rces and 1136
Characteristics
Anode and Cathode Rinse Water 1136
Spent Electrolyte 1137
Casting Contact Cooling Water, 1137
Casting Furnace Scrubber Liquor 1137
By-Product Recovery 1137
SELECTION OF POLLUTANT PARAMETERS 1153
Conventional and Nonconventional Pollutant 1153
Parameters
Conventional and Nonconventional Pollutant 1154
Parameters Selected
SELECTION OF POLLUTANT PARAMETERS 1154
Toxic Pollutants Never Detected 1154
Toxic Pollutants Never Found Above Their 1155
Analytical Quantification Limit
Toxic Pollutants Detected but Present Solely 1155
. as a Result of its Presence in the Intake
Waters
Toxic Pollutants Present Below Concentrations 1155
Achievable by Treatment
Toxic Pollutants Selected for Consideration 1156
for Establishing Limitations and Standards
Control and Treatment Technologies 1163
Technical Basis of BPT 1163
Current Control and Treatment Practices 1163
Electrolytic Refining 1163
Anode and Cathode Rinse Water 1164
Casting 1164
Casting Scrubber Water 1165
By-Product Recovery 1165
Control and Treatment Options 1165
Option A , H69
Option B 1170
Option C 1170
Treatment Technologies Rejected at Proposal 1167
1092
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGOR5T
Section
VIII
IX
X
TABLE OF CONTENTS (ContInued)
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS
Treatment Options Considered
Option A
Option B
Option C „
Costing Methodology
Nonwater Quality Aspects
Energy Requirements
Solid Waste
Air Pollution
BEST PRACTICABLE TECHNOLOGY CURRENTLY
AVAILABLE
BEST AVAILABLE TECHNOLOGY ECONOMICALLY
AVAILABLE
Technical Approach to BAT
Option A
Option B
Recycling of Casting Contact Cooling Water
Through Cooling Towers
Recycle of Water Used in Anode and Cathode
Rinsing
Option C
Industry Cost and Pollutant Reduction
Benefits
Estimated Pollutant Removals
Compliance Costs
BAT Option Selection
Wastewater Discharge Rates
Anode and Cathode Rinse Wastewater
Spent Electroylyte
Casting Contact Cooling Wastewater
Casting Wet Air Pollution Control
By-Product Recovery
Regulated Pollutant Parameters
Stormwater and Precipitation Allowances
Effluent Limitations
1169
1169
1169
1170
1170
1170
1171
1171
1171
1172
1175
1177
1177
1178
1178
1178
1178
1179
1179
1179
1180
1181
1182
1182
1182
1183
1183
1183
1184
1185
1186
1093
-------
PRIMARY ELECTROLYTIC COPPER REPINING SUBCATEGORY
Section
TABLE OF CONTENTS (Continued)
Paqe
XI
XII
NEW SOURCE PERFORMANCE STANDARDS
Technical Approach to BDT
BDT Option Selection
Regulated Pollutant Parameters
New Source Performance Standards
PRETREATMENT STANDARDS
Technical Approach to Pretreatment
Pretreatment Standards for Existing Sources
Pretreatment Standards for New Sources
PSNS Option Selection
Regulated Pollutant Parameters
Pretreatment Standards
1194
1194
1194
1195
1195
1199
1199
1200
1200
1200
1201
1201
XIII
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY 1205
1094
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
LIST OF TABLES
Section Page
III-l Initial Operating Years (Range) Summary 1119
of Plants in the Primary Copper Electrolytic
Refining Subcategory by Discharge Type
III-2 Production Ranges for the Primary Copper 1120
Refining Subcategory
III-3 Primary Copper Electrolytic Refining 1120
Subcategory Summary of Processes and
Associated Waste Streams
V-l Indicated Presence or Absence of 1139
Toxic Metal Pollutants, DCP Data
V-2 Electrolyte Use and Discharge Rates for 1140
Cathode Copper Production
V-3 Water Use and Discharge Rates for CASTING 1141
Contact Cooling
V-4 Water Use and Discharge Rates for By-Product 1142
Recovery
V-5 Primary Electrolytic Copper Refining Data, 1143
Refining Spent Electrolyte and Cathode Wash,
Raw Wastewater
V-6 Primary Electrolytic Copper Refining Data, 1144
Fire Refined Copper Casting Contact Cooling Water,
Raw Wastewater
V-7 Primary Electrolytic Copper Refining Data, 1145
Treated Wastewater v
VI-1 Frequency of Occurrence of Toxic Pollutants, 1158
Primary Electrolytic Copper Refining Raw
Wastewater
VI-2 Toxic Pollutants Never Detected 1159
VI-3 Toxic Pollutants Never Found Above the 1161
Analytical Quantification Level
VIII-1 Costs of Compliance for the Primary Copper 1173
Subcategory
X-l Pollutant Removal Estimates for Primary 1187
Copper Electrolytic Refining,
Direct Dischargers •
1095
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
Section
LIST OF TABLES (Continued)
Paqe
X-2 BAT Wastewater Discharge Rates for the Primary 1188
Electrolytic Copper Refining Subcategory
X-3 BAT Effluent Limitations for the Primary 1189
Electrolytic Copper Refining Subcategory
(Based on Option B)
XI-1 NSPS Wastewater Discharge Rates for the 1196
Primary Electrolytic Copper Refining
Subcategory
XI-2 NSPS for the Primary Electrolytic Copper 1197
Refining Subcategory
XII-1 PSNS Wastewater Discharge Rates for the 1202
Primary Electrolytic Copper Refining
Subcategory
XII-2 PSNS for the Primary Electrolytic Copper 1203
Refining Subcategory
1096
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
LIST OF FIGURES
Section Page
III-l Primary Electrolytic Copper Refining Process 1121
III-2 Silver By-Product Recovery Process 1122
III-3 Gold By-Product Recovery Process 1123
III-4 Palladium By-Product Recovery Process 1124
III-5 Platinum By-Product Recovery Process 1125
III-6 Selenium By-Product Recovery Process 1126
III-7 Tellurium By-Product Recovery Process 1127
III-8 Geographic Locations of Primary Electrolytic 1128
Copper Plants
V-l Sampling Sites at Primary Copper Refinery 1150
Plant A
V-2 Sampling Sites at Primary Copper Smelting and 1151
Refining Plant C
X-l BAT Treatment Scheme for Option A 1191
X-2 BAT Treatment Scheme for Option B 1192
X-3 BAT Treatment Scheme for Option C 1193
1097
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
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1098
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - I
SECTION I
SUMMARY
On February 27, 1975 (40 FR 8514), EPA promulgated interim
technology-based effluent limitations for existing sources and
proposed new source performance and pretreatment standards for
the primary copper subcategory of the nonferrous metals
manufacturing point source category. These effluent guidelines
and standards limited the quantities of total suspended solids,
copper, cadmium, lead, zinc, and pH in primary copper subcategory
wastewaters.
For primary electrolytic copper refiners not located on-site with
primary copper smelters, the interim BPT regulation allowed the
discharge of process wastewater from electrolytic refining and
casting subject to mass limitations for facilities located in
areas of net precipitation.
The 1975 BPT limitations for copper refining required zero
discharge of all process wastewater for facilities located in net
evaporation areas with two rainfall related exceptions. When a
10-year 24-hour rainfall event occurred, refiners were allowed to
discharge a volume of water equal to that resulting from the 10-
year 24-hour rainfall event falling within a refiners wastewater
impoundment. In addition, a discharge of process wastewater was
permitted during a calendar month equal to the difference between
the net evaporation and precipitation for that month. This
monthly rainfall allowance was subject to concentration-based,
limitations. For those refiners located in areas of net
precipitation, a discharge of process wastewater was allowed in
accordance with mass-based limitations.
The 1975 BAT limitations for refineries not located on-site with
smelters and in areas of net evaporation required discharge
standards similar to the BAT primary copper smelting standards.
For facilities located in areas of net precipitation, a constant
discharge of refining wastewater was allowed subject to mass
limitations.
Revised BPT limitations were issued for the primary electrolytic
copper refining subcategory on July 2, 1980 (45FR44926). The
major modification to the interim regulation was to delete the
net precipitation provisions and allow a constant discharge of
process wastewater from all refiners regardless of location and
subject them to mass limitations.
In the March 1984 rulemaking (49FR8742) EPA promulgated
modifications to BAT, NSPS, and PSNS for this subcategory
pursuant to the provisions of Sections 301, 304, 306 and 307 of
the Clean Water Act as amended. This supplement provides a
compilation and analysis of the background material used to
develop these effluent limitations and standards. The BPT
regulations which were promulgated in 1980 remain unchanged, and
1099
-------
PRIMARY ELECTROLYTIC COPPER REPINING SUBCATEGORY SECT - I
are discussed later for information purposes.
The primary electrolytic copper refining subcategory is comprised
of 14 plants. Of the 14 plants, three discharge directly to
rivers , lakes and streams; none discharge indirectly through
publicly owned treatment plants (POTW); and 11 achieve zero
discharge of process wastewaters.
EPA first studied the primary electrolytic copper refining
subcategory to determine whether differences in raw materials,
final products, manufacturing processes, equipment, age and size
of plants, and water usage required the development of separate
effluent limitations and standards for different segments of the
subcategory. This involved a detailed analysis of wastewater
discharge and treated effluent characteristics, including (1) the
sources and volume of water used, the processes employed, and the
sources of pollutants and wastewaters in the plant; and (2) the
constituents of wastewaters, including toxic pollutants.
EPA also identified several distinct control and treatment
technologies (both in-plant and end-of-pipe) applicable to
primary electrolytic copper refining. The Agency analyzed both
historical and newly generated data on the performance of these
technologies, including their nonwater quality environmental
impacts (such as air quality impacts and solid waste generation)
and energy requirements. EPA also studied various flow reduction
techniques reported in the data collection portfolios (dcp) and
plant visits.
Engineering costs were prepared for each of the control and
treatment options considered for the subcategory. These costs
were then used by the Agency to estimate the impact of
implementing the various options on the subcategory. For each
control and treatment option that the Agency found to be most
effective and technically feasible in controlling the discharge
of pollutants, the number of potential closures, number of
employees affected, and impact on price were estimated. These
results are reported in a separate document entitled Economic
Impact Analysis of Effluent Limitations Guidelines and Standards
for the Nonferrous Smelting and Refining Industry.
Based on consideration of the above factors, EPA identified
various control and treatment technologies which formed the basis
of BAT, and selected control and treatment appropriate for each
set of standards and limitations. The limitations and standards
for BPT, BAT, NSPS, and PSNS are presented in Section II.
For BAT, the Agency has built upon the primary electrolytic
copper refining - BPT basis by adding in-process control
technologies which include recycle of process water from air
pollution control and metal contact cooling wastewater streams.
Filtration is added as an effluent polishing step to the end-of-
pipe treatment. -For one plant, sulfide precipitation and pressure
filtration is added before lime precipitation and sedimentation
to assure achieving the performance of lime, settle, and filter
1100
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - I
technology. To meet the BAT effluent limitations based on this
technology, the primary electrolytic copper refining subcategory
is estimated to incur a capital cost of $0.266 million (1982
dollars) and an annual cost ...of-$0.171'.million (1982 dollars).
The best
basis of
recognized
best and
technology
determined
demonstrated technology (BDT), which is the technical
NSPS, is equivalent to BAT. In selecting NSPS, EPA
that new plants have the opportunity to implement the
most efficient manufacturing processes and treatment
As such, the technology basis of BAT has been
as the best demonstrated technology.
The Agency is not promulgating pretreatment standards for
existing source (PSES) since there are no indirect discharging
plants in the primary electrolytic copper refining subcategory.
The technology basis for pretreatment standards for new sources
(PSNS) is the best demonstrated. As such, the PSNS are identical
to NSPS for all waste streams.
1101
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - I
THIS PAGE INTENTIONALLY LEFT BLANK
1102
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - II
SECTION II
CONCLUSIONS
EPA has divided primary copper plants into two subcategories:
the primary copper smelting subcategory and the primary
electrolytic copper refining subcategory. The primary
electrolytic copper refining subcategory has been divided into
five subdivisions for the purpose of effluent limitations and
standards. These subdivisions are:
(a) Anode and cathode rinse,
(b) Spent electrolyte,
(c) Casting contact cooling,
(d) Casting wet air pollution control, and
(e) By-product recovery.
EPA promulgated BPT effluent limitations for the primary
electrolytic copper refining subcategory on July 2, 1980
(45FR44926) as Subpart E of 40 CFR Part 421. No modifications
are now being promulgated for the 1980 BPT.
BPT effluent limitations for the primary electrolytic copper
refining subcategory were promulgated based on the performance
achievable by the application of chemical precipitation and
sedimentation (lime and settle) technology. The following BPT
effluent limitations were promulgated for existing sources:
Effluent Limitations
Pollutant or
Pollutant Property
Maximum for
Any One Day
Average of Daily Values
for 30 Consecutive
.Days Shall not exceed
Metric units, kg/kkg of product;
English units, lbs/1,000 Ib of product
Total Suspended Solids
Copper
Cadmium
Lead
Zinc
pH
0.100
0.0017
0.0006
0.0006
0.0012
0.050
0.0008
0.00003
0.00026
0.0003
Within the range of 6.0 to 9.0
EPA has amended BAT effluent limitations based on the performance
achievable by the application of in-process flow reduction and
end-of-pipe . treatment technology consisting of chemical
precipitation, sedimentation, and multimedia filtration (lime,
settle, and filter) technology. The following BAT effluent
limitations are promulgated for existing sources:
1103
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - II
Casting Contact Cooling
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of copper cast
English Units - Ibs/million Ibs of copper cast
Arsenic
Copper
Nickel
0.692
0.638
0.274
(b) Anode and Cathode Rinse
Pollutant or
Pollutant Property
Maximum for
Any One Day
0.309
0.304
0.184
Maximum for
Monthly Average
Metric Units - mg/kg of cathode copper production
English Units - Ibs/million Ibs of cathode copper
production
Arsenic
Copper
Nickel
(c) Spent Electrolyte
Pollutant or
Pollutant Property
0.000
0.000
0.000
Maximum for
Any One Day
0.000
0.000
0.000
Maximum for
Monthly Average
Metric Units - mg/kg of cathode copper production
English Units - Ibs/millions Ibs of cathode copper
production
Arsenic
Copper
Nickel
0.068
0.063
0.027
Casting Wet Air Pollution Control
Pollutant or
Pollutant Property
Maximum for
Any One Day
0.031
0.030
0.018
Maximum for
Monthly Average
Metric Units - mg/kg of casting production
English Units - Ibs/million Ibs of casting production
Arsenic
Copper
Nickel
0.000
0.000
0.000
0.000
0.000
0.000
1104
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - II
(e) By-Product Recovery
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of product recovered from
electrolytic slimes processing
English Units - Ibs/million Ibs of product recovered
from electrolytic slimes processing
Arsenic
Copper
Nickel
0.000
0.000
0.000
0.000
0.000
0.000
NSPS are promulgated based on the performance achievable by the
application of chemical precipitation, sedimentation, and
multimedia filtration (lime, settle, and filter) technology and
in-process flow reduction control methods. The following
effluent standards are promulgated for new sources:
(a) Casting Contact Cooling
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of copper cast
English Units - Ibs/million Ibs of copper cast
Arsenic
Copper
Nickel
TSS
pH
0.692
0.638
0.274
7.470
0.309
0.304
0.184
5.976
Within the range of 7.0 to 10.0
at all times
(b) Anode and Cathode Rinse
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of cathode copper production
English Units - Ibs/million Ibs of cathode copper
production '
Arsenic 0.000 0.000
Copper 0.000 0.000
Nickel 0.000 0.000
TSS 0.000 0.000
pH Within the range of 7.0 to 10.0
at all times
1105
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - II
(c) Spent Electrolyte
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Arsenic
Copper
Nickel
TSS
pH
Metric Units - mg/kg of cathode copper production
English Units - Ibs/million Ibs of cathode copper
production
0.068 9.031
0.063 0.030
0.027 0.018
0.735 6.588
Within the range of 7.0 to 10.0
at all times
(d) Casting Wet Air Pollution Control
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Arsenic
Copper
Nickel
TSS
pH
Metric Units - mg/kg of copper casting production
English Units - Ibs/million Ibs of copper casting
production
0.000 0.000
0.000 0.000
0.000 0.000
0.000 0.000
Within the range of 7.0 to 10.0
at all times
(e) By-Product Recovery
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of product recovered from
electrolytic slimes processing
English Units - Ibs/million Ibs of product recovered
from electrolytic slimes processing
Arsenic
Copper
Nickel
TSS
pH
0.000
0.000
0.000 0.000
0.000 0.000
o.ooo b.ooo
Within the range of 7.0 to 10.0
at all times
EPA is not promulgating pretreatment standards for existing
sources (PSES) in the primary electrolytic copper refining
subcategory since there are no existing indirect dischargers in
this subcategory.
1106
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - II
9 . •
PSNS are promulgated based on the performance achievable by the
application of chemical precipitation, sedimentation, and
multimedia filtration (lime, settle, and filter) technology and
in-process flow reduction control methods. The following
pretreatment standards are promulgated for new sources:
(a) Casting Contact Cooling
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of copper cast
English Units - Ibs/million Ibs of
Arsenic
Copper
Nickel
0.692
0.638
0.274
copper cast
0.309
0.304
0.184
(b) Anode and Cathode Rinse
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Arsenic
Copper
Nickel
Metric Units - mg/kg of cathode copper production
English Units - Ibs/million Ibs of cathode copper
production
0.000
0.000
0.000
0.000
0.000
0.000
(c) Spent Electrolyte
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of cathode copper production
English Units - Ibs/million Ibs of cathode copper
production
Arsenic
Copper
Nickel
0.068
0.063
0.027
0.031
0.030.
0.018
1107
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - .!•!>
(d) Casting Wet Air Pollution Control
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Arsenic
Copper
Nickel
Metric Units - mg/kg of casting production
English Units - Ibs/million Ibs of casting production
0.000
0.000
0.000
0.000
0.000
0.000
(e) By-Product Recovery
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of product recovered from
electrolytic slimes processing
English Units - Ibs/million Ibs of product recovered
from electrolytic slimes processing
Arsenic
Copper
Nickel
0.000
0.000
0.000
0.000
0.000
0.000
1108
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - III
SECTION III
SUBCATEGORY PROFILE
This section of the primary electrolytic copper refining
supplement describes the raw materials and processes used in
electrolytically refining copper bearing raw materials to produce
pure (99.99%) copper and presents a profile of the primary
electrolytic copper plants identified in this study.
DESCRIPTION OF PRIMARY COPPER PRODUCTION
The manufacturing of copper from copper sulfides through
pyrometallurgical processes usually produces a raw metal product
which must be further refined before use. Hydrometallurgical
processes are also used to process copper concentrates and this
is the chief process used to process copper oxide, but it also
may be used to process copper sulfides. The products from both
pyrometallurgical and hydrometallurgical processes require
further refining. The commonly used steps in electrolytic
refining are tabulated below.
Primary Electrolytic Refining
1. Electrolytic refining
2. Electrowinning
3. Casting
4. By-product recovery
In addition to the smelting and refining of copper, several
facilities also recover precious metals from insoluble wastes
(anode slimes) generated during electrolytic refining. Precious
metals present within the slimes may include silver, selenium,
tellurium, gold, platinum, and palladium. Recovery of these
metals from refinery wastes will be discussed with emphasis on
sources of wastewater within each recovery process.
RAW MATERIALS
There are approximately 160 known copper minerals, about a dozen
of which are commercially important. The most important copper
ores in the United States are chalcopyrite, chalcocite,
covellite, chrysocolla, bornite, cuprite, and malachite. These
are either sulfide, silicate, or oxide ores. Most of the copper
ore processed in the United States is a copper sulfide. At the
mine site, copper bearing ore is concentrated into copper sulfide
which forms the main raw material for copper smelting.
Roasting, smelting, converting, fire refining and casting of the
blister copper from copper bearing ores is discussed in the
Primary Copper Smelting Subcategory Supplement.
ELECTROLYTIC REFINING
1109
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - Ill-
More extensive refining of .copper is usually necessary if it is
to be used in electrical applications. By using electrolysis,
the copper can be refined to a purity of 99.98 percent or
greater, and the precious metals contained as impurities in the
copper can be recovered. Fire refined or blister copper from the
smelting operation, sulfuric acid, and copper sulfate are the
principal _ raw materials used in electrolytic refining. For use
in a refinery, blister copper is cast into anodes which are
rectangular plates with lugs or hooks on two corners used for
hanging. Each anode weighs approximately 460 pounds.
At the refinery, anodes and starter sheets of refined copper are
suspended in solutions of sulfuric acid and copper sulfate.
Through electrolysis, positive copper ions from the anode migrate
through the copper sulfate-sulfuric acid medium and are deposited
on the starter sheet which has become the cathode. To drive the
reaction, an electric current is passed through each cell. The
migration of the copper ion takes place through the following
anode-cathode reaction:
Anode:
Cu > Cu
2+
2e
Cathode: Cu2+ —-—> 2e + Cu
Impurities released into the electrolyte either go into solution
or settle to the bottom of the tank. The electrolyte is
continuously circulated through the system of cells with a small
slip stream removed for purification to control the amount of
dissolved solids. Those impurities settling to the bottom of
each tank are commonly referred to as anode slimes and are
removed from the bottom of each cell. Further processing of the
slimes may be done on site to recover the precious metals
contained within the slime as a by-product of copper refining or
they may be sold to outside refiners.
After approximately two weeks, when the cathodes reach a
designated1 size, generally 180 pounds, they -are removed and
rinsed. Another set of starter sheets is inserted with the
anodes for another two week period. At the end of the second
cycle, both the cathodes and anodes are removed. The anodes are
not completely consumed, but if they were left in the cell they
soon would break, falling into the cell and short-circuiting it.
Scrap anodes may be rinsed and then returned back to anode
casting. The cathodes are either sold and shipped with no
further refining, or they are cast into wire bar, ingots, or
billets for copper forming operations. A block diagram
illustrating the electrolytic refining process is shown in Figure
III-l (page 1121).
In a cell, the number of anodes and cathodes is dependent on the
size of the cell and the spacing between anodes and cathodes.
Normally an electrolytic cell contains 30 to 40 anodes and
cathodes. In a tank house, the number of cells is usually
between 1,000 and 2,000. Circulation of the electrolyte is done
to prevent separation of the sulfuric acid and copper sulfate.
1110
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - III
The electrolyte is removed from the top of each cell and
introduced into the bottom of the next cell. The electric
current passing through each cell moves from anode to cathode in
the cell, and is then transmitted to the next cell through the
support bars.
ELECTROWINNING
As mentioned earlier, a slip stream of electrolyte is removed
from the tank house for purification. Removal of soluble
impurities and excess copper in the electrolyte must be
controlled to maintain an optimum Defining process. Significant
soluble impurities are nickel and arsenic; however, the major
impurity in the anode copper is copper oxide, CU2O. When
copper oxide is released into the electrolytic solution, it
reacts with the sulfuric acid forming copper sulfate:
CU2O + H2S04 > CuSO14 + Cu + H20
As the copper sulfate concentration approaches saturation, it
will begin to precipitate and settle to the bottom of the tank.
The copper molecule released into the solution when copper oxide
reacts with the sulfuric acid settles to the bottom of the tank
because it is not electrically charged. Impurities settling to
the bottom of each tank are removed for further processing to
recover precious .metals.
Processing the spent electrolyte is accomplished with various
methods, but the most popular uses a two-stage process. In the
first step, commonly referred to as electrowinning, copper is
removed from solution by electrolysis in much the same way as was
done in the tank house. The major difference is that an
insoluble anode, such as lead or iron, is used. Copper is forced
out of the solution and plated onto a cathode. This process uses
two to three liberator cells connected in a series. In the first
cell, the cathode copper is of high purity with slight lead
contamination and may be used with no additional refining. As
the copper concentration in the electrolyte decreases, the purity
of the copper cathode also decreases. Recovered copper from the
last two liberator cells is returned for smelting or anode
casting, depending on the purity.
The last liberator cell
AsH3. As the copper is.
arsenic begins to react
collect this poisonous
atmosphere. The arsenic
collected as a sludge and
must be hooded to control arsine gas,
depleted from the spent electrolyte,
with hydrogen. Hoods above the cell
gas and disperse it safely to the
that does not escape as arsine gas is
returned to the smelter.
The spent electrolyte is now composed of nickel sulfate and
sulfuric acid. Through evaporation, the decopperized solution is
concentrated and then cooled. As the solution cools, nickel
sulfate is precipitated, leaving what is known as black acid.
The acid is usually recycled back to the refining process, but it
may be used for leaching operations or fertilizer manufacture.
1111
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - III
Wastewater generated from copper refining is due to cathode and
anode rinse water and the discharge of spent electrolyte.
Normally the anodes and cathodes are rinsed above the
electrolytic cells so that the rinse water is captured in the
electrolytic cells. Discharge of spent electrolyte is not
generally practiced since the electrolyte can be recycled to the
refining process after electrowinning. One hundred percent reuse
of the spent acid after treatment is site-specific. The
magnitude of impurities in the electrolyte is a function of the
raw material. Those plants containing low nickel values have
difficulty recycling spent acid. If the nickel concentration is
allowed to increase so that nickel sulfate can be recovered,
other impurities increase in the electrolyte which affect product
quality. Currently one of the 14 copper refiners discharges
spent electrolyte. Although a wet scrubber could be used to
control arsine gas, no plant reported use of wet scrubbers for
this purpose.
CASTING
Casting is the final step for copper refining. Electrolytic
copper, is cast into wire bar or billets for eventual use in the
forming processes. Wastewater associated with casting is due
primarily to furnace scrubber liquor and casting contact cooling
water. One plant currently is using a wet scrubber to control
air pollution emissions from its casting furnaces. There are
nine plants that discharge casting contact cooling water.
BY-PRODUCT RECOVERY
Many of the impurities found within blister copper have economic
value and may be recovered as a by-product of the electrolytic
copper refining process. During electrolysis, impurities present
in the anode are released into solution. The soluble impurities
include arsenic and nickel, while those that are not soluble, and
settle to the bottom of the tank, include silver, selenium,
tellurium, gold, platinum, and palladium. For a facility to
recycle its spent electrolyte after electrowinning, the
concentration of the nickel sulfate must be reduced to insure
optimum operating conditions in the tank house.
Six plants reported in their dcp recycling 99 percent or more of
their electrolyte. At the same time, there were six plants that
reported processing slimes on site to recover precious metals.
Three plants currently operate by-product recovery processes. In
the discussions that follow, a brief description of the methods
used to recover these metals and the wastewater generated from
their recovery will be presented.
Nickel Sulfate Recovery
The bleed stream removed from the copper electrolytic tank house
is composed primarily , of sulfuric acid, copper sulfate, and
nickel sulfate. Removal of copper sulfate from the electrolyte,
1112
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT -III
as discussed earlier, is similar to the copper refining process
in that electrolysis is used. The major difference, however, is
an insoluble anode replaces the copper anodes used in the tank
house. The decopperized solution still contains nickel sulfate,
among others, as an impurity. Removal of the soluble nickel is
accomplished through partial evaporation to initiate the
precipitation of nickel sulfate. The spent electrolyte can then
be recirculated back to the tank house or sold for use in the
manufacture of fertilizer. The nickel sulfate may be marketed
with no further refining, or a vacuum crystallizer may be used to
produce a more refined product.
of nickel
additional
Noncontact wastewater generated from the recovery
sulfate occurs if a barometric condenser is used when
refining takes place.
Silver Recovery
As mentioned earlier, anode slimes removed from the bottom of the
electrolytic cells contain varying amounts of precious and base
metals, specifically silver, selenium, tellurium, gold, platinum,
palladium, and copper. The principal component of the slimes is
copper, which may account for as much as 30 percent of the slime.
Preliminary treatment of the slime to remove copper is essential
to enhance the silver recovery process. To begin, the slime is
passed through a trammel screen to remove copper sulfate
precipitate. The slime is fed into a revolving cylindrical
screen (trammel) at one end, the copper sulfate drops through the
holes, and the slime is delivered at the other end. The
remaining copper is leached from the slime using a variety of
methods such as sulfuric acid, hexavalent chromium, or
solubilizing the copper and leaching with water. The leachate is
then returned to the electrowinning process to recover the
copper. The remaining slime is filtered and pressed to form a
cake for further processing in a cupel furnace. A cupel furnace
is a small scale reverberatory furnace that is refractory lined
with heat supplied-between the roof and charge.
As shown in Figure III-2 (page 1122), pressed, filtered slimes
and fluxes (iron, silica, and limestone) are charged to a cupel
furnace. Impurities react with the fluxing agents, forming slag,
and are removed from the top of the furnace. Dore, the remaining
metallic material, is approximately 95 percent silver, while the
soda slag consists primarily of selenium and tellurium. Also
removed from the furnace is a slag containing recoverable
concentrations of lead which are sent to a lead smelter.
Durinq the silver smelting operation, selenium volatilizes and
leaves the furnace with the off-gases. .Consequently, wet
scrubbers are used to capture the selenium and return it tor
further processing as described later.
One plant charges anode slimes directly to kilns after _removing
the copper sulfate with filters. In the kilns, the slimes are
fused and selenium volatilizes. Wet scrubbers capture the
1113
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - III
selenium for further processing. This plant also uses a wet
scrubber to control sulfur dioxide (SO2) fumes in the kiln off-
gases. The plant discharges the scrubber wastewater to its
wastewater treatment plant but the flow is negligible when
compared to other plant flows. Copper is leached from the
"fused" slimes, as described above, and charged to a cupel
furnace to produce dore. Wet scrubbers are used on the dore
furnace to recover precious metal particulates that may be
present in the off-gases. The scrubber water is recycled to the
copper leaching operation.
An electrolysis process is used to recover silver in the dore
metal. In this electrolytic process, dore is cast into anodes
approximately 20 inches square and one inch thick. Several
anodes are suspended in an electrolytic medium consisting of
copper nitrate and silver nitrate. Each anode is suspended on
glass rods with a filter basket suspended under the anodes. In
this configuration, the bottom of the cell becomes the cathode
where silver crystals form. Gold slimes released into the
solution are captured in the filter basket and removed for
further processing. Silver crystals forming on the bottom of the
cell are removed every three to four hours, washed, and then cast
into silver bricks using an induction furnace.
Wastewaters are usually not discharged from this process because
each potential waste stream contains economically important
quantities of silver, selenium, and tellurium. The silver
nitrate used as the electrolyte medium is recycled, while the
cupel furnace or fusion kiln scrubber liquors contain
approximately one half the selenium present in the charge.
Consequently, the scrubber liquor is used during the processing
of the soda slag to extract the selenium and tellurium present in
the scrubber liquor and slag. However, there are two waste
streams currently discharged to treatment at one copper plant.
Contact cooling water used during the casting of dore anodes is
sent to a central wastewater treatment plant. Also, wastewater
from the fusion kiln SO2 scrubber is treated at the same
facility.
Gold Recovery
Gold slimes captured in the silver electrolytic cells are
processed in bench-scale operations through leaching with hot
sulfuric acid to remove any residual silver entrained in the
slime. The gold is recovered either electrolytically or using
dissolution and precipitation steps. In the electrolytic method,
gold is refined in a heated electrolytic cell using a silver
chloride medium as shown in Figure III-3 (page 1123). Impurities
present at this stage include platinum and palladium slimes,
which are recovered by further processing. An induction furnace
is used to melt and cast the gold which is approximately 99.9
percent pure.
The potential for wastewater in this process is due primarily to
spent leachate from the preliminary silver preleaching step.
1114
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - III
Spent leachate is treated through cementation to recover minor
amounts of silver and gold. Since this is a small scale
operation, the volume of leachate is negligible and will not
affect the design or performance of the plant treatment system.
In the precipitation method, the solids containing gold are
dissolved in aqua regia (one part concentrated nitric acid and
three to four parts hydrochloric acid). Aqua regia is the only
known reagent that dissolves gold. The gold is precipitated from
solution with sulfur dioxide or chlorine gas. Gold precipitate
is removed from solution by filtration. The filtrate, which
contains palladium and platinum, is further processed. The gold
solids are cast into anodes to be further refined
electrolytically. The purified gold is collected on cathodes
which are then melted and cast in an induction furnace. Spent
electrolyte and water used to wash cathodes is reused in the
electrolytic cell or treated and recycled as makeup water.
Palladium Recovery
Slimes from gold electrolytic separation and solutions from gold
precipitation steps contain recoverable amounts of palladium and
platinum. Palladium is usually recovered first, using either an
electrolytic separation or a dissolution and precipitation method
as shown in Figure III-4 (page 1124). The electrolytic method is
similar to the electrolytic separations used for silver and gold.
Palladium and platinum slimes from the gold electrolytic cell are
melted and cast into anodes. Palladium is then collected on a
cathode in another electrolytic cell and the platinum is released
into solution. The palladium cathodes are melted and cast as
final product. Platinum slimes are captured at the bottom^of the
cell and further processed. Spent electrolyte is reused in the
electrolytic cell or reprocessed in the copper slimes leaching
step described above.
In the precipitation method, palladium and platinum are recovered
by precipitating them as palladium and platinum chloride, usually
using ammonium chloride. Filtration is used to separate the
precipitates from the non-precious metals solution, which is
treated and reused at the one plant with this process. The
filter cake is then dissolved in solution with chlorine gas or
hydrochloric acid. The platinum remains as a solid and is
removed for further processing. The palladium is purified using
a series of dissolution and precipitation steps. Palladium is
precipitated from solution with hydrochloric acid and separated
by filtration. The filtered metal may be washed to remove
residual acid and impurities. Ammonium hydroxide is then used to
dissolve the metal and the precipitation and filtration steps are
repeated. When palladium of sufficient purity is obtained, the
metal is calcined, then crushed or ground into powder.
The sources of wastewater from this process are the
precipitation, filtration, and washing steps. At the plant
currently using this process, these solutions are treated and
reused as makeup water for other processes. This plant uses a
1115
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - III
wet scrubber to control acid and base fumes from the dissolution
and precipitation steps. The same scrubber controls fumes from
the platinum precipitation process. The scrubber wastewater is
neutralized and reused in other plant processes.
Platinum Recovery
Platinum is recovered from slimes from palladium electrolytic
separation and from impure platinum precipitated in the palladium
precipitation process. Figure III-5 (page 1125) schematically
depicts the two methods used for platinum recovery. Platinum
from slimes is usually recovered in an electrolytic cell. Slimes
are melted and cast into anodes. The electrolytic process
results in platinum cathodes which are melted and cast as
platinum metal. Spent electrolyte and cathode wash water are
possible sources of wastewater. However, this water is recycled
within the cell or reprocessed in the copper slimes leaching step
described above.
Impure platinum precipitated in the palladium precipitation
process is purified through a series of dissolution and
precipitation steps, much like palladium. First, impurities and
residual palladium are dissolved with a hydrochloric and nitric
acid mixture. Following filtration and washing, the filtrate is
sent to the palladium recovery process. The filter cake, which
contains platinum, is dissolved with hydrochloric acid. Ammonium
chloride is then added to precipitate platinum chloride. The
platinum chloride is filtered and washed. The filter cake is
calcined, ground, and recalcined to form the final platinum
product.
Wastewater generated at the one plant currently using which
process consists of supernatant, filtrate, and wash water from
the precipitation and filtration steps. This wastewater is
treated and reused in other plant processes. This plant uses a
wet scrubber to control acid and base fumes from the platinum
dissolution and precipitation steps. The same scrubber is used
on the palladium precipitation process. The scrubber wastewater
is neutralized and reused in other plant processes.
Selenium Recovery
As discussed earlier, volatile selenium gas escaping from the
cupel furnace or fusion kiln is collected with wet scrubbers.
This scrubber liquor is acidified with nitric acid and mixed with
ground soda-niter slag (NaNOa) from the cupel furnace containing
selenium and tellurium. When these two materials are mixed,
tellurium precipitates as TeO2 and is removed for further
processing. The remaining solution is neutralized and then the
selenium is precipitated by adding hydrochloric acid, sulfuric
acid, steam, and sulfur dioxide. The selenium precipitate is
filtered, dried, and marketed. Spent and dirty solution from the
precipitation and filtration of selenium is treated with sulfuric
acid, hydrochloric acid, and sulfur dioxide to precipitate low
grade selenium which is returned to the cupel furnace. An
1116
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - III
illustration of this process is shown in Figure III-6 (page
1126).
Spent solutions are generated from the precipitation and
filtration steps. Specifically, spent solution after selenium
precipitation and filtration, and sludge removal from the
selenium scrubber liquor are possible sources of wastewater.
This waste water is recycled to recovery processes, such as
copper slimes leaching, or treated and reused in other plant
processes.
One plant operates a wet scrubber to capture metal particulates
in the selenium drier off-gases. The scrubber wastewater is sent
to the copper slimes leaching operation for metals recovery.
Tellurium Recovery
During the processing of selenium, tellurium is precipitated as
TeO? and removed from the selenium recovery process. Shown in
Figure III-7 (page 1127) is a schematic of the tellurium recovery
system. As can be seen in this diagram, TeO2 goes through a
series of pH adjustments to remove impurities. The first of
these is a caustic leach designed to remove any residual copper.
Another pH adjustment is performed to neutralize the tellurium
bearing alkaline solution and precipitate tellurium as TeO2« At
this point, TeO-? can be either marketed with no further refining
or refined further through electrolysis to produce tellurium
metal.
Wastewater generated in the tellurium processing cycle consists
primarily of washing TeO2 after precipitation with sulfuric acid.
Spent electrolyte from electrolysis is normally in a closed loop
with a preceding caustic leach step.
SUMMARY OF WASTEWATER SOURCES
In summary, the principal uses of water in the primary
electrolyic copper refining subcategory are due to five
processes:
1. Anode and cathode rinse water,
2. Spent electrolyte,
3. Casting contact cooling,
4. Casting scrubber, and
5. By-product recovery.
There are other wastewater streams associated with the refining
of primary electrolytic copper. These wastewater streams include
electrowinning arsine wet air pollution control, maintenance and
cleanup water, and storm water runoff. These waste streams are
not considered as a part of this rule making. EPA believes the
flows and pollutant loadings associated with these waste streams
are insignificant relative to the waste streams selected and are
best handled by the appropriate permit authority on a case-by-
case basis under the authority of Section 402 of the Clean Water
1117
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PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - III
Act.
AGE, PRODUCTION, AND PROCESS PROFILE
The primary electrolytic copper industry consists of 14 refining
operations. The location and discharge status of the primary
electrolytic copper refining locations are shown in Figure III-8
(page 1128). In some cases both smelting and refining operations
are found at or near the same site. As a rule, however, smelters
are located near copper mines and mills in the Southwest, and
electrolytic refineries are either found near smelters or near
maritime centers.
Table III-l (page 1119) shows the average age of the electrolytic
refiners as 30 years. As seen in Table III-2 (page 1120) the
average electrolytic refining plant production is 115,000 tons
per year of electrolytic refined copper. The six electrolytic
refineries processing anode slimes produce an average 11.5
million troy ounces of silver, 243,000 troy ounces of gold,
72,200 pounds of selenium, 221,000 pounds of tellurium, and
73,000 pounds of platinum and palladium per year.
As shown in Table III-l, there are three direct discharging and
11 zero discharging copper refiners. Table III-3 (page 1120)
presents a summary of the number of facilities with a reported
process and the number of facilities generating wastewater within
that process. Table m-3 shows five facilities generating
wastewater from electrolytic refining. All 14 primary
electrolytic copper refineries considered in this rulemaking have
the potential to discharge spent electrolyte. However, five of
these plants generate wastewater by rinsing anodes when they are
removed from the electrolytic cells.
1118
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - III
TABLE III-l
INITIAL OPERATING YEARS (RANGE) SUMMARY OF PLANTS IN THE
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
BY DISCHARGE TYPE
Electrolytic Copper Refining Plant Age Range (Years)
1983- 1972- 1967- 1957- 1947- 1937- 1917- Before
1973 1968 1958 1948 1938 1918 1903 1903
Discharge
Type 0-10
Direct
Zero
Total
2
2
10-15 15-25 25-35 35-45 45-65 65-80 80- + NR
12 - - - - -
1 2 - 1 1-4
1 3 2 0 1 1 0 4
1119
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - III
TABLE III-2
PRODUCTION RANGES FOR
PRIMARY ELECTROLYTIC COPPER REFINING PLANTS
(tons/yr)
Production (1976)
Range
0 - 50000
50000 - 100000
100000 - 150000
150000 - 200000
200000 - Above
NR
TOTAL PLANTS
Number of
Copper Refiners
3
2
0
2
2
5
14
TABLE II1-3
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SUMMARY OF PROCESSES AND ASSOCIATED WASTE STREAMS
No. of Plants
With Process
Process
Electrolytic Refining 14
Casting 19
Casting Air pollution Control 3
By-Product Recovery 3
No. of Plants
Reporting Generating
Wastewater*
5
17
1
3
* Through reuse or evaporation practices, a plant may generate a
wastewater from a particular process but not discharge it.
1120
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY "SECT - til
Copper
Electroviaain*
Deeoppertzed Electrolyte
Centrifuge
Gate
Dryer
NISO,
Bliatar Copper
Air
Pel*
Anode Furnace
Bat«
Casting
Cooling
Electrolyte Bleed
tfaatevatar
Cached* Sheeta
Electrolytic
Cell
Scrap Anadea
SUM* eo ly frmUicc leco
CatoodM
Cathode
tfaatewacer
Helting
Furnace
Black Acid
Water
Caatlng
Cooliex
Waatawater
Altemete Uae
or Disposal
Copper
Producta
FIGURE III-l
PRIMARY ELECTROLYTIC COPPER REFINING PROCESS
1121
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - III
Electrolytic Slim**
\
Copper
Returned to
Kaflaerr
Leaching of
SliBaa EO Raenve
Copper
Case* aad duat to Selenium."
Tellurium Recovery Circuit
• Fluxes (Iron, Silica, and Liaeatone)
Cupel
Furnace
•Slag
S««le«r
"Soda Slag Containing Selenium, Tellurium,
Silver, and Cold to Selenium-Tellurium
Recovery Circuit
Casting of
Cold Scad Containing
Cold. PlaclnuB and
to Farther
d«ctroljrt«
Praparacloo
• Nitric Acid
Copper
Electrolytic Separation of
Cold and Silver
Silver Crjr»tal»
Silver Nitrate-Copper Nitrate Solution
Silver Anode
Scrap
Induction
Furnace
Silver
Sara
FIGURE III-2
SILVER BY-PRODUCT RECOVERY PROCESS
1122
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - III
Silver
Dore Metal Anode*
to Cupel Furnace
Electrolytic
S«p«r«cion of
Gold and
Silver
Gold Mud. Flu* Silver, Palladium, aod Platinum
Silver Nitrate Solution to
Electrolytic Cell*
Hoc Hater Leach,
Filtration, Hot Sul-
furic Acid Leach,
Water faeb
Liquor
> Minor Recovery of
Silver and Gold by
Cementation
Aqua Refia
(Hydrochloric Acid"
and Nitric Acid)
Sulfur Dioxide or.
Chlorine Gaa
Gold Anode
Caiting
Electrolytic Separa-
tion of Gold and
Che Flatiooei Croup
M«r.1«
Plaeiaum
Gold Aned* Scrap-
Cold Cathode*
Spent Electrolyse
Ha*b Baeer
Bauead or Eacyeled
to Copper Leaehlag
Geld Cathodes
Induction Furnace
Melting and
C**ting
Gold
FIGURE III-3
GOLD BY-PRODUCT RECOVERY PROCESS
1123
-------
PRIMARY ELECTROLYTIC COPPER REPINING SUBCATEGORY SECT - III
CUCTULTTXC MllHUO
SUM* fro* Geld
&eetrolytic Separation
Anode Caaclns
t» Copper Laachinf •*-
SUB**
to Forth** fro-
PRECIPITATION METHOD
Solution from Gold
Defining Operation
Electrolytic
Separation of
Prccipieation
Aood*
Scrap
W«t«r
Chlorin«/aydr
chloric Acid
Hydrochloric Acid*
Filtration aad
Waab
Di»solution
Precipitation
Filtration and
Uaah
DiaaolntloD
Malelaff ••
Caatta*
Brdrochloric Acid
Uaear.
Precipitation.
Filcraelon aad
Haah
I
Calcination
Cruahing/
Criadins
^ Honpracioua
"*"Matala Solution
Praclpitats to
"^Placinua Ra-
flning
Woatavatar
'Treated aad
buaad
Traatad and
Raoaad
Palladlua
FIGURE II1-4
PALLADIUM BY-PRODUCT RECOVERY PROCESS
_
1124
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - III
ELECTROLTTIC MtlHUU
Sliau £roa P«Hadlu»
Elsctrolrtie S«p«r«tioa
teed* CMCtag
«p«ns Kacerolyta _
eo Copper L*«cb- ^""1
las
METHOD
Impflr* Platlmra
from 'Pallcdiiai PTOCM*
Eltetz«lreie
tell
ErdreeUocie AeidA.
Hiertc
Oiacalueioa
FUtraeicn
Serap
Hydrechlortc Ar1rt/„.,.»
eo
CUeri4«
Precipitation
PUcrstioB
HMh
Trassod
Canting
Ctiodiat
Platiaua
FIGURE II1-5
PLATINUM BY-PRODUCT RECOVERY PROCESS
1125
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - III
Electrolytic Sllaee
Dor« Metal
Hoe Hater
Circulation of
Acid Seleniua
Solutioo
Kttrtc
Acid
Settlinc T«nk
Fredpitator
Lota to
Ataoapbara
Sludge
Solid Residue to Saelter
or Cupel Furnace
Solution
Evaporator
Acidified
Selenium
Solatia*
Mcutraliution
Tank
Filtn
Sludge Katumed to
Cupd.
•Tellurium to Further
Proceaalng
Keutral S*leai«»
Solution Hydrochloric Acid, Sulfuric
-s*' Acid, Seen, Sulfur Dioxide
Freeipitatioa
Tank
> tiaatevater
Low Grade Seleniuat Co
Spent Solutionl Cupel Furnace '>
Elemental
Seleniuai
Filtration. CenerifuRintt,
Drying, .PnckinK. R
Low Grade
Selenlua
Precipitation
Dirty Solution
Depleted Solution
SeleniuB
FIGURE III-6
SELENIUM BY-PRODUCT RECOVERY PROCESS
1126
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - III
Don Itaui AaodM
Gclallat, Hoc Hater r«arMng.
S»tciiE» mt rueracioa of
lartn* Coluc
from «"••'<— «-t
Idu* To Cup«i
furcfacr Froc«s«int
FIGURE III-7
TELLURIUM BY-PRODUCT RECOVERY PROCESS
1127
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - III
W
Pi
Pi
O
H
1
O
oo w
M W
M
M JM
D M
U «
CO
I
M
I
O
CJ
M
K
1128
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - IV
SECTION IV
SUBCATEGORIZATION
This section summarizes the factors considered during the
designation of the primary electrolytic copper refining
subcategory and its related building blocks.
Primary electrolytic copper refiners located onsite with primary
copper smelters were considered as a single subcategory during
the previous 1975 rulemaking. Primary copper refiners not
located with smelters were considered as a separate subcategory.
That rulemaking established interim BPT and BAT limitations,
along with NSPS and PSNS for the primary copper subcategory. In
1980, a modified BPT regulation was promulgated for the primary
copper subcategory that divided smelting and refining into two
separate subcategories regardless of location. The rational for
this 1980 subcategorization__was detailed as part of that
rulemaking.
FACTORS CONSIDERED IN SUBDIVIDING THE PRIMARY ELECTROLYTIC COPPER
REFINING SUBCATEGORY
The factors listed for general subcategorization were each
evaluated when considering subdivision of the primary
electrolytic copper refining subcategory. In the discussion that
follows, the factors will be described as they pertain to this
particular subcategory.
The rationale for considering further subdivision of the primary
electrolytic copper refining subcategory is based primarily on
the production process used. Within this subcategory, a number
of different operations are performed, which may or may not have
a water use or discharge, and which may require the establishment
of - separate effluent limitations. Since primary electrolytic
copper refining is a single subcategory, xa thorough examination
of the production processes, water use and discharge practices,
and pollution generation rates has illustrated the need for
limitations and standards based on a specific set of waste
streams. Possible sources of wastewater from an electrolytic
refiner include these subdivisions or building blocks:
1. Anode and cathode rinse,
2. Spent electrolyte,
3. Casting contact cooling,
4. Casting wet air pollution control, and
5. By-product recovery.
A number of other factors considered in this evaluation supported
the establishment of the five subdivisions or were shown to. be
inappropriate bases for primary copper refining
subcategorization. These are discussed briefly below.
1129
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - IV
RAW MATERIALS
The principle raw material for electrolytic copper refining is
fire refined blister copper from a copper smelter. Blister
copper is approximately 98 percent pure copper with slight
impurities of nickel, thallium, selenium, and precious metals.
These raw materials warrant subcategorization for primary
electrolytic copper refining separate from the production of
other metals. In addition, no factors pertaining to raw materials
have been identified that affect the ability of plants in the
primary copper electrolytic refining subcategory to achieve
effluent limitations.
PLANT SIZE
A review of the 14 copper refining plants who reported sufficient
information showed that two plants have capacities of less than
90,000 metric tons (100,000 short tons) per year, four plants
have capacities between 90,000 and 180,000 metric tons (100,000
and 200,000 short tons) per year, and two plants have capacities
greater than 180,000 metric tons (200,000 short tons) per year.
No factors relating to this distribution of plant size and
pertaining to a given plant's ability to achieve effluent
limitations have been identified,.
PLANT AGE
Primary copper smelting and electrolytic refining is a relatively
new industrial process which evolved as a result of the
availability of electricity in large quantities. Through the
past century, new methods for manufacturing copper have developed
which may combine several of the traditional smelting steps into
one. In addition, new advances have been made in
hydrometallurgical processes to handle copper oxide ore. These
newer processes, however, are simply subsets of the older
smelting or refining processes in terms of wastewater generated.
Therefore, the oldest plants built in the early 1900's are
fundamentally equivalent to those built today. As a result,
neither the concentration of constituents in wastewater nor the
capability to meet limitations is related to plant age. Because
of the general uniformity of copper process technology, the
application of most wastewater treatment systems is dependent on
factors other than age.
Through the years, electrolytic copper refining has not changed
dramatically. The same chemical principles used in the early
1900's are still practiced today. New advances in this area have
been primarily in the development of automated methods to
mechanically handle intermediate and final products. Neither the
concentration of constituents in wastewater nor the effluent
performance attainable is related to plant age.
1130
-------
PBIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - IV
PRODUCT
Product is a good reason for subdividing the primary copper
operations from production of other metals since manufacturing
operations and wastewater characteristics are usually unique for
a particular product. The end result of primary copper refining
is cathode copper, 99.99 percent pure copper, which may be cast
or marketed with no further processing. Prom the survey taken of
primary copper producers, 40 percent of the smelting facilities
also contain electrolytic refining facilities onsite. This
indicates that a substantial amount of primary copper
electrolytic refining is a subset of the copper integrated
manufacturing operations. Therefore, product cannot be
considered as a means of subdividing primary copper smelting from
refining.
PRODUCTION NORMALIZING PARAMETERS
As discussed previously, the effluent limitations and standards
developed in this document establish mass limitations on the
discharge of specific pollutant parameters. To allow this
regulation to be applied to plants with various production
capacities, the mass of pollutant discharge must be related to a
unit of product. This factor is known as the production
normalizing parameter (PNP). In general, the amount of copper
produced by the respective manufacturing process is used as the
PNP. This is based on the principle that the amount of water
generated is proportional to the amount of product made. For
primary electrolytic copper refining, actual production has been
selected as the PNP for all of the subdivisions as shown below:
3,
4,
5,
Subdivision
Anode and cathode rinse water
Spent electrolyte
Casting contact cooling
Casting wet air pollution control
By-product recovery
PNP
kkg of cathode copper
produced
kkg of cathode copper
produced
kkg of copper cast
kkg of copper cast
kkg of by-product
recovered from
electrolytic slimes
processing
Other PNPs were considered for certain subdivisions;
they were rejected and are discussed below.
ANODE AND CATHODE RINSE WATER
however,
The production normalizing parameter selected for this
subdivision is cathode copper produced. Capacity, rather than
1131
-------
PRIMARY ELECTROLYTIC COPPER REPINING SUBCATEGORY SECT - IV
actual production, was considered for use as the production
normalizing parameter. When analytical samples were taken,
however, the pollutant concentration calculations were based on
Actual measured flows and production rates. In order to be
consistent when determining pollutant loadings, the cathode
copper production was chosen. Use of actual production also
eliminates the need for plants to reduce water flow during years
in which actual production is greater than design capacity.
The casting production was also considered as a production
normalizing parameter. This production cannot be used because
not all cathode copper is cast before marketing.
SPENT ELECTROLYTE
The production normalizing parameter for spent electrolyte is
also cathode copper. For those same reasons discussed above,
electrolytic capacity and casting production were not chosen as
production normalizing parameters. This preserves the
relationship between the sampling data and the rates at the time
of sampling.
CASTING CONTACT COOLING
The production normalizing parameter chosen for this process is
actual casting production. Cathode production from the
electrolytic tank house cannot be used because not all
electrolytic copper is cast before leaving the plant. To
preserve the relationship between sampling data and production,
the casting capacity could not be used as discussed earlier.
CASTING WET AIR POLLUTION CONTROL
To control air emissions from a furnace, wet air pollution
methods may be used. The production normalizing parameter has
been chosen as actual casting production instead of capacity.
Originally it was thought that capacity might be a more
appropriate measure than actual production because water use in
the scrubber is independent of production. Consistency in the
application of sampling data, however, necessitated the use of
casting production as the production normalizing parameter. This
will ensure that higher capacity utilization will not reduce the
production normalized flow allowance from this operation.
BY-PRODUCT RECOVERY
The production normalizing parameter chosen for the recovery of
nickel sulfate and precious metals is actual production of these
materials. As an alternative, cathode copper was considered as
the production normalizing parameter, but this does not allow for
a difference in the quantities of impurities contained within
anode copper. Furthermore, for consistency, the final product
and not an intermediate was chosen as the PNP.
1132
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - V
SECTION V
WATER USE AND WASTEWATER CHARACTERISTICS
This section describes the characteristics of wastewater
associated with the primary electrolytic copper refining
subcategory. Data used to quantify wastewater flow and pollutant
concentrations are presented, summarized, and discussed. The
contribution of specific production processes to the overall
wastewater discharge from primary copper refining plants is
identified whenever possible.
TWO principal data sources were used in the development of
effluent limitations and standards for this subcategory: data
collection portfolios and field sampling results. Data
collection portfolios, completed for the primary copper refining
subcategory, contain information regarding wastewater flows and
production levels.
Since the data collection portfolios were collected, the Agency
has learned that two primary copper electrolytic refiners have
shut down. Flow and production data from these plants are still
included in this section and in the remainder of the document.
Analytical data gathered at one of the plants are also presented.
Although these plants are closed, flow and production data from
the plants are an integral part of the flow components of the BAT
effluent mass limitations because these plants remain
representative of flow and production rates in this industry.
The Agency believes that these data provide useful measures of
the relationship between production and wastewater discharge. In
light of this conclusion, EPA is using these data in its
consideration of BAT performance. Therefore, it is necessary to
present this information so that the limitations are documented.
Additionally, the Agency received updated and revised flow and
production data for some waste streams through comments on the
proposed regulation and through special requests. These data are
also included in this section.
In order to quantify the pollutant discharge from primary copper
electrolytic refining plants, a field sampling program was
conducted. Wastewater samples were collected in two phases:
screening and verification. The first phase, screen sampling,
was to identify which toxic pollutants were present in the
wastewaters from production of the various metals. Screening
samples were analyzed for 125 of the 126 toxic pollutants and
other pollutants deemed appropriate. Because the analytical
standard for TCDD was judged to be too hazardous to be made
generally available, samples were never analyzed for this
pollutant. There is no reason to expect that TCDD would be
present in primary copper electrolytic refining wastewater. A
total of 10 plants were selected for screen sampling in the
1133
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - V
nonferrous metals manufacturing category. A complete list of the
pollutants considered and a summary of the techniques used in
sampling and laboratory analyses are included in Section V of
Vol. 1. In general, the samples were analyzed for three classes
of pollutants: toxic organic pollutants, toxic metal
pollutants, and criteria pollutants (which includes both
conventional and nonconventional pollutants).
As described in Section IV of this supplement, the primary copper
electrolytic refining subcategory has been further categorized
into five building blocks. This regulation contains mass
discharge limitations and standards for five unit processes
discharging process wastewater. Differences in the wastewater
characteristics associated with these subdivisions are to be
expected. For this reason, wastewater streams corresponding to
each subdivision are addressed separately in the discussions that
follow.
WASTEWATER SOURCES, DISCHARGE RATES, AND CHARACTERISTICS
The wastewater data presented in this section were evaluated in
light of production process information compiled during this
study. As a result, it was possible to identify the principle
wastewater sources in the primary electrolytic copper refining
subcategory. These include:
1. Anode and cathode rinse water,
2. Spent electrolyte,
3. Casting contact cooling water,
4. Casting wet air pollution control, and
5. By-product recovery.
Data supplied by dcp responses were used to calculate the amount
of water used and discharged per metric ton of production. The
two ratios calculated are differentiated by the flow rate used in
the calculation. Water use is defined as the volume of water of
other fluid (e.g., electrolyte) required for a given process per
mass of copper product and is therefore based on the sum of
recycle and make-up flows to a given process. Wastewater flow
discharged after pretreatment or recycle (if these are present)
is used in calculating the production normalized flow—the volume
of wastewater, discharged from a given process to further
treatment, disposal, or discharge per mass of copper produced.
Differences between the water use and wastewater flows associated
with a given stream result from recycle, evaporation, and carry
over on the product. The production values used in calculations
correspond to the production normalizing parameter, PNP, assigned
to each stream, as outlined in Section IV. The production
normalized flows were compiled and statistically analyzed by
stream type. Where appropriate, an attempt was made to identify
factors that could account for variations in water use. This
information is summarized in this section. A similar analysis of
factors affecting the wastewater values is presented in Sections
X, XI, and XII where representative BAT, BDT and pretreatment
discharge flows are selected for use in calculating the effluent
1134
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - V
limitations. As an example, anode and cathode rinse wastewater
flow is related to the cathode copper production. As such, the
discharge 'rate is expressed in liters of rinse wastewater per
metric ton of cathode copper production (gallons of rinse water
per ton of cathode copper production).
Characteristics of wastewater from the previously listed
processes were determined from sampling data collected at primary
copper refiners. These data were used in two ways. First,
pollutants were selected for regulation based on the sampling
data. ^Secondly, the sampling data was used to estimate the
yearly mass of pollutant generated by each waste stream for the
entire industry. There were four site visits at two refiners,
which represents 14 percent of the copper refiners. Diagrams
indicating the sampling sites and contributing production
processes are shown in Figures V-l and V-2 (pages 1150 and 1151).
In the data collection portfolios, plants were asked to indicate
whether or not any of the toxic pollutants were believed to be
present in their wastewater. Responses for the toxic metals
selected as pollutant parameters are summarized below for those
plants responding to that portion of the questionnaire. Results
of the responses from facilities with electrolytic refining only
and facilities having both smelting and electrolytic refining are
shown in Table V-l (page 1139). These responses demonstrate that
primary copper refinery facilities know that process wastewater
contains quantifiable concentrations of toxic metal pollutants.
The raw wastewater sampling data for the primary copper refining
subcategory is presented in Tables V-5 and V-6 (pages 1143 and
1144). Treated wastewater sampling data are shown in Table V-7
(page 1145). The stream codes displayed in Tables V-5 through V-
7 may be used to identify the location of each of the samples on
the process flow diagrams in Figures V-l and V-2. Where no data
are listed for a specific day of sampling, the wastewater samples
for the stream were not collected. If the analyses did not
detect a pollutant in a waste stream, the pollutant was omitted
from the table.
The data tables included some samples measured at concentrations
considered not quantifiable. The base neutral extractable, acid
extractable, and volatile toxic organics generally are considered
not quantifiable at concentrations equal to or less than 0.010
mg/1. Below this concentration, organic analytical results are
not quantitatively accurate; however, the analyses are useful to
indicate the presence of a particular pollutant. The_ pesticide
fraction is considered not quantifiable at concentrations equal
to or less than 0.005 mg/1. Nonquantifiable results are
designated in the tables with an asterisk (double asterisk for
pesticides).
These detection limits shown on the data tables are not the same
in all cases as the published detection limits for these
pollutants by the same analytical methods. The detection limits
used were reported with the analytical data and hence are the
1135
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - V
appropriate limits to apply to the data. Detection limit
variation can occur as a result of a number of laboratory-
specifier equipment-specific, and daily operator-specific
factors. These factors can include day-to-day differences in
machine calibration, variation in stock solutions, and variation
in operators.
The statistical analysis of data includes some samples measured
at concentrations considered not quantifiable. Data reported as
an asterisk are considered as detected but below quantifiable
concentrations, and a value of zero is used for averaging. Toxic
organic, nonconventional, and conventional pollutant data
reported with a "less than" sign are considered as detected but
not further quantifiable. A value of zero is also used for
averaging. If a pollutant is reported as not detected, it is
excluded in calculating the average. Finally, toxic metal values
reported as less than a certain value were considered as not
detected and a value of zero is used in the calculation of the
average. For example, three samples reported as ND, *, and 0.021
rag/1 have an average value of 0.010 mg/1. The averages
calculated are presented with the sampling data. These values
were not used in the selection of pollutant parameters.
In the following discussion, water use and field sampling data
are presented for each operation. Appropriate tubing or
background blank and source water concentrations are presented
with the summaries of the sampling data. Figures V-l through V-4
show the location of wastewater sampling sites at each facility.
The method by which each sample was collected is indicated by
number, as follows:
1. one-time grab
2. 24-hour manual composite
3. 24-hour automatic composite
4. 48-hour manual composite
5. 48-hour automatic composite
6. 72-hour manual composite
7. 72-hour automatic composite
COPPER REFINING WASTEWATER SOURCES AND CHARACTERISTICS
:' .. '" >'",•'.',' •• I/" !' • . "<• • ",• •: ,
Presented below is a discussion of the characteristics of the
significant wastewater sources attributable to the refining of
copper.
Anode and Cathode Rinse Water
Cathodes and anodes removed from electrolytic cells are often
rinsed before further processing. The waste rinse water is
characterized by significant concentrations of toxic metal
pollutants such as nickel (4,200 mg/1) and zinc (32 mg/1). These
pollutants are a result of impurities in the anodes that are
released into the electrolyte. Table V-5 summarizes the field
sampling data for the toxic and selected conventional and
nonconventional pollutants detected in wastewater from a cathode
1136
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - V
rinsing operation.
Of the six plants who reported rinsing anodes and cathodes, only
one discharges spent rinse water. The production normalized flow
calculated for this plant is 552 liters per metric ton (1/kkg) of
cathode copper produced (132 gal/ton).
Spent Electrolyte
To maintain a correct electrolytic balance during refining, a
slip stream of electrolyte is continuously removed for
purification. There are two plants in the primary copper
electrolytic refining subcategory Who discharge this stream after
purification. Table V-2 (page 1140) illustrates the volumes of
electrolyte used and discharged on a production basis for these
two plants.
Spent electrolyte from an electrowinning process is characterized
by significant concentrations of toxic metal pollutants such as
nickel (4,200 rag/1) and zinc (32 mg/1). These toxic metals are a
result of impurities present in anodes and are released into the
electrolyte during refining. These pollutants are soluble in the
electrolyte and are not removed during electrowinning. Table V-5
(page 1143) presents the sampling data gathered from this
operation.
Casting Contact Cooling Water
There are two types of casting that can take place at a copper
refiner. Partially consumed anode butts from the refining
process are removed in monthly cycles for recasting, and cathode
copper is cast into usable shapes for forming processes. The
Agency collected one raw wastewater sample from a smelter casting
operation. Wastewater samples collected at this site indicate
casting contact cooling water contains low concentrations of
toxic metals. As might be expected, the significant toxic
pollutant found in wastewater from a casting operation is copper.
As can be seen in Table V-6 (page 1144), sampling data from this
site found the copper concentration as 1.6 mg/1. Table V-3 (page
1141) illustrates the water usage and discharge rates on a
production basis for casting contact cooling water.
Casting Furnace Scrubber Liquor
There was one facility that reported controlling emissions from a
furnace with a wet air pollution control system. This facility
reported a production normalized water usage and discharge rate
of 16 liters per metric ton of copper cast (3.8 gal/ton). The
Agency did not collect any raw wastewater samples from furnace
scrubbing operations. The water quality characteristics of this
waste stream are expected to be very similar to casting contact
cooling. Loadings of toxic metal pollutants will be slightly
lower than those found in casting contact cooling, while the
level of suspended solids is expected to be higher in furnace
scrubber water.
1137
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - V
By-Product Recovery
The recovery of precious and base metals is done through a series
of smelting, leaching, precipitation, and electrolytic refining
processes. In several of the leaching, precipitation, and
filtration steps, there is the potential of discharge of
leachate, supernatant, and filtrate. These waste streams are
expected to contain toxic metal pollutants. Some plants recycle
this wastewater within the by-product recovery process or treat
and reuse the water in other plant processes. Wastewater from
scrubbers on cupel furnaces, drying furnaces, and precipitation
steps contains precious and base metals that can be recovered.
Wastewater from these scrubbers is used as makeup water within
the by-product recovery process or treated and used in other
plant processes. In addition, the electrolytic media are also a
potential source of wastewater. Spent leaching solutions and
discarded supernatant may contain such toxic metal pollutants as
copper, arsenic, lead, and nickel. Spent electrolyte from silver
electrolytic refining and gold electrolytic refining consists of
silver nitrate, silver chloride, and copper nitrate. Spent
electrolyte may become a waste stream after the silver and copper
are removed from the solutions through cementation. Spent
electrolyte from palladium and platinum electrolytic refining is
also a potential wastewater source. However, one plant reports
sending this wastewater to the copper slimes leaching operation
for reprocessing. Contact cooling water used in casting dore
anodes is discharged to a wastewater treatment system at one
plant. However, the Agency believes there is no need to treat
casting contact cooling water from by-product recovery. EPA
sampled casting contact cooling water from similar operations at
a secondary precious metals plant in the nonferrous metals
manufacturing category. The pollutant loadings in this
wastewater are insignificant compared with the other waste
streams selected. (The sampling data are presented in the
secondary precious metals subcategory supplement.)
One plant operates a wet scrubber on fusion kilns to control
sulfur dioxide (SO2) in the kiln off-gases. The scrubber water
is not recycled but is discharged to the plant wastewater
treatment system. However, the scrubber wastewater flow rate
comprises less than one percent of the total plant regulatory
flow. Table V-4 (page 1142) presents the volumes of wastewater
generated during by-product recovery.
_
1138
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - V
TABLE V-l
INDICATED PRESENCE OR ABSENCE OF TOXIC METAL POLLUTANTS
DCP DATA
For plants having electrolytic refining only
Antimony
Cadmium
Chromium
Copper
Lead
Nickel
Selenium
Zinc
Known
Present
2
2
1
5
3
4
2
3
Believed
Present
1
1
3
0
1
0
2
2
Believed
Absent
2
2
1
0
1
1
1
0
Known
Absent
0
0
0
0
0
0
0
0
For plants having both smelting and refining
Antimony
Cadmium
Chromium
Copper
Lead
Nickel
Selenium
Zinc
Known
Present
4
4
4
7
5
4
4
5
Believed
Present
1
1
0
0
1
2
2
2
Believed
Absent
2
2
3
0
1
1
1
0
Known
Absent
0
0
0
0
0
0
0
0
1139
-------
PRIMARY ELECTROLYTIC COPPER REPINING SUBCATEGORY SECT - V
TABLE V-2
ELECTROLYTE USE AND SPENT ELECTROLYTE DISCHARGE RATES FOR
CATHODE COPPER PRODUCTION
(1/kkg of cathode copper refined)
Plant
Code
214
216(a)
62
60
201
202(b)
206
203
205(c)
211(a)
215
217(d)
218
7000
Production Production
Percent Normalized Normalized
Recycle Electrolyte Use Discharoe Flow
NR
99
100
100
100
100
100
NR
0
0
NR
0
NR
NR
(1/kkg)
NR
1182.5
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
(gal/ton)
NR
283.0
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
(1/kkg) (gal/ton)
48.9
11.5
0
0
0
0
0
NR
8.7
NR
NR
260
NR
NR
11.
2.
0
0
0
0
0
NR
2.
NR
NR
62.
NR
NR
73
75
08
4
NR - Present, but not reported in dcp.
(a) - Spent electrolyte is ultimately evaporated.
(b) - Plant closed.
(c) - Deep well injection, no electrowinning.
(d) - Sold as copper sulfate, no electrowinning.
1140
_
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - V
TABLE V-3
WATER USE AND DISCHARGE RATES FOR
CASTING CONTACT COOLING
(1/kkg of copper cast)
Plant
202(a)
214(b)
215
216
214
217
62
206
205
211
Production
Percent Normalized
recycle Water Use
0
0
98
98
NR
93
100
100
NR
NR
(1/kkg)
15273
2298
46592
26325
NR
555
NR
NR
NR
NR
( gal/ton )
3655
550
11150
6300
NR
133
NR
NR
NR
NR
Production
Normalized
Discharge Flow
(1/kkg)
15273
2298
932
526
137
29
0
0
NR
NR
(gal/ton)
3655
550
223
126
33
7
o
0
NR
NR
NR — Data not reported in dcp
(a) — Plant closed
(b) — Plant operates two casting operations
1141
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGQRY SECT - V
4 TABLE V-4
WATER USE AND DISCHARGE RATES FOR BY-PRODUCT RECOVERY
(1/kkg of total by-product)
Plant
Code
62
205
2061
211
214
216!
Percent
Recycle
100
0
NR
NR
NR
100
Production
Normalized
Water Use
2620
4902
NR
NR
NR
1533647
Production
Normalized
Discharge Flow
0
0*
NR
NR
94318
0
1 — Facility no longer operates by-product recovery
* — Wastewater disposed through deep well disposal
NR— Data not reported in dcp
1142
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - V
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1148
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - V
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1149
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - V
i 'i
—®
VOA Blank
Source Water
Casting
Contact
Cooling
Cooling
Tower
Batch
Discharge
0.01483 MGD
Sludge
Lime
FIGURE V-l
SAMPLING SITES AT PRIMARY COPPER REFINER PLANT A
1150
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - V
Slag
Granulation
Noncoatact
Cooling
6.134 MOD
Conctneri
tor
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A
0.4598 HOD
0.0062 MOD
FIGURE V-2
SAMPLING SITES AT PRIMARY COPPER REFINER PLANT C
1151
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - V
THIS PAGE INTENTIONALLY LEFT BLANK
1152
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - VI
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
This section examines chemical analysis data presented in Section
V from primary electrolytic copper refining plant sampling visits
and discusses the selection or exclusion of pollutants for
potential limitation in this subcategory.
- i
Each pollutant selected for potential limitation is discussed in
Section VI of Vol. 1. That discussion provides information
concerning the origin of each pollutant (i.e., whether it is a
naturally occurring substance, processed metal, or a manufactured
compound), general physical properties and the form of the
pollutant, toxic, effects of the pollutant in humans and other
animals, and behavior of the pollutant in POTW at the
concentrations expected in industrial discharges.
The discussion that follows describes the analysis that was
performed to select or exclude pollutants for consideration for
limitations and standards. Pollutants are considered for
limitations and standards if they are present in concentrations
treatable by the technologies considered in this analysis. The
treatable concentrations used for the toxic metals were the long-
term performance values achievable by lime precipitation,
sedimentation, and filtration. The treatable concentrations used
for the toxic organics were the long-term performance values
achievable by carbon adsorption (see Section VII of Vol. 1 —
Combined Metals Data Base).
After the February 1983 proposal, the Agency re-evaluated the
treatment performance of activated carbon adsorption to control
toxic organic pollutants. The treatment performance for the acid
extractable, base-neutral extractable, and volatile organic
pollutants has been set equal to the analytical quantification
limit of 0.010 mg/1. The analytical quantification limit for
pesticides and total phenols (by 4-AAP method) is 0.005 mg/1,
which is below the 0.010 mg/1 accepted for the other toxic
organics. However, to be consistent, the treatment performance
of 0.010 mg/1 is used for pesticides and total phenols. The
0.010 mg/1 concentration is achievable, assuming enough carbon is
used in the column and a suitable contact time is allowed. The
frequency of occurrence for 36 of the toxic pollutants has been
re-determined based on the revised treatment'performance value.
However, no toxic organic pollutants have been selected for
consideration for limitation. The pollutants selected are
identical to those selected at proposal, for the reasons
discussed below.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETER
This study examined samples from the primary electrolytic copper
refining subcategory for three conventional pollutant parameters
1153
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - VI
•- •v:'"^iV{\;;;.;v.^
(oil and grease, total suspended solids, and pH) and three
nonconventional pollutant parameters (chemical oxygen demand,
total organic carbon, and total phenols).
"i ' • ' l!',li, i , ' ;' , ' ' "^ ,' V \ , , ' ', | '
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETERS SELECTED
. , . .. . , , , . ., .-
No nonconventional pollutants were selected for limitation in
this subcategory. For conventional pollutants, total suspended
solids (TSS) and pH were the parameters selected. Total
suspended solids concentrations were found to be 18 and 1,140
mg/1 from the two samples considered for pollutant selection.
These two samples are above the treatable concentration
attainable by available specific treatment processes.
Furthermore, most of the specific methods for removing toxic
metals do so by precipitation, and the resulting toxic metals
precipitates should not be discharged. Meeting a limitation on
TSS also aids in removal of precipitated toxic metals. For these
reasons, total suspended solids is considered for specific
limitation in this subcategory.
* •,••'! Vl!1 ' ''• ' ' ' I,' ' ' . '
The pH values obtained from the two samples considered were 1.2
and 7.6. Effective removal of toxic metals by chemical
precipitation requires careful control of pH. Therefore, pH is
considered for specific limitation in this subcategory.
TOXIC POLLUTANTS
The frequency of occurrence of the toxic pollutants in the
wastewater samples taken is presented in Table VI-1 (page 1158).
These data provide the basis for the categorization of specific
pollutants, as discussed in the following sections. Table VI-1
is based on raw wastewater data from streams 216 and 222 (see
Section V) . Treatment plant sampling data were not used for the
frequency count, although stream 55, containing treated
wastewater, was used for toxic organic pollutant selection.
During the field sampling program, only stream 55 was tested for
toxic organics. The Agency believes, due to raw materials and
processing agents, there are no treatable concentrations of toxic
organics in wastewaters from electrolytic copper refineries. The
waste stream on which the organic analysis was performed was
pretreated with chemical precipitation and sedimentation methods.
This method of treatment is designed for dissolved metals removal
and is expected to have very little effect on the concentration
of toxic organics in the wastewater.
TOXIC POLLUTANTS NEVER DETECTED
The toxic pollutants listed in Table VI-2 (page 1159) below were
not detected in any raw wastewater samples from this subcategory.
Therefore, they are not selected for consideration in
establishing limitations.
:!;:;: i":.
1154
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - VI
TOXIC POLLUTANTS NEVER FOUND ABOVE THEIR ANALYTICAL
QUANTIFICATION LIMIT
The toxic pollutants listed in Table VI-3 (page 1161) were never
found above their analytical quantification concentration in any
wastewater samples from this subcategory; therefore, they are not
selected for consideration in establishing limitations.
TOXIC POLLUTANTS DETECTED BUT PRESENT SOLELY AS A RESULT OF ITS
PRESENCE IN THE INTAKE WATERS
Listed below are those pollutants that were detected above
quantification limit but were also detected in the source water
or a blank and are therefore not selected for regulation:
23. chloroform (trichloromethane)
66. bis(2-ethylhexyl) phthalate
67. butyl benzyl phthalate
68. di-n-butyl phthalate
69. di-n-octyl phthalate
TOXIC POLLUTANTS PRESENT BELOW CONCENTRATIONS ACHIEVABLE BY
TREATMENT
The pollutants listed below are not selected for consideration in
establishing limitations because they were not found in any
wastewater samples from this subcategory above concentrations
considered achievable by existing or available treatment
technologies. These pollutants are discussed individually
following the list.
114. antimony
125. selenium
Antimony was detected above its analytical quantification limit
in one of the two raw wastewater samples taken from the primary
electrolytic copper refining subcategory. The concentration of
antimony in the sample was 0.400 mg/1. This value is below the
0.47 mg/1 concentration considered attainable by identified
treatment technology. Therefore, because antimony was not
detected above concentrations considered attainable by identified
treatment technology, it is eliminated from further consideration
for limitation.
Selenium was detected above its analytical quantification limit
in one of the two raw wastewater samples taken from the primary
electrolytic copper refining subcategory. The concentration of
selenium in the sample was 0.015 mg/1. This value is below the
0.20 mg/1 concentration considered attainable by identified
treatment technology. Therefore, because selenium was not
detected above concentrations considered attainable by identified
treatment technology, it is eliminated from further consideration
for limitation.
1155
-------
PRIMARY ELECTROLYTIC COPPER REPINING SUBCATEGORY
SECT - VI
TOXIC POLLUTANTS SELECTED FOR CONSIDERATION FOR ESTABLISHING
LIMITATIONS AND STANDARDS
The toxic pollutants listed below are selected for further
consideration for establishing limitations and standards for this
subcategory. The toxic pollutants selected are each discussed
following the list:
115.
119.
120.
122.
124.
126.
128.
arsenic
chromium
copper
lead
nickel
silver
zinc
Arsenic was detected above its analytical quantification limit in
one of the two raw wastewater samples taken from the primary
electrolytic copper refining subcategory. The concentration of
arsenic in the sample was 1.20 mg/1. This value is above the
0.34 mg/1 concentration considered attainable by identified
treatment technology. Therefore, arsenic is selected for further
consideration for limitation.
Chromium was detected above its analytical quantification limit
in one of the two raw wastewater samples taken from the primary
electrolytic copper refining subcategory. The concentration of
chromium in the sample was 0.076 mg/1. This value is above the
0.070 mg/1 concentration considered attainable by identified
treatment technology. Therefore, chromium is selected for
further consideration for limitation.
Copper was detected above its analytical quantification limit in
two of the two raw wastewater samples taken from the primary
electrolytic copper refining subcategory. The concentration of
copper in the samples was 3.9 mg/1 and 1.55 mg/1. This value is
above the 0.39 mg/1 concentration considered attainable by
identified treatment technology. Therefore, copper is selected
for further consideration for limitation.
Lead was detected above its analytical quantification limit in
one of the two raw wastewater samples taken from the primary
electrolytic copper refining subcategory. The concentration of
lead in the sample was 1.4 mg/1. This value is above the 0.08
mg/1 concentration considered attainable by identified treatment
technology. Therefore, lead is selected for further
consideration for limitation.
Nickel was detected above its analytical quantification limit in
one of the two raw wastewater samples taken from the primary
electrolytic copper refining subcategory. The concentration of
nickel in the sample was 4,200 mg/1. This value is above the
0.22 mg/1 concentration considered attainable by identified
treatment technology. Therefore, nickel is selected for further
consideration for limitation.
1156
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - VI
Silver was detected above its analytical quantification limit in
one of the two raw wastewater samples taken from the primary
electrolytic copper refining subcategory. The concentration of
silver in the sample was 0.130 mg/1. This value is above the
0.070 mg/1 concentration considered attainable by identified
treatment technology. Therefore, silver is selected for further
consideration for limitation.
Zinc was detected above its analytical quantification limit in
both of the raw wastewater samples taken from the primary
electrolytic copper refining subcategory. The concentration of
zinc in the samples was 31.5 mg/1 and 0.052 mg/1. A value of
31.5 mg/1 is well above the 0.23 mg/1 concentration considered
attainable by identified treatment technology. Therefore, zinc
is selected for further consideration for limitation.
1157
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - VI
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-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - VI
TABLE VI-2
TOXIC POLLUTANTS NEVER DETECTED
2. acrolein
3. acrylonitrile
5. benzidene
6. carbon tetrachloride (tetrachloromethane)
7. chlorobenzene
8. 1,2,4-trichlorobenzene
9. hexachlorobenzene
10. 1,2-dichloroethane
12. hexachloroethane
13. 1,1-dichloroethane
14. 1,1,2-trichloroethane
16. chloroethane
17. DELETED
18. bis(2-chloroethyl) ether
19. 2-chloroethyl vinyl ether (mixed)
20. 2-chloronaphthalene
21. 2,4,6-trichlorophenol
22. parachlorometa cresol
24. 2-chlorophenol
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
28. 3,3'-dichlorobenzidine
31. 2,4-dichlorophenol
32. 1,2-dichloropropane
33. 1,2-dichloropropylene (1,3-dichloropropene)
34. 2,4-dimethylphenol
35, 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. 1,2-diphenylhydrazine
38. ethylbenzene
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. bis(2-chloroisopropyl) ether
43. bis(2-choroethoxy) methane
44. methylene chloride (dichloromethane)
45. methyl chloride (chloromethane)
46. methyl bromide (bromomethane)
47. bromoform (tribromomethane)
48. dichlorobromomethane
49. DELETED
50. DELETED
51. chlorodibromomethane
52. hexachlorobutadiene
53. hexachlorocyclopentadiene
54. isophorone
56. nitrobenzene
57. 2-nitrophenol
58. 4-nitrophenol
59. 2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
1159
-------
PRIMARY ELECTROLYTIC COPPER REPINING SUBCATEGORY SECT - VI
'••";; ' *'f ' k'" :': '":'" '
TABLE VI-2 (Continued)
TOXIC POLLUTANTS NEVER DETECTED
61. N-nitrosodimethylamine
62. N-nitrosodiphenylamine
63. N-nitrosodi-n-propylamine
64. pentachlorophenol
65. phenol
70. diethyl phthalate
72. benzo(a)anthracene (1,2-benzanthracene)
74. 3,4-benzofluoranthene
77. acenaphthylene
79. benzo(ghi)perylene (1,11-benzoperylene)
80. fluorene
82. dibenzo(afh)anthracene (1,2,5,6-dibenzanthracene)
83. indeno(l,2,3-cd)pyrene (w,e,-o-phenylenepyrene)
86. toluene
88. vinyl chloride (chlorethylene)
89. aldrin
90. dieldrin
94. 4,4'DDD (pfp'TDE)
105. delta-BHC
113. toxaphene
116. asbestos (Fibrous)
117. beryllium
118. cadmium
121. cyanide (Total)
123. mercury
127. thallium
129. 2,3,7,8-tetra chlorodibenzo-p-dioxin (TCDD)
1160
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - VI
1.
4.
11.
15.
29.
30.
39.
55.
71.
73.
75.
76.
78.
81.
84.
85.
87.
91.
92.
93.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
106.
107.
108.
109.
110.
111.
112.
TABLE VI-3
TOXIC POLLUTANTS NEVER FOUND ABOVE THEIR ANALYTICAL
QUANTIFICATION LIMIT
acenaphthene
benzene
1,1,1-trichlOrethane
1,1,2,2-tetrachloroethane
1,1-dichloroethylene
1,2-trans-dichloroethylene
fluoranthene
naphthalene
dimethyl phthalate
benzo(a)pyrene (3,4-benzopyrene)
benzo(k)fluoranthane (11,12-benzofluoranthene)
chrysene
anthracene (a)
phenanthrene (a)
pyrene
tetrachloroethylene
trichloroethylene
chlordane (technical mixture and metabolites)
4,4'-DDT
4,4'-DDE (p,p'DDX)
a-endosulfan-Alpha
b-endosulfan-Beta
endosulfan sulfate
endrin
endrin aldehyde
heptachlor
heptachlor epoxide
a-BHC-Alpha
b-BHC-Beta
r-BHC (lindane)-Gamma
PCB-1242 (Arochlor 1242) (b)
1254) (b)
1221) (b)
1232) (c)
PCB-1254
PCB-1221
PCB-1232
PCB-1248
PCB-1260
PCB-1016
(Arochlor
(Arochlor
(Arochlor
(c)
(Arochlor
(Arochlor
1260)
1016)
(c)
(c)
(a), (b), (c) Reported together, as a combined value,
1161
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - VI
THIS PAGE INTENTIONALLY LEFT BLANK
1162
.. J T ,,il:'", ,v'i!i I
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - VII
SECTION VII
CONTROL AND TREATMENT TECHNOLOGIES
The preceding sections of this supplement discussed the waste
water sources, flows, and characteristics of the wastewaters from
primary electrolytic copper refining plants. This section
summarizes the description of these wastewaters and indicates the
level of treatment which is currently practiced by the primary
electrolytic copper refining industry for each waste stream.
TECHNICAL BASIS OF BPT
As mentioned in Section III, EPA promulgated BPT effluent
limitations guidelines for the primary electrolytic copper
refining subcategory on July 2, 1980. The BPT regulations
established by EPA limit the discharge of copper, cadmium, lead,
zinc, and TSS, and require the control of pH. The best
practicable control technology identified is the treatment of
wastewater by lime and settle technology. To obtain the values
required at BPT, the agency acknowledges that in some cases it
may be necessary to use chemical flocculants to enhance settling.
CURRENT CONTROL AND TREATMENT PRACTICES
This section presents a summary of the control and treatment
technologies that are currently applied to each of the sources
generating wastewater in this subcategory. As discussed in
Section V, wastewater associated with the primary copper
electrolytic refining subcategory is characterized by the
presence of the toxic metal pollutants and suspended solids.
(The raw (untreated) wastewater data for specific sources as well
as combined waste streams is presented in Section V.) Generally,
these pollutants are present in each of the waste streams at
treatable concentrations, so these waste streams are commonly
combined for treatment to reduce the concentrations of these
pollutants. Construction of one wastewater treatment system for
combined treatment allows plants to take advantage of economies
of scale and, in some instances, to combine streams of differing
alkalinity to reduce treatment chemical requirements. Ten plants
in this subcategory currently have combined wastewater treatment
systems, five have lime precipitation and sedimentation, and no
plants have lime precipitation, sedimentation, and filtration.
After proposal, three options were selected for consideration for
BAT, BDT, and pretreatment in this subcategory, based on combined
treatment of these compatible waste streams.
ELECTROLYTIC REFINING
Copper anodes obtained from smelters are " inserted in an
electrolytic bath consisting of sulfuric acid and copper sulfate.
As copper ions migrate from the anode to the cathode, impurities
contained within the anode are released. Several of these
1163
-------
PRIMARY ELECTROLYTIC COPPER REPINING SUBCATEGORY
SECT - VII
impurities are soluble in the electrolyte, while others, such as
precious metals, are not, and they settle to the bottom of the
cells. A bleed stream is continuously removed from the
electrolytic tank house to control the levels of soluble
impurities and the concentration of copper sulfate in the
electrolyte. The bleed stream is electrowinned to remove copper
present as copper sulfate, and then partially evaporated to
initiate the precipitation of nickel sulfate. At most refineries
the stream is returned to the tank house as make up acid. One
plant, however, reported discharging this waste stream after pH
adjustment and sedimentation. Two refineries located in areas of
net evaporation reported partial recycle and evaporation of spent
electrolyte. Two facilities reported the sale of spent
electrolyte to copper sulfate manufacturers. One plant reported
disposing of its spent electrolyte in a deep well, and three
facilities did not provide information on treatment practices.
The remaining six electrolytic refiners reported a 100 percent
recycle of spent electrolyte.
Spent electrolyte after electrowinning and nickel sulfate removal
is characterized by a low pH (2.5) with dissolved treatable toxic
metals. This waste stream is treatable through pH adjustment .to
precipitate the dissolved metals and settling to remove the
precipitate. A better method, as demonstrated in the
subcategory, is complete recycle after electrowinning and nickel
sulfate removal to eliminate the discharge of all toxic
pollutants.
ANODE AND CATHODE RINSE WATER
Anodes are removed from the electrolytic cells in monthly cycles
and often rinsed before being returned to a casting furnace.
There were six plants who reported washing anode butts upon
removal from the cells, five of which reported a zero discharge
or 100 percent recycle of this wastewater. Generally the washing
is done above the cells so that all wastewater is captured in the
cell and not discharged. One facility reported discharging a
blowdown from this waste stream as it was recycled. This
facility also indicated that the blowdown was not treated before
discharge.
As with spent electrolyte, anode and cathode rinse water is
characterized by a low pH with dissolved toxic metals.
Accordingly, this waste stream is treatable through pH adjustment
to precipitate the dissolved metals and settling to remove the
precipitate. Industry has demonstrated, however, that this waste
stream can be eliminated if anodes and cathodes are rinsed above
the electrolytic cells.
CASTING
Blister copper and anode copper are cast into usable shapes for
further processing. Wastewater from this operation is due to
contact cooling and furnace scrubber liquor. From dcp responses
it was determined that two of four plants discharging casting
1164
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - VII
contact cooling water recycle greater than 90 percent of the
water used. Before discharge, two plants treat the cooling water
with lime and settle technology, one plant passes its water
through settling ponds before discharge, and the other plant
discharges a blow down from its cooling tower without treatment.
To achieve zero discharge, a variety of methods are used,
including chemical precipitation and sedimentation followed by
100 percent recycle, deep well injection, cooling towers, solar
evaporation, and 100 percent reuse in other plant processes.
Both casting contact cooling and casting scrubber liquor will
exhibit similar wastewater characteristics, treatable
concentrations of dissolved metals and suspended solids.
Wastewater from these two sources is best treated with lime and
settle technology. Further reduction of pollutant discharge can
be accomplished through cooling towers and recycle.
CASTING SCRUBBER LIQUOR
Control of particulate matter from casting furnaces is
accomplished with a wet system at one plant with ultimate
disposal of this wastewater through deep well injection. The
remaining refineries reported no control of emissions from
casting furnaces.
BY-PRODUCT RECOVERY
Many of the impurities present in anode copper have economic
value and may be recovered as a by-product of electrolytic copper
refining. From the dcp responses, it was determined that three
electrolytic refiners recover precious metals on site as by-
products. Of these three facilities, one plant reported
discharging wastewater from the processing of anode slimes and
wastewater from a fusion kiln SO2 scrubber; while one reported
discharging wastewater through deep well injection, and one
reported 100 percent recycle. The plant practicing 100 percent
recycle treats the wastewater by iron cementation and
neutralization with caustic before reusing the water.
The principal source of wastewater from by-product recovery is
due to leaching and precipitation throughout the by-product
recovery process to remove impurities. Many of the spent
solutions are acidic and could be treated through pH adjustment
to initiate precipitation followed by sedimentation. EPA
believes, however, that these wastewaters can be recycled or
reused in other processes. This is demonstrated by one facility
located in an area of net precipitation.
CONTROL AND TREATMENT OPTIONS
Based on an examination of the wastewater sampling data, three
control and treatment technologies that effectively control the
pollutants found in primary electrolytic copper refining waste
waters were selected for evaluation. Other treatment
technologies considered for the category included activated
1165
-------
PRIMARY ELECTROLYTIC COPPER REFINING. SUBCATE(3dRY SECT - VII
alumina adsorption (Option D) and activated carbon adsorption
(Option E). However, these technologies were not selected for
evaluation in this subcategory because they are not applicable to
primary electrolytic copper refining. Although arsenic was found
in process wastewaters at treatable concentrations, activated
alumina technology (Option D) is not demonstrated in the
nonferrous metals manufacturing category, nor is it clearly
transferable. No toxic organic pollutants were found in process
waste waters above their treatable concentrations. Also, organic
pollutants are not characteristics of the raw materials and
processing agents used in this subcategory. Therefore, activated
carbon is not considered necessary. The options selected for
evaluation are discussed below.
OPTION A
Option A for the primary electrolytic copper refining subcategory
is equivalent to BPT. The BPT model end-of-pipe treatment
consists of chemical precipitation and sedimentation (lime and
settle) technology. Chemical precipitation and sedimentation
removes metals and suspended solids from the casting contact
cooling water by the addition of lime followed by sedimentation.
OPTION B
Option B for the primary electrolytic copper refining subcategory
requires control and treatment technologies to reduce the
discharge of wastewater volume and pollutant mass. Water recycle
and reuse are the principal control mechanisms for flow
reduction.
The Option B treatment model is based on the same chemical
precipitation and sedimentation technology as BPT (Option A), but
it allows a discharge from casting contact cooling only. Recycle
and reuse are also required for casting contact cooling water to
control solids. A 100 percent recycle or reuse are required for
spent electrolyte and anode and cathode rinse water. Chemical
precipitation is used to remove metals by .the addition of lime
followed by settling. Suspended solids are also removed from the
process.
OPTION C
The Option C treatment scheme builds on Option B (treatment of
chemical precipitation, sedimentation, and in-process flow
reduction) with the addition of preliminary treatment consisting
of sulfide precipitation, pressure filtration, and multimedia
filtration end-of-pipe treatment. Sulfide precipitation is used
to further reduce the concentration of dissolved metals at one
primary copper refiner operating a metallurgical acid plant.
Multimedia filtration is used to remove suspended solids,
including precipitates of metals beyond the concentration
attainable by gravity sedimentation. The filter suggested is of
the gravity, mixed media type, although other forms of filters
such as rapid sand filters or pressure filters would perform
1166
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PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - VII
satisfactorily. The addition of filters also provides consistent
removal during periods of time in which there are rapid increases
in flows or loadings of pollutants to the treatment system.
TREATMENT TECHNOLOGIES REJECTED AT PROPOSAL
Other treatment technologies included activated alumina
adsorption (Option D), activated carbon adsorption (Option E),
and reverse osmosis (Option F). These technologies were not
considered because they are not applicable to the primary
electrolytic copper refining subcategory. Although arsenic was
found in process wastewaters at treatable concentrations,
activated alumina technology (Option D) is not demonstrated in
the nonferrous metals manufacturing category, nor is it clearly
transferable. Activated carbon adsorption technology (Option E)
was not considered because treatable .concentrations of toxic
organic pollutants were not detected in wastewater from primary
copper electrolytic refiners. Also, organic pollutants are not
characteristic of the raw materials and processing agents used in
this subcategory. Therefore, activated carbon adsorption is not
applicable.
Option F for the primary copper refining subcategory consisted of
reverse osmosis and evaporation technology added at the end of
the lime precipitation, sedimentation, in-process flow reduction,
and multimedia filtration considered for Option C. Option F was
used for complete recycle of the treated water by controlling the
concentration of dissolved solids. Multiple-effect evaporation
is used to dewater the brines rejected from reverse osmosis.
Reverse osmosis, however, was rejected because it was not
demonstrated in the nonferrous metals manufacturing category, nor
is it clearly transferable.
1167
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PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - VII
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1168
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PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - VIII
SECTION VIII
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS
This section describes the method used to develop the costs
associated with the control and treatment technologies discussed
in Section VII for wastewaters from primary electrolytic copper
refining plants. The energy requirements of the considered
options as well as solid waste and air pollution aspects are also
discussed in this section.
Cost estimates, based on the preliminary and end-of-pipe
treatment of casting contact cooling and spent electrolyte water,
are presented in this section for the primary electrolytic, copper
refining subcategory.
In Section VI of this supplement, several pollutants and
pollutant parameters are selected for limitation for the primary
electrolytic copper refining subcategory. These pollutants or
pollutant parameters include copper, lead, nickel, total
suspended solids, and pH. Metals are most economically removed
by chemical precipitation, sedimentation, and filtration. The
recycle of casting contact cooling water through cooling towers
may also be added as a preliminary flow reduction measure which
decreases the discharge flow from casting and results in the
concentration of pollutants in the effluent stream. Treatment of
a more concentrated effluent allows 'achievement of a greater net
pollutant removal and introduces the possible economic cost-
effectiveness associated with treating a lower volume of
wastewater. Therefore, the basic control and treatment
technologies considered for the primary electrolytic copper
refining subcategory are cooling towers, chemical precipitation
and sedimentation (lime and settle and filtration), with
preliminary treatment for arsenic with sulfide precipitation and
pressure filtration where appropriate.
TREATMENT OPTIONS CONSIDERED
As discussed in Section VII of this supplement, three control and
treatment options are considered for treating wastewater from the
primary electrolytic copper refining subcategory. The control and
treatment options are described below and schematically presented
in Figures X-l through X-3 (pages 1189 - 1193).
OPTION A
Casting contact cooling wastewater and spent electrolyte are
treated by chemical precipitation and sedimentation. This option
represents no additional costs since the promulgated 1980 BPT is
based on lime precipitation and sedimentation.
1169
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PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - VIII
OPTION B
The casting contact cooling water is recycled through a cooling
tower and a blowdown stream, along with spent electrolyte, is
treated by chemical precipitation and sedimentation.
OPTION C
The casting contact cooling water is recycled through a cooling
tower and a blowdown stream, along with spent electrolyte, and is
treated by chemical precipitation, sedimentation, sulfide
precipitation (and filtration), and multimedia filtration. The
sulfide precipitation is included for one primary copper refiner
operating a metallurgical acid plant. The cost of the sulfide
precipitation is attributed entirely to the acid plant.
COSTING METHODOLOGY
A detailed discussion of the methodology used to develop the
compliance costs is presented in Section VIII of the General
Development Document. Plant-by-plant compliance costs have been
estimated for the nonferrous metals manufacturing category and
are presented in the administrative record supporting this
regulation. A comparison of the costs developed for proposal and
the revised costs for the final regulation are presented in Table
VIII-1 (page 1173) for the direct discharges.
Each of the major assumptions used to develop compliance costs is
presented in Section VIII of the General Development Document.
Each subcategory contains a unique set of waste streams requiring
certain subcategory-specific assumptions to develop compliance
costs. Five major assumptions are discussed briefly below.
i , '',',:, ,' ' , 'nil,! ' , , ', i . 1 ,', ; ' / ,
, ' i," •('.•: '.•<'.' ,", '••• • '• '• i ,'•';.',' , '"' . ',' ; ;.;.
(1) No discharge of process wastewater from the anode and
cathode rinse operation is accomplished via in-plant
process modifications. As such, no compliance costs are
attributable to th|.s regulation.
" _ '' 1 i!''1 '• t; '•'.: It '' • • ,' i ' ' •. • ,' ' • ; ".' '! ''•';
(2) Because the compliance costs need only represent
incremental costs that primary copper refineries may be expected
to incur in complying with this regulation, operation and
maintenance costs for in-place treatment usedto comply with the
previously promulgated BPT regulation for this subcategory are
not included in a plant's total cost of compliance for this
regulation. .
(3) Capital and annual costs for the plant discharging
wastewater in both the primary copper and metallurgical acid
plant subcategories are attributed to each subcategory on a flow-
weighted basis.
(4) No cost is included for directdischarges to comply
with elimination of net precipitation allowances for primary
copper plants.
'(1,1.
1170
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PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - VIII
(5) Recycle of casting contact cooling water is based on
recycle through cooling towers. Annual costs associated with
maintenance and chemicals to prevent biological growth,
corrosion, and scale formation are included in the estimated
compliance costs. If a plant currently recycles casting contact
cooling water, capital costs of the recycle equipment (cooling
tower, pumps, and piping) were not included in the compliance
costs.
NONWATER QUALITY ASPECTS
Nonwater quality impacts specific to primary electrolytic copper
refining, including energy requirements, solid waste and air
pollution are discussed below.
ENERGY REQUIREMENTS
The methodology used for determining the energy requirements for
the various options is discussed in Section VIII of the General
Dev£lopment Document. Energy requirements are estimated at 0.14
MW-hr/yr and 0.17 MW-hr/yr for Options B and C, respectively. No
additional energy is required for Option A as a result of this
regulation since BPT is in place. Option C represents roughly
five percent of a typical plant's electrical usage. It is
therefore concluded that the energy requirements of the treatment
options considered will have no significant impact on total, plant
energy consumption.
SOLID WASTE
Sludges associated with the primary electrolytic copper refining
subcategory will necessarily contain additional quantities (and
concentrations) of toxic metal pollutants. Wastes generated by
primary smelters and refiners are currently exempt from
regulation by Act of Congress (Resource Conservation and Recovery
Act (RCRA), Section 3001(b). Consequently, sludges generated
from treating primary industries' wastewater are not presently
subject to regulation as hazardous wastes.
The technology basis for one plant in the primary copper
electrolytic refining subcategory includes separate sulfide
precipitation for the control of arsenic. In developing
compliance costs for this plant, sulfide precipitation was used
as a preliminary treatment to lime, settle, and multimedia
filtration treatment. Precipitants generated during - sulfide
precipitation are removed in a pressure filter and backwashed to
lime and settle. The Agency believes sludge generated through
sulfide precipitation will be classified as hazardous under RCRA.
The costs of hazardous waste disposal were . considered in the
economic analysis for the one copper plant (even though the waste
is now exempt from RCRA regulation) and they were determined to
be economically achievable. Sludges generated by the other
primary copper direct discharges are not expected to be hazardous
if a small (5-10%) excess of lime is added during treatment.
Multimedia filtration will not generate any significant amount of
1171
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PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGQRY
SECT - VI1I
sludge over that resulting from lime precipitation
precipitation.
and sulfide
Although it is the Agency's view that lime sludges generated as a
result of these guidelines are not expected to be hazardous
(except for the one plant), generators of these wastes must test
the waste to determine if the wastes meet any of the
characteristics of hazardous waste (see 40 CFR 262.11).
If these wastes should be identified or are listed as hazardous,
they will come within the scope of RCRA's "cradle to grave"
hazardous waste management program, requiring regulation from the
point of generation to point of final disposition. EPA's
generator standards would require generators of hazardous
nonferrous metals manufacturing wastes to meet containerization,
labeling, recordkeeping, and reporting requirements; if plants
dispose of hazardous wastes off-site, they would have to prepare
a manifest which would track the movement ofthe wastes from the
generator's premises to a permitted off-site treatment, storage,
or disposal facility. See 40 CFR 262.20 45 FR 33142 (May 19,
1980), as amended at 45 FR 86973 (December 31, 1980). The
transporter regulations require transporters of hazardous wastes
to comply with the manifest system to assure that the wastes are
delivered to a permitted facility. See 40 CFR 263.20 45 FR 33151
(May 19, 1980), as amended at 45 FR 86973 (December 31, 1980).
Finally, RCRA regulations establish standards for hazardous waste
treatment, storage, and disposal facilities allowed to receive
such wastes. See 40 CFR Part 464 46 FR 2802 (January 12, 1981),
47 FR 32274 (July 26, 1982). Must be disposed of in compliance
with the Subtitle D open dumping standards, implementing 4004 of
RCRA. See 44 FR 53438 (September 13, 1979). The Agency has
calculated as part of the costs for wastewater treatment the cost
of hauling and disposing of these wastes.
AIR POLLUTION
There is no reason to believe that any substantial air pollution
problems .will result from implementation of chemical
precipitation, sedimentation, multimedia filtration and reverse
osmosis. These technologies transfer pollutants to solid waste
and do not involve air stripping or any other physical process
likely to transfer pollutants to air. Minor amounts of sulfur
may be emitted during sulfide precipitation, and water vapor
containing some particulate matter will be released in the drift
from the cooling tower systems which are used as the basis for
flow reduction in the primary electrolytic copper refining
subcategory. However, the Agency does not consider this impact
to be significant.
1172
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PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - VIII
TABLE VIII-1
COST OF COMPLIANCE FOR THE PRIMARY COPPER SUBCATEGORY
DIRECT DISCHARGERS
(March, 1982 Dollars)
Option
B
C
Proposal Costs
Capital Annual
Promulgation Costs
Capital Annual
2,120,000
3,153,000
1,549,000
1,876,000
197,000
266,000
133,000
171,000
1173
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PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - VIII
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:'"<. t
1174
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PRIMARY ELECTROLYTIC COPPER REPINING SUBCATEGORY
SECT - IX
SECTION IX
BEST PRACTICABLE TECHNOLOGY CURRENTLY AVAILABLE
EPA promulgated BPT effluent limitations for the primary copper
smelting and electrolytic refining subcategories on July 2, 1980,
as Subpart D and Subpart E of 40 CFR Part 421. EPA is not
making any modifications to these limitations. Subpart E applies
to primary electrolytic copper refining and by-product recovery
operations and allows a discharge of process wastewater subject
to mass-based limitations.
Pollutants regulated by these limitations are copper, cadmium,
lead, zinc, total suspended solids and pH. The effluent
limitations established by BPT standards for the primary
electrolytic copper refining subcategory are based on chemical
precipitation and sedimentation and are as follows:
EFFLUENT LIMITATIONS
Effluent
Characteristic
Maximum for
Any One Day
Average of Daily Values
for 30 Consecutive
Days Shall Not Exceed
Metric Units - kilograms per 1,000 kg of product
English Units - Ibs per 1,000 Ibs of product
Total Suspended Solids
Copper
Cadmium
Lead
Zinc
pH
0.100
0.0017
0.0006
0.0006
0.0012
0.050
0.0008
0.00003
0.00026
0.0003
within the range of 6.0 to 9.0
1175
-------
i.,,!; 41 :
.' ',, +!',".
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - IX
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1176
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PRIMARY ELECTROLYTIC COPPER REPINING SUBCATEGORY
SECT - X
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
These effluent limitations are based on the best control and
treatment technology used by a specific point source within the
industrial category or subcategory, or by another category where
it is readily transferable. Emphasis is placed on additional
treatment techniques applied at the end of the treatment systems
currently used for BPT, as well as reduction of the amount of
water used and discharged, process control, and treatment
technology optimization.
The factors considered in assessing best available technology
economically achievable (BAT) include the age of equipment and
facilities involved, the processes used, process changes,
nonwater quality environmental impacts (including energy
requirements), and the costs of application of such technology
(Section 304 (b) (2) (B) of the Clean Water Act). At a minimum,
BAT represents the best available technology economically
achievable at plants of various ages, sizes, processes, or other
characteristics. Where the Agency has found the existing
performance to be uniformly inadequate, BAT may be transferred
from a different subcategory or category. BAT may include
feasible process changes or internal controls, even when not in
common industry practice.
The required assessment of BAT considers costs and economic
achievability, but does not require a balancing of costs against
effluent reduction benefits (see Weyerhaeuser v. Costle, 590
F.2d. 1011 (D.C. Cir. 1978)). However, in assessing BAT, the
Agency has given substantial weight to the economic achievability
of the technology.
TECHNICAL APPROACH TO BAT
The Agency reviewed a wide range of technology options and
evaluated the available possibilities to ensure that the most
and beneficial technologies were used as the basis of
accomplish this, the Agency elected to examine four
options prior to proposing mass limitations which
applied to the primary electrolytic copper refining
as BAT options. Three of these technology options
effective
BAT. TO
technology
could be
subcategory
were re-evaluated prior to promulgation of mass limitations
the primary copper electrolytic refining subcategory.
for
In summary, the treatment technologies considered for the primary
electrolytic copper refining subcategory are:
Option A (Figure X-l page 1191) is based on
o Chemical precipitation and sedimentation
1177
-------
PRIMARY ELECTROLYTIC COPPER REPINING SUBCATEGORY
SECT - X
Option B (Figure X-2 page 1192) is based on
'.• . ' •'',',', i .'i'i1!!! '!,!' ',1", '" ,• ",: ' ': . i ', , ,. I
o Chemical precipitation and sedimentation
o Flow reduction
Option C (Figure X-3 page 1193) is based on
o Sulfide precipitation and pressure filtration (at
one plant)
o Chemical precipitation and sedimentation
o Flow reduction
o Multimedia filtration
These three technology options considered for BAT are discussed
in greater detail below. The first option considered is the same
as the BPT^ treatment and control technology. The remaining
options provide additional pollutant removal beyond that achieved
by BPT.
OPTION A
Option A for the primary electrolytic copper refining subcategory
is chemical precipitation and sedimentation (lime and settle).
Chemical precipitation and sedimentation, the technology
established as BPT for the primary electrolytic copper refining
subcategory, removes metals and suspended solids from the casting
contact cooling water and spent electrolyte by the addition of
lime followed by sedimentation.
OPTION B
Option B for the primary copper refining subcategory decreases
pollutant discharge by building upon the BPT end-of-pipe
treatment technology, chemical precipitation and sedimentation
(Option A) by including flow reduction measures. Flow reduction
measures, including in-process changes, result in the elimination
of some wastewater streams and the concentration of pollutants in
other effluents as explained in Section VII of Vol. 1. Treatment
of a more concentrated effluent allows achievement of a greater
net pollutant removal and introduces the possible economic
benefits associated with treating a lower volume of wastewater.
Methods used in Option B to reduce process wastewater generation
or discharge rates include a 100 percent recycle of anode and
cathode rinse water and partial recycle of casting contact
cooling water.
ilr , „ , „
Recycling of Casting Contact Cooling Water Through Cooling Towers
The cooling and recycle of contact cooling water is practiced by
six of the nine plants reporting this wastewater. The function
of casting contact cooling water is to quickly remove heat from
the newly formed casting product. Therefore, the principal
requirements of. the water are that it be cooland not contain
dissolved solids at a concentration that would cause water marks
or other surface imperfections. There is sufficient experience
1178
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PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - X
with casting contact cooling wastewater within the nonferrous
metals manufacturing category to assure the success of this
technology using cooling towers or heat exchangers (refer to
Section VII of the General Development Document). Although two
plants have reported that they do not discharge any casting
contact cooling wastewater, a blowdown or periodic cleaning may
be needed to prevent a build-up of dissolved and suspended
solids. (EPA has determined that a blowdown of 10 percent of the
water applied in a process is adequate).
Recycle of_ Water Used in Anode and Cathode Rinsing
Total recycle or reuse of anode rinse water is practiced by six
of the seven plants generating this wastewater. The amount of
recycle used by the single discharging plant was not reported.
The Option B treatment scheme consists of cooling towers for the
casting cooling water followed by the treatment scheme of Option
A, which consists of chemical precipitation -•"* «^«*.«,i-ai-4««
technology (lime and settle).
and sedimentation
OPTION C
Option C for the primary electrolytic copper refining subcategory
consists of preliminary treatment with sulfide precipitation and
pressure filtration and multimedia filtration end-of-pipe
technology added to the lime precipitation, sedimentation, and
in-process flow reduction considered for Option B. The Option C
treatment scheme is presented in Figure X-3 (page 1195). Sulfide
precipitation is considered for one primary copper refiner and
smelter .operating a metallurgical acid plant. Sulfide
precipitation followed by pressure filtration will remove toxic
metals to levels otherwise achievable by lime and settle
treatment. Multimedia filtration is used to remove suspended
solids, including precipitates of metals, beyond the
concentration attainable by gravity sedimentation. The filter
suggested is of the gravity, mixed media type, although other
forms of filters, such as rapid sand filters or pressure filters,
would perform satisfactorily.
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
As one means of evaluating each technology option, EPA developed
estimates of the pollutant removal estimates and the compliance
costs associated with each option. The methodologies are
described on the following pages.
ESTIMATED POLLUTANT REMOVALS
A complete description of the methodology used to calculate the
estimated pollutant reduction achieved by the application of the
various treatment options is presented in Section X of the
General Development Document. The pollutant removal estimates
have been revised from proposal based on comments and on new
data; however, the methodology for calculating pollutant removals
1179
-------
PRIMARY ELECTROLYTIC COPPER REFINING SOBCATEGORY
SECT - X
was not changed. The data used for estimating removals are
same as those used to revised the compliance costs.
the
Sampling data collected during the field sampling program were
used to characterize the major waste streams considered for
regulation. At each sampled facility, the sampling data were
production normalized for each unit operation (i.e., mass of
pollutant generated per mass of product manufactured). This
value, referred to as the raw waste, was used to estimate the
mass of toxic pollutants generated within the primary
electrolytic copper refining subcategory. By multiplying the
total subcategory production for a unit operation by the
corresponding raw waste value, the mass of pollutant generated
for that unit operation was estimated.
The volume of wastewater discharged after the application of each
treatment option was estimated for each operation at each plant
by comparing the actual discharge to regulatory flow. The
smaller of the two values was selected and summed with the other
plant flows. The mass of pollutant discharged was then estimated
by multiplying the achievable concentration values attainable by
the option (mg/1) by the estimated volume of process wastewater
discharged by the subcategory. The mass of pollutant removed is
the difference between the estimated mass of pollutant generated
within the subcategory and the mass of pollutant discharged after
application of the treatment option. The pollutant removal
estimates for the primary electrolytic copper direct dischargers
are presented in Table X-l (page 1187).
COMPLIANCE COSTS
Compliance costs presented at proposal were estimated using cost
curves, relating the total costs.associated with installation and
operation of wastewater treatment technologies to plant process
wastewater Discharge. EPA applied these curves on a per plant
basis, a plant's costs — both capital, and operating and
maintenance — being determined by what treatment it has in place
and by its individual process wastewater discharge (from dcp).
The final step was to annualize the capital costs, and to sum the
annualized capital costs, and the operating and maintenance
costs, yielding the cost of compliance for the subcategory.
Since proposal, the cost estimation methodology has been revised
as discussed in Section VIII of this document. A design model
and plant specific information were used to size a wastewater
treatment system for each discharging facility. After completion
of_ the design, capital and annual costs were estimated for each
unit of the wastewater treatment system. Capital costs were
developed from vendor quotes and annual costs were developed from
literature. Table VIII-1 (page 1173) shows the revised
compliance costs of the various options for the primary
electrolytic copper refining subcategory.
The compliance costs presented in Section VIII represent the
incremental cost of wastewater treatment not already in place.
For example, if a plant operates a lime precipitation and
1180
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PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - X
sedimentation treatment system of sufficient sizei, capital costs
are not included in the compliance costs estimates since this
expenditure has already been incurred by the plant. It is also
worth noting that a comparison was made between actual flows and
the regulatory flows. The smaller of the two was chosen to use
for sizing of the wastewater treatment equipment. The cost of
flow reduction was accounted for by developing costs for cooling
towers and holding tanks to allow for recycle.
BAT OPTION SELECTION
EPA proposed both Option B and Option C as the basis for
alternative BAT effluent limitations for the primary electrolytic
copper refining subcategory due to adverse structural economic
changes that were not reflected in the Agency's economic
analysis. These alternative limitations were based on lime
precipitation, sedimentation, and in-process control technologies
to reduce the volume of process wastewater discharged for Option
B. Lime precipitation, sedimentation, in-process control
technologies, and multimedia filtration were proposed for Option
C.
As discussed earlier, plant-by-plant compliance costs have been
re-evaluated for this subcategory. In addition, the .economic
analysis, the Agency has determined that Option C, which includes
in-process flow reduction, lime precipitation, sedimentation, and
multimedia filtration with sulfide precipitation preliminary
treatment, is economically achievable. Therefore, "the
promulgated BAT technology basis for primary copper electrolytic
refining is based on Option C technology. Figure X-3 (page 1193)
illustrates this treatment scheme.
Filtration is not demonstrated in this subcategory, but it is
transferred from the primary aluminum, secondary copper, primary
zinc, primary lead, secondary lead, and secondary silver
subcategories .
Extensive effluent data submitted to the Agency by an integrated
copper refiner and smelter have indicated that the proposed
arsenic mass limitations based on lime and settle treatment may
not be achievable for this plant. The Agency believes that the
larger arsenic values in the plant's ore contribute significant
quantities of arsenic to the treatment system. Arsenic
concentrations in excess of 100 mg/1 are common at this plant,
making the combined metals data base inappropriate. The Agency
believes that the mass limitations as proposed for the primary
electrolytic copper refining subcategory and metallurgical acid
plant subcategory are achievable for this plant by adding sulfide
precipitation followed by pressure filtration to the model
treatment technology. The Agency thus has determined that the
combination of sulfide precipitation preliminary treatment, and
lime precipitation, sedimentation, and multimedia filtration end-
of-pipe technology will achieve the mass limitations promulgated
and has included this technology in its compliance cost estimates
for this one plant. However, the costs associated with sulfide
1181
-------
-!! ><-i •. , •!"!ii»!", "i*v KS • <<> T!i*-.«ii-'.
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - X
precipitation on the total process flow were attributed entirely
to the metallurgical acid plants subcategory because the refinery
wastewater contributes only a small fraction of the combined
discharge.
EPA estimates that the promulgated BAT will remove 48,730 kg/yr
of toxic metals over raw discharge estimates. The final BAT
effluent mass limitations will remove 770 kg/yr of toxic metals
over the intermediate option considered, which lacks filtration.
Both options are economically achievable. The Agency believes
that the incremental removal justifies selecting of filtration as
part of BAT model technology. Implementation of the promulgated
BAT limitations is expected to result in an estimated capital
cost of $0.266 million (March, 1982 dollars) and an estimated
annual cost of $0.171 million. EPA is not including any cost for
elimination of the catastrophic storm and net precipitation
allowances based on its elimination from BPT in 1980.
Jii ' . ' " j ;',,', ' ; ' ' „', '' '
WASTEWATER DISCHARGE RATES
' • • • , .''.-; ';: ,',;,' , '. '..••:'., ,•, j.l.
Important production operations in the primary electrolytic
copper refining subcategory are electrolytic refining and
casting. Both of these operations are potential sources of
wastewater and are evaluated to establish effluent limitations
for the subcategory.
Specific wastewater streams associated with the primary
electrolytic copper refining subcategory are cathode and anode
rinsing wastewater, spent electrolyte, casting contact cooling
waste water, and casting wet air pollution control wastewater.
Table X-2 (page 1188) lists the production normalized wastewater
discharge rates allocated at BAT for these wastewater streams.
The values represent the best existing practices of the
subcategory, as determined from the analysis of dcp.
ANODE AND CATHODE RINSE WASTEWATER
The BAT wastewater discharge allowance is not provided for anode
and cathode rinsing. Six of the 14 primary copper refining
facilities reported this waste stream. Five of these plants
practice total recycle or reuse of this waste stream, while only
one plant discharges the rinsing wastewater. The BAT discharge
rate is based on the five plants who do not discharge this waste
water.
SPENT ELECTROLYTE
No BAT discharge allowance was provided for spent electrolyte in
the proposed regulation. The BAT discharge rate was based on the
13 plants that did not discharge spent electrolyte.
Data supplied to the Agency through comments and Section 308
requests indicate spent electrolyte cannot be recycled 100
percent after electrowinning for some plants. Recycle rates are
highly dependent on raw materials and contaminate levels in the
1182
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PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - X
anode. As copper is released into solution from the anode,
impurities contained in the anode are also released into
solution. Several of these impurities, such as silver, gold,
lead, and selenium are insoluble in the electrolyte and settle to
the bottom of the electrolytic cell. Soluble impurities
contained in the cathode consist primarily of bismuth, antimony,
and iron. Purity of the cathode copper is very dependent on the
concentration of impurities in the electrolyte. Therefore, a
portion of the electrolyte is bled from the system and processed
in an electrowinning circuit followed by nickel sulfate recovery.
In certain instances, raw materials may contain minimal
concentrations of nickel making nickel sulfate recovery
inappropriate. The bleed rate could be decreased so that nickel
concentrations increase and nickel sulfate recovery can be used.
However, this will concentrate the bismuth, antimony, and iron
impurities and affect product purity. For these reasons, the
Agency is modifying the proposed zero discharge requirement for
spent electrolyte. The BAT discharge rate is based on the only
plant that discharges this wastewater source, and it is equal to
49 1/kkg (12 gal/ton) of cathode copper production.
CASTING CONTACT COOLING WASTEWATER
Nine of the 14 copper refining plants reported this waste stream.
Recycle of this, waste stream is practiced at five of these
plants. Two plants reported total recycle of their casting
contact cooling water; however, three plants reported discharging
a bleed stream. Wastewater rates for casting contact cooling are
presented in Table V-2 (page 1143). The BAT discharge rate is
based on the mean normalized discharge flow of the three plants
that recycle and discharge a bleed stream (plants 215, 216,, and
217). The BAT discharge rate is 498 1/kkg (119 gal/ton) of
casting production.
CASTING WET AIR POLLUTION CONTROL
Only one of the 14 copper refining plants reported the use of a
casting scrubber. This plant achieves zero discharge of the
scrubbing wastewater by deep well injection. Since only one
plant uses casting wet air pollution control and this plant is a
zero discharger, no BAT discharge allowance is provided for
casting wet air pollution control.
BY-PRODUCT RECOVERY
No BAT wastewater discharge allowance is provided for by-product
recovery. Two of the three plants which recover by-products from
electrolytic copper refining do not discharge wastewater. The
single discharging plant generates bleed streams from scrubbers
and casting contact cooling associated with by-product recovery
after electrowinning. The scrubber is used to control sulfur
dioxide (SO2) emissions from fusion kilns. The scrubber water is
not recycled but is discharged to the plant wastewater treatment
system. However, the scrubber wastewater flow rate comprises
less than one percent of the total -plant regulatory flow and is
1183
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - X
thus considered negligible. Contact cooling water used in
casting dore anodes is also discharged to the plant wastewater
treatment system. However, the Agency believes there is no need
to treat casting contact cooling water from by-product recovery.
EPA sampled casting contact cooling water from similar operations
at a secondary precious metals plant in the. nonferrous metals
manufacturing category. The pollutant loadings in this waste
water are insignificant compared to the other waste streams
selected. The sampling data are presented in the secondary
precious metals supplemental development document. Wastewater
use and discharge rates for by-product recovery are presented in
Table V-4 (page 1142). EPA believes that the solution from
electrowinning can be reused in electrolytic refining. In
addition, EPA received no comments questioning the proposed zero
discharge allowance for this waste stream. For these reasons,
and because zero discharge from by-product recovery is
demonstrated by two of three plants, EPA has not provided a
discharge allowance for by-product recovery.
REGULATED POLLUTANT PARAMETERS
In implementing the terms of the Consent Agreement in NRDC v.
Train,. Op. Cit., and 33 U.S.C. 1314 (b) (2) (A and B) (1976), the
Agency placed particular emphasis on the toxic pollutants. The
raw wastewater concentrations from individual operations and the
subcategory as a whole were examined to select certain pollutants
and pollutant parameters for consideration for limitation. This
examination and evaluation, presented in Section VI, concluded
that 11 pollutants and pollutant parameters arepresent in
primary electrolytic copper refining wastewaters at
concentrations that can be effectively reduced by identified
treatment technologies. (Refer to Section VI).
\ • . ',:''' '',::' r '",'"'•• i!!'!!?"1'1™, i •' " ' •: • . ' "'|i; ' '' .1
However, the cost associated with analysis for toxic metal
pollutants has prompted EPA to develop an alternative method for
regulating and monitoring toxic pollutant discharges from the
nonferrous metals manufacturing category. Rather than developing
specific effluent mass limitations and standards for each of the
toxic metals found at treatable concentrations in the raw waste
waters from a given subcategory, the Agency is promulgating
effluent mass limitations only for those pollutants generated in
the greatest quantities as shown by thepollutant reduction
benefit analysis. The pollutants selected for specific
limitation are listed below:
115. arsenic
120. copper
124. nickel
'''.' " '' V' •• ' .:,,;! .''"ll !" '" ,' , ,:'>r , * • ' ,' ,;,'.:» ''. "O. ,'".-'
By establishing limitations and standards for these selected
toxic metal pollutants, dischargers are expected to attain the
same degree of control over toxic metal pollutants as they would
have been requir-ed to achieve had all the toxic metal pollutants
been directly limited.
1184
;!'" .„
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY* ' ' SECT - X
This approach is justified technically since the .treatable
concentrations used , for lime precipitation and sedimentation
technology are based on optimized treatment for concomitant
multiple metals removal. Thus/ even though metals have somewhat
different theoretical, solubilities, they will be removed at very
nearly the same rate in a lime precipitation and sedimentation
treatment system operated for multiple metals removal.
Filtration as part of the technology basis is likewise justified
because this technology removes metals non-preferentially.
The following toxic pollutants are excluded from limitation on
the basis that they are effectively controlled by the limitations
developed for arsenic, copper, and nickel:
119. chromium
122. lead
126. silver
128. zinc
The pollutant parameters proposed for limitation were copper,
lead, and nickel. However, with the addition of a spent
electrolyte discharge, the pollutant arsenic has been substituted
for lead. Analytical data available to the Agency show arsenic
concentrations in spent electrolyte exceeding 100 mg/1. In fact,
arsenic is second to copper in mass generated and discharged by
this subcategory. Arsenic limitations are also added to allow
for central treatment with copper acid plant wastewaters where
arsenic is a regulated pollutant parameter. As discussed above,
lead will be effectively controlled by the limitations developed
for arsenic, copper, and nickel based on optimized treatment for
concomitant multiple metals removal. Therefore, the promulgated
regulation limits three pollutants, copper, nickel, and arsenic.
STORMWATER AND PRECIPITATION ALLOWANCES
The 1975 BAT effluent limitatipns included net precipitation and
catastrophic storm allowances. -Primary copper smelters were
allowed a discharge of process wastewater which is equivalent to
the volume of precipitation that falls within the wastewater
impoundment in excess of that attributable to the 25-year, 24-
hour rainfall event, when such event occurs. In addition,
smelters were allowed to discharge a volume of process wastewater
on a monthly basis that is equal to the net difference between
the rainfall falling on the impoundment and the mean evaporation
from the pond water surface. This monthly discharge was subject
to concentration-based standards, whereas the catastrophic storm
was not subject to any effluent limitations.
The 1975 BAT regulation for refineries not located on-site with
smelters and in areas of net evaporation required discharge
standards similar to the BAT primary copper smelting limitations.
For refineries located in areas of net precipitation, a constant
discharge of refining wastewater was allowed, subject to mass
limitations.
1185
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - X
EPA modified the primary copper smelting and electrolytic
refining storm water and precipitation allowances for BPT in 1980
(refer to Section IX). However, no modifications were made to
BAT in that rule. Wastewater generated at primary copper
smelters is due primarily to slag granulation and anode casting
contact cooling, which can be recycled or reused in other plant
processes. There is no monthly allowance for net precipitation
from cooling impoundments because they require much smaller
surface areas than evaporative impoundments. The Agency is,
however, retaining the catastrophic storm water allowances for
the 25-year, 24-hour storm event for the primary copper smelting
subcategory.
For primary electrolytic copper refining, no stormwater discharge
allowances are allocated at BAT. The revised BAT effluent
limitations, however, allow a discharge of process wastewater
subject to limitations based on sulfide precipitation and
pressure filtration (where appropriate), followed by lime
precipitation, sedimentation, and filtration. This technology is
not as affected by rainfall events because the storm water does
not enter the water processing circuits. Therefore, a storm
allowance is not provided for the primary electrolytic copper
refining subcategory.
EFFLUENT LIMITATIONS
: . . •:. • , • '• ' . - :: ••• -tk,H > .•'•ov:••...!.:•
The treatment performance achievable by application of the BAT
technology is summarized in Table VII-21 of Vol. 1 (page 248).
These treatment performance concentrations (both one day maximum
and monthly average) are multiplied by the BAT normalized
discharge flows summarized in Table X-3 (page 1191) to calculate
the mass of pollutants allowed to be discharged per mass of
product. The results of these calculations in milligrams of
pollutant per kilogram of product represent the BAT effluent
limitations for the primary electrolytic copper refining
subcategory.
'?- ':•;
1186
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - X
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PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - X
TABLE X-2
BAT WASTEWATER DISCHARGE RATES FOR THE
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
Wastewater Stream
Anode and cathode rinse water
Spent electrolyte
Discharge Rate
1/kkg gal/ton
49
Casting contact cooling water 498
0
Casting wet air pollution
control
By-product recovery
0
12
119
0
0
Production
Normalizing
Parameter
Cathode copper
production
Cathode copper
production
Copper cast
Copper cast
By-product
production
1188
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - X
Table X-3
BAT EFFLUENT LIMITATIONS FOR THE
PRIMARY COPPER ELECTROLYTIC REFINING SUBCATEGORY
(a) Casting Contact Cooling
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of copper cast
English Units - Ibs/million Ibs of copper cast
Arsenic* 0.692
Chromium 0.184
Copper* 0.638
Lead 0.139
Nickel* 0.274
Silver 0.144
Zinc 0.508
(b) Anode and Cathode Rinse
Pollutant or
Pollutant Property
Maximum for
Any One Day
0.309
0,075
0.304
0,065
0.184
0,060
0.209
Maximum for
Monthly Average
Metric Units - mg/kg of cathode copper production
English Units - Ibs/million Ibs of cathode copper
production
Arsenic*
Chromium
Copper*
Lead
Nickel*
Silver
Zinc
(c) Spent Electrolyte
Pollutant or
Pollutant Property
Metric Units •
English Units
Arsenic*
Chromium
Copper*
Lead
Nickel*
Silver
Zinc
0.000
0.000
0.000
0.000
0.000
0.000
0.000
Maximum for
Any One Day
0.000
0.000
0.000
0.000
0.000
0.000
0.000
Maximum for
Monthly Average
mg/kg of cathode copper production
- Ibs/millions Ibs of cathode copper
production
0.068
0.018
0.063
0.014
0.027
0.014
0.050
0.031
0.007
0.030
0.006
0.018
0.006
0.021
1189
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCAfEGORY
SECT - X
(d) Casting Wet Air Pollution Control
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of casting production
English Units - Ibs/million Ibs of casting production
Arsenic*
Chromium
Copper*
Lead
Nickel*
Silver
Zinc
(e) By-Product Recovery
Pollutant or
Pollutant Property
0.000
0.000
0.000
0.000
0.000
0.000
0.000
Maximum for
Any One Day
0.000
0.000
0.000
0.000
0.000
0.000
0.000
Maximum for
Monthly Average
Metric Units - mg/kg of product recovered from
electrolytic slimes processing
English Units - Ibs/million Ibs of product recovered
from electrolytic slimes processing
Arsenic*
Chromium
Copper*
Lead
Nickel*
Silver
Zinc
0.000
0.000
0.000
0.000
0.000
0.000
0.000
o.ooo
0.000
0.000
0.000
0.000
o.ooo
o.ooo
1190
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - X
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1191
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PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
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1193
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - X
THIS PAGE INTENTIONALLY LEFT BLANK
1194
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - XI
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
The basis for new source performance standards (NSPS) under
Section 306 of the Act is the best available demonstrated
technology (BDT). New plants have the opportunity to design the
best and most efficient production processes and wastewater
treatment technologies without facing the added costs and
restrictions encountered in retrofitting an existing plant.
Therefore, Congress directed EPA to consider the best
demonstrated process changes, in-plant controls, and end-of-pipe
treatment technologies which reduce pollution to the maximum
extent feasible. This section describes technologies for
treatment of wastewater from new sources, and presents mass
discharge standards of regulated pollutants for NSPS based on the
selected treatment technology.
TECHNICAL APPROACH TO BDT
All of the treatment technology options applicable to a new
source were previously considered for BAT options. Three options
were considered for BDT for the primary electrolytic copper
refining subcategory. The options considered for BDT are"
identical to the BAT options discussed in Section X. The
treatment technologies used for the three BDT options are
OPTION A
OPTION B
O
o
Chemical precipitation and sedimentation
Chemical precipitation and sedimentation
Flow reduction
OPTION C
o
o
o
Sulfide precipitation and pressure filtration (for one
plant only)
Chemical precipitation and sedimentation
Flow reduction
Multimedia filtration
Partial or complete reuse or recycle of wastewater is an
essential part of Options B and C. Reuse or recycle can precede
or follow end-of-pipe treatment.
BDT OPTION SELECTION
EPA is promulgating the best available demonstrated technology
1195
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - XI
for the primary electrolytic copper refining subcategory equal to
the chemical precipitation, sedimentation, and filtration
technology at BAT. Additional flow reduction and more stringent
treatment technologies are not demonstrated or readily
transferable to the primary electrolytic copper refining
subcategory.
REGULATED POLLUTANT PARAMETERS
The Agency has no reason to believe that the pollutants that will
be found in treatable concentrations in processes within new
sources will be any different than with existing sources.
Accordingly, pollutants and pollutant parameters selected for
limitation under NSPS are identical to those selected for BAT
with the addition of the conventional pollutant parameters TSS
and pH.
NEW SOURCE PERFORMANCE STANDARDS
The NSPS discharge flows are the same as the BAT discharge flows
for all processes associated with the primary electrolytic copper
refining subcategory. The discharge flows are listed in Table
XI-1 (.page 1202). The mass of pollutant allowed to be discharged
per mass of product is calculated by multiplying the achievable
treatment concentration (mg/1) by the normalized «-.««•«•—»•—
discharge flow (1/kkg). The BDT achievable
concentrations are identical to the BAT achievable
concentrations and are presented in Table VII-21 of Vol
248). New source performance standards, as determined
above procedure, are shown in Table XI-2 (page 1203).
wastewater
treatment
treatment
, 1 (page
from the
1196
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - XI
TABLE XI-1
NSPS WASTEWATER DISCHARGE RATES FOR THE
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
Wastewater Stream
Anode and cathode rinse water
Spent electrolyte
Discharge Rate
1/kkg gal/ton
0
49
Casting contact cooling water 498
0
Casting wet air pollution
control
By-product recovery
0
12
119
0
0
Production
Normalizing
Parameter
Cathode copper
production
Cathode copper
production
Copper cast
Copper cast
By-product
production
1197
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - XI
TABLE XI-2
NEW SOURCE PERFORMANCE STANDARDS FOR THE
PRIMARY COPPER ELECTROLYTIC REFINING SUBCATEGORY
(a) Casting Contact Cooling
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of copper cast
English Units - Ibs/million Ibs of copper cast
Arsenic*
Chromium
Copper*
Lead
Nickel*
Silver
Zinc
TSS*
pH*
0.692
0.184
0.638
0.139
0.274
0.144
0.508
7.470
0.309
0,075
0.304
0,065
0.184
0,060
0.209
5.976
Within the range of 7.0 to 10.0
at all times
(b) Anode and Cathode Rinse
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of cathode copper production
English Units - Ibs/million Ibs of cathode copper
production
Arsenic*
Chromium
Copper*
Lead
Nickel*
Silver
Zinc
TSS*
pH*
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
Within the range of 7.0 to 10.0
at all times
1198
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - XI
(c) Spent Electrolyte
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Arsenic*
Chromium
Copper*
Lead
Nickel*
Silver
Zinc
TSS*
pH*
Metric Units - mg/kg of cathode copper production
English Units - Ibs/million Ibs of cathode copper
production
0.068
0.018
0.063
0.014
0.027
0.014
0.050
0.735
0.031
0.007
0.030
0.006
0.018
0.006
0.021
0.588
Within the range of 7.0 to 10.0
at all times
(d) Casting Wet Air Pollution Control
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Arsenic*
Chromium
Copper*
Lead
Nickel*
Silver
Zinc
TSS*
pH*
Metric Units - mg/kg of copper casting production
English Units - Ibs/million Ibs of copper casting
production
0.000 0.000
0.000 0.000
0.000 0.000
0.000 0.000
0.000 0.000
0.000 0.000
0.000 0.000
0.000 0.000
Within the range of 7.0 to 10.0
at all times
1199
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - XI
(e) By-Product Recovery
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of product recovered from
electrolytic slimes processing
English Units - Ibs/million Ibs of product recovered
from electrolytic slimes processing
Arsenic* 0.000 0.000
Chromium 0.000 0.000
Copper* 0.000 0.000
Lead 0.000 0-000
Nickel* 0.000 0.000
Silver 0.000 0.000
Zinc 0.000 0.000
TSS* 0.000 0.000
pH* Within the range of 7.0 to 10.0
at all times
1200
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - XII
SECTION XII
PRETREATMENT STANDARDS
INTRODUCTION
Section 307(b) of the Act requires EPA to promulgate pretreatment
standards for existing sources (PSES), which must be achieved
within three years of promulgation. PSES are designed to prevent
the discharge of pollutants which pass through, interfere with,
or are otherwise incompatible with the operation of publicly
owned treatment works (POTW). The Clean Water Act of 1977
requires pretreatment for pollutants, such as toxic Metals, that
limit POTW sludge management alternatives. Section 307(c) of the
Act requires EPA to promulgate pretreatment standards for new
sources (PSNS) at the same time that it promulgates NSPS. New
indirect discharge facilities, like new direct discharge
facilities, have the opportunity to incorporate the best
available demonstrated technologies, including process changes,
in-plant controls, and end-of-pipe treatment technologies, and to
use plant site selection to ensure adequate treatment system
installation. Pretreatment standards are to be technology-based,
analogous to the best available technology for removal of toxic
pollutants.
This section describes the control and treatment technologies for
pretreatment of process wastewaters from existing sources and new
sources in the primary electrolytic copper refining subcategory.
Pretreatment standards for regulated pollutants are presented
based on the selected treatment technology.
TECHNICAL APPROACH TO PRETREATMENT
Before proposing pretreatment standards, the Agency examines
whether the pollutants discharged by the industry pass through
the POTW or interfere with the POTW operations or its chosen
sludge disposal practices. In determining whether pollutants
pass through a well-operated POTW, achieving secondary treatment,
the Agency compares the percentage of a pollutant removed by POTW
with the percentage removed by direct dischargers applying the
best available technology economically achievable. A pollutant
is deemed to pass through the POTW when the average percentage
removed nationwide 'by well-operated POTW meeting secondary
treatment requirements, is less than the percentage removed by
direct dischargers complying with BAT effluent limitations
guidelines for that pollutant (see 46 FR 9415-16, January 28,
1981). This definition of pass through satisfies two competing
objectives set by Congress: (1) that standards for indirect
dischargers be equivalent to standards for direct dischargers,
while at the same time, (2) that the treatment capability and
performance of the POTW be recognized and taken into account in
regulating the discharge of pollutants from indirect dischargers.
1201
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGdRY
SECT - XII
The Agency compares percentage removal rather than the mass or
concentration of pollutants discharged because the latter would
not take into account the mass of pollutants discharged to the
POTW from non-industrial sources nor ..jtlje dilution of the
pollutants in the POTW effluent to lower"concentrations due to
the addition of large amounts of non-industrial wastewater.
PRETREATMENT STANDARDS FOR EXISTING SOURCES
There are no indirect discharging primary electrolytic copper
refining plants in the United States. Consequently, the Agency
has elected to not promulgate pretreatment standards for existing
sources.
PRETREATMENT STANDARDS FOR NEW SOURCES
Options for pretreatment of wastewaters are based on increasing
the effectiveness of end-of-pipe treatment technologies. All in-
plant changes and applicable end-of-pipe treatment processes have
been discussed previously in Sections X and XI. The treatment
options for PSNS, therefore, are the same as the options
discussed in Section X.
A description of each option is presented in Section X, while a
more detailed discussion, including pollutants controlled by each
treatment process and expected effluent quality for each option,
is presented in Section VII of the General Development Document.
Treatment technologies used for the PSNS options for the primary
electrolytic copper refining subcategory are:
Option A
o Chemical precipitation and sedimentation
Option B
o Chemical precipitation and sedimentation
o Flow reduction
Option C .
o Chemical precipitation and sedimentation
o Flow reduction .
o Multimedia filtration
PSNS OPTION SELECTION
EPA has selected chemical precipitation, sedimentation, in-
process flow reduction, and filtration (Option C) as the
technology basis for PSNS for the primary electrolytic copper
refining subcafcegory. As with NSPS, EPA believes that the
addition of filtration is feasible for new indirect dischargers.
No additional flow reduction is required for PSNS because the
If:1,!'
1202
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - XII
only other applicable flow reduction technology, reverse osmosis,
is not demonstrated or clearly transferable for nonferrous metals
manufacturing wastewater.
REGULATED POLLUTANT PARAMETERS
With the exception of conventional pollutant parameters TSS and
pH, the toxic pollutants and pollutant parameters selected for
limitation, in accordance with the rationale of Sections VI and
X, are identical to those selected for limitation for BAT. PSNS
prevents the pass-through of arsenic, copper and nickel.
PRETREATMENT STANDARDS
The PSNS discharge flows for the primary electrolytic copper
refining subcategory are the same as the BAT discharge flows for
all processes. The discharge flows are listed in Table XII-1
(page 1204). The mass of pollutant allowed to be discharged per
mass of product is calculated by multiplying the PSNS achievable
treatment concentration (mg/1) by the normalized wastewater
discharge flow (1/kkg). The PSNS achievable treatment
concentrations are identical to the BAT achievable treatment
concentrations and are presented in Table VII-21 of Vol. 1 (page
248). Pretreatment standards for new sources, as determined from
the above procedure, are shown in Table XII-2 (page 1205).
Mass-based standards are promulgated for the primary electrolytic
copper refining subcategory to ensure that the standards are
achieved by means of pollutant removal rather than by dilution.
They are particularly important since the standards are based
upon flow reduction. Pollutant limitations associated with flow
reduction cannot be measured any other way but as a reduction of
mass discharged.
1203
-------
;,, . i.\ . >' <•' .'iff •', 'V* '
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - XI I'
TABLE XII-1
PSNS WASTEWATER DISCHARGE RATES FOR THE
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
Wastewater Stream
Anode and cathode rinse water
Spent electrolyte
Discharge Rate
1/kkg gal/ton
49
Casting contact cooling water 498
0
Casting wet air pollution
control
By-product recovery
0
12
119
0
Production
Normalizing
Parameter
Cathode copper
production
Cathode copper
production
Copper cast
i !• , : ' ,',, "|' '.'i' ' ' •• |,
Copper cast
By-product
production
1204
i, kli; :•... ,,'fcli •
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - XII
TABLE XII-2
PRETREATMENT STANDARDS FOR NEW SOURCES FOR THE
PRIMARY COPPER ELECTROLYTIC REFINING SUBCATEGORY
(a) Casting Contact Cooling
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Arsenic*
Chromium
Copper*
Lead
Nickel*
Silver
Zinc
Metric Units - mg/kg of copper cast
English Units - Ibs/million Ibs of copper cast
0.692
0.184
0.638
0.139
0.274
0.144
0.508
0.309
0,075
0.304
0,065
0.184
0,060
0.209
(b) Anode and Cathode Rinse
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of cathode copper production
English Units - Ibs/million Ibs of cathode copper
production
Arsenic*
Chromium
Copper*
Lead
Nickel*
Silver
Zinc
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
1205
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY
SECT - XII
(c) Spent Electrolyte
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Arsenic*
Chromium
Copper*
Lead
Nickel*
Silver
Zinc
Metric Units - mg/kg of cathode copper production
English Units - Ibs/million Ibs of cathode copper
production
0.068
0.018
0.063
0.014
0.027
0.014
0.050
0.031
0.007
0.030
0.006
0.018
0.006
0.021
(d) Casting Wet Air Pollution Control
Pollutant or
Pollutant Property
Metric Units •
English Units
Arsenic*
Chromium
Copper*
Lead
Nickel*
Silver
Zinc
(e) By-Product Recovery
Pollutant or
Pollutant Property
Metric Units -
English Units
Arsenic*
Chromium
Copper*
Lead
Nickel*
Silver
Zinc
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg of casting production
- Ibs/million Ibs of casting production
0.000
0.000
0.000
0.000
0.000
0.000
0.000
Maximum for
Any One Day
0.000
o.ooo
0.000
0.000
0.000
0.000
0.000
Maximum for
Monthly Average
mg/kg of product recovered from
electrolytic slimes processing
- Ibs/million Ibs of product recovered
from electrolytic slimes processing
0.000
0.000
0.000
o.ooo
0.000
0.000
0.000
0.000
0.000
0.000
o.ooo
0.000
0.000
0.000
1206
• *! v!/. :;
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - XIII
SECTION XIII
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY
EPA is not promulgating best conventional pollutant control
technology(BCT) for the primary electrolytic copper refining
subcategory at this time.
1207
-------
PRIMARY ELECTROLYTIC COPPER REFINING SUBCATEGORY SECT - XIII
THIS PAGE INTENTIONALLY LEFT BLANK
1208
-------
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
DEVELOPMENT DOCUMENT SUPPLEMENT
for the
Secondary Copper Subcategory
William K. Reilly
Administrator
Rebecca Hanmer
Acting Assistant Administrator for Water
Martha Prothro, Director
Office of Water Regulations and Standard
Thomas P. O'Farrell, Director
Industrial Technology Division
Ernst P. Hall, P.E., Chief
Metals Industry Branch
and
Technical Project Officer
May 1989
U.S. Environmental Protection Agency
Office of Water
Office of Water Regulations and Standards
Industrial Technology Division
Washington/ D. C. 20460
1209
-------
1210
•I',1: •' 1FW!
-------
SECONDARY COPPER SUBCATEGORY
Section
TABLE OF CONTENTS
SUMMARY
Page
1219
II
CONCLUSIONS
1223
III
SUBCATEGORY PROFILE
Description of Secondary Copper Production
Raw Materials
Pretreatment of Scrap
Stripping
Briquetting
Size Reduction
Crushing
Residue Concentration
Residue Pelletizing and Roll Briquetting
Drying
Burning
Sweating
Smelting of Low-Grade Scrap and Residues
Melting, Refining, and Alloying Intermediate-
Grade Copper-Based Scrap
Refining High-Grade Copper Scrap
Fire Refining
Skimming
Electrolytic Refining
Postelectrolytic Melting and Refining
1225
1225
1225
1226
1226
1226
1226
1227
1227
1227
1227
1228
1228
1229
1230
1232
1232
1232
1233
1233
1211
-------
SECONDARY COPPER SUBCATEGORY
Section
III
TABLE OF CONTENTS (Continued)
CASTING
Brass and Bronze Ingot
Black and Blister Copper
Anodes
Refined Copper
Copper Shot
Process Wastewater Sources
Other Wastewater Sources
Age, Production, and Process Profile
Paqe
1234
1234
1234
1235
1235
1235
1236
1236
1236
IV
VI
SUBCATEGORIZATION 1245
' . :ii;:; , . • .. ' , '.;!' : •!••
Factors Considered in Subcategorization 1245
Factors Considered in Subdividing the Secondary 1245
Copper Subcategory
Other Factors 1246
Production Normalizing Parameters 1246
WATER USE AND WASTEWATER CHARACTERISTICS 1249
Wastewater Sources, Discharge Rates, and 1249
Characteristics
Secondary Copper Wastewater Sources and 1252
Characteristics
Residue Concentration 1252
Slag Granulation 1253
Reverberatory and Rotary Furnace Wet Air 125.3
Pollution Control
Spent Electrolyte 1253
Scrap Anode Rinsing 1254
Casting Contact Cooling 1254
Casting Wet Air Pollution Control 1254
SELECTION OF POLLUTANT PARAMETERS 1291
Conventional and Nonconventional Pollutant 1291
Parameters
Conventional Pollutant Parameters Selected 1292
1212
-------
SECONDARY COPPER SUBCATEGORY
Section
VI
VII
VIII
IX
TABLE OF CONTENTS (Continued)
TOXIC POLLUTANTS
Toxic Pollutants Never Detected
Toxic Pollutants Never Found Above Their
Analytical Quantification Concentration
Toxic Pollutants Present Below Concentrations
Achievable by Treatment
Toxic Pollutants Detected in a Small Number
of Sources
Toxic Pollutants Selected for Further
Consideration for Limitation
CONTROL AND TREATMENT TECHNOLOGIES
Technical Basis of Promulgated BPT
Current Control and Treatment Practices
Residue Concentration
Slag Granulation
Reverberatory and Rotary Furnace Wet Air
Pollution Control
Scrap Anode Rinsing
Spent Electrolyte
Casting Contact Cooling
Casting Wet Air Pollution Control
Control and Treatment Options Considered
Option A
Option G
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS
Treatment Options Costed for Existing Sources
Costing Methodology
Nonwater Quality Aspects
Energy Requirements
Solid Waste
Air Pollution
Best Practicable Control Technology Currently
Available
1292
1292
1293
1294
1298
1307
1307
1308
1309
1310
1310
1310
1311
1312
1312
1313
1313
1315
1315
1315
1316
1316
1316
1317
1319
1213
-------
SECONDARY COPPER SUBCATEGORY
Section
X
XI
XII
XIII
TABLE OF CONTENTS (Continued)
BEST AVAILABLE TECHNOLOGY ECONOMICALLY
ACHIEVABLE
NEW SOURCE PERFORMANCE STANDARDS
PRETREATMENT STANDARDS
Technical Approach to Pretreatment
Pretreatment Standards for Existing Sources
Option A
Option G
Industry Cost and Pollutant Removal Estimates
Pollutant Removal Estimates
Compliance Costs
PSES Option Selection
PSNS Option Selection
Wastewater Discharge Rates
Residue Concentration
Slag Granulation
Reverberatory and Rotary Furnace Wet Air
Pollution Control
Spent Electrolyte
Scrap Anode Rinsing
Casting Contact Cooling
Casting Wet Air Pollution Control
Stormwater and Precipitation Allowances
Pretreatment Standards for Existing and New
Sources
BEST CONVENTIONAL CONTROL TECHNOLOGY
1323
1325
1325
1326
1326
1327
1327
1327
1328
1328
1328
1328
1329
1329
1329
1329
1330
1330
1330
1330
1331
1335
1214
-------
SECONDARY COPPER SUBCATEGORY
LIST OF TABLES
Number Page
III-l Initial Operating Year (Range) Summary of Plants 1237
in the Secondary Copper Subcategory by Discharge
Type .
III-2 Production Ranges for Processing Plants of the 1238
Secondary Copper Subcategory
III-3 Production Processes Utilized by the Secondary 1239
Copper Subcategory
IV-1 Building Blocks and Production Normalizing 1247
Parameters for the Secondary Copper Subcategory
V-l Toxic Metals Believed to be Present in Secondary ±256
, 'Copper Wastewater, DCP Data
V-2 Water Use and Discharge Rates for Residue 1257
Concentration
V-3 Water Use and Discharge Rates for Slag 1258
Granulation
V-4 Water Use and Discharge Rates for Reverberatory 1259
and Rotary Furnace Wet Air Pollution Control
V-5 Electrolyte Use and Discharge Rates 1260
V-6 Water Use and Discharge Rates for Scrap Anode 1261
Rinsing
V-7 Water Use and Discharge Rates for Casting 1262
Contact Cooling
y-8 Water Use and Discharge Rates for Casting 1263
Wet Air Pollution Control
V-9 Secondary Copper Sampling Data Residue 1264
Concentration Raw Wastewater
V-10 Secondary Copper Sampling Data Wet Air 1268
Pollution Control Raw Wastewater
V-ll Secondary Copper Sampling Data Spent 1270
Electrolyte Raw Wastewater
V-12 Secondary Copper Sampling Data Casting 1272
Contact Cooling Raw Wastewater
V-13 Secondary Copper Sampling Data Miscellaneous 1274
Raw Wastewater.
1215
-------
SECONDARY COPPER SUBCATEGORY
Number
V-14
V-15
V-16
V-17
VI-1
VI-2
VI-3
VIII-1
XII-1
LIST OF TABLES (Continued)
Secondary Copper Sampling Data Treatment Plant
Samples - Plant A
Secondary Copper Sampling Data Treatment Plant
Samples - Plant B
Secondary Copper Sampling Treatment Plant
Samples - Plant C
' •' •• • , .' •..../. :VX»:^T*&V;^:':: .;"
Secondary Copper Sampling Data Treatment Plant
Samples - Plant E
Frequency of Occurrence or" Toxic Pollutants
Secondary Copper Raw Wastewater
Toxic Pollutants Never Detected
Toxic Pollutants Detected in Only a Small
Number of Sources
Pollutant Removal Estimates for Secondary Copper
Indirect Dischargers
Page
1279
1280
1281
1283
1300
1304
1316
1318
1332
1216
-------
SECONDARY COPPER SUBCATEGORY
SECONDARY COPPER SUBCATEGORY
LIST OF FIGURES
Number , Page
III-l Secondary Copper Production Process Scrap 1240
Pretreatment
III-2 Secondary Copper Production Process Smelting 1241
III-3 Secondary Copper Production Process Electrolytic 1242
Refining
III-4 Geographic Locations of the Secondary Copper 1243
Subcategory
V-l Sampling Sites at Secondary Copper Plant A 1285
V-2 Sampling Sites at Secondary Copper Plant B 1286
V-3 Sampling Sites at Secondary Copper Plant C 1287
V-4 Sampling Sites at Secondary Copper Plant D 1288
V-5 Sampling Sites at Secondary Copper Plant E 1289
XII-1 PSES Treatment Scheme Option A 1333
Secondary Copper Subcategory
XII-2 PSES Treatment Scheme Option G 1334
Secondary Copper Subcategory
1217
-------
SECONDARY COPPER SUBCATEGORY
THIS PAGE INTENTIONALLY LEFT BLANK
1218
-------
SECONDARY COPPER SUBCATEGORY SECT. - I
SECTION I
SUMMARY
On February 27, 1975, EPA promulgated technology-based effluent
limitations for the secondary copper subcategory of the
Nonferrous Metals Manufacturing Point Source Category. Effluent
limitations were established based on the best practicable
control technology currently available (BPT) and best available
technology economically achievable (BAT). Under these
limitations, the discharge of process wastewater pollutants into
navigable waters was prohibited with the following exceptions.
For the BPT effluent limitations, discharge without limitation
was allowed for a volume of process wastewater equivalent to the
volume of stormwater in excess of that attributable to a 10-year,
24-hour rainfall event falling on a wastewater cooling
impoundment. The BAT effluent limitations also contain the
stormwater exemption except the storm is a 25-year, 24-hour
rainfall event. For both the BPT and BAT effluent limitations,
discharge, subject to concentration-based limitations, was
allowed for a volume of process wastewater equal to the net
monthly precipitation on the wastewater cooling impoundment.
On December 15, 1976, (41 FR 54850) EPA promulgated pretreatment
standards for existing sources (PSES) for the secondary copper
subcategory. These standards allowed a continuous discharge of
process waste- water to publicly owned treatment works (POTW)
subject to concentration-based standards for oil and grease,
copper, and cadmium. These PSES were based on lime precipitation
and sedimentation treatment technology.
In the March 1984 rulemaking (49 FR 8742), EPA promulgated
modifications to BAT, and PSES and promulgated NSPS and PSNS for
the secondary copper subcategory pursuant to the provisions of
Sections 301, 304, 306, and 307 of the Clean Water Act as
amended. This supplement provides a compilation and analysis of
the background material used to develop these effluent
limitations and standards.
The secondary copper subcategory is comprised of 31 plants. Of
the 31 plants, five discharge directly to rivers, lakes, or
streams; six discharge to publicly owned treatment works (POTW);
and 20 achieve zero discharge of process wastewater pollutants.
EPA first studied the secondary copper subcategory to determine
whether differences in raw materialsr final products,
manufacturing processes, equipment, age and size of plants, and
water usage required the development of separate effluent
limitations and standards for different segments of the
subcategory. This involved a detailed analysis of wastewater
discharge and treated effluent characteristics, including: (1)
the sources and volume of water used, the processes used, and the
sources of pollutants and wastewaters in the plant; and (2) the
1219 .
-------
SECONDARY COPPER SUBCATEGORY
SECT. - I
constituents of waste waters, including toxic pollutants.
Several distinct control and treatment technologies (both in-
plant and end-of-pipe) applicable to the secondary copper
subcategory were identified. The Agency analyzed both historical
and newly generated data on the performance of these
technologies. EPA also studied various flow reduction and
complete recycle techniques reported in the data collection
portfolios (dcp) and plant visits.
Based on consideration of the above factors, EPA identified
various control and treatment technologies which formed the basis
for BAT and selected control and treatment appropriate for each
set of standards and limitations. The mass limitations and
standards for BPT, BAT, NSPS, PSES, and PSNS are presented in
Section II.
For BAT, the Agency is eliminating the discharge allowance for
net monthly precipitation on cooling impoundments. The BAT
effluent limitations will still allow a discharge for stormwater
resulting from the 25-year, 24-hour rainfall event. EPA is
eliminating the net precipitation discharge for BAT because these
limitations are based on the use of cooling ponds rather than
evaporative impoundments. Cooling impoundments require much
smaller surface areas than the evaporative impoundments for which
the net precipitation discharge was allowed.
;„,; ', ..,'., •': , • ,; »••' '»,;' -jfj, ,;' » ,,;!, , ''; ' ' ,;,,- • , ;'. 'l;J "!iv;!i,'
Costs for cooling towers were developed for BAT in the 1975
rulemaking when a plant had insufficient existing cooling
impoundment capacity or cooling impoundments were not feasible
due to space limitations. EPA believes that secondary copper
plants can accommodate the small volume of water resulting from
net precipitation on cooling impoundments. There is no cost
associated with the promulgated BAT effluent limitations.
For NSPS, EPA is promulgating a standard prohibiting the
discharge of process wastewater pollutants to waters of the
United States. In selecting NSPS, EPA recognizes that new plants
have the opportunity to implement the best and most efficient
manufacturing processes and treatment technology. EPA believes
that new sources can be constructed with cooling towers
rather than impoundments and clarification devices rather than
settling ponds. The Agency is thus eliminating the allowance for
catastrophic stormwater discharge provided at BAT.
For PSES, EPA is promulgating a standard prohibiting the
introduction of process wastewater pollutants into POTW. The
technology basis for the promulgated PSES is lime precipitation
and sedimentation with cooling towers and holding tanks to
achieve zero discharge of process wastewaterpollutants. The
PSES will allow a discharge resulting from the 25-year, 24-hour
rainfall event with no net precipitation allowance. EPA believes
that the costs associated with installation and operation of
cooling towers and holding tanks for indirect dischargers will be
insignificant. In addition, costs for cooling towers and holding
1220
'.:,:,, «:;! i. J ;:.
-------
SECONDARY COPPER SUBCATEGORY SECT. - I
tanks were considered during the 1976 PSES rulemaking. At that
time EPA concluded that the additional cost was not significant.
For PSNS, EPA is also promulgating a standard prohibiting the
introduction of process wastewater pollutants into POTW. There is
no allowance for discharge from a catasthrophic rainfall
event. The Agency believes that all of the factors set forth
above for as a basis for PSES apply. In addition, a new source
has the option of selecting new technology and locations which
are conducive to the achievement of the standard without the need
for a catastrophic rainfall allowance.
1221
-------
SECONDARY COPPER SUBCATEGORY
SECT. - I
THIS PAGE INTENTIONALLY LEFT BLANK
' **•;•!<;
) , l''1' „ !4li „„
1222
-------
SECONDARY COPPER SUBCATEGORY"
SECT. - II
SECTION II
CONCLUSIONS
The secondary copper subcategory has been divided into seven
subdivisions for the purpose of effluent limitations and
standards. These subdivisions are:
(a) Residue concentration,
(b) Slag granulation,
(c) Reyerberatory and rotary furnace wet air pollution
control,
(d) Spent electrolyte,
(e) Scrap anode rinsing,
(f) Casting contact cooling, and
(g) Casting wet air pollution control.
EPA promulgated BPT effluent limitations for the secondary
copper subcategory on February 27, 1975 (46 FR 8513) as Subpart F
of 40 CFR Part 421. Promulgated BPT for the secondary copper
subcategory is no discharge of all process wastewater
pollutants with two exceptions. Facilities in the secondary
copper subcategory may discharge without restriction the volume
of water falling within a cooling impoundment in excess of the
10-year, 24-hour precipitation event, when a storm of at least
that magnitude occurs. Further, they can discharge, subject to
concentration-based effluent limitations, a volume of water equal
to the difference between monthly precipitation and evaporation
on the cooling impoundment in that month. Process wastewater
discharged pursuant to the net precipitation allowance must
comply with the following concentration-based effluent
limitations: . .
BPT EFFLUENT LIMITATIONS
Pollutant or
pollutant property
Maximum for
any one day
Average of Daily Values
for 30 Consecutive
days shall not exceed
Total Suspended Solids
Copper
Zinc
Oil and Grease
pH
50
0.5
10
20
Metric Units (mg/1)
English Units (ppm)
25
0.25
5
10
Within the range of 6.0 to 9.0
1223
-------
SECONDARY COPPER SUBCATEGORY
if!,;!, '|.^Ittjli.',^'.''.'""' •'',"'.'ff,
SECT. - II
r'"„;«, • "!(lr
-------
SECONDARY COPPER SUBCATEGORY SECT. - III
SECTION III
SUBCATEGORY PROFILE
This section of the secondary copper Subcategory supplement
profiles the secondary copper subcategory and describes the raw
materials and processes used in smelting and refining secondary
copper and copper-base alloys, and presents a profile of the
secondary copper subcategory. For a discussion of the purpose,
authority, and methodology for this study and a general
description of the nonferrous metals manufacturing category,
refer to Section III of Vol. I.
DESCRIPTION OF SECONDARY COPPER PRODUCTION
There are a variety of manufacturing processes involved in the
production of secondary copper or copper-base alloys. The raw
materials and desired end product play an important role in
determining the manufacturing process of a particular plant. The
principal steps involved in the production of secondary copper
and copper-base alloys are tabulated below. Each of these
production steps, along with raw materials, is discussed in
detail below.
1. Pretreatment of scrap;
2. Smelting of low-grade scrap and residues;
3. Melting, refining, and alloying intermediate-grade
copper-base scrap and residues;
4. Refining high-grade copper scrap; and
5. Casting.
RAW MATERIALS
Discarded consumer products, industrial copper-bearing scrap
metal (solids) and melting wastes (slags and residues) are the
basic raw materials used in secondary copper facilities. About
two-thirds of the recycled copper tonnage is in the form of brass
and bronze, with the remaining one-third in the form of copper.
Additional copper values are recovered from copper-bearing
wastes, such as skimmings, grindings, ashes, irony brass and
copper residues and slags. The United States Department of
Interior has estimated that 60 percent of all copper-base metal
is reclaimed as old metal and comes back into'production again.
The cycle between its original use and recovery is approximately
40 years.
The segregation and classification of scrap metal are important
steps in the production of alloyed ingots or pure copper.
Segregation of copper-base scrap is done in a preliminary way by
1225
-------
SECONDARY COPPER SUBCATEGORY
SECT. - III
the scrap dealer (old scrap) or by the fabrication plant as the
scrap is generated (new scrap). The copper-bearing scrap sold to
the smelters contains metallic and nonmetallic impurities.
Included among these are lead, zinc, tin, antimony, iron,
manganese, nickel, chromium, precious metals, and organic-base
constituents, such as insulation (plastic and other types), oil,
grease, paint, rubber, and antifreeze.
PRETREATMENT OF SCRAP
Before scrap, in the form of solids (metal) and residues, is used
by the smelter, various types of pretreatment are performed. The
materials are usually presorted by secondary material dealers or
shipped directly by foundries and metal shops; however,
additional sorting is often done by the smelter to attain tighter
control of the alloy constituents and the copper content. The
steps used in the pretreatment of scrap depend on the type of
scrap being processed. These pretreatment steps are shown
schematically in Figure III-l (page 1240) and are discussed below
in the context of the type of scrap being processed.
Stripping
Insulation and lead sheathing are removed from electrical
conductors, such as cables, by specially designed stripping
machines or by hand. Water is not used or generated during
stripping and atmospheric emissions are not generated by this
process. The lead is sold, reclaimed, or used in producing
copper-base alloys. The organic solid wastes are reclaimed or
disposed by burning or other solid waste disposal methods.
Briguetting
Compressing bulky scrap, such as borings, turnings, tubing, thin
plate, wire screen, and wire, into small bales compacts the
scrap, allows for less storage area, and makes for easier
handling and faster melting. The problem of oxidation of the
metal is also diminished. Briquetting is carried out by
compacting the scrap with hydraulic presses. Water is not used
of generated during briquetting and atmospheric emissions are not
generated by this process.
Size Reduction
Size reduction is used for all types, of scrap materials. Large
thin pieces of scrap metal are reduced in size by pneumatic
cutters, electric shears, and manual shearing. Tramp iron
liberated from the scrap by size reduction is removed from the
shredded product magnetically. The iron-free products are
usually briquetted for easy handling. Shredding is also used in
the separation of insulation on copper wire. The insulation is
broken loose from metal by shearing action and removed from the
metal by air classification.
When treating bulky metal items, the process produces small
1226
-------
SECONDARY COPPER SUBCATEGORY SECT. - III
quantities of atmospheric emissions, consisting of dusts of
approximately the same composition as the metal. Collection of
the dust via dry cyclones or baghouses permits recovery of the
metal value. -
Crushing
Previously dried, brittle, spongy turnings, borings, and long
chips are processed in hammer mills or ball mills. After
crushing, tramp iron is removed magnetically. Dust particles
consisting of dirt, organic compounds, and finely divided metal
are generally collected using dry cyclones.
Residue Concentration
Some secondary copper plants concentrate the copper values in
slags and other residues, such as drosses, skimmings, spills, and
sweepings, before charging the concentrates into rotary or
reverberatory furnaces. Slags may be crushed, screened through a
coarse screen to remove trash and lumps of copper, pulverized
with a ball mill, and concentrated on a table classifier. The
concentrate usually contains 70 to 90 percent copper or copper
alloy, and the gangue, or depleted slag, contains 4 or 5 percent
copper alloy. The depleted slag is usually retained at the plant
site as landfill. Lower grade residues are wet milled and
concentrated by gravity and table classifiers.
The concentration of residues is usually done by wet grinding and
classifying. The water associated with this processing contains
some milling fines as suspended solids and dissolved solids from
the soluble components of the residue and metals. To limit water
consumption, the water used for milling is recycled from holding
tanks or ponds.
Residue Pelletizing and Roll Briquetting
Most small brass and bronze ingot makers (facilities) do not
process residues, but actually sell their copper bearing residues
to the larger refineries for processing to recover the copper
values. Some of the large refineries charge the residues into
their cupola or blast furnaces for the recovery of the copper
content in the slag or residues.
The fine portions of the copper rich slags or other residues are
palletized by adding water and a binder, if necessary, and
rolling the material in a disk or drum pelletizer until most of
the fines are in the form of small marble size pellets. Although
water is used in pelletizing, it is completely consumed during
processing and wastewater is not discharged.
Drying
Borings, turnings, and chips from machining are covered with
cutting fluids, oils, and greases. These contaminants are
1227
-------
SECONDARY COPPER SUBCATEGORY
SECT. - III
removed in the drying process. The scrap is generally heated in
a rotary kiln to vaporize and burn the contaminants.
Drying results in the evolution of considerable quantities of
hydrocarbons, depending on the amount present in the scrap. The
oils, greases, and cutting fluids contain sulfonated and
chlorinated hydrocarbons. Therefore, gaseous emissions evolve
and are composed of the oxidation products that include sulfur
oxides, hydrogen chloride, hydrocarbons, and other combustion
products.
The atmospheric emissions are controlled by burning the vaporized
fumes in afterburners, which oxidize the hydrocarbons to carbon
dioxide and water. Inorganic particulates settle out in the
afterburner section. Sulfur oxides and chloride emissions are
usually uncontrolled. As such, water is not used or generated
during drying.
Burning
Scrap may be covered with paper and organic polymer insulation,
such as rubber, polyethylene, polypropylene, or polyvinyl
chloride. These materials are usually not removed by stripping.
They are most effectively removed from the scrap by the burning
process using furnaces, such as rotary kilns.
i '• ;• • v" •• '••. • • '•!•' , , • f :; ' ' "
The burning process generates combustion products such as carbon
dioxide and water. Emissions from the burning of polyvinyl
chloride may contain such gases as phthalic anhydride and
hydrogen chloride. Pluorocarbon insulation releases hydrogen
fluoride when burned. Many of these gases are highly toxic and
corrosive. These gases may be controlled through the use of wet
scrubbers, however, no plants in this subcategory report the use
of wet scrubbers for controlling burning furnace emissions.
Sweating
Scrap containing low melting point materials, such as radiators,
journal bearings, and lead sheathed cables, can be sweated to
remove babbitt, lead, and solder as valuable by-products, which
would otherwise contaminate a melt. Scrap may be added directly
to a melt without sweating if the melt requires substantial
amounts of the sweatable constituents. Sweating is done by
heating in an oil- or a gas-fired muffle type furnace with a
sloped hearth, so that the charge can be kept on the high side
and away from the fluid, low melting point components. The
molten metal is collected in pots, and the sweated scrap is raked
until most of the low melting metals have been freed. The
process can be a continuous or a batch operation. Sweating is
also done in pots by dumping the scrap into molten alloy, which
absorbs the sweated babbitt, lead, or solder. Rotary kilns have
been used on small size scrap. The tumbling action aids in
removing the molten metals. For items which are difficult to
sweat, a reverberatory furnace equipped with a shaking grate is
used. Continuous sweating is done in tunnel furnaces that have
1228
-------
SECONDARY COPPER SUBCATEGORY SECT. - III
provisions for solder, lead, and babbitt recovery.
Atmospheric emissions consist of fumes and combustion products
originating from antifreeze residues, soldering fluxes,
rubber hose remains, and the fuel used to heat the sweat furnace.
None of the plants in this subeategory use wet scrubbing for
sweating furnaces.
SMELTING OP LOW-GRADE SCRAP AND RESIDUES
Drosses, slags, skimmings, and low-grade copper and brass scrap
are processed in blast furnaces or cupola furnaces. These low-
grade, copper-bearing materials are melted to separate the copper
values from slags or residues and to produce molten metal that
can be processed further immediately after recovery, or after
being cast into ingots or shot for later use or sale. The
smelting process is shown in Figure III-2 (page 1241)
The product of cupola or blast furnace melting is known as black
copper or cupola melt. It generally consists of a mixture of
copper and variable amounts of most of the common alloying
elements such as tin, lead, zinc, nickel, iron, phosphorus, and
to a lesser extent arsenic, antimony, aluminum, beryllium,
chromium, manganese, silicon, and precious metals. A matte is
also formed when sufficient sulfur is present to form a complex
cqpper-iron-nickel-lead sulfide. Other specialty furnaces, such
as crucible or induction furnaces, are sometimes used for special
alloy production or precious metal recovery.
The charge to the blast or cupola furnace may be in the form of
irony brass and copper, fine insulated wire, motor armatures,
foundry sweepings, slags, drosses, and many other low-grade;
materials. Fine materials are pretreated by pelletizing or
briquetting to reduce losses in the stack gas. Limestone and
mill scale are added as fluxes to produce iron silicate slags
(depleted slag). Low sulfur coke is used in cupolas or blast
furnaces to reduce matte (copper sulfide) formation.
During the cupola and blast furnace processes, the metallic
constituents melt, while the limestone, aluminum, silicon and
iron oxides , fuse in the smelting zone and form a molten slag,
which mixes with the metals. The copper compounds are reduced by
the coke. The molten materials flow downward through the coke
bed and are collected in a crucible below. After a period of
quiescence, the metal and slag form separate layers and are
tapped. The slag, containing less than one percent copper value,
is granulated with a high pressure water spray or by directing it
into a quench pit while still in its molten state. The
granulated slag is then sent to a slag pile.
Cupola and blast furnace operations produce large quantities of
particulate matter from dusty charge materials, such as fine
slags, fine fluxes, and coke ash, as well as metal oxide fumes.
These particulates and fumes are controlled through the use of
air pollution control devices. Dry air pollution control devices
1229
-------
SECONDARY COPPER SUBCATEGORY
SECT. - III
1 ;•• "if;L,.."': -•'. '•>:,:
such as baghouse filters and cyclones are currently
contain these particulates and fumes.
used to
The process of conversion in the secondary copper subcategory can
be done in furnaces called converters or in other types of
furnaces in which molten metal is contained. The operation is
derived from primary copper operation in which the sulfide matte
is converted to an oxide-rich copper melt by oxidation with air
or oxygen-enriched air. In secondary copper operations, however,
only small amounts of sulfide are present in the black copper,
but it is heavily contaminated with alloy metals, such as zinc,
lead, nickel, iron, manganese, aluminum, tin, antimony, silicon,
silver, or other metals and nonmetals contained in the scrap or
residues. Since the sulfur content is low in secondary black
copper, fuel is required for converting operations; unlike
primary copper where the sulfur serves as the fuel.
With the use of converters or converter-oriented operations, the
copper value in mixed alloys is reclaimed by oxidizing most of
the alloying elements and removing the oxides as a slag. Molten
metal is sometimes oxidized in a converter by blowing air through
ports in the bottom of the furnace until most of the oxidizable
alloying elements and some of the copper are oxidized (blister
copper). More commonly, the molten metal in reverberatory or
rotary furnaces is oxidized by inserting water cooled lances into
the bath and blowing the bath with air or oxygen under a silicate
slag cover until the alloy impurities are reduced to the desired
level. The slag containing the alloy metal oxides and some
copper is removed, and the oxygen in the remaining copper is
reduced with charcoal, green wood, natural gas or other reducing
agent inserted into the bath. Depending on the extent of
reduction, various grades of refined copper are produced.
Generally, after conversion, a blister copper is produced that is
subsequently refined in the same plant or sold or transported to
other plants.
''' '•'', .1 • -'' ' ' '' '",• • ,' J , .' ''
Air emissions from cpnverter furnaces are currently contained
through the use of dry air pollution control devices. The
control of reverberatory and rotary furnace air emission will be
discussed later in this section.
MELTING,
SCRAP
REPINING, AND ALLOYING INTERMEDIATE-GRADE COPPER-BASED
As shown in Figure III-2 (page 1241), copper-based scrap metals,
intermediate-grade copper metal scrap, black and blister copper,
and residues with known origin or composition are melted,
refined, and alloyed, if necessary, to produce either brass or
bronze ingots of specific composition. These same materials are
refined further to produce fire refined copper suited for end use
or for casting anodes for electrolytic refining. Direct fired
reverberatory and rotary furnaces are used to produce the product
metals, brass and bronze, and fire refined copper.
In the production of brass and bronze ingots, the extent of
1230
-------
SECONDARY COPPER SUBCATEGORY SECT. -Ill
refining is usually small, if the scrap is well sorted. If the
residues are of known origin (usually a toll recovery operation),
refining is also kept to a minimum. In the production of copper,
the extent of refining is greater. The chemical principles of
refining are applicable to both brass and bronze ingot
manufacture and the preparation of fire refined copper.
In the refining step, impurities and other constituents of the
charge, present in excess of specifications, are oxidized.
Elements, such as iron, manganese, silicon, and aluminum, are
normally considered to be contaminants in copper base alloys and
must be removed by refining. In the preparation of refined
copper, the alloying elements common to brass and bronze must
also be removed. The methods used in refining vary with the type
of furnace, the types of scrap in the charge, as well as the type
of product being produced.
The reverberatory or rotary furnace is charged with scrap metal
at the start of the heat and at intervals during the melt down
period. Air is blown into the molten metal bath with lances in
order to oxidize metals in near accordance with their position in
the electromotive series. Thus, iron, manganese, aluminum, and
silicon are oxidized. In the production of refined copper, the
blowing is for a longer duration, since most of the metal
elements must be removed.
The oxidized metals form a slag layer on the surface of the melt,
since the oxides have a lower density than the molten metal.
These oxides combine with the slag cover, which is usually added
to aid in the removal of the oxidized impurities. Borax, slaked
lime or hydrated lime, glass or silica, soda ash, and caustic
soda are all used as fluxes to modify the characteristics of the
slag cover. The most common material used by the brass and
bronze smelters is anhydrous rasorite, a sodium borate flux
(Na2B4O7), which has a great affinity for metal oxides and
siliceous materials. The slag cover protects the molten metal
surface from unwanted oxidation and reduces volatilization of
zinc.
To oxidize or degasify, as well as to alloy, a brass or bronze
melt, metal fluxing agents are added to the melt. In almost all
cases, these melt modifiers are binary alloys of copper with
silicon, phosphorus, manganese, magnesium, lithium, or cadmium.
The highly oxidized, refined copper melt, containing an
appreciable amount of CU2O can be cast from the reverberatory or
rotary furnace into blister copper shapes and used in the
subsequent preparation of fire refined copper. More typically,
however, the molten oxidized melt is reduced in the reverberatory
or rotary furnace in which it was formed, by using carbon-based
reducing agents and then poling. These operations are discussed
in detail in the section on refining of high grade copper scrap.
Once a melt meets specifications, principally chemical analysis,
the brass or bronze is cast into ingots, cooled, and then
packaged for shipping. Refined copper, that has been analyzed
1231
-------
ill1!,!''"!'1',"!,'1"!.,,, !,,, '
SECONDARY COPPER SUBCATEGORY
; ,,'• ', '.Hiiii'i!;!;','1!' "•; ,„;,' ,' '„'•", ,,:' • •' /
SECT. - III
and found to meet specification, is either cast into blister
copper ingots or is subsequently reduced in the furnace as a
continuation of the fire refining operation.
•/] . ' 'I . i I. . . II I ', .••".'• ' '." '' ,' , ' ',.' «'
Fumes of metal oxides are produced when the molten metal is blown
with air or oxygen to remove metallic impurities, or when green
wooden poles are inserted into the bath to reduce the heat. Dust
is produced during the charging of fine slags and fine flux
materials. The dusts and fumes are controlled through the use of
baghouse filters or wet scrubbers. The wet scrubbers on the
reverberatory and rotary furnaces are the sole source of
wastewater.
'• ..„•''' ;'•••;' i '!?l,':>":i'":""': ',• :' ••':•/, >:' l1"''1' • >f'r
REFINING HIGH-GRADE COPPER SCRAP
';" ;!. "'' . ' '" ';*'•; »;; >'": ••#•?'•/' '• •,' '°"';tf '>'"':' s" •••' '":;;1 '•'••
Black copper produced from smelting of low-grade scrap, slags,
drosses, and sludges, and blister copper prepared from
intermediate-grade scrap, are eventually brought together with
high quality copper scrap (usually No. 2 copper wire. No. 1 heavy
copper, No. 2 copper, and light copper) for full fire refining.
Full fire refining is required to produce specification copper
billets, slabs, cakes, and wire bars. Copper ingots and shot are
also produced for making copper base alloys. Fire refined copper
may be even further refined by casting the metal into anodes for
electrolytic refining. The extent of refining is governed in
part by the amount and type of metal impurities and the need for
or difficulty of their removal (by fire refining) to meet
specifications for the product.
Fire Refining
Fire refining is used to remove excess zinc, lead, iron and tin.
Fire refining involves blowing air or oxygen through the molten
metal in a reverberatory or rotary furnace. In the production of
pure copper products, the blowing is continued until the
contained zinc, lead, iron, tin, and other impurities, along with
about three percent of the copper, are removed by oxidation.
Most of the oxides are trapped in the slag cover. After the
contaminated slag is removed, the refined copper is reduced with
green wood poles under a charcoal or coke cover. Once the oxygen
content meets specifications, the copper Is cast into anodes for
electrolytic refining or into billets, wire bars, etc. Selected
types of flux materials are generally added to assist in the
removal of the impurities before poling.
The slags may contain various proportions of the fluxes, silica,
iron oxide, phosphorus pentoxide, soda ash, rasorite (a borax
type flux), and limestone depending on impurities needed to be
removed to obtain the desired composition. Copper-rich slags are
reprocessed or sold for that purpose. Copper-poor slags are
discarded or sold.
;" • .'•''.'• ''Jv ••: ;•''"' ••.'. "': '':!i, v':;": ";; ''''••;' •
Skimming
After a copper alloy has been refined in a reverberatory or
•I';.'' : ;;lli, I1" ,.!"'!
'•i ;.
1232
-------
SECONDARY COPPER SUBCATEGORY
SECT. - III
rotary furnace, it is analyzed and adjusted in composition if
necessary. The temperature is adjusted and slags are skimmed
from the furnace. These slags are generally reprocessed to
remove copper values trapped in the slag. The slag may be
processed by the smelter or sold to larger smelters for
processing.
The slags are either crushed wet or dry and wet screened or
tabled to concentrate the copper content, or the entire copper-
rich slag may also be charged into a blast furnace or cupola for
remelting and separation of the copper from the other
ingredients. If the metal content of the slag is 45 percent or
above, some facilities will charge the slag directly into a
rotary or reverberatory furnace. Wastewater is generated in
plants that use wet crushing and concentrating.
Electrolytic Refining
" .'(••'•
High-purity cathode copper is produced through electrolytic
refining. Anode copper, often containing precious metals and
impurities such as nickel, are placed into the cells in an
alternating fashion with thin copper starter sheets, which after
electrolytic deposition become cathodes of refined copper. The
electrolytic refining process is shown schematically in Figure
III-3 (page 1242).
The cathodes are removed periodically from the electrolytic
cells, melted, and cast into fine-shape castings, such as wire
bar and billets. Used anodes are removed from the cells, rinsed
to remove adhering acid, and remelted into new anodes. If nickel
is present in the anodes, the nickel content of the electrolyte,
as well as the copper content, will build up and a bleed from the
circuit must occur. This bleed is often subjected to
electrowinning for copper removal (where a lead cathode is used)
and cementation.
The spent electrolyte, depleted in copper content, may be
partially evaporated by open or barometric condensers in order to
produce nickel sulfate as a by-product. Precious metals are
recovered as a slime in the bottom of the electrolytic cells and
are usually dried and sold to other facilities for precious metal
value recovery.
Postelectrolytic Melting and Refining
Refined copper in the form of cathodes along with No. 1 copper
wire scrap are melted in reverberatory furnaces or shaft furnaces
and cast into desired product shapes such as cakes, billets, and
wire bars, as well as ingots. , The melting process in the
reverberatory furnace may be followed by a blpwing step, skimming
of the melt, and then poling, followed by preparation for pouring
and casting.
The shaft furnace, which uses natural gas.as a fuel and operates
on the principle of a cupola furnace, continuously melts
1233
-------
SECONDARY COPPER SUBCATEGORY
SECT. - III
cathodes, home scrap, and No. 1 copper wire scrap/ with
"refining" by poling or charcoal reduction being done in a small
reverberatory holding furnace just before casting. The molten
copper is continuously cast into billets and cakes. Water is
used principally for noncontact cooling in the two types of
melting furnaces.
Particulate air emissions from the operation are usually
controlled by means of baghouses. Wet air pollution control may
also be used to control air emissions. In such cases a waste-
water is generated.
CASTING
Molten metal from the smelting operations described above is cast
into various shapes suitable for shipping, handling, or use in
subsequent operations. Copper-base alloys are usually cast into
ingots. Black copper, blister copper, and anode copper are also
cast in molds and shapes suited for the specific product. Refined
copper is cast into shapes suitable for subsequent fabrication
steps, taking the form of billets, cakes, wire bars, wire rod,
and ingots, or it may be quenched into shot. Casting operations
for the various products are described below.
, ': - • . • ;,'.. •• ; i ' i
Brass and Bronze Ingot
• •. " •. • I
The melt, which has been analyzed and found to meet
specifications, is adjusted to the proper temperature before
pouring. Rotary and reverberatory furnaces containing the molten
metal are tapped, and the metal is poured into various ingot
filling systems. The metal may pour directly into a moving,
automatically controlled mold line, in which one or more molds
are filled at once; then the flow shuts off while a new set of
molds moves into position on an endless conveyer. In another
variation, the metal from the furnace is tapped into a ladle and
then moved to a mold line, which may be stationary or movable.
Molds are sprayed with a mold wash and then dried thoroughly
before the ingot is cast. Automatic devices are often used . to
sprinkle ground charcoal in the molds or onto the molten metal in
the molds to provide a special smooth top on the ingots.
The molds are cooled by a water spray or partial immersion of the
mold in a tank of water. Once the molten metal has solidified,
the ingots are quenched in a pit from which they are removed by a
drag conveyer. After drying, they are packed for shipment.
Generally, only steam is discharged during the operation, and
water is recycled after cooling and storage in tanks or ponds.
The wastewater is discharged periodically to permit the storage
tanks to be cleaned of charcoal and mold wash sludges containing
some metals or their oxides.
Black and Blister Copper
71 - , "
Black copper (or cupola melt) produced from blast or cupola
1234
-------
SECONDARY COPPER SUBCATEGORY SECT. - III
furnace operations is usually transported or transferred to a
converter or a reverberatory or rotary furnace in the molten
state to conserve heating requirements. In some cases where the
conversion-oriented operation is backlogged or out of
synchronization with black copper production, the black copper
might be cast into convenient shapes for later use. These shapes
take the form of shot, pigs, sows, or any convenient mold shape
available. Crude molds formed in sand are often used to cast
pigs, sows, or other shapes. Blister copper production may also
be out of phase with subsequent reduction operations due to a
furnace failure or plant shutdown. In such cases, the blister
copper is cast into almost any available mold shape for
subsequent use. These molds may be contact or noncontact cooled
with water, or they can be air cooled. In those cases where the
blister copper is an end product of the smelter, the molds are
made of graphite and are air cooled.
Anodes
Partially fire refined copper, that is-to be electrolytically
refined to remove impurities that are not removed by fire
refining or to recover impurities of value, is cast into anodes.
The molten metal from the anode furnace is cast in a circular
mold conveying system (known as a casting wheel) or a conveyer.
The molds may be cooled indirectly, or spray cooled, or both,
after the metal has been cast. Once the molten metal has
solidified, it is removed from the mold and quenched in a tank of
water. The mold is treated with a mold coating or "wash,"
commonly synthetic bone ash (calcium phosphate), before receiving
the next charge of molten anode copper. Much of the spray water
is converted to steam. Wastewater containing residual mold wash
and some metal oxide scale is generated.
Refined Copper
Fully fire refined copper and melted cathode copper are cast into
various shapes suitable for fabrication end use. These shapes
are billets, cakes, slabs, wire bar, wire rod, and ingots. Wire
bar and ingots are cast into permanent molds on a casting wheel
that is internally cooled with water. Once solidified, the wire
bar or ingots are removed from the mold and quenched in tanks.
The molds are treated with a mold wash and dried before reuse.
Billets, cakes, and wire rod are usually continuously cast or
directly chill cast, and the metal is cooled within dies using
noncontact and contact cooling water that is recirculated after
passing through cooling towers. Wire-rod casting uses
exclusively noncontact cooling water as the cast rod is reduced
in diameter through a series of water-cooled rolls.
Copper Shot
Copper for alloying purposes is sometimes produced in the form of
shot to facilitate handling and remelting. In some cases, the
copper is alloyed with phosphorus to increase hardness. Copper
1235
-------
SECONDARY COPPER SUBCATEGORY
SECT. - III
shotting operations consist of pouring the molten refined copper
directly into a quench pit. Wastewater is generated when the
quench pit is periodically discharged for cleaning, and by wet
air pollution control devices operating on gas streams generated
by the melting furnace.
PROCESS WASTEWATER SOURCES
The principal sources of wastewater in the secondary copper
subcategory are:
',' V1 i '.'.,. ;:' 'I1''"! i,;, ' • '. ?.'. : '".'
1. Residue concentration,
2. Slag granulation,
3. Reverberatory and rotary furnace wet air pollution
control,
4. Spent electrolyte,
5. Scrap anode rinse water,
6. Casting contact cooling water, and
7. Casting wet air pollution control.
OTHER WASTEWATER SOURCES
There are other wastewater streams associated with the
manufacture of secondary copper. These wastewater streams
include but are not limited to stormwater runoff, and maintenance
and cleanup water. These waste streams are not considered as a
part of this rulemaking. EPA believes that the flows and
pollutant loadings associated with these waste streams are
insignificant relative to the waste streams selected and are best
handled by the appropriate permit authority on a case-by-case
basis under authority of Section 402 of the Clean Water Act.
AGE, PRODUCTION, AND PROCESS PROFILE
A distribution of the secondary copper plants in the United
States is shown in Figure III-4 (page 1243). Figure III-4 shows
that most of the secondary copper plants are located around the
Great Lakes and New England states.
Table Ill-l (page 1237) shows that the average plant age is 20 to
30 years, and that there are five direct, six indirect, and 20
zero discharge plants in the secondary copper subcategory. Table
III-2 (page 1238) summarizes the distribution of secondary copper
plants for 1976 production levels. Table III-3 (page 1239)
provides a summary of the number of secondary copper plants that
generate the various process wastewaters identified previously in
this section.
1236
-------
SECONDARY COPPER SUBCATEGORY
SECT. - III
m o
en -p
oo
in
vo
ol
CM|
ro
m td
3 -P
w (d
fl P
n
r*- en
rH O O
rH|
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Cn -P Cn
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CM|
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r- oo
m o CM
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n
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en 4J en
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Type
of Plant
Discharge
Direct
Indirect
0
M
(0
N
TOTAL
1237
-------
SECONDARY COPPER SUBCATEGpRY SECT, - III
TABLE III-2
PRODUCTION RANGES FOR PROCESSING PLANTS
OF THE SECONDARY COPPER SUBCATEGORY
Production Ranges for 1976
tons/year)
0 - 5,000
5,001 - 10,000
10,001 - 20,000
20,001 - 30,000
30,001 +
No Data Reported in dcp
Total Number of Plants in Survey
Number of Plants
," 11
3 . 'r
6
i 4
4
3
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31
"f'A, "? ">
' "
1238
-------
SECONDARY COPPER SUBCATEGORY
SECT. - III
TABLE II1-3
PRODUCTION PROCESSES UTILIZED BY THE
SECONDARY COPPER SUBCATEGORY
Production Process
Residue Concentration
Slag Granulation
Reverberatory and
Rotary Furnace Air
Pollution Control
Electrolytic Refining
Casting
Casting Air Pollution
Control**
Number of Plants Number of Plants
with Process Generating Wastewater*
7
5
18
6
29
8
7
5
5
6
22
3
*Due to in-process flow reduction measures, a plant may generate
a wastewater but not discharge it.
**Reverberatory and rotary furnace air pollution control plants
are not included in the count for casting air pollution
control. An attempt was made to distinguish the reverberatory
and rotary furnace wet air pollution control systems and the
casting wet air pollution control systems that do not use
reverberatory and rotary furnaces for casting.
1239
-------
: !'«
SECONDARY COPPER SUBCATEGORY SECT - III
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1240
-------
SECONDARY COPPER SUBCATEGORY
SECT. - III
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1241
-------
SECONDARY COPPER SUBCATEGORY SECT. - III
Copper Anodes _
from Refining*
Low Grade.
Residue*
Casting Contact
Cooling Hater to_
Waste Treatment
Casting Scrubber^.
Liquor to Haste
Treataent
Electrolytic
Refining
'Sludge
•Cathodes
Melting/
Refining
Furnace
Cast/Cool
T
High Purity Capper
Billets, Cake, Rods, Etc.
High Grade
Scrap from
Pretreatnent
FIGURE III-3
SECONDARY COPPER PRODUCTION PROCESS ELECTROLYTE REFINING
1242
-------
SECONDARY COPPER SUBCATEGORY
SECT. - III
M
-------
SECONDARY COPPER SUBCATEGORY
SECT. - III
THIS PAGE INTENTIONALLY LEFT BLANK
1244
-------
SECONDARY COPPER SUBCATEGORY SECT. - IV
SECTION IV
SUBCATEGORIZATION
This section summarizes the factors considered during the
designation of the secondary copper subcategory and its related
subdivisions.
FACTORS CONSIDERED IN SUBDIVIDING THE SECONDARY COPPER
SUBCATEGORY
The general subcategorization factors listed previously were each
evaluated when considering subdivision of the secondary copper
subcategory. In the discussion the follows, the factors will be
discussed as they pertain to this particular subcategory.
The rationale for considering further segmentation of the
secondary copper subcategory is based primarily on differences in
the production processes and raw materials used. Within this
subcategory, a number of different operations are performed,
which may or may hot have a water use or discharge, and which may
require the establishment of separate effluent limitations. While
secondary copper is still considered a single subcategory, a more
thorough examination of the production processes has illustrated
the need for limitations and standards based on a specific set of
waste streams. Limitations will be based on specific flow
allowances for the following segments or building blocks.
1. Residue concentration,
2. Slag granulation,
3. Reverberatory and rotary furnace wet air pollution
control,
4. Spent electrolyte,
5. Scrap anode rinsing,
6. Casting contact cooling, and
7. Casting wet air pollution control.
Two building blocks have been established for wastewater generated
in the processing of slags and residues. Slag covers on
reverberatory and rotary furnaces are generally raked off before
the furnace is tapped. The copper content of the slag can be
recovered by melting the slag (along with scrap copper, coke, and
fluxes) in a cupola or blast furnace, or by milling and
classifying the slag into a waste gangue material and a copper
rich concentrate. Wastewater is generated in the concentration
of slags or other residues such as drosses, skimming, spills, and
sweepings through wet milling and classifying. When slags are
melted with scrap copper, coke, and fluxes in blast or cupola
furnaces, two products are tapped, a waste or depleted slag, and
black copper. . The waste slag is granulated in a quench pit or
with a high pressure water stream, producing slag granulation
wastewater.
1245
-------
SECONDARY COPPER SUBCATEGORY
SECT. - IV
Wet scrubbers are used to remove particulates and metal oxide
fumes from reverberatory and rotary furnace off-gases.
Therefore, a subdivision for reverberatory and rotary furnace wet
air pollution control wastewater is necessary.
A building block has not been established for blast, cupola, or
converter furnace wet air pollution control, since no plants in
the subcategory use wet air pollution control devices in
conjunction with these furnaces.
Two building blocks are established for wastewater associated
with electrolytic refining. These subdivisions are established
for spent electrolyte wastewaters and scrap anode rinse water.
Spent electrolyte is sometimes bled to prevent the build up of
copper and nickel, in the electrolyte. Depleted anodes are
removed from the electrolytic cells and subsequently rinsed with
water to remove adhering electrolyte.
Contact cooling water is used for metal cooling at 22 plants.
Therefore a casting contact cooling subdivision is necessary. A
subdivision has also been established for casting wet air
pollution control, since three plants use wet scrubbers to remove
fumes and particulates from casting operations.
OTHER FACTORS
,"'',' '''„ !'i,, " i" • ' •' :l1' ' '" . • i '' J* •'! ' ' ' ' '•• i1'
The other factors considered in this evaluation were shown to be
inappropriate bases for further segmentation. Air pollution
control methods, treatment costs, and total energy requirements
are functions of the selected subcategorization factors—metal
product/ raw materials, and production processes. Therefore,
they are not independent factors and do affect the segmentation
presented. Certain other factors, such as plant age, plant
size, _and the number of employees, were also evaluated and
determined to be inappropriate as the bases for segmentation of
secondary copper plants.
PRODUCTION NORMALIZING PARAMETERS
'"' ' ' i I:' ' ' ' ',' ! ,:ij! 'i'' ' ' " ' I11"'1"' • ,. .' "'
The effluent limitations and standards developed in this document
establish mass limitations on the discharge of specific pollutant
parameters. To allow these regulations to be applied to plants
with various production capacities, the mass of pollutant
discharged must be related to a unit of production. This factor
is known as the production normalizing parameter (PNP).
The PNPs for the seven segments or building blocks in the
secondary copper subcategory are shown in Table IV-1 page 1247).
1246
-------
SECONDARY COPPER SUBCATEGORY
SECT. - IV
TABLE IV-1
BUILDING BLOCKS AND PRODUCTION NORMALIZING PARAMETERS
IN THE SECONDARY COPPER SUBCATEGORY
Building block
1. Residue concentration
2. Slag granulation
3. Reverberatory and
furnace wet air
pollution control
4. Spent electrolyte
5. Scrap and rinse water
6. Casting contact cooling
7. Casting wet air
pollution control
PNP
kkg of slag or residue processed
kkg of blast and cupola furnace
copper produced
kkg of reverberatory and rotary
furnace copper produced
kkg of cathode copper produced
kkg of cathode copper produced
kkg of copper cast
kkg of copper cast
1247
-------
SECONDARY COPPER SUBCATEGORY SECT. - IV
: ,1 .I'll!1" .Ill "II "fill' III
"-' ""i';.";.!, ."if iff'/.Mi' i:"'!""'1'1" I
;i;;*>te!'i,[:*1;j
THIS PAGE INTENTIONALLY LEFT BLANK
-,, '•' a
. • "i1!:
1248
!"'Mill-Hill! il't1"-'-!! 4" il, til
-------
SECONDARY COPPER SUBCATEGORY SECT. - V
SECTION V
WATER USE AND WASTEWATER CHARACTERISTICS
This section describes the characteristics of wastewater
associated with the secondary copper subcategory. Data used to
quantify wastewater flow and pollutant concentrations are
presented, summarized, and discussed. The contribution of
specific production processes to the overall wastewater discharge
from secondary copper plants is identified whenever possible.
The two principal data sources used in the development of
effluent limitations and standards for this subcategory are data
collection portfolios and field sampling results. Data
collection portfolios, completed for the secondary copper
subcategory, contain information regarding wastewater flows and
production levels.
In order to quantify the pollutant discharge from secondary
copper plants, a field sampling program was conducted.
Wastewater samples were collected in two phases: screening and
verification. The first phase, screen sampling, was to identify
which toxic pollutants were present in the wastewaters from
production of the various metals. Screening samples were
analyzed for 125 of the 126 toxic pollutants and other pollutants
deemed appropriate. Because the analytical standard for TCDD was
judged to be too hazardous to be made generally available,
samples were never analyzed for this pollutant. There is no
reason to expect that TCDD would be present in secondary copper
wastewater. A total of 10 plants were selected for screen
sampling in the nonferrous metals manufacturing category. A
complete list of the pollutants considered and a summary of the
techniques used in sampling and laboratory analyses are included
in Section V of Vol. 1. In general, the samples were analyzed for
three classes of pollutants: toxic organic pollutants, toxic
metal pollutants, and criteria pollutants (which includes both
conventional and nonconventional pollutants).
As described in Section IV of this supplement, the secondary
copper subcategory has been further segmented into seven building
blocks. As such, the promulgated regulation contains mass
discharge limitations and standards for seven unit processes
discharging process wastewaters. Differences in the wastewater
characteristics associated with these building blocks are to be
expected. For this reason, wastewater streams corresponding to
each segment are addressed separately in the discussions that
follow.
WASTEWATER SOURCES, DISCHARGE RATES, AND CHARACTERISTICS
The wastewater data presented in this section were evaluated in
light of production process information compiled during this
1249
-------
SECONDARY COPPER SUBCATEGORY
SECT. - V
study. As a result, it was possible to identify the principal
wastewater sources in the secondary copper subcategory. These
include: " " *
1. Residue concentration,
2. Slag granulation,
3. Reverberatory and rotary furnace wet air pollution
control,
4. Spent electrolyte,
5. Scrap anode rinsing,
6. Casting contact cooling, and
7. Casting wet air pollution control.
Data supplied by dcp responses were used to calculate the amount
of water used and discharged per metric ton of production. The
two ratios calculated are differentiated by the flow rate used in
the calculation. Water use is defined as the volume ofwater or
other fluid (e.g., electrolyte) required for a given process per
mass of copper product and is therefore based on the sum of
recycle and make-up flows to a given process. Wastewater flow
discharged after pretreatment or recycle (if these are present)
is used in calculating the production normalized flow—the volume
of wastewater discharged from a given process to further
treatment, disposal, or discharge per mass of copper produced.
Differences between the water use and wastewater flows associated
with a given stream result from recycle, evaporation, and carry
over on the product. The production values used in calculations
correspond to the production normalizing parameter, PNP, assigned
to each stream, as-outlined in Section IV. The production
normalized flows were compiled and statistically analyzed by
stream type. Where appropriate, an attempt was made to identify
factors that could account for variations in water use. This
information is summarized in this section. As an example, scrap
anode rinse wastewater flow is related to the cathode copper
production. As such, the discharge rate is expressed in liters
of rinse waste water per metric ton of cathode copper production
(gallons of rinse water per ton of cathode copper production).
Characteristics of wastewater from the previously listed
processes were determined from sampling data collected at
secondary copper plants. This data was used in two ways.
Pollutants were selected for regulation based on the data and the
sampling data was also used to estimate the yearly mass of
pollutant generated by each waste stream for the entire
subcategory. There were a total of five site visits, which
represents 11 percent of the secondary copper subcategory.
Diagrams indicating the sampling sites and contributing
production processes are shown in Figures V-l to V-5 (pages 1285
- 1289)
In the data collection portfolios, plants were asked to indicate
whether or not any of the toxic pollutants were believed to be
present in their, wastewater. The responses for the toxic metals
are summarized in Table V-l (page 1256).
1250
-------
SECONDARY COPPER SUBCATEGORY
SECT. - V
All plants responding to the portion of the dcp concerning the
presence of the toxic organic pollutants indicated that they all
were either known or believed to be absent with the exception of
fluorene. Two plants reported that fluorene was known to be
present while one plant reported that fluorene was believed to be
present. However, as reported in Section VI, fluorene was not
detected in 12 samples from five waste streams collected during
the Agency's sampling and analysis program.
The raw wastewater sampling data for the secondary copper
subcategory are presented in Tables V-9 through V-13 (pages 1264
- 1274). Treated wastewater sampling data are shown in Tables V-
14 through V-17 (pages 1279 - 1283). The stream codes displayed
in Tables V-8 through V-16 may be used to identify the location
of each of the samples on the process flow diagrams in Figures V-
1 through V-5. Where no data are listed for a specific day of
sampling, the wastewater samples for the stream were not
collected. If the analyses did not detect a pollutant in a waste
stream, the pollutant was omitted from the table.
The data tables included some samples measured at concentrations
considered not quantifiable. The base neutral extractable, acid
extractable, and volatile toxic organics generally are considered
not quantifiable at concentrations equal to or less than 0.010
mg/1. Below this concentration, organic analytical results are
not quantitatively accurate; however, the analyses are useful to
indicate the presence of a particular pollutant. The pesticide
fraction is considered not quantifiable at concentrations equal
to or less than 0.005 mg/1. Nonquantifiable results are
designated in the tables with an asterisk (double asterisk for
pesticides).
These detection limits shown on the data tables are not the same
in all cases as the published detection limits for these
pollutants by the same analytical methods. The detection limits
used were reported with the analytical data and hence are the
appropriate limits to apply to the data-. Detection limit
variation can occur as a result of a number of laboratory-
specific, equipment-specific, and daily operator-specific
factors. These factors can include day-to-day differences in
machine calibration, variation in stock solutions, and variation
in operators.
The statistical analysis of data includes some samples measured
at concentrations considered not quantifiable. Data reported as
an asterisk are considered as detected but below quantifiable
concentrations, and a value of zero is used for averaging. Toxic
organic, nonconventional, and conventional pollutant data
reported with a "less than" sign are considered as detected but
not further quantifiable. A value of zero is also used for
averaging. If a pollutant is reported as not detected, it is
excluded in calculating the average. Finally, toxic metal values
reported as less than a certain value were considered as not
detected and a value of zero is used in the calculation of the
average. For example, three samples reported as ND, *, and .0.021
\
1251
-------
SECONDARY COPPER SUBCATEGORY
SECT. - V
mg/1 have an average value of 0.010 mg/1. The averages
calculated are presented with the sampling data. These values
were not used in the selection of pollutant parameters.
In the following discussion, water use and field sampling data
are presented for each operation. Appropriate tubing or
background blank and source water concentrations are presented
with the summaries of the sampling data. Figures V-l through V-5
(pages 1285 - 1289) show the location of wastewater sampling
sites at each facility. The method by which each sample was
collected is indicated by number, as follows:
1 one-time grab
2 24-hour manual composite
3 24-hour automatic composite
4 48-hour manual composite
5 48-hour automatic composite
6 72-hour manual composite
7 72-hour automatic composite
SECONDARY COPPER WASTEWATER SOURCES AND CHARACTERISTICS
Presented below is a discussion of the characteristics of the
significant wastewater sources attributable to the processing of
secondary copper.
Residue Concentration
The copper content can be concentrated in slags and other
residues, such as drosses, skimmings, spills, and sweepings,
before charging the concentrates into rotary or reverberatory
furnaces. The residues are sometimes concentrated by wet milling
and classifying, producing a residue concentration waste stream.
The water use and discharge rates for residue concentration in
liters of water per metric ton of slag or residue processed are
shown in Table V-2 (page 1257).
Raw wastewater data for residue concentration are presented in
Table V-9 (page 1264). This waste stream is characterized by
treatable concentrations of dissolved toxic metal pollutants and
suspended solids. The toxic metals are soluble components of the
slags and residues, and the suspended solids are from milling
fines entrained in the water.
Slag Granulation
•• ;: ,f ' ' .; ' " ". ; • • ,..;j .!.'.' 'U.iK.'i'if.it','..1 ; ••• • :: ' ' •'•''*L '• •' • ••'''••!' ' 'i
Five plants report the use of water for blast or cupola furnace
slag granulation. This wastewater is generated when slag is
granulated with high pressure water jets, or in quench pits prior
to disposal. The water use and discharge rates for slag
granulation in liters of water per metric ton of blast or cupola
furnace production are shown in Table V-3 (page 1258).
The Agency did not collect any raw wastewater sampling data from
slag granulation operations at secondary copper plants. However,
";:: f Mil
1252
-------
SECONDARY COPPER SUBCATEGORY SECT. - V
the characteristics of this wastewater are generally comparable
to those of residue concentration wastewater, since materials
from nearly identical sources are being treated in either case.
Thus, slag granulation wastewater contains treatable
concentrations of dissolved toxic metal pollutants and suspended
solids.
Reverberatory and Rotary Furnace Wet Air Pollution Control
Five plants report the use of wet air pollution control devices
to contain metal oxide fumes and dust from reverberatory and
rotary furnace operations. Fumes of metal oxides are produced
when the molten metal is blown with air or oxygen to remove
metallic impurities, or when green wooden poles are inserted into
the bath to deoxidize the heat. Dust will be produced during the
charging of fine slags or fine flux materials. When wet air
pollution control is used, the metal oxides and dust will be
contained in the water as suspended solids and dissolved toxic
metals. Raw wastewater data for reverberatory and rotary furnace
wet air pollution control are shown in Table V-10 (page 1268). As
expected, toxic metal pollutants and suspended solids are present
in treat- able concentrations. Table V-10 also shows that this
wastewater is acidic (pH of 1.6 to 2.5).
The water use and discharge rates for reverberatory and rotary
furnace wet air pollution control are presented in Table V-4 page~
1259).
Spent Electrolyte
Normally, electrolyte is continuously circulated through
thickeners and filters to remove solids, and recycled back
through the electrolytic cells. It is necessary to blowdown a
fraction of the electrolyte to prevent the build-up of copper and
nickel. This slip stream is treated to recover nickel and copper,
and recycled or discharged. Table V-5 (page 1260) presents the
electrolyte use and discharge rates for spent electrolyte in
liters per metric ton of cathode copper produced.
Raw wastewater sampling data for spent electrolyte are shown in
Table V-ll (page 1270). This waste stream is characterized by
treatable concentrations of toxic metal pollutants (particularly
copper, lead, and zinc) and suspended solids. The pH of the
spent electrolyte in the wastewater samples ranged from 1.48 to
3.45.
Scrap Anode Rinsing
Anodes removed from electrolytic cells are sometimes rinsed
before further processing. As shown in Table V-6 (page 1261),
only two plants reported the use of rinse water for scrap anode
cleaning, and both of those plants practice 100 percent recycle
of the rinse water. The Agency did not collect any raw
wastewater samples from anode rinsing operations. Wastewater
from this operation should contain treatable concentrations of
1253
-------
SECONDARY COPPER SUBCATEGORY
SECT. - V
total suspended solids and dissolved toxic metal pollutants,
which are a result of impurities in the modes that are released
into the rinse water.
Casting Contact Cooling
, i. ' , "" : ; ,"'"•. '"•',% . ' •. i. l •'<'" '• .' , '•',:: '€. t
Twenty-two plants report the use of contact cooling water to cool
molten metal cast into ingots, shot, and anodes. Anodes and
rough brass or bronze ingots are generally water spray-cooled to
rapidly solidify the casting, and the casting is then quenched in
a tank of water. Smooth brass or bronze ingots must be slowly
cooled in the mold under a layer of charcoal to produce _the
smooth surface requested by certain customers. Ingot mold lines
are quite long for the production of smooth ingots. The ingots
are permitted to air cool in the mold during the first portion of
the conveyer travel, the bottom of the ingot mold is submerged in
a tank of water during the second portion of the conveyer travel,
and finally the solidified ingot is discharged into a quenching
tank of water. Part of the charcoal burns during the ingots
travel period on the conveyer. The unburned charcoal and
charcoal ash all go into the ingot cooling water. These residues
settle as a sludge and are periodically cleaned out of the
quenching tanks and subsequent settling tanks or ponds. The
water may or may not be recycled. In addition to the charcoal
and charcoal ash, the wastewater pollutants associated with
contact cooling are metal oxides from the ingot surface,
refractory mold wash (calcium phosphate), and flour du£Jt-
Charcoal is not used when casting copper anodes, but the mold
wash is used and the wash ends up in the contact cooling water.
The raw waste water data for casting contact cooling water is
presented in Table V-12 (page 1272). Copper, lead, zinc, and
total suspended solids are all present in treatable
concentrations.
The water use and discharge rates for casting contact cooling in
liters of water per metric ton of copper cast are shown in Table
V-7 (page 1262).
Casting Wet Air Pollution Control
Wet air pollution control devices are used to control fumes
produced from casting operations at three plants. Two of these
plants use scrubbers to contain fumes produced from alloying
copper with phosphor in induction furnaces. The third plant did
not report why it uses a scrubber for casting, however, this
plant casts brass and bronze ingots which produce metal oxide
fumes when poured. These fumes can be controlled by a scrubber.
pollution
cast are
The water use and discharge rates for casting wet air
control in liters"of water per metric ton of copper
shown in Table V-8 (page 1263).
Raw wastewater samples were not collected for this stream.
However, since both casting, and reverberatory and rotary furnace
water pollution control devices control metal oxide fumes, their
1254
-------
SECONDARY COPPER SUBCATEGORY SECT. - V
wastewaters will be similar. Therefore, casting wet air
pollution wastewater contains toxic metal pollutants and
suspended solids.
1255
-------
SECONDARY COPPER SUBCATEGORY SECT. - V
TABLE V-l
TOXIC METALS BELIEVED TO BE PRESENT IN SECONDARY COPPER WASTEWATER
DCP DATA
Toxic
Metal
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Zinc
Known
Present
2
1
1
3
2
7
6
2
4
1
7
Believed
Present
1
1
1
1
1
1
1
Believed
Absent
7
8
9
7
7
2
3
6
5
9
8
1
Known
Absent
1
1
1256
-------
SECONDARY COPPER SUBCATEGORY
SECT. - V
TABLE V-2
WATER USE AND DISCHARGE RATES FOR RESIDUE CONCENTRATION
(1/kkg of slag or residue processed)
Plant Code
15
23
49
50
55
220
4507
Production
Production
Normalized
Percent
Recycle
0
100
100
100
100
NR
100
Normalized
Water Use
6,702
NR
6,680
NR
NR
NR
NR
Dischar
Flow
6,702
0
0
0
0
677
0
NR - Present, but data not reported in dcp.
1257
-------
SECONDARY COPPER SUBCATEGORY
SECT. - V
TABLE V-3
WATER USE AND DISCHARGE RATES FOR SLAG GRANULATION
(1/kkg of blast and cupola furnace production)
Plant Code
26*
35
36
49
62
...
Production
Percent
Recycle
NR
100
100
100
100
Normalized
Water Use
NR
NR
1 i ' '", ' !• ; " ' •.."! ". ' , ,i''i,' •
• ,,17,210' ;"."'.'/
40,900
65,800
Production
Normalized
Discharge
Flow _
0
0
0
0
;M?," .a** v.1
Jill ' Hill1,!', fj
*Wastewater is evaporated.
NR - Present, but data not reported in dcp.
1258
-------
SECONDARY COPPER SUBCATEGORY
SECT. - V
TABLE V-4
WATER USE AND DISCHARGE RATES FOR REVERBERATORY AND
ROTARY FURNACE WET AIR POLLUTION CONTROL
(1/kkg of reverberatory and rotary furnace copper produced)
Production
Production
Normalized
Plant Code
22
46
50
52
207
Percent
Recycle
100
0
100
100
81
Normalized
Water Use
274,200
7,226
NR
NR
25,000
Dischari
Flow
0
7,226
0
0
4,695
NR - Present, but data not reported in dcp.
1259
-------
SECONDARY COPPER SUBCATEGORY
SECT. - V
TABLE V-5
ELECTROLYTE USE AND DISCHARGERATES
•jii11
(1/kkg of cathode copper produced)
Production
*Spent electrolyte is contract hauled.
NR - Present, but data not reported in dcp.
Production
Normalized
Plant Code
„
22*
62
78*
207
Percent
Recycle
0
100
NR
NR
Normalized
Water Use
• • •>.
263.2
f • . ,' ' . . " "
NR
NR
.'' ' ' •,• • I,'"1 ; '.
NR
Discnarg
Flow
' «" ' "l1"!'
263.
0
1,499
'•; i'1!!,1 '" ii
1,124
e
2
1260
-------
SECONDARY COPPER SUBCATEGORY
SECT. - V
TABLE V-6
WATER USE AND DISCHARGE RATES FOR SCRAP ANODE RINSING
(1/kkg of cathode copper produced)
Plant Code
78
670
Percent
Recycle
100
100
Production
Normalized
Water Use
NR
NR
Production
Normalized
Discharge
Flow
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0
NR — Present/ but data not reported in dcp.
1261
-------
SECONDARY COPPER SUBCATEGORY
SECT. - V
TABLE V-7
' •'• •'•", • , : T",.;N ' :'$. •:'-;, -\- : :• ,, ":• ; :
WATER USE AND DISCHARGE RATES FOR CASTING' CONTACT COOLING
(1/kkg of copper cast)
Plant Code
15
16
17
18
21
22
23
26
35
36
37
49
50
52
55
58*
62
207
220
662
4508
9050
Percent
Recycle
0
0
0
100
100
0
100
100
100
100
NR
100
NR
100
100
0
100
0
99
0
0
0
Production
Normalized
Water Use
Production
Normalized
Discharge
Flow
148
925
1,
NR
NR
21/586
NR
NR
NR
14,720
NR
6,070
NR
NR
NR
109
NR
12,614
23,700
4,100
917
109
45
148
925
1.
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0
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1,406
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109
0
12,614
237
4,100
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109
45
*Contact cooling water is dry well injected.
NR - Present, but data not reported in dcp.
1262
-------
SECONDARY COPPER SUBCATEGORY SECT. - V
TABLE V-7
WATER USE AND DISCHARGE RATES FOR CASTING WET AIR
POLLUTION CONTROL
(1/kkg of copper cast)
Plant Code
36
37
78
Percent
Recycle
100
NR
0
Production
Normalized
Water Use
NR
NR
337
Production
Normalized
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Flow
0
281
337
NR - Present, but data not reported in dcp.
1263
-------
SECONDARY COPPER SUBCATEGORY
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1267
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1269
-------
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SECT - V
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-------
SECONDARY COPPER SUBCATEGORY
SECT - V
in
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1282
-------
SECONDARY COPPER SUBCATEGORY
SECT - V
o
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1283 '
-------
SECONDARY COPPER SUBCATEGORY
SECT - V
"',! ' :•'»(•'?• •;*• !!" W:
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1284
-------
SECONDARY COPPER SUBCATEGORY
SECT. - V
SOURCE
WATER
CITY
NON-CONTACT
BLOW DOWN
FURNACE
SCRUBBER
WATER
PRECIOUS
METAL
ACID
TANKS
SCRUBBERS
-»» DISCHARGE
RAPID
MIX
No OH
Fet (£
DISCHARGE
O.W5 MS)
FIGURE V-l
SAMPLING SITES AT SECONDARY COPPER PLANT A
1285
-------
SECONDARY COPPER SUBCATEGORY SECT. - V
RUNOFF
SLAG
MH.UINVJ
& RUNOFF
"i
SLAG
GRANULATION
^
0.01 3MGO
(
GRIT
BASIN
102J (X)
CONTACT
COOLING
WATER
NON-CONTACT
COOLING
WATER
SOURCE
CITY
WATER
HOLDING
LAGOON
DISCHARGE
LIME ADDITION
MIXING-SETTLING
TRI-MEDIA
FILTRATION
ACID-
NEUTRALIZATION
RECYCLE
HOLDING
TANK
0.071 MOD
DISCHARGE
FIGURE V-2
SAMPLING SITES AT SECONDARY COPPER PLANT B
1286
-------
SECONDARY COPPER SUBCATEGORY SECT. - V
119
CONTACT
COOLING
WATER
PISCHABGE
FIGURE V-3
SAMPLING SITES AT SECONDARY COPPER PLANT C
1287
-------
,;; ' , -, '" E rt'.i >;!'!;• ".. Ill ' Wiriit:' :••'•• ' •' J'/'i,:^ t;.'•'" W.VK »• ;:,3 .-'ilv'i !W!ffWB/
SECONDARY COPPER SUBCATEGORY
SECT. - V
cmr
WATCT
MAKE-UP
FURNACE
SCRUBBER
SETTLING
POND
NO. 1
INGOT
COOLING
CONTACT
0.019 MGO
FIGURE V-4
SAMPLING SITES AT SECONDARY COPPER PLANT D
1288
-------
SECONDARY COPPER SUBCATEGORY
.SECT. - V
COPPER PRECIPITATE
WASTE HzO
FROM
ELECTROLYTIC
PROCESS
DISCHARGE
FIGURE V-5
SAMPLING'SITES AT SECONDARY COPPER PLANT E
1289
-------
SECONDARY COPPER SUBCATEGORY SECT. - V
THIS PAGE INTENTIONALLY LEFT BLANK
1290
-------
SECONDARY COPPER SUBCATEGORY SECT. - VI
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
This section examines chemical analysis data presented in Section
V from secondary copper plants and discusses the selection or
exclusion of pollutants for potential limitation in this
subcategory.
Each pollutant selected for potential limitation is discussed in
Section VI of Vol. 1. That discussion provides information
concerning where the pollutant originates (i.e., whether it is a
naturally occurring substance, processed metal, or a manufactured
compound); general physical properties and the form of the
pollutant; toxic effects of the pollutant in humans and other
animals; and behavior of the pollutant in POTW at the
concentrations expected in industrial discharges.
The discussion that follows describes the analysis that was
performed to select or exclude pollutants for further
consideration for limitations and standards. Pollutants are
selected for further consideration if they are present in
concentrations treatable by the technologies considered in this
analysis. The treatable concentrations used for the toxic metals
were the long-term performance values achievable by lime
precipitation, sedimentation, and filtration. The treatable
concentrations for the toxic organics were the long-term
performance values achievable by carbon absorption (see Section
VII of Vol. 1 —Combined Metals Data Base).
After proposal, the Agency re-evaluated the treatment performance
of activated carbon absorption to control toxic organic
pollutants. The treatment performance for the acid extractable,
base-neutral extractable,- and volatile organic pollutants has
been set equal to the analytical quantification limit of 0.010
mg/1. The analytical quantification limit for pesticides and
total phenols (by 4-AAP method) is 0.005 mg/1, which is below the
0.010 mg/1 accepted for the other toxic organics. However, to be
consistent, the treatment performance of 0.010 mg/1 is used for
pesticides and total phenols. The 0.010 mg/1 concentration is
achievable, assuming enough carbon is used in the column and a
suitable contact time is allowed.
The frequency of occurrence for 36 of the toxic pollutants has
been redetermined based on the revised treatment performance
value. However, no toxic organic pollutants have been selected
for consideration for limitation. ,
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETERS
This study considered samples from the secondary copper
subcategory for three conventional pollutant parameters (oil and
? 1291
-------
SECONDARY COPPER SUBCATEGORY
SECT. - vi
I'll1
grease, total suspended solids, and pH) and seven nonconventional
pollutant parameters (aluminum, ammonia, chemical oxygen demand,
chloride, fluoride, total organic carbon, and total phenols).
CONVENTIONAL POLLUTANT PARAMETERS SELECTED
The conventional pollutants and pollutant parameters selected for
consideration for limitation in this subcategory are:
total suspended solids (TSS)
oil and grease
PH ' ' "" ' " " " '
Total suspended solids ranged from 3 to 8,790 mg/1. All samples
had TSS concentrations above that considered achievable by
identified treatment technology (2.6 mg/1).Furthermore, most of
the technologies used to remove toxic metals do so by
precipitating the metals. A limitation on total suspended solids
ensures that sedimentation to remove precipitated toxic metals is
effectively operating. Therefore, total suspended solids is
selected for consideration for limitation.
Oil and grease concentrations in the wastewaters sampled ranged
from 2 to 180 mg/1 in 10 samples. Residue concentration is the
principal source of these pollutants. The concentration in 2 of
'the 10 samples analyzed exceeded the treatable concentration (10
mg/1). Thus, this pollutant is selected for consideration for
limitation.
The pH values observed ranged from 1.5 to 7.0. Effective removal
of toxic metals by precipitation requires careful control of pH.
Therefore, pH is considered for limitation in this subcategory.
TOXIC POLLUTANTS
The frequency of occurrence of the toxic pollutants in the
wastewater samples taken is presented in Table VI-1 (page 1300).
These data provide the basis for the categorization of specific
pollutants, as discussed below. Table VI-1 is based on the raw
wastewater data from streams 2, 104, 58, 19, and 121 (see
Section V). Miscellaneous wastewater andtreatment plant samples
were not considered in the frequency count.
>• , ' •..'" ". • ,• • >»• . v '.' , "it'.', ' : -,. '• • •'' •' .' • ' •.: '• •: •• •,<'«' ,'!
Toxic Pollutants Never Detected
The toxic pollutants listed in Table VI-2 (page 1304) were not
detected in any wastewater samples from this subcategory.
Therefore, they are not selected for consideration in
establishing regulations.
Toxic Pollutants Never Found Above Their Analytical
Quantification Level
The toxic pollutants listed below were never found above, their
analytical quantification concentration in any wastewater samples
1292
1; (, ''.,,'
-------
SECONDARY COPPER SUBCATEGORY SECT. - VI
from this subcategory. Therefore, they are not selected for
consideration in establishing regulations.
15. 1,1,2,2-tetrachloroethane
71. dimethyl phthalate
74. benzo(b)fluoranthene (a)
75. benzo(k)fluoranthene (a)
109. PCB-1232 (b)
110. PCB-1248 (b)
111. PCB-1260 (b)
112. PCB-1016 (b)
116. asbestos
(a), (b) Reported together as a combined value
Toxic Pollutants Present Below Concentrations Achievable by
Treatment
The pollutants listed below are not selected for consideration in
establishing limitations because they were not found in any
wastewater samples from this subcategory above concentrations
considered achievable by existing or available treatment
technologies. These pollutants are discussed individually
following the list.
114. antimony
117. beryllium
121. cyanide
123. mercury
126. silver
Antimony was detected above its analytical quantification limit
in three of thirteen samples from five plants; however, these
sample concentrations were below that attainable by treatment.
Therefore, antimony is not selected for limitation.
Beryllium was detected above its analytical quantification limit
in eight of thirteen samples from five plants; however, these
sample concentrations were below that attainable by treatment.
Therefore, beryllium is not selected for limitation.
Cyanide was detected above its analytical quantification limit in
six of eleven samples from four plants; however, these sample
concentrations were below that attainable by treatment. There
fore, cyanide is not selected for limitation.
Mercury was detected at, or above, its 0.0001 mg/1 analytical
quantification limit in thirteen of thirteen samples from five
plants. All of the values are below the 0.026 mg/1 concentration
considered achievable by identified treatment technology.
Therefore, mercury is not considered for limitation.
Silver was detected above its analytical quantification limit in
three of ten samples from four plants; however, these sample
1293
-------
SECONDARY COPPER SUBCATEGORY
SECT. - VI
concentrations were below that attainable by
Therefore, silver is not selected for limitation.
treatment.
Toxic Pollutants Detected in a Small Number of Sources
Toxic pollutants detectable in the effluent from only a small
number of sources within the subcategory and it „ is uniquely
related to only those sources are not appropriate for limitation
in a national regulation. The toxic pollutants listed in Table
VI-3 (page 1306) were not selected for limitation on this basis.
Although these pollutants were not selected for consideration in
establishing nationwide limitations, it may be appropriate, on a
case-by-case basis, for the local permitter to specify effluent
limitations.
Acenapthene was found above its analytical quantification limit
in two of twelve samples from five plants. The detected
concentrations were 0.019 mg/1 and 0.036 mg/1 in the spent
electrolyte wastewater sample. Both of these values are above
the concentration considered achievable by identified technology.
However, since the third sampling date at the plant showed a "not
detected" value, acenapthene is not considered for limitation
because it is believed to be unique to that particular plant and
is not expected to be a common pollutant in spent electrolyte
wastewater.
Benzene was detected in three of twelve samples taken from four
plants. Only one value was above its analytical quantification
limit. The value was 0.019 mg/1 which is above the 0.010 mg/1
concentration considered attainable by identified technology.
Because it was found at a treatable concentration in only one
sample, benzene is not considered for limitation.
Carbon tetrachloride was found in just one of ten samples from
four plants. The reported value was 0.116 mg/1, which is above
the concentration considered achievable by identified technology.
This pollutant was not detected in any of the other nine samples.
Because it was found in just one sample, carbon tetrachloride is
not considered for limitation.
, , . . , ,
1,2-Dichloroethane was detected in three of ten samples collected
from four plants. The pollutant was found in two of four raw
wastewater streams. Two of the detected values were above the
0.010 mg/1 concentration considered achievable by identified
treatment technology. Analyses of two other samples from the two
raw wastewater streams that contained 1,2-dichloroethane did not
detect this pollutant. Also, in the dcp, all of the secondary
copper plants indicated that this pollutant was either known or
believed to be absent. Therefore, 1,2-dichloroethane is not
considered for limitation.
-1. , , , ' • " , ,.; "' ' , ' l«: ••!.: SI": ,,,',. ' „. ...... ,. • :; ... • • ' ^i ' . /,
Chloroform, a common laboratory solvent, was detected above its
analytical quantification limit in all ten samples from four
plants. Also, it was found above the concentration considered
'V'.iif"*: ::<'•!.•'
1294
-------
SECONDARY COPPER SUBCATEGORY SECT. - -VI.
achievable by identified technology in all ten samples, ranging
from 1.11 mg/1 to 1.19 mg/1. Concentrations above the analytical
concentration limit in four blanks (0.070 mg/1, 0.181 mg/1, 0.127
mg/1, and 0.043 mg/1) analyzed raise the likelihood of sample
contamination. Also, in the dcp, all of the secondary copper
plants indicated that this pollutant was either known or believed
to be absent. Chloroform, therefore, is not selected for
consideration for limitation.
The toxic pollutants 1,2-dichlorobenzene, 1,3-dichlorobenzene,
and 1,4-dichlorobenzene are not clearly separated by the
analytical protocol used in this study; thus, they are reported
together. The sum of these pollutants was found above its
analytical quantification limit in two of twelve samples from
five plants. The detected concentrations were 0.117 mg/1 and
0.113 mg/1 in the spent electrolyte wastewater sample. Both of
these values are above the concentration considered achievable by
identified technology. However, since the third sampling day at
the plant showed a "not detected" value, 1,2-dichlorobenzene,
1,3-dichlorobenzene, and 1,4-dichlorobenzene are not considered
for limitation because they are believed to be unique to that
particular plant and are not expected to be common pollutants in
spent electrolyte wastewater.
1,1-Dichloroethylene was found in concentrations above its
analytical quantification limit in two of ten samples from four
plants. The values were 0.038 mg/1 and 0.667 mg/1, which are
above the 0.010 mg/1 concentration considered achievable by
identified treatment technology. Three other samples, that were
from the same two raw wastewater streams in which 1,1-
dichloroethylene concentration was detected, did not contain 1,1-
dichloroethylene. Therefore, 1,1-dichloroethylene is not
considered for limitation.
1,2-trans-dichloroethylene was found in concentrations above its
analytical quantification limit in three of ten samples from four
plants, with values ranging from 0.012 mg/1 to 0.157 mg/1. All
three concentrations are above the 0.010 mg/1 concentration
considered achievable by identified treatment technology. Two of
seven samples reported as "not detected" were from the same two
raw wastewater streams that did contain 1,2-trans-
dichloroethylene. Therefore, 1,2-trans-dichloroethylene is not
considered for limitation.
Fluoranthene was found above its analytical quantification limit
in two of twelve samples from five plants. The detected
concentrations were 0.069 mg/1 and 0.258 mg/1 in the spent
electrolyte wastewater sample. One of these values is above the
concentration considered achievable by identified technology.
However, since the third sampling day at the plant showed a "not
detected" value, fluoranthene is not considered for limitation
because it is believed to be unique to that particular plant and
is not expected to be a common pollutant in spent electrolyte
wastewater.
1295
-------
SECONDARY COPPER SUBCATEGORY
SECT. - VI
Methylene chloride, a common laboratory solvent, was found above
its analytical quantification limit.in two of ten samples from
four plants. The detected concentrations were 0.64 mg/1 and 0.58
mg/1. Analyses of three other samples from the raw wastewater
streams in which methylene chloride was found did not detect any
raethylene chloride. The presence of this pollutant is not
attributable to materials or processes associated with the
secondary copper subcategory. Therefore, methylene chloride is
not considered for limitation.
Bis(2-ethylhexyl) phthalate was found above its analytical
quantification limit in 11 of 12 samples from five plants. The
concentrations observed ranged from 0.019 to 0.4 mg/1. The
presence of this pollutant is not attributable to materials or
processes associated with the secondary copper subcategory. It
is commonly used as a plasticizer in laboratory and field
sampling equipment. EPA suspects sample contamination as the
source of this pollutant. Therefore, bis(2-ethylhexyl) phthalate
is not considered for limitation.
Butyl benzyl phthalate was found above its analytical
quantification limit in two of 12 samples from five plants. The
concentrations were 0.011 and 0.056 mg/1. The presence of this
pollutant is not attributable to materials or processes
associated with the secondary copper subcategory. It is commonly
used as a plasticizer in laboratory and field sampling equipment.
EPA suspects sample contamination as the source of this
pollutant. Therefore, butyl benzyl phthalate is not considered
for limitation.
- '> ' ' ")' • ' " " "''.' • l;' ,' ! ,:;',' i 'iif' V"1'' " . ':.',' f' '•''
Di-n-butyl phthalate was found above its analytical
quantification limit in seven of 12 samples from five plants.
The concentrations observed ranged from 0.012 to 0.4 mg/1. All
seven samples showed concentrations above the 0.010 mg/1
treatable concentration. The presence of this pollutant is not
attributable to materials or processes associated with the
secondary copper subcategory. It is commonly used as a
plasticizer in laboratory and field sampling equipment. EPA
suspects sample contamination as the source of this pollutant.
Therefore, di-n-butyl phthalate is not considered for
limitation.
Di-n-octyl phthalate was found aboveits analytical"
quantification limit in one of 12 samples from five plants. The
concentration observed was 0.067 mg/1. The presence of this
pollutant is not attributable tomaterials or processes
associated with the secondary copper subcategory. It is commonly
used as a plasticizer in laboratory and field sampling equipment.
EPA suspects sample contamination as the source of this
pollutant. Therefore, di-n-octyl phthalate is not considered for
limitation.
Diethyl phthalate was found above its analytical quantification
limit in two of 12 samples from five plants. The concentrations
observed were 0.042 mg/1 and 0.083 mg/1. The presence of this
1296
-------
SECONDARY COPPER SUBCATEGORY SECT. - VI
pollutant is not attributable to materials or processes
associated with the secondary copper subcategory. It is commonly
used as a plasticizer in laboratory and field sampling equipment.
EPA suspects sample contamination as the source of this
pollutant. Therefore, diethyl phthalate is not considered for
limitation.
Chrysene was detected above its analytical quantification limit
in just one of 12 samples from five plants. Since it was found
in only one sample, chrysene is not considered for limitation.
The toxic pollutants anthracene and phenanthrene are,not clearly
separated by the analytical protocol used in this study; thus,
they are reported together as a combined value. The sum of -these
pollutants was measured at a concentration greater than the
analytical quantification limit in one of 12 samples from five
plants. The detected concentration was 0.1 mg/1, which is
greater than the concentration considered attainable by
identified technology. Because they were found at a treatable
concentration in only one sample, anthracene and phenanthrene are
not considered for limitation.
Pyrene was found above its analytical quantification limit in two
of 12 samples from five plants. The detected concentrations were
0.159 mg/1 and 0.204 mg/1 in the spent electrolyte wastewater
Cample. Both of these values are above the concentration
considered achievable by identified technology. However, since
the third sampling day at the plant showed a "not detected"
value, pyrene is not considered for limitation because it is
believed to be unique to that particular plant and is not
expected to be a common pollutant in spent electrolyte
wastewater.
Tetrachloroethylene was found above its analytical quantification
limit in one of 10 samples from four plants. The detected
concentration was 0.072 mg/1, which is greater than the
concentration considered attainable by identified technology.
Because it was found at a treatable concentration in only one
sample, tetrachloroethylene is not considered for limitation.
Toluene was detected in two of ten samples collected and two of
four raw wastewater streams from four plants. Both detected
concentrations were above the 0.010 mg/1 concentration considered
achievable by identified treatment technology. Analyses of three
other samples from the two raw wastewater streams containing
toluene did not detect this pollutant. Also, in the dcp, all of
the secondary copper plants indicated that this pollutant was
either known or believed to be absent. Therefore, toluene is not
considered for limitation.
Arsenic was found above its analytical quantification limit in
seven of 13 samples taken from five plants. Concentrations
ranged from 0.01 to 1 mg/1. Only one sample contained a
concentration above the 0.34 mg/1 considered attainable by
1297
-------
SECONDARY COPPER SUBCATEGORY
SECT. - VI
identified technology. Because
concentration in only one sample,
limitation.
it was found at a treatable
arsenic is not considered for
Selenium was found above its analytical quantification limit in.
seven of 10 samples taken from four plants. Concentrations
ranged from 0.005 to 0.5 mg/1. Only two samples contained a
concentration above the 0.20 mg/1 considered attainable by
identified technology. Because it was found at a treatable
concentration in only two samples, selenium is not considered for
limitation.
Toxic Pollutants Selected for Further Consideration for
Limitation
The toxic pollutants listed below are selected for further
consideration in establishing limitations for this subcategory.
The toxic pollutants selected are each discussed following the
list.
55. naphthalene
77. acenaphthylene
.87. trichlorethylene
118. cadmium
119. chromium
120. copper
122. lead
1 124. nickel , ' ' .. ; ',' ' ' , ' „; ";."'.'.!. . '.'.'".. "."" . "... ." ,' ,' ".'".
128. zinc
Naphthalene was found above its analytical quantification limit
in three of 12 samples from five plants. The concentrations
measured in the spent electrolyte were 0.042 mg/1, 5.0 mg/1, and
1.6 mg/1. All three of these values are above the 0.010 mg/1
concentration attainable by identified treatment technology.
Because it is present at treatable concentrations in this spent
electrolyte stream, naphthalene is selected for further
consideration for regulation.
Acenaphthylene was found above its analytical quantification
limit in three of 12 samples from five plants. The
concentrations measured in the spent electrolyte were 0.042 mg/1,
0.117 mg/1, and 0.113 mg/1. All of these values are above the
0.010 mg/1 concentration available by identified treatment
technology. Because it is present at treatable concentrations in
this spent electrolyte stream, acenaphthylene is selected for
further consideration for regulation.
Trichloroethylene was found above its analytical quantification
limit in four of 10 samples from four plants. The concentrations
measured in the residue concentration wastewater were 0.023 mg/1
and 0.058 mg/1. Both of these values are above the 0.010 mg/1
concentration attainable by identified treatment technology.
Because it is present at treatable concentrations in this residue
concentration stream, trichloroethylene is selected for further
1298
Hill Hill I Illlllllllilllllill ill In
-------
SECONDARY COPPER SUBCATEGORY SECT. - VI
consideration for regulation.
Cadmium was measured above its analytical quantification limit in
10 of 13 samples, taken from five'plants, with concentrations
ranging from 0.006 to 2.0 mg/1. Seven samples were above the
0.049 mg/1 concentration attainable by identified treatment
technology. Therefore, cadmium is selected for further
consideration for limitation.
Chromium was found above its analytical quantification limit in
11 of 13 samples, taken from five plants, with concentrations
ranging from 0.008 to 5.0 mg/1. Eleven samples were above the
0.07 mg/1 concentration attainable by identified treatment
technology. Therefore, chromium is selected for further
consideration for limitation.
Copper was measured above its analytical quantification limit in
all 13 samples, taken from five plants, with concentrations
ranging from 0.3 to 3,630 mg/1. Twelve samples were above the
0.39 mg/1 concentration attainable by identified treatment
technology. Therefore, copper is selected for further
consideration for limitation.
Lead was found in concentrations above its analytical
quantification limit in all 13 samples taken from five plants,
with concentrations ranging from 0.2 to 40 mg/1. All 13 samples
were above the 0.08 mg/1 concentration attainable by identified
treatment technology. Therefore, lead is selected for further
consideration for limitation.
Nickel was measured above its analytical quantification limit in
all 13 samples, taken from five plants, with concentrations
ranging from 0.007 to 530 mg/1. Since nine samples were also
above the 0.22 mg/1 concentration attainable by identified
treatment technology, nickel is selected for further
consideration for limitation.
Zinc was measured above its analytical quantification
concentration in all 12 samples taken from five plants, with
concentrations ranging from 0.7 to 300 mg/1. All 12 samples were
above the 0.23 mg/1 concentration attainable by the identified
treatment technology. Therefore, zinc is selected for further
consideration for limitation.
1299
-------
SECONDARY COPPER SUBCATEGORY
SECT - VI
1
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-------
SECONDARY COPPER SUBCATEGORY
SECT - VI
[ 1 £j •
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a) >-i d o
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10
SECONDARY COPPER SUBCATEGORY
SECT - VI
3
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-------
SECONDARY COPPER SUBCATEGORY
SECT - VI
1
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1303
-------
SECONDARY COPPER SUBCATEGORY
SECT. - VI
TABLE VI-2
TOXIC POLLUTANTS NEVER DETECTED
11 • , • • • . ,i , .• •, j1 . i,j; '.«, ,, jii'jjij y, 7,. ,, ,
2. acrolein
3. acrylonitrile
5. benzidine
7. chlorobenzene
8. 1,2,4-trichlorobenzene
9. hexachlorobenzene
11. 1,1,1-trichloroethane
12. hexachloroethane
13. 1,1-dichloroethane
14. 1,1,2-trichloroethane
16. chloroethane
17. DELETED
18. bis(2-chloroethyl) ether
19. 2-chloroethyl vinyl ether
20. 2-chloronaphthalene
21. 2,4,6-trichlorophenol
22. parachlorometa cresol
24. 2-chlorophenol
28. 3f3'-dichlorobenzidiene
31. 2,4-dichlorophenol
32. 1,2-dichloropropane
33. 1,3-dichloropropylene
34. 2,4-dimethylphenol
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. 1,2-diphenylhydrazine
38. ethylbenzene
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. bis(2-chloroisopropyl) ether
43. bis(2-chloroethoxy) methane
45. methyl chloride
46. methyl bromide
47. bromoform
48. dichlorobromomethane
49. DELETED
50. DELETED
51. chlorodibromomethane
52. hexachlorobutadiene
53. hexachlorocyclopentadiene
54. isophorone
56. nitrobenzene
57. 2-nitrophenol
58. 4-nitrophenol
59. 2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
61. N-nitrosodimethylamine
62. N-nitrosodiphenylamine
63. N-nitrosodi-n-propylamine
64. pentachlorophenol
65. phenol
1304
-------
SECONDARY COPPER SUBCATEGORY
SECT. - VI
TABLE VI-2 (Continued)
TOXIC POLLUTANTS NEVER DETECTED
72. benzo(a)anthracene
73. benzo(a)pyrene
79. benzo(ghi)perylene
80. fluorene
82. dibenzo(a,h)anthracene
83. ideno(l,2,3-cd)pyrene
88. vinyl chloride
89. aldrin
90. dieldrin
91. chlordane $ •
92. 4-4'-DDT
93. 4-4'-DDE
94. 4-4'-ODD
95. alpha-endosulfan
96. beta-endosulfan
97. endosulfan sulfate
98. endrin
99. endrin aldehyde
100. heptachlor
101. heptachlor epoxide
102. alpha-BHC
103. beta-BHC
104. gamma-BHC
105. delta-BHC
106. PCB-1242 (a)
107. PCB-1254 (a)
108. PCB-1221 (a)
113. toxaphene
127. thallium
129. 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
(a) Reported-together as a single value
1305
-------
',; i"
.' s-
SECONDARY COPPER SUBCATEGORY
K'l^^ip^^^^^^^.^^iJ
SECT. - VI
TABLE VI-3
TOXIC POLLUTANTS DETECTED IN A SMALL NUMBER OFSOURCES
1. acenapthene
4. benzene
6. carbon tetrachloride
10. 1,2-dichloroethane
23. chloroform
25. 1,2-dichlorobenzene (a)
26. 1,3-dichlorobenzene (a)
27. 1,4-dichlorobenzene (a)
29. 1,1-dichloroethylene
30. 1y 2-trans-dichloroethylene
39. fluoranthene
44. methylene chloride
66. bis(2-ethylhexyl) phthalate
67. butyl benzyl phthalate
68. di-n-butyl phthalate
69. di-n-octyl phthalate
70. diethyl phthalate
76. chrysene
78. anthracene (b)
"81. phenanthrene (b)
84. pyrene
85. tetrachloroethylene
86. toluene
115. arsenic
125. selenium
(a), (b) Reported together as a combined value
1306
-------
SECONDARY COPPER SUBCATEGORY
SECT. - VII
SECTION VII
CONTROL AND TREATMENT TECHNOLOGIES
The preceding sections of this supplement discussed the
wastewater sources, flows, and characteristics of the wastewaters
from secondary copper plants. This section summarizes the
description of these wastewaters and indicates the
technologies which are currently practiced by the
copper subcategory for each waste stream.
TECHNICAL BASIS OF PROMULGATED BPT
treatment
secondary
EPA promulgated BPT effluent limitations for the secondary copper
subcategory on February 27, 1975 under Subpart F of 40 CFR Part
421. These effluent limitations prohibit the discharge of
process wastewater pollutants into navigable waters, and are
based on control technologies for specific waste streams. The
best practicable control technology for process wastewater
generated during the contact cooling of copper ingots, anodes,
billets, or shot is the elimination of this discharge through
recycle and reuse of all contact cooling water. With the reuse
and recycle of casting contact cooling water, the needs for
solids and oil removal would be dictated by plant operational
procedures. Removal of solids such as charcoal used to cover
copper alloy ingots and the oxide scale and mold wash from anode
casting requires sedimentation and filtration before the water is
reused. The pond used for sedimentation will also provide
cooling. Alternately, a cooling tower can provide settling and
cooling capacity.
The best practicable control technology for process wastewater
generated from the quenching and granulation of copper-rich slags
is the elimination of this discharge by the recycle and reuse of
all slag granulation wastewater. Suspended solids are removed by
sedimentation and filtration prior to recycle and reuse.
Alternately, the molten slag may be air cooled after it has been
cast into slag pots for subsequent metal recovery by dry methods.
When quenching and granulating depleted (waste) slags, the best
practicable control technology is the total recycle and reuse of
this wastewater after treatment to reduce suspended solids by
sedimentation and filtration.
The best practicable control technology for process wastewater
generated during copper-rich slag milling and classifying
(residue concentration) is the elimination of this discharge by
either total recycle and reuse of this wastewafcer, or by
melt agglomerating the metal in a blast, cupola, or rotary
furnace.
Prior to recycle and reuse, solids are removed b'y lime
precipitation, if necessary, sedimentation, and filtration.
1307
-------
SECONDARY COPPER SUBCATEGORY
i:,; ..... :•;;» ,,,
SECT
- VII
.: , , , , ; ,,-. , . .
The best practicable control technology for process wastewater
produced from furnace exhaust scrubbing is the elimination of
wastewater discharge by recycling all of the furnace scrubber
water. Before recycling, the scrubber water is treated by
sedimentation and filtration or centrifugation. Another
alternative to the elimination of this waste stream isconversion
to dry air pollution control equipment.
. ,:i M . •• ,„.'i ' ,„: ;pii •'.,,,IN I' !, ii i'1. ,!,iUi *•'*'• • l..ihP!i , • ' , ' , "./•'',,,' " ,•' * '*•, '.''''fii' ,,, ' !
The best practicable control technology for wastewater from
electrolytic refining is the elimination of this wastewater
discharge by treating the bleed stream from electrolytic cell
operations, so that it is suitable for reuse in other plant
processes. The treatment consists of removal of copper by
cementation with iron metal, lime precipitation, and sand
filtering this stream to remove solids. The resulting water is
then discharged to a combined process wastewater reservoir
serving other plant water needs.
CURRENT CONTROL AND TREATMENT PRACTICES
This section presents a summary of the control and treatment
technologies that are currently applied to each of the sources
generating wastewater in this subcategory. As discussed in
Section V, wastewater associated with the secondary copper
subcategory is characterized by the presence of the toxic metal
pollutants and suspended solids. 'This analysis is supported by
raw (untreated) wastewater data presented for specific .sources as
well as combined waste streams in Section V. Generally, these
pollutants are present in each of the waste streams at treatable
concentrations, so these waste streams are commonly combined for
treatment to reduce the concentrations of these pollutants.
Construction of one wastewater treatment system for combined
treatment allows plants to take advantage of economies of scale
and, in some instances, to combine streams of differing
alkalinity to reduce treatment chemical requirements.
Six plants in this subcategory treat combined wastewater. At
three of these plants, combined waste streams are settled in one
or more settling ponds and then completely recycled. One plant
treats combined wastewater by screening, sedimentation in ponds,
and filtration, and combined wastewater is neutralized with
caustic prior to discharge at another plant. At the remaining
plant, combined waste streams are treated by lime precipitation,
sedimentation, and filtration prior to discharge.
Residue Concentration
Residue concentration wastewater is generated when the copper
value is recovered from reverberatory and rotary furnace slags,
and other residues such as drosses, skimmings, spills, and
sweepings, through wet milling and classifying. Seven, plants
generate this waste stream. Five of these plants achieve zero
discharge of residue concentration wastewater through 100 percent
recycle. One discharging plant does not recycle this waste
I
•w.« ij-fvi I
fS\
1308
-------
SECONDARY COPPER SOBCATEGORY SECT. - VII
stream and the other discharging plant did not report its recycle
practices.
The residue concentration wastewater is treated by six of the
seven plants prior to recycle or discharge. The treatment
schemes include the following:
1. Preliminary treatment consisting of acid neutralization,
polymer flocculation, and sedimentation for residue
concentration wastewater only. Following preliminary
treatment, the residue concentration wastewater is
combined with other process wastewater and settled in
lagoons, screened, filtered, and then completely
recycled.
2. Sedimentation with lagoons, total recycle (combined
treatment).
3. Filtration, total recycle (no combined treatment).
4. Sedimentation with classifiers and jigs, screening,
sedimentation with lagoons, total recycle (no combined
treatment).
5. Sedimentation in lagoons, discharge (no recycle, or
combined treatment).
6. Grit removal for residue concentration wastewater, and
combined treatment consisting of lime precipitation,
sedimentation, and filtration, followed by discharge
(recycle practices not reported).
The seventh plant recycles 100 percent of this waste stream, but
did not report if the stream is treated prior to recycle.
Residue concentration wastewater is characterized by treatable
•concentrations of suspended solids and dissolved toxic metal
pollutants.
Slag Granulation
This wastewater is generated when blast or cupola furnace slag is
granulated with high pressure water jets, or in quench pits. Five
plants generate a slag granulation waste stream. Four of these
plants practice complete recycle, and the remaining plant
evaporates its slag granulation wastewater. Prior to recycle,
the slag granulation wastewater is treated by one or more of the
following steps:
1. Screening,
2. Settling ponds or basins, and
3. Filtration.
At two of the total recycle plants, the slag granulation water is
combined with other process wastewater when treated.
1309
-------
SECONDARY COPPER SUBCATEGORY
SECT. - VII
Slag granulation wastewater contains treatable concentrations of
dissolved metals and suspended solids.
Reverberatory and Rotary Furnace Wet Air Pollution Control
Wet air pollution control devices are used by five secondary
copper plants to contain metal oxide fumes and dust produced from
rotary and reverberatory furnace operations. Three of the five
plants completely recycle this waste stream, and one plant
recycles 81 percent. The remaining plant does not-recycle this
waste stream. The control and treatment practices of the five
plants are as follows:
1. Settling ponds, total recycle;
' . . i i - , • •, - ". ..'•• ;;: i , /. v •,•".;', ' 2\^.;; •'.,'. •: • •;.,.'.£' >• >'••• ,."
2. Settling ponds (combined with other process wastewater),
total recycle;
3. Settling tanks, centrifuge, total recycle;
4. Holding tank, 81 percent r'ecycle, settling tanks,
discharge; and
1 , i , • , , :• ,; •" ; '' '' ; ", • • , •, ', . • ' • • i
5. Lime and caustic neutralization, flqcculationwith iron
salts and polymers, clarification, and filtration
followed by discharge.
'"! • • ' , -•,.';' .•"• : .'•• .:••.'• if•••'•'•••.. t •. 'W- ""i-""' •..
As shown above, only one of the five plants combines it furnace
wet air pollution control water with other process wastewater for
treatment.
Reverberatory and rotary furnace wet air pollution control water
is characterized by treatable concentrations of suspended solids
and dissolved toxic metals.
Scrap Anode Rinsing
This wastewater is generated when anodes are removed from
electrolytic cells and rinsed before further processing. Two
plants rinse scrap anodes. Both plants recycle or reuse 100
percent of their scrap anode rinse water. This wastewater is
characterized by treatable concentrations of suspended solids and
dissolved toxic metal pollutants.
Spent Electrolyte
Electrolyte is continuously circulated through thickeners and
filters to remove anode mud slimes, and recycled back through the
electrolytic cells. A bleed stream is necessary to prevent the
build-up of nickel and copper in the electrolyte. Usually,
nickel or copper is recovered from the electrolyte bleed before
recycle or discharge. Copper is recovered from the electrolyte
by cementation with iron. In this process, scrap iron is added
to the spent electrolyte and the solution is heated to about
:•» .'
1310
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SECONDARY COPPER SUBCATEGORY SECT. - VII
180°F, where copper precipitates from solution. An alternate
method for recovering copper from solution is electrowinning.
Nickel is recovered by evaporating the electrolyte^- bleed to
produce nickel sulfate crystals and sulfuric acid. Six plants in
the secondary copper subcategory have an electrolytic refining
process. Two of those plants discharge spent electrolyte without
treatment. One of those two plants contract hauls the spent
electrolyte. At two plants, copper is cemented from an
electrolytic bleed stream with iron, and the resulting solution
is either discharged (at one plant) or contract hauled (at the
other plant). The remaining two plants each achieve zero
discharge of spent electrolyte through the following treatment
schemes:
1. An electrolyte bleed stream is electrowinned to recover
copper and evaporated to recover nickel sulfate crystals
and sulfuric acid.
2. An electrolyte bleed stream is evaporated to recover
nickel sulfate and sulfuric acid.
Spent electrolyte is acidic and contains treatable concentrations
of dissolved metals (particularly copper).
Casting Contact Cooling
Contact cooling water is used by 22 plants in the 'secondary
copper subcategory. As discussed in Section III, there are a
variety of methods for cooling the various types of castings.
In the case of ingots, anodes, and billets, the molten metal is
solidified by spray cooling, and then quenched in tanks.
Finished refined copper shapes are usually prepared by cooling
the molten metal by non-contact cooling techniques, and then
quenching the solidified metal. Shot is manufactured by
directing a small stream of molten copper directly into a quench
pit.
Eleven of the 22 plants which produce casting contact cooling
water achieve zero discharge through total recycle. One achieves
zero discharge through dry well injection. There are a variety
of control and treatment practices utilized by both zero
discharge and discharging plants. These control and treatment
practices are as follows:
1. No recycle, discharge without treatment (five plants);
2. Partial recycle, caustic neutralization, discharge
(one plant);
3. Cooling pond,, partial recycle, settling pond, discharge
(one plant);
4. Partial recycle through cooling towers (two plants);
5. 99 percent recycle with a blowdown stream treated by
1311
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SECONDARY COPPER SUBCATEGORY
SECT. - VII
lime precipitation, sedimentation, and filtration prior
to discharge (one plant);
6. No treatment, total recycle (three plants);
. •: ;i" :,,''"• '''','!;",' f1 '''I1'' "' i'ff iii'V..11',:1.!!111111!,1:''1'""' " '• ' ' ' '
7. Screening, total recycle (one plantj;
8. Settling, total recycle (four plants);
. , ,„ . ..
Screening, settling, filtration, total recycle
(one plant);
10
11
"i.,"1!!!!!1';, •"'!„ '
Settling pits, holding tanks, cooling tower, centri-
fuge, total recycle (one plant);
i ," .IB:,! B
Neutralization with lime, flocculation with polymers,
settling, total recycle (one plant); and
;,i!!' is :i
12. No recycle, dry well injection (one plant).
:*:'. '«i:I
', ti/i;*'!1*?
At five of the above plants, casting contact cooling water is
combined with other process wastewater when treated.
• '! ' ' • • , •.',.• '" ' '"':" "' ' ' ' " " I'' '
Casting contact cooling water is characterized by treatable
concentrations of lead, zinc, copper, and total suspended solids.
Casting Wet Air Pollution Control
Three plants control fumes from casting operations with wet air
pollution control devices. One plant completely recycles casting
scrubber water after neutralizatiQn wifehcaustic and settling,
and one plant contract hauls a casting scrubber water bleed
stream. The remaining plant discharges a casting scrubber water
bleed stream after neutralization with caustic.
CONTROL AND TREATMENT OPTIONS CONSIDERED
Based on an examination of the wastewater sampling data, three
control and treatment options that effectively control the
pollutants found in secondary copper wastewaters were selected
for evaluation. These technology options are discussed below.
Reverse osmosis (Option F) is theoretically applicable to waste
waters generated in the secondary copper subcategory; however, it
is not demonstrated in the nonferrous metals manufacturing
category, nor is it clearly transferable. Activated alumina
absorption (Option D) and activated carbon absorption (Option E)
were not considered for secondary copper because pollutants
(arsenic, fluoride and the toxic organics) generally treatable by
these technologies are not present at treatable concentrations or
in quantities warranting control.
in1:1 ,.:,
:,!t iiirti,' ,'' ' , I wll; '"
1312
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SECONDARY COPPER SUBCATEGORY SECT. -VII
OPTION A
Option A for the secondary copper subcategory is equivalent to
the technology basis for the promulgated pretreatment standards
for existing sources. The Option A treatment scheme consists of
chemical precipitation and sedimentation (lime and settle)
applied to combined waste streams. Chemical precipitation and
sedimentation consists of lime addition to precipitate metals
followed by gravity sedimentation for the removal of suspended
solids, including the metal precipitates.
OPTION G
Option G for the secondary copper subcategory is based on total
recycle of all process wastewater with lime precipitation and
sedimentation treatment. In-process flow reduction prior to lime
and settle treatment is also included for casting contact cooling
and furnace scrubber liquor. Flow reduction for these two waste
streams is based on cooling towers and holding tanks,
respectively. The water obtained from lime and settle treatment
is of sufficient quality for reuse in secondary copper
operations.
1313
-------
SECONDARY COPPER SUBCATEGORY SECT. - VII
THIS PAGE INTENTIONALLY LEFT BLANK
1 ",', "' "!l!',i, ' , 'u "limn il'IHI' '|| I
1314
-------
SECONDARY COPPER SUBCATEGORY SECT. - VIII
SECTION VIII
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS
This section describes the method used to develop the costs
associated with the control and treatment technologies of Options
A and G discussed in Section VII for wastewaters from secondary
copper plants. Plant-by-plant compliance costs for these options
were revised following the 1983 proposal. These revisions
calculate incremental costs, above treatment already in place,
necessary to comply with these effluent limitations and
standards. The energy requirements of the considered options as
well as solid waste and air pollution aspects are also discussed.
TREATMENT OPTIONS COSTED FOR EXISTING SOURCES
As discussed in Section VII, two treatment options have been
developed for secondary copper sources. The options are
summarized below and schematically presented in Figures XII-1 and
XII-2 (pages 1333 and 1334).
OPTION A'
Option A consists of lime precipitation and sedimentation end-of-
pipe technology.
OPTION G
Option G consists of in-process flow reduction measures and lime
precipitation and sedimentation end-of-pipe technology. The in-
process flow reduction measure consists of the recycle of
scrubber water through holding tanks and recycle of casting
contact cooling water through cooling towers.
Cost Methodology
Plant-by-plant compliance costs have been estimated for the
secondary copper subcategory and are presented in the
administrative record supporting this regulation. A comparison
of the costs developed for proposal and the revised costs for the
final regulation are presented in Table VIII-1 (page 1318) for
the indirect dischargers. EPA is promulgating BAT effluent
limitations equivalent to those established in 1975 with the
exception of storm water. With this rulemaking, EPA has
eliminated the net monthly precipitation allowance. These
guidelines are based on cooling impoundments rather than settling
and evaporative impoundments. Cooling impoundments require much
smaller surface areas than the settling and evaporative
impoundments for which the net precipitation discharge was
allowed. Costs for cooling towers were developed for BAT in the
1975 rulemaking for when a plant had insufficient existing
impoundment capacity or cooling impoundments were not feasible
due to space limitations •. EPA believes that secondary- copper
1315
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SECONDARY COPPER SUBCATEGORY
SECT. - VIII
plants can accommodate the small volume of water resulting from
net precipitation on cooling impoundments. There is no cost
associated with the modified BAT effluent limitations.
Each of the major assumptions used to develop compliance costs is
presented in Section VIII of Vol. 1. However, each subcategory
contains a unique set of waste streams requiring certain
subcategory-specific assumptions to develop compliance costs.
Three major assumptions are discussed briefly below.
(1) Monitoring costs are not included for 100 percent
recycle since the option is zero discharge.
(2) Where equipment of sufficient treatment capacity is in
place, annual costs are not included since these were
incurred by the existing PSES regulation. However,
co'sts for cooling towers, which were not included under
promulgated PSES are included for this regulation.
i • , . .. •(.'. ., , • . , i. ii •'.; ."!• i *•,!*! 'ft!; i",;.',;' •' '.i; y i1 . i!' •,( "tijiji. ,' i. »•,,'
(3) No cost is included for direct dischargers to comply
with elimination of net precipitation allowances.
!f" ,i,j; „ t ' , i,;/ ", , " ' ',, "" ', '! ' ' ' ' ' '•' ,'"' "''; , ''!„?' ll!|llil!"', '" '' ,," ''" „ '';'"' ™:iii:'.i" li:!;!,
NONWATER QUALITY ASPECTS
A general discussion of the nonwater quality aspects of the
control and treatment options considered for the nonferrous
metals category is contained in Section VIII of Vol. 1. Nonwater
quality impacts specific to the secondary copper subcategory,
including energy requirements, solid waste and air pollution are
discussed below.
ENERGY REQUIREMENTS
'i ' ,,,.,"!• i" ' " '»'lii / ', ,• V , !' • ' , „ , ', ,„ • I'' ' •' I'M:1,,, I1 i'1"11
The methodology used for determining the energyrequirements for
the various options is discussed in Section VIII of the General
Development Document. Energy requirements for the two options
considered are estimated at 0.15 MW hr/yr and 0.18 MW hr/yr for
Options A and G, respectively. Option G represents roughly one
percent of a typical plant's electrical usage. It is therefore
concluded that the energy requirements of the treatment options
considered will have no significant impact on total plant energy
consumption.
SOLID WASTE
Sludge generated in the secondary copper subcategory is due to
the precipitation of metal hydroxides and carbonates using lime.
Sludges associated with the secondary copper subcategory will
necessarily contain additional quantities (and concentrations) of
toxic metal pollutants. If a small excess of lime is added
during treatment, the Agency does not believe these sludges would
be identified as hazardous under RCRA in any case. (Compliance
costs include this amount of lime.) Solid waste generation was
considered for the promulgated 1975 BPT regulation; no additional
solid waste generation is attributed to this regulation.
1316
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SECONDARY COPPER SUBCATEGORY SECT. - VIII
Although it is the Agency's view that solid waste generated as a
result of these guidelines are not expected to be hazardous,
generators of these wastes must test the waste to determine if
the wastes meet any of the characteristics of hazardous waste
(see 40 CFR 262.11).
If these wastes should be identified or are listed as hazardous,
they will come within the scope of RCRA's "cradle to grave"
hazardous waste management program, requiring regulation from the
point of generation to point of final disposition. EPA's
generator standards would require generators of hazardous
nonferrous metals manufacturing wastes to meet containerization,
labeling, record keeping, and reporting requirements; if plants
dispose of hazardous wastes off-site, they would have to prepare
a manifest which would track the movement of the wastes from the
generators' premises to a permitted off-site treatment, storage,
or disposal facility. See 40 CFR 262.20 45 FR 33142 (May 19,
1980), as amended at 45 FR 86973 (December 31, 1980). The
transporter regulations require transporters of hazardous wastes
to comply with the manifest system to assure that the wastes are
delivered to a permitted facility. See 40 CFR 263.20 45 FR 33151
(May 19, 1980), as amended at 45 FR 86973 (December 31, 1980).
Finally, RCRA regulations establish standards for hazardous waste
treatment, storage, and disposal facilities allowed to receive
such wastes. See 40 CFR Part 464 46 FR 2802 (January 12, 1981),
47 FR 32274 (July 26, 1982).
Even if these wastes are not identified as hazardous, they still
must be disposed of in compliance with the Subtitle D open
dumping standards, implementing 4004 of RCRA. See 44 FR 53438
(September 13, 1979). The Agency has calculated as part of the
costs for wastewater treatment the cost of hauling and disposing
of these wastes. For more details, see Section VIII of Vol. 1.
AIR POLLUTION
There is no reason to believe that any substantial air pollution
problems will result from implementation of cooling towers and
chemical precipitation and sedimentation. These technologies
transfer pollutants to solid waste and are not likely to transfer
pollutants to air.
1317
-------
SECONDARY COPPER SUBCATEGORY
SECT. - VIII
,
TABLE VIII-1
COST OF COMPLIANCE FOR THE
SECONDARY COPPER SUBCATEGORY
Indirect Dischargers
(March, 1980 Dollars)
Option
A
": B
Capital Cost
608432
698498
'Annual" Cost
• ,,!'!ii;" 'i .'I,'"1 "ff';!'!1'1!1 „» :
270832 ........
277353
•'i, •'.„;,!'>;,• , -iTli'S" iff I
'i- • '.ill. :S"l:'S':'.
1318
-------
SECONDARY COPPER SUBCATEGORY SECT. - IX
SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
EPA promulgated BPT effluent limitations for the secondary copper
subcategory on February 27, 1975 as Subpart F of 40 CFR Part 421.
EPA is not promulgating any modifications to these limitations.
With the exception of continuous rod casting, existing point
sources may not discharge process wastewater pollutants to waters
of the United States. Continuous copper rod casting performed at
secondary copper plants is regulated under the metal molding and
casting (foundries) point source category.
The zero discharge of process wastewater pollutants may be
achieved by the application of lime precipitation, sedimentation,
and filtration technology followed by the total recycle and reuse
of treated water. The BPT effluent limitations include net
precipitation and catastrophic storm allowances. A process
wastewater impoundment which is designed, constructed and
operated so as to contain the precipitation from the 10-year, 24-
hour rainfall event as established by the National Climatic
Center, National Oceanic and Atmospheric Administration, for the
area in which such impoundment is located may discharge that
volume of process wastewater which is equivalent to the volume of
precipitation that falls within the impoundment in excess of that
attributable to the 10-year, 24-hour rainfall event, when such
event occurs. Also, during any calendar month there may be
discharged from a process wastewater impoundment either a volume
of process waste water equal to the difference between the
precipitation for that month that falls within the impoundment
and either the evaporation from the pond water surface area for
that month, or a volume of process wastewater equal to the
difference between the mean precipitation for that month that
falls within the impoundment and the mean evaporation from the
pond water surface area as established by the National Climatic
Center, National Oceanic and Atmospheric Administration, for the
area in which such impound is located (or as otherwise determined
if no monthly data have been established by the National Climatic
Center), whichever is greater.
The BPT limitations for the secondary copper subcategory
continue:
Subject to the provisions of paragraphs (b), (c>, and (d) of this
section/ there shall be no discharge of proces's wastewater
pollutants into navigable waters.
(b) A process wastewater impoundment which is designed,
constructed, and operated so as to contain the precipitation from
the 10-year,24-hour rainfall event as established by the National
Climatic Center, National Oceanographic and Atmosphe-ric
Administration, for the area in which such impoundment is located
may discharge that volume of process wastewater equivalent to the
1319
-------
SECONDARY COPPER SUBCATEGORY
SECT. -"'IX
volume precipitation that falls within the impoundment in excess
of that attributable to the 10-year, 24-hour rainfall event, when
such event occurs. ' _ / \ \ ^,,',", ",' ", ... ',,,,',,
(c) During any calendar month there may be discharged from a
process wastewater impoundment either a volume of process
wastewater equal to the difference between the precipitation for
the month that falls within the impoundment and either the
evaporation from the pond water surface area for that month, or a
volume of process wastewater equal to the difference between the
mean precipitation for that month that falls within the
impoundment and the mean evaporation from the pond water surface
area as established by the National Climatic Center, National
Oceanic and Atmospheric Administration, for the area in which
such impoundment is located (or as otherwise determined if no
monthly data have been established by the National Climatic
Center), whichever is greater.
(d) Any process wastewater discharged pursuant to paragraph (c)
of this section shall comply with each of the following
requirements:
BPT Effluent Limitations
BPT Effluent
Limitations
Maximum for
any one day
Average of Daily Values
for 30 Consecutive
days shall not exceed
Pollutant or
Pollutant Parameter
Total Suspended Solids
Copper
Zinc
Oil and Grease
PH
Metric Units (mg/1)
English Units (ppm)
50
0.5
10
20
25
0.25
5
10
£* \j
Within the range of 6.0 to 9.0
1320
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SECONDARY COPPER SUBCATEGORY SECT. - X
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
EPA promulgated BAT effluent limitations for the secondary copper
subcategory on February 27,,1975 as Subpart F of 40 CFR Part 421.
With the exception of continuous rod casting, these BAT effluent
limitations prohibit the discharge of process wastewater
pollutants into U.S. waters. Continuous copper rod casting is
principally a copper forming or foundry operation because the
copper is formed immediately after casting. Casting of products
at copper forming facilities is regulated under the metal molding
and casting (foundries) point source category., The zero
discharge of process wastewater pollutants may be achieved by the
application of lime precipitation, sedimentation and filtration
technology followed by the total recycle and reuse of treated
water. The BAT effluent limitations include the same net
precipitation and catastrophic storm allowances as the existing
BPT effluent limitations except the catastrophic storm is a 25-
year, 24-hour rain fall event.
As discussed in Section IX of Vol. 1, the Agency is modifying its
approach to stormwater. EPA is promulgating modifications to the,
1975 BAT effluent limitations for the secondary copper
subcategory to eliminate the net precipitation allowance. The
impoundments used for cooling and settling process wastewater
prior to recycle and reuse require much smaller surface areas
than the settling evaporative impoundments for which the net
precipitation discharge was allowed. Since cooling and settling
impoundments have a much smaller surface area than evaporative
impoundments, the net precipitation on these impoundments is
small enough for secondary copper plants to accommodate. Costs
for cooling towers were developed for BAT in the 1975 rulemaking
when a plant had insufficient existing cooling impoundment
capacity or cooling impoundments were not feasible due to space
limitations. Thus, EPA is requiring that net precipitation on
cooling and settling impoundments be used in secondary copper
processes instead of being discharged. The promulgated BAT
effluent limitations are, therefore, zero discharge of process
wastewater pollutants to U.S. waters with allowances for the 25-
year, 24-hour storm.
The promulgated BAT effluent limitations for the secondary copper
Subcategory are as follows:
Subject to the provisions of paragraph (b) of this section, there
shall be no discharge of process wastewater pollutants into
navigable waters.
(b) A process wastewater impoundment which is designed,
constructed, and operated so as to contain the precipitation from
the 25-year,24-hour rainfall event as established by the National
Climatic Center, National Oceanographic and Atmospheric
1321
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SECONDARY COPPER SUBCATEGORY
SECT. - x
Administration, for the area in which such impoundment is located
may discharge that volume of process waste'waterequivalent to the
volume precipitation that falls within the impoundment in excess
of that attributable to the 25-year, 24-hour rainfall event, when
such event occurs. " ' ' ' ' '"' •
1322
-------
SECONDARY COPPER SUBCATEGORY SECT. - XI
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
source Performance standards (NSPS) under
? P£ocess. Ganges, in-plant controls, arid- end-of-pipe
exeneasib?e? 916S which reduce P^lution to the maximum
f?A niS/rPr£mUl9a4ng NSPS for ^e secondary copper subcategory
as no discharge of process wastewater pollutants. EPA is also
eliminating the allowance for catastrophic stormwater dilcharqe
?nn^rSd, f ^T ' T^e A<3ency believes that new souses can be
constructed with cooling towers exclusively, and that the cost of
ex?stJLt0o!antinfiead,°f coolin?. ^P^ndmlnts is minimal SoSe
existing plants already use cooling towers rather than coolina
noTc±^S; th"efofe' EPA believls that NSPS, as SSfineS? doel
not constitute a barrier to entry for new plants.
1323
-------
SECONDARY COPPER SUBCATEGORY SECT. - XI
THIS PAGE INTENTIONALLY LEFT BLANK
.if 'i
1324
-------
SECONDARY COPPER SUBCATEGORY
SECT. - XII
SECTION XII
PRETREATMENT STANDARDS
INTRODUCTION
Section 307(b) of the Act requires EPA to promulgate pretreatment
standards for existing sources (PSES), which must be achieved
within three years of promulgation. PSES are designed to prevent
the discharge of pollutants which pass through, interfere with,
or are otherwise incompatible with the operation of publicly-
owned treatment works (POTW). The Clean Water Act of 1977
requires pretreatment for pollutants, such as toxic metals, that
limit POTW sludge management alternatives. Section 307(c) of the
Act requires EPA to promulgate pretreatment standards for new
sources (PSNS) at the same time that it promulgates NSPS. New
indirect discharge facilities, like new direct discharge
facilities, have the opportunity to incorporate the best
available demonstrated technologies, including process changes,
in-plant controls, and end-of-pipe treatment technologies, and to
use plant site selection to ensure adequate treatment system
installation. Pretreatment standards are to be technology-based,
analogous to the best available technology for removal of toxic
pollutants.
EPA promulgated PSES for the secondary copper subcategory on
December 15, 1976 as Subpart P of 40 CFR Part 421. The
promulgated PSES allows a continuous discharge of process
wastewater subject to specific limitations based on treatment
with lime precipitation and sedimentation. Promulgated BAT (and
promulgated BPT) for this subcategory require the zero discharge
of process wastewater pollutants to U.S. waters. EPA is
promulgating modifications to PSES to eliminate the disparity
between BAT and PSES. Accordingly, EPA is promulgating PSES for
the secondary copper subcategory equal to zero discharge of
process waste water pollutants to POTW.
This section describes the control and treatment technologies for
pretreatment of process wastewaters from existing sources and new
sources in the secondary copper subcategory. Pretreatment
standards for regulated pollutants are presented based on the
selected treatment technology.
TECHNICAL APPROACH TO PRETREATMENT
Before promulgating pretreatment standards, the Agency examines
whether the pollutants discharged by the industry pass through
the POTW or interfere with the POTW operations or its chosen
sludge disposal practices. In determining whether pollutants
pass through a well-operated POTW, achieving secondary treatment,
the Agency compares the percentage of a pollutant removed by POTW
with the percentage removed by direct dischargers applying the
best available technology economically achievable. A pollutant
1325
-------
SECONDARY COPPER SUBCATEGORY
SECT. - XII
is deemed to pass through the POTW when the average percentage
removed nationwide by well-operated POTW meeting secondary
treatment requirements, is less than the percentage removed by
direct dischargers complying with BAT effluent limitations
guidelines for that pollutant. (See generally, 46 FR at 9415-16
(January 28, 1981).)
This definition of pass through satisfies two competing
objectives set by Congress: (1) that standards for indirect
dischargers be equivalent to standards for direct dischargers,
while at the same time, (2) that the treatment capability and
performance of the POTW be recognized arid taken into account in
regulating the discharge of pollutants from indirect dischargers.
, _ ' , , _. •• , ..;
The Agency compares percentage removal rather than the mass or
concentration of pollutants discharged because the latter would
not take into account the mass of pollutants discharged to the
POTW from non-industrial sources nor the dilution of the
pollutants in the POTW effluent to lower concentrations due to
the addition of large amounts of non-industrial wastewater.
PRETREATMENT STANDARDS FOR EXISTING SOURCES
The treatment technologies considered for secondary copper plants
discharging to POTW are:
Option A (Figure XII-1, page 1333) is based on:
1 ' ',, . : , ; ;' • • : -'V •,"!:(:!"''','«',;, " ':,V. */'• ' .&' "" ' ' .'; V' * '•!?'•,'
o Lime precipitation and sedimentation
Option G (Figure XII-2, page 1334) is based on:
o Lime precipitation and sedimentation
o In-process flow reduction with cooling towers and
holding tanks
o Total recycle and reuse of treated water
These two technology options for PSES are discussedin greater
detail below. The first option considered (Option A) is
identical to the technology basis for the existing PSES. The
remaining option provides additional pollutant removal beyond
that achieved by Option A.
1 '"I! • ' ' ' . i • •!,' ' ' hi i 11'," ii . " -, . I'll! f : •" • ' , " :»;; ,? :, ,i|
Option A
Option A for the secondary copper subcategory is lime
precipitation and sedimentation (lime and settle). Lime
precipitation and sedimentation removes metals and suspended
solids from process wastewater by the addition of lime followed
by sedimentation.
"if •• • 1;
1326
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SECONDARY COPPER SUBCATEGORY SECT. - XII
Option G
Option G consists of the lime precipitation and sedimentation
technology of Option A, followed by complete recycle and reuse of
the treated water. In-process flow reduction measures consisting
of the recycle of process wastewater through cooling towers or
holding tanks is also added for Option G.
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
As one means of evaluating each technology option, EPA developed
estimates of the pollutant removal and the compliance costs
associated with each option. These methodologies are described
below.
POLLUTANT REMOVAL ESTIMATES
A complete description of the methodology used to calculate the
estimated pollutant reduction achieved by the application of the
various treatment options is presented in Section X of vol. 1.
The pollutant removal estimates have been revised from proposal
based on comments and new data. The data used for estimating
pollutant removals are the same as those used to revise the
compliance costs. However, the methodology for . calculating
pollutant removals was not changed.
Sampling data collected during the field sampling program were
used to characterize the major waste streams considered for
regulation. At each sampled facility, the sampling data were
production normalized for each unit operation (i.e., mass of
pollutant generated per mass of product .manufactured). This
value, referred to as the raw waste, was used to estimate the
mass of toxic pollutant generated within the secondary copper
subcategory. By multiplying the total subcategory production for
a unit operation times the corresponding raw waste value, the
mass of pollutant generated for that unit operation was
estimated.
The volume of wastewater discharged after the application of each
treatment option was estimated for each operation at each plant
by comparing the actual discharge to the regulatory flow. The
smaller of the two values was selected and summed with the other
plant flows. The mass of pollutant discharged was then estimated
for each operation at each plant by comparing the actual
discharge to the regulatory flow. The smaller of the two values
was selected and summed with the other plant flows. The mass of
pollutant discharged was then estimated by multiplying the
achievable concentration values attainable by the option (mg/1)
by the estimated volume of process wastewater discharged by the
subcategory. The mass of pollutant removed is simply the
difference between the estimated mass of pollutant generated
within the subcategory and the mass of pollutant discharged after
application of the treatment option. The pollutant removal
estimates for indirect discharges in the secondary copper
subcategory are presented in Table'XII-1 (page 1332).
1327
-------
SECONDARY COPPER SUBCATEGORY
SECT. - XII
COMPLIANCE COSTS
It I!
Compliance costs presented at proposa (February 1983) were
estimated using cost curves, which related the total costs
associated with installation and operation of wastewater
treatment technologies to plant process wastewater discharge.
EPA applied these curves on a per plant basis, a plant's 'costs--'
both capital, and operating and maintenance — being determined by
what treatment it has in place and by its individual process
wastewater discharge (from dcp) . The final step was to annualize
the capital costs, and to sum the annualized capital costs, and
the operating and maintenance costs, yielding the cost of
compliance for the subcategory.
Since proposal, the cost estimation methodology has been changed
as discussed in Section VIII of this document and in Section VIII
of Vol. 1. A design model and plant specific information were
used to size a wastewater treatment system for each discharging
facility. After completion of the design, capital and annual
costs were estimated for each unit of the wastewater treatment
system. Capital costs rely on vendor quotes, while annual costs
were developed from the literature. The revised compliance costs
for indirect dischargers are presented in Table VIII-1 (page
1318).
P3ES OPTION SELECTION
X ' ' " , ' •:.!'• >•'•: I/1',! I1'', ;' !:'.jtf H fc ! .':,'•. '' \'..- , &• •' "(< , '' .'i. 'i',i;: ..
EPA has selected Option G as the basis for PSES. Option G
consists of chemical precipitation and sedimentation, with
cooling towers and holding tanks to achieve zero discharge of
process wastewater pollutants. Implementation of Option G would
remove an estimated 9",500 kg of toxic pollutants over estimated
raw discharge. The estimated capital cost for achieving PSES is
$654,000 (March, 1982 dollars), and the estimated annual cost is
$277,000.
PSNS OPTION SELECTION
The technology basis for promulgated PSNS is identical to NSPS
and BAT, which is zero discharge of all process wastewater
pollutants (including no allowance for catastrophic stormwater
discharges). PSNS does not increase costs compared to PSES or
BAT, and EPA does not believe that PSNS will prevent the entry of
new plants.
WASTEWATER DISCHARGE RATES
Specific wastewater streams associated with the secondary copper
subcategory are residue concentration wastewater, slag
granulation wastewater, reverberatory and rotary furnace wet air
pollution control wastewater, spentelectrolyte, scrap anode
rinsing wastewater, casting contact cooling wastewater and
casting wet air pollution control wastewater. None of these
wastewater streams are allocated a discharge allowance for the
promulgated PSES. The zero discharge requirement will eliminate
i! ;:»
1328
-------
SECONDARY COPPER SUBCATEGORY
SECT. - XII
the disparity between the 1976 PSES and the promulgated BAT
effluent limitations. Each wastewater stream is discussed
individually below.
RESIDUE CONCENTRATION
No .discharge allowance is provided for residue concentration for
PSES. Seven plants in the secondary copper subcategory generate
residue concentration wastewater. The water use and discharge
rates for residue concentration at these plants are shown in
Table V-2 (page 1257). As shown in Table V-2, five of the seven
plants practice total recycle and reuse of this waste stream,
while only two plants discharge the residue concentration
wastewater. The zero discharge of residue concentration
wastewater is based on the five plants who do not discharge this
wastewater.
SLAG GRANULATION
No discharge allowance is provided for slag granulation for PSES.
Five plants in the secondary copper subcategory generate this
waste stream. The water use and discharge rates for slag
granulation at these plants are shown in Table V-3 (page 1258).
As shown by Table V-3, all five plants practice total recycle and
reuse of this waste stream. Accordingly, no discharge allowance
is provided for slag granulation.
REVERBERATORY AND ROTARY FURNACE, WET AIR POLLUTION CONTROL
No discharge allowance is provided for reverberatory and rotary
furnace wet air pollution control for PSES. Five plants in the
secondary copper subcategory use wet air pollution control on
their rotary and reverberatory furnaces. The production
normalized water use and discharge rates for reverberatory
rotary furnace wet air pollution control of these plants
shown in Table V-4 (page 1259). Three of the five plants
completely recycle and reuse this waste stream. In addition, 13
plants control reverberatory and rotary furnace fumes and dust
with dry air pollution control devices. Therefore, based on
total recycle or dry air pollution control, no discharge
allowance is provided. for reverberatory and rotary furnace wet
air pollution control.
SPENT ELECTROLYTE
No discharge allowance is provided for spent electrolyte for the
PSES. Six plants in the secondary copper subcategory have an
electrolyte refining process. The production normalized
electrolyte use and discharge rates at these plants are shown' in
Table v-5 (page 1260). Four plants achieve zero discharge of
spent electrolyte by either complete recycle (two plants) or by
contract hauling (two plants). EPA believes that spent
electrolyte is suitable for reuse in other plant operations after
treatment consisting of cementation with iron (for copper
recovery), lime precipitation, and sedimentation. For this
and
are
1329
-------
SECONDARY COPPER SUBCATEGORY
SECT. - XII
reason, and since four of the six plants already achieve zero
discharge for spent electrolyte, 'a'discfiafgie allowance is not
provided.
SCRAP ANODE RINSING
No discharge allowance is provided for scrap anode rinsing for
PSES. Two plants reported this waste stream. The water use and
discharge rates for scrap anode rinsing at these plants are shown
in Table V-6 (page 1261). Table V-6 shows that both of the
plants with scrap anode rinsing practice 100 percent recycle.
Accordingly, a discharge allowance is not provided for scrap
anode rinsing.
CASTING CONTACT COOLING
With the exception of continuous rod casting, no discharge
allowance is provided for casting contact cooling water.
Continuous rod casting is principally a copper forming operation,
and casting in this point source category is covered by the metal
molding casting guidelines where continuous rod casting is given
a discharge allowance. Twenty-two plants use casting contact
cooling water in the secondary copper subcategbry. The water use
and discharge rates for casting contact cooling at these plants
are shown in. Table V-.7. (page 1262). As shown in Table V-7, 10 of
the 22 plants achieve zero discharge of this wastewater. EPA
believes that the 12 plants which discharge this wastewater can
also achieve zero discharge through recycle and reuse with
cooling towers and holding tanks. Therefore, no discharge
allowance is provided for casting contact cooling water.
CASTING WET AIR POLLUTION CONTROL
No discharge allowance is provided for castingwet air pollution
control. Three plants in the secondary copper subcategory use
wet air pollution control devices to control fumes from casting
melting furnaces or pouring. The water use and discharge rates
for casting wet air pollution control are shown in Table V-8
(page 1263). Table V-8 shows that one of the three plants
completely recycle and reuses this waste stream. In addition,
five plants use dry air pollution control devices to control
fumes from casting operations. Therefore, based on total recycle
or dry air pollution control, no discharge allowance is provided
for casting wet air pollution control.
STORMWATER AND PRECIPITATION ALLOWANCES
No discharge allowance is provided for net precipitation
stormwater for the promulgated PSES and PSNS. These standards
are1 based on the use of cooling towers and holding tanks rather
than cooling impoundments. Because cooling towers are not
substantially affected by precipitation and the water using
processes are water consuming, the balance between precipitation
and evaporation should have no effect on the operability of the
facility.
1330
.i
-------
SECONDARY COPPER SUBCATEGORY SECT. - XII
Catastrophic stormwater allowance is continued for PSES so that
the requirements for direct dischargers meeting BAT and indirect
dischargers meeting PSES are equivalent. Facilities using
settling ponds to remove solids prior to recycle may need to
discharge water after receiving water from a major precipitation
event which exceeds their design parameters.
Because new plants have the opportunity to design to remove
solids from wastewater using technologies that are not
appreciably affected by rainfall, there is no catastrophic
stormwater allowance provided for PSNS.
PRETREATMENT STANDARDS FOR EXISTING AND NEW SOURCES
EPA is promulgating a standard prohibiting the discharge of
process wastewater pollutants for both PSES and PSNS for the
secondary copper subcategory. The facility which discharges to a
POTW will need to meet the same requirements as a facility
discharging directly to the waters of the United States.
The pretreatment standard for an existing source (PSES) is:
(a) There shall be no discharge of process wastewater pollutants
into a publicly owned treatment works subject to the provisions
of paragraph (b) of this section.
{b) A process wastewater impoundment which is designed,
constructed, and operated so as to contain the precipitation from
the 25-year,24-hour rainfall event as established by the National
Climatic Center, National Oceanographic and Atmospheric
Administration, for the area in which such impoundment is located
may discharge that volume of process wastewater equivalent to the
volume precipitation that falls within the impoundment in excess
of that attributable to the 25-year, 24-hour rainfall event, when
such event occurs.
The pretreatment standard for a new source (PSNS) is:
There shall be discharge of process wastewater pollutants into a
publicly owned treatment works.
1331
-------
SECONDARY COPPER SUBCATEGORY
SECT. - XII
TABLE XII-1
POLLUTANT REMOVAL ESTIMATES FOR SECONDARY COPPER
INDIRECT DISCHARGERS
OPTION G
POLLUTANT
Arsenic
Cadmium
Chromium
Lead
Nickel
Selenium
Copper
Zinc
TOTAL TOXIC METALS
TOTAL
Aluminum
Ammonia
Fluoride
Iron
NONCONVENT IONALS
TSS
Oil & Grease
TOTAL CONVENTIONALS
TOTAL POLLUTANTS
FLOW (1/yr)
RAW WASTE DISCHARGED
(kg/yr) (kg/yr)
7«. / v,,, .';
0.9
0.6
18.1
286.6
6,978.9
0.0
1,680.1
496.2
if
9,461.5
20.1
107.9
0.0
7,645.1
7,773.1
3,358.8
720.9
4,079.6
21,314.2
it
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
"" ' '"'o.o'
'••• ;";":;:o".6'i
0.0
0.0
0.0
0.0
2. 0'°
0
REMOVED
(kg/yr)
t 1
0.9
0.6
18.1
286.6
6,978.9
0.0
1,680.1
496.2
II
9,461.5
20.1
107.9
" """" ••:•"•" 6".0'"
7,645.1
7,773.1
3,358.8
720.9
4,079.6
'" 21, 3 14.2 '
NOTE: TOTAL TOXIC METALS = Arsenic + Cadmium + Chromium + Lead
+ Nickel + Selenium + Copper + Zinc
TOTAL NONCONVENTIONALS = Aluminum + Ammonia + Fluoride
+ Iron
TOTAL CONVENTIONALS = TSS + Oil & Grease
TOTAL POLLUTANTS = Total Toxic Metals + Total Nonconven-
tionals + Total Conventionals
OPTION G = In-Process Flow Reduction, Lime Precipitation
and Sedimentation followed by complete recycle
or reuse of treated water.
1332
-------
SECONDARY COPPER SUBCATEGORY
SECT - XII
3
€
g r*, 83
•»« II «*• M
i W-* 81
M O
HW
CuH
0<
U
M Cd OT
X K
(U OT Cd
2
^i
|
GO
3
2
a a a
1-s
SSS
T
a
u
GO
•O I
s
e
o
a
zo
OT O
W H
COOT
cu
1333
-------
SECONDARY COPPER SUBCATEGORY
SECT - XII
b]
CM Cd.CQ
I S3
M Cd W
-------
SECONDARY COPPER SUBCATEGORY SECT, - XIII
'»
fr
SECTION XIII
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY
EPA is not promulgating best conventional pollutant control
technology (BCT) for the secondary copper subcategory at this
time.
1335
-------
SECONDARY COPPER SUBCATEGORY SECT. - XIII
THIS PAGE INTENTIONALLY LEFT BLANK
1336
-------
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
DEVELOPMENT DOCUMENT SUPPLEMENT
for the
Metallurgical Acid Plants Subcategory
William K. Reilly
Administrator
Rebecca Hanmer
Acting Assistant Administrator for Water
Martha Prothro, Director
Office of Water Regulations and Standards
^K--J*> Si
mj
Thomas P. O'Farrell, Director
Industrial Technology Division
Ernst P. Hall, P.E., Chief
Metals Industry Branch
and
Technical Project Officer
May 1989
U.S. Environmental Protection Agency
Office of Water
Office of Water Regulations and Standards
Industrial Technology Division
Washington, D. C. 20460
1337
-------
1338
i (i in
-------
METALLURGICAL ACID PLANT SUBCATEGORY
Section
TABLE OF CONTENTS
SUMMARY
Page
1345
II
CONCLUSIONS
1349
III
IV
V
SUBCATEGORY PROFILE
Description of Metallurgical Acid Plants
Raw Materials
Copper
Lead
Molybdenum
Zinc
Applicability of Metallurgical Acid Plants
Process Description
Cooling
Cleaning
Conditioning
Mist Precipitation
Drying
Compression
Acid Production
Process Wastewater Sources
Other Wastewater Sources
Age, Production, and Process Profile
SUBCATEGORIZATION
Factors Considered in Subcategorization
Factors Considered in Subdividing the
Metallurgical Acid Plants Subcategory
Production Normalizing Parameters
WATER USE AND WASTEWATER CHARACTERISTICS
Water use and Wastewater Discharge Rates
Wastewater Characteristics
1353
1353
1353
1353
1355
1355
1356
1356
1357
1357
1357
1357
1358
1358
1358
1358
1359
1359
1360
1365
1365
1365
1366
1367
1368
1368
1339
-------
Number
METALLURGICAL ACID PLANT gUBCATEGORY
TABLE OF CONTENTS (Continued)
VI
VII
VIII
IX
SELECTION OF POLLUTANTS 1389
Conventional and Nonconventional Pollutant 1389
Parameters
Conventional and Nonconventional Pollutant 1389
Parameters Selected
Tpxic Pollutants 1390
Toxic Pollutants Never Detected 1390
Toxic Pollutants Never Found Above 1391
Their Analytical Quantification Concentration
Toxic Pollutants Present Below 1391
Concentrations Achievable by Treatment
Toxic Pollutants Detected in a 1391
Small Number of Sources
Toxic Pollutants Selected for 1393
Consideration in Establishing Limitations
CONTROL AND TREATMENT TECHNOLOGIES 1405
Technical Basis of BPT 1405
Current Control and Treatment Practices 1405
Control and Treatment Options 1407
Option A 1407
Option B 1407
Option C 1407
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS 1409
Treatment Options Costed for Existing Sources 1409
Option A 1409
Option B 14Q9
Option C 1409,
Cost Methodology 1410
Nonwater Quality Aspects 1411
Energy Requirements 1411
Solid Waste 1411
Air Pollution 1412
BEST PRACTICABLE CONTROL TECHNOLOGY 1415
CURRENTLY AVAILABLE
Industry Cost and Pollutant Removal Estimates 1416
1340
-------
METALLURGICAL ACID PLANT SUBCATEGORY
Section
X
XI
XII
XIII
TABLE OF CONTENTS (Continued)
Page
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE 1419
Technical Approach to BAT 1419
Option A 1420
Option B 1420
Option C 1421
Industry Cost and Pollutant Retrieval Estimates 1421
Pollutant Removal Estimates 1421
Compliance Costs 1422
BAT Option Selection - Proposal 1123
BAT Option Selection - Promulgation 1123
Final Amendments to the Regulation 1424
Wastewater Discharge Rates 1424
Regulated Pollutant Parameters 1425
Effluent Limitations 1427
NEW SOURCE PERFORMANCE STANDARDS 1435
Technical Approach to BDT 1435
BDT Option Selection 1436
Regulated Pollutant Parameters 1436
New Source Performance Standards 1436
PRETREATMENT STANDARDS 1439
Technical Approach to Pretreatment 1439
Pretreatment Standards for Existing 1440
and New Sources
Industry Cost and Pollutant Removal Estimates 1440
PSES and PSNS Option Selection 1440
Regulated Pollutant Parameters 1441
Pretreatment Standards 1442
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY 1447
1341
-------
METALLURGICAL ACID PLANT SUBCATEGORY
".';.••• •' "'"; ; ''. " "III ' 'I ' •
LIST OF TABLES
,'1'TIf;':1
1'{;, iti'i • JiiBiiiil1!
Table
III-l
III-2
V-l
V-2
VI-1
VI-2
VI-3
VIII-1
VIII-2
IX-1
X-l
X-2
XI-1
XII-1
XII-2
XII-3
Title
Summary of Discharge Status in the Metallurgical
Acid Plants Subcategory
Production Ranges for Metallurgical Acid Plants
Water Use and Wastewater Discharge Flow Rates
for Metallurgical Acid Plants
Metallurgical Acid Plants Sampling Data Acid
Plant Slowdown
Toxic Pollutants Never Detected
Toxic Pollutants Never Detected Above Their
Analytical Quantification Limit
Frequency of Occurrence of Priority Pollutants
Metallurgical Acid Plants Raw Wastewater
Cost of Compliance for the Metallurgical Acid
Plants Subcategory
Cost of Compliance for the Metallurgical Acid
Plants Subcategory
BPT Effluent Limitations for the Metallurgical
Acid Plants Subcategory
Pollutant Removal Estimates for Metallurgical
Acid Plants Direct Dischargers
BAT Mass Limitations for the Metallurgical
Acid Plants Subcategory
NSPS for the Metallurgical Acid Plants
Subcategory
. i . ' i|i| •„,.! . .V!!!! , . , • ' ' . , ' ' i .
Pollutant Removal Estimates for Metallurgical
Acid Plants Indirect Dischargers
PSES for the Metallurgical Acid Plants
Subcategory
PSNS for the Metallurgical Acid Plants
Subcategory
1342
: : . . . •
Page
'^'''orv'*'*!!1!'!!'1 »;;
1361
1361
1371
1372
• ', '.• ;
1396
1398
• ' V".1 'I i..,,,",'1 "ti"i" lk.ii,
1400
1413
„ i
1413
1417
1428
1429
1437
1 ' ' 'i' SIM, ' !,'i ',
•, ' " In,1' . '" I.
v ' I,,.'. • ;.:•; ,i,,
1443
1444
1,1 * ' !li!:l '" 'Ji,ii: i
1445
• " • ; " '
-------
METALLURGICAL ACID PLANT SUBCATEGORY
LIST OF FIGURES
Figure Title Page
III-l Typical Metallurgical Acid Plant lock Flow 1362
Diagram
III-2 Geographic Locations of Metallurgical Acid 1363
Plants
V-l Sampling Sites at Primary Lead Plant B 1381
V-2 Sampling Sites at Primary Zinc Plant B 1382
V-3 Sampling Sites at Primary Zinc Plant C 1383
V-4 Sampling Sites at Primary Zinc Plant D 1384
V-5 Sampling Sites at Primary Copper Smelting and 1385
Refining Plant C
V-6 Sampling Sites at Primary Copper Smelter Plant B 1386
V-7 Sampling Sites at Primary Zinc Plant G 1387
V-8 Sampling Sites at Primary Molybdenum Plant B 1388
IX-1 BPT Treatment Scheme for the Metallurgical Acid 1418
Plants Subcategory
X-l BAT Treatment Scheme Option A Metallurgical 1430
Acid Plants Subcategory
X-2 BAT Treatment Scheme Model B, Metallurgical 1431
Acid Plants Subcategory
X-3 BAT Treatment Scheme Option C for Lead and 1432
Zinc Metallurgical Acid Plants
X-4 BAT Treatment Scheme Option C for one Primary 1433
Copper and all Primary Molybdenum Metallurgical
Acid Plants
1343
-------
METALLURGICAL ACID PLANT SUBCATEGORY
THIS PAGE INTENTIONALLY LEFT BLANK
1344
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - I
SECTION I
SUMMARY
On April 8, 1974, EPA promulgated technology-based effluent
limitations and standards for several subcategories of the
Nonferrous Metals Manufacturing Point Source Category. This
regulation included BPT, BAT, NSPS, and PSNS limitations.
EPA promulgated technology-based effluent limitations for the
metallurgical acid plant subcategory of the Nonferrous Metals
Manufacturing Point Source Category on July 2, 1980 (45 FR
44926). Best practicable control technology currently available
(BPT) effluent limitations were established. This new
subcategory covered all operations associated with, the
manufacture of by-product sulfuric acid at primary copper plants
and included associated air pollution control (or gas
conditioning systems) for sulfur dioxide off-gases from
pyrometallurgical Operations.
On March 8, 1984 (49 FR 8742), EPA expanded the metallurgical
acid plant subcategory and established BAT, NSPS, PSES, and PSNS
pursuant to the provisions of Sections 301, 304, 306 and 307 of
the Clean Water Act, as amended. EPA expanded this subcategory to
include analogous operations associated with the manufacture of
by-product sulfuric acid from primary lead and primary zinc
plants. On September 20, 1985 (50 FR 38276) the metallurgical
acid plants subcategory was further expanded to include by-
product sulfuric acid plants associated with primary molybdenum
roasting operations. The pollutants regulated at BPT, BAT, NSPS
and PSNS were revised to take into account pollutants specific to
primary molybdenum acid plants by adding the pollutants
molybdenum and fluoride to the regulated pollutants for
molybdenum acid plants only, however, PSES was not revised
because there are no indirect discharging primary molybdenum acid
plants. This supplement provides a compilation and analysis of
the background, material used to develop these effluent
limitations and standards.
EPA entered into a settlement agreement in June 1987, with AMAX,
Inc., and GTE Products Corp., two petitioners affected by the
regulations for the Metallurgical Acid Plants Subcategory. This
Settlement Agreement concerns one topic, molybdenum limitations,
which is briefly described here, and more fully described
elsewhere in this document. The molybdenum limitations were
suspended until petitioners install the model technology, iron
coprecipitation, and submit data to the Agency. EPA agreed to
recommend two sets of interim limits to permit writers. The
first set of interim limits would be based on a monthly average
treatment effectiveness of 30 mg/1 and a daily maximum of 60 mg/1
and will be effective until April 30, 1988. At that time, if no
full-scale data are available, the second set of interim limits
will be based on the results of bench-scale iron coprecipitation
data obtained under the supervision of the Agency.
1345
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - I
The metallurgical acid plant subcategory is comprised of 22
facilities. Of the 22 plants, 10 discharge directly to rivers,
lakes, or streams; two discharge to a publicly owned treatment
works (POTW); and 10 achieve zero discharge of process
wastewater.
EPA first studied the metallurgical acid plant subcategory to
determine whether differences in raw ma,t:e,ri§3Ls, final products,
manufacturing processes, equipment, age and size of plants, water
usage, required the development of separate effluent limitations
and standards for different segments of the subcategory. This
involved a detailed analysis of wastewater discharge and treated
effluent characteristics, including (1) the sources and volume of
water used, the processes used and the sources of pollutants and
wastewaters in the plant; and (2) the constituents of waste
waters, including toxic pollutants.
EPA also identified several distinct control and treatment
technologies (both in-piant and end-of-pipe) applicable to the
metallurgical acid plant subcategory. The Agency analyzed both
historical and newly generated data on the performance of these
technologies, including their nonwater quality environmental
impacts (such as air quality impacts or solid waste generation)
and energy requirements. EPA also studied various flow reduction
techniques reported in the data collection portfolios (dcp) and
plant visits.
Engineering costs were prepared for each of the control and
treatment options considered for the category. These costswere
then used by the Agency to estimate theimpactof implementing
the various options on the industry. For each control and
treatment option that the Agency foundto bemost effective and
technically feasible in controlling the discharge of pollutants,
the number of potential closures, number of employees affected,
and impact on price were estimated. These results are reported
in a separate document entitled Economic Impact Analysis of
Effluent Limitations and Standards for .the Nonferrous Metals
Smelting" and Refining Industry.
Based on consideration of the above factors, EPA identified
various control and treatment technologies which formed the basis
for BAT andselected control and treatment appropriate for each
set, of limitations and standards. .",TheT' ^mass, ., i limitations,, and,
standards for BAT, NSPS, PSES, and PSNS are presented in Section
ii. ,„ ' , ; ' " :",;;;,;;;„; :";;,;, ,"^'w",'.,' ,.'..".,. „,..,...,..",.'.', :
• ,,l / 'II" : ' »'. • ,„ ji' "'I"',; T,?.1', ' ati ill1 !'i,I'"Bill I1-'I liiK-'liiHi'lfclV1:.'!1'! .I,1!!11"' '''I,'1.. 'V, /III11'/!1 ''.li'11!"!'.,.",::: t . '. " I'll1!' ^
For BAT, the Agency has built upon the BPT basis of lime
precipitation and sedimentation by adding in-process control
technologies which include recycle of pj:ocess water from air
pollution control and metal contact cooling wastewater streams.
Sulfide precipitation may also be a necessary treatment step at
various facilities. Irqn CQ-precipitation may be necessary for
primary molybdenum acid plants in "order to achieve the
limitations for molybdenum. Filtration is added as an effluent
X'-TV1., ' ..'I Vllii ,1
1346
-------
METALLURGICAL ACID PLANT SUBCATEGORY
SECT - I
polishing step to the end-of-pipe treatment scheme. To meet the
BAT effluent limitations based on this technology, the
metallurgical acid plant subcategory is estimated to incur a
capital cost of $2.5 million (1982 dollars) and an annual cost of
$2.0 million (1982 dollars).
The best demonstrated technology (BDT), which is the technical
basis of NSPS, is equivalent to BAT. In selecting BDT, EPA
recognizes that new plants have the opportunity to implement the
best and most efficient manufacturing processes and treatment
technology. As such, the technology basis of BAT has been
determined as the best demonstrated technology.
The Agency is promulgating pretreatment standards for existing
sources (PSES) equal to BAT. To meet the PSES, the metallurgical
acid plant subcategory is estimated to incur a capital cost of
$0.161 million (1982 dollars) and an annual cost of $0.085
million (1982 dollars). The technology basis for pretreatment
standards for new sources (PSNS) is the best demonstrated
technology, which is BAT. As such, the PSNS are identical to
NSPS for all waste streams.
1347
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - I
|. • '. '• ' " - . • 'I '. •., ,« . ," '•'•»» iStli'i E '.'.,• ' .'",'
THIS PAGE INTENTIONALLY LEFT BLANK
1348
-------
METALLURGICAL ACID PLANT SUBCATEGORY
SECT - II
SECTION II
CONCLUSIONS
EPA has not divided the metallurgical acid plant subcategory into
segments for the purpose of effluent limitations and standards.
This single building block is referred to as acid plant blowdown
and generally includes wastewater generated through wet scrubbing
and humidification to precondition gases before they enter an
acid plant along with the acid plant wastewater which is mostly
generated by eliminating entrained mist before the gas is
discharged to the atmosphere.
EPA promulgated BPT effluent limitations for the metallurgical
acid plants subcategory on July 2, 1980 (45 FR 44928) as Subpart
I of 40 CPR Part 421. These BPT effluent limitations apply to
process wastewater discharges resulting from or associated with
the manufacture of by-product sulfuric acid at primary copper
smelters, including any associated air pollution control or gas-
conditioning systems for sulfur dioxide off-gases from
pyrometallurgical operations. On March 8, 1984 (49
-------
, . . , .. .. •. .,, .. . ..- •
METALLURGICAL ACID PLANT SUBCATEGORY SECT - II
/"iiJis:1 B1 i
multimedia filtration (lime, settle, and filter) technology and
in-process flow reduction control methods. Sulfide precipitation
is added at various facilities to achieve the performance of
lime, settle, and filter technology. Iron co-precipitation is
added for acid plants associated with primary molybdenum roasting
operations in order to control discharges of molybdenum. The
following BAT effluent limitations are promulgated for existing
sources:
(a) Acid Plant Slowdown
. '": •. " - ' ! :, • • ' ' ' • ','< ' ' " I
BAT EFFLUENT LIMITATIONS
Pollutant or
Pollutant Property
Maximum For
Any One Day
Maximum For
Monthly Average
mg/kg (Ibs/million Ibs) of 100 percent sulfuric acid capacity
Arsenic
Cadmium
Copper
Lead
Zinc
Fluoride1
Molybdenum1
3.550
0.511
3.269
0.715
2.605
89.390
Reserved
1.584
0.204
1.558
0.332
1.073
50.820
Reserved
•'•For molybdenum acid plants only.
- ' : , i ,ii • in
NSPS are promulgated based on the performance achievable by the
application of chemical precipitation, sedimentation, and
multimedia filtration (lime, settle, and filter) technology and
in-process flow reduction control methods.Sulfide precipitation
is added at various facilities to achieve the performance of
lime, settle, and filter technology. Iron co-precipitation is
added for acid plants associated with primary molybdenum roasting
operations to achieve the effluent standards for molybdenum. The
following effluent standards are promulgated for new sources:
1350
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - II
(a) Acid Plant Blowdown NSPS
Pollutant or
Pollutant Property
Maximum For
Any One Day
Maximum For
Monthly Average
mg/kg (Ibs/million Ibs) of 100 percent sulfuric acid capacity
Arsenic
Cadmium
Copper
Lead
Zinc
Fluoride1
Molybdenum1
TSS
pH
3.550
0.511
3.269
0.715
2.605
89.390
Reserved
38.310
Within the range of 7.5 to 10.0
at all times
1.584
0.2O4
1.558
0.332
1.073
50.820
Reserved
30.650
LFor molybdenum acid plants only.
PSES are promulgated based on the performance achievable by the
application of chemical precipitation, sedimentation, and
multimedia filtration (lime, settle, and filter) technology and
in-process flow reduction control methods. .Sulfide precipitation
is added at various facilities to achieve the performance of
lime, settle, and filter technology. The following pretreatment
standards are promulgated for existing sources:
(a) Acid Plant Blowdown PSES
Pollutant or
Pollutant Property
Maximum For
Any One Day
Maximum For
Monthly Average
rog/kg (Ibs/million Ibs) of 100 percent sulfuric acid capacity
Cadmium
Zinc
0.511
2.605
0.204
1.073
PSNS are promulgated based on the performance achievable by the
application of chemical precipitation, sedimentation, and
multimedia filtration (lime, settle, and filter) technology and
in-process flow reduction control methods. Sulfide precipitation
is added at various facilities to achieve the performance of
lime, settle, and filter technology. Iron co-precipitation is
1351
-------
METALLURGICAL ACID PLANT SUBCATEGORY
SECT - II
added for acid plants associated with primary molybdenum roasting
operations in order to control discharges of molybdenum. The
following pretreatment standards are promulgated for new sources:
•'•'< ' . . •' " 'i.; • ,' '''"',:••""• ^M:.S^';!'/; ,.i ;•; <: ^^v::- •• (-> \; ' i,1
(a) Acid Plant Slowdown PSNS
11
Pollutant or
Pollutant Property
Maximum For
Any One Day
Maximum For
Monthly Average
mg/kg (Ibs/million Ibs) of 100 percent sulfuric acid capacity
Arsenic
Cadmium
Copper
Lead
Zinc
Fluoride1
Molybdenum1
3.550
0.511
3.269
0.715
2.605
89.390
Reserved
1.584
0.204
1.558
0.332
1.073
50.820
Reserved
molybdenum acid plants only.
1352
-------
METALLURGICAL ACID PLANT SUBCATEGORY
SECT - III
SECTION III
SUBCATEGORY PROFILE
This section introduces the raw materials and processes used in
the production of sulfuric acid from SO2 off-gases from primary
copper, lead, molybdenum, and zinc plants, and presents a profile
of the acid plants identified in this study. «m«
DESCRIPTION OF METALLURGICAL ACID PLANTS
Metallurgical acid plants produce sulfuric acid from the
emissions of pyrometallurgical operations. By producing acid,
the acid plants not only clean the smelter emissions of many tons
~
This section describes the metallurgical acid plant processes and
the steps which may be required to pretreat the gas. These
processes are shown in Figure I1I-1 (page 1361). An acid plant
catalytically converts sulfur dioxide in a smelter off-gas stream
to sulfur tnoxide, and then absorbs it into a sulfuric acid
stream. The sulfur trioxide combines with the water in the
absorbing sulfuric acid which, in effect, increases the strength
?ha L°?? 2? aCld stream' Prior to entering the acid plant,
the smelter off -gas stream will usually undergo one or more
pretreatment steps. ^ «= wj. more
RAW MATERIALS
Primary copper, lead, molybdenum, and zinc are predominantly
produced from sulfide ore concentrates. in the various
pyrometallurgical operations used to produce these metals, large
amounts of sulfur oxides are evolved. Air pollution regulations
?c?S? 9 sm?J-ters' in the form of State Implementation Plans
(SIP), as well as federal new source performance standards, set
limits on the mass of SO2 discharged. In order to meet these
limits, S02 is removed from the smelter off-gases often
resulting in installation of permanent SO2 controls at
primary metals plants such as metallurgical acid plants.
As used in this supplement, "acid plant" also includes plants
producing elemental sulfur and liquid SO2, since these operations
use similar conditioning and cleaning prior to production of the
sulfur-containing product. These products are produced usina the
same raw material {high-sulfur-content emissions) as a sulfuric
acid plant. This section will discuss the origin of the sulfur
oxides in the production sequence for each metal.
Copper
The most important type of copper ore in the United States is
mined from the "porphyry" copper deposits. These low-grade
1353
-------
METALLURGICAL ACID PLANTSUBCATEGORY SECT - III
deposits are extensive masses of rock containing crystals of
various copper minerals which may be profitably mined on a
massive, non-selective scale. Copper minerals generally
associated with the porphyrys are various oxides, such as cuprite
and malachite, which have been formed from parent minerals near
the surface of a deposit through weathering processes. Deeper in
a deposit, various sulfide minerals, such as chalcocite,
covellite. and chalcopyrite, typically occur. Porphyry ores are
mined by open pit methods. Other major types of deposits are
vein, pipe, and bedded deposits, which yield higher grade ores
and are usually mined using underground methods. Copper minerals
in these deposits commonly include chalcopyrite, bornite,
chalcocite, and covellite. A few American deposits are deep
seated and contain some copper-arsenic minerals, such as
enargite. Native copper is only found in important quantities in
Michigan, where it is found in conjunction with covellite. The
compositions of the more important copper minerals are shown
below. • •• • • ...
Mineral
'Ejprnite
Chalcocite
Chalcopyrite
Covellite
Cuprite
Enargite
Malachire
Native Copper
Composition
Cu2s
CuP'e'S2
CuS
CU2O
CU3AS5S4
CuC03'Cu(OH)12s
Cu
Oxides of sulfur are released during the principal
pyrometallurgical operations at primary copper smelters. If
roasting is practiced at the smelter, about 25 percent of the
sulfur in the feed will be converted to sulfur oxides,
principally sulfur dioxide; 25 percent will be oxidized during
smelting in the reverberatory or electric furnace; and the
remaining 50 percent will evolve from the converting operation.
At smelters which do not use roasters, about 40 percent of the
sulfur in the feed is oxidized during smelting in the
reverberatory furnace, and the remaining 60 percent is evolved
during converting.
, 'i', Hi,',11' ,, 'I'M' iln!1"'"
sulfur dioxide concentration in roaster and converter off-
gases can be maintained between 4 and 14 percent by volume,
providing that leaks of infiltrating air into the flues are
minimized and good operating practices are followed.
The
/IF) I" . '",•;;•>' ",' ';•' I ..... I1'1 •• !•"'• 'i, •')' '. ' ' '• ..... ........ ...... ' ...... W :|l!:Wil- ClIBH'li, ..... HM"^'1- ' ..... '"£'•; ......... ...... v,'.i"vi/ ..... . - ..... U i ........
The SO2 concentration in roaster off-gases can be high enough (5
percent SO2 in new hearth roaster gases, and 8 to 10 percent S02
in fluid bed roaster gases) to permit sulfuric acid manu-facture.
However, older hearth roaster systems produce a lower
concentration in the off-gases because of infiltrating air.
Typical concentrations are about 1.0 to 2.5 percent.
i •: ...... . • '• • • „ ..... ;, ' , , • ' , , '':•!„ •':, , i ."i • '. • '.i,, :, .',1'. if . ,1 wiiiiii1 tt1 iKhiii ...... • • i, :. '! : „,:' ' ., .I* ; i • ,:„ •' v/1" » • ........ * • , ; : d, ,, i'lf! .'.'f " • :. • '• • i i • i
Roasted concentrates are charged to a smelting furnace where
1354
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - III
fluxing agents are added. Iron present in the charge reacts with
the fluxing agents forming an iron silicate slag. The slag is
skimmed from the top of the reverberatory furnace leaving a white
metal about 70 percent copper and 24 percent sulfur. Gaseous
emissions from the reverberatory furnace contain an average of
0.4 to 1.5 percent SC>2, too low for direct processing in a
sulfuric acid plant.
Copper matte tapped from the bottom of the smelting furnace is
charged to a converter for further purification. In the
converter, compressed air is blown through the copper to oxidize
impurities including sulfur. This is known as the slag blow
which produces average off-gas SC-2 concentrations of 10 percent.
When collected by the primary converter hood, this value will be
diluted to an average of 5 percent. Further blowing converts
most of the remaining sulfur to SO2, leaving a final blister
copper usually containing between 98.5 and 99.3 percent copper,
0.3 percent sulfur, some dissolved oxygen, and other impurities.
Lead
The major lead mineral is galena, PbS, which is commonly
associated with cerussite (PbCOs) and anglesite (PbSC>4), both of
which result from weathering of galena. Typical lead
concentrates range from 45 to 80 percent lead, with 10 to 30
percent sulfur, as well as traces of other metals and
contaminants. The concentrated ore is sintered so that it can be
used in the blast furnace. The majority of the sulfur contained
in the feed concentrate is converted to SC-2 in the front portion
of the sintering machine. This gas stream may be segregated from
the weaker (lower SC>2 concentration) off-gases from the rear
section of the sintering machine. Some plants collect all the
sinter machine off-gases in one flue, and they are emitted after
only particulate control. These plants, which have no acid
plant, are not included in this subcategory.
Molybdenum
The primary source of molybdenum is a molybdenum sulfide ore
called molybdenite (MoS2>. Most domestic molybdenite is mined
and concentrated at two large mines in Colorado and a smaller
amount comes from a mine in New Mexico. Molybdenite is also
recovered as a by-product from concentrating porphyry copper
ores. Molybdenum sulfide is converted to technical grade
molybdic oxide, MoC>3, in multiple hearth furnaces. The
temperature- must be controlled to ensure complete oxidation of
all sulfur and to limit losses due to volatilization of MoC>3
which becomes significant at 1,300°F. Molybdenite roaster
off-gases may contain fluoride in addition to SC-2. Fluoride
is removed from the feed gas in a water scrubber prior to
sulfuric acid production.
1355
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - III
Zinc
The most important zinc mineral is sphalerite, ZnS. Some zinc
deposits contain oxide, carbonate, or silicate zinc minerals.
Often, zinc is found in the same or adjacent deposits with lead.
In such an occurrence, it is separated from the lead ores in the
concentrator. Since zinc sulfide is insoluble in the sulfuric
acid used for leaching at electrolytic plants, the sulfide ore
concentrates are rqasted as completely as possible to form zinc
oxide and sulfur oxide. Roastingmay takeplace in a multiple
hearth, fluid bed, or flash roaster. Concentrations of SC>2 in
the off-gas vary with the type of roaster used. In a multiple
hearth roaster, the concentration ranges from about 4.5 to 6.5
percent 803. Off-gas from a suspension roaster has a higher SO2
concentration, averaging 10 to 13 percent. Sp2 concentrations in
the off-gas from a fluidized bed roaster range from 7 to 12
percent, although the higher figure is more common. A fluid
column roaster averages 11 to 12 percent S02 in the flue gas.
APPLICABILITY OF METALLURGICAL ACID PLANTS
> ' '•;..; : ••'™-'.:-'; v^/^m^^^ I
The applicability of metallurgical acid plants for controlling
smelting off-gases is dependent upon the SO2 concentrations in
the off-gases. Pyrometallurgical processes used in the
production of copper, lead, molybdenum, and zinc from sulfide
ores release SO2 to the off-gas systems at concentrations ranging
from less than 1 percent to over 10 percent.
Sulfuric acid plants are usually designed for an SO2
concentration of 4 to 10 percent with any higher concentrations
being diluted with air. Elemental sulfur and liquid SO2 plants
are favored for highly concentrated S02 streams (e.g., 80
percent). Since the SO2 concentrations in copper, lead,
molybdenum, and zinc plant off-gases are generally in the 1 to 10
percent range, most of these plants produce sulfuric acid as the
by-product of SO2 control.
Modern smelting processes, such as electric furnaces, oxygen
enrichment, flash smelting, and continuous smelting produce off-
gases with higher SO2 concentrations than many of the older
processes. For example, reverberatory furnace gases from
conventional equipment usually contain 0.5 to 2 percent SO2- For
the same amount of SO2 per hour, the more concentrated the gas
stream is, the cheaper the acid plant is to build and operate.
Because of this, some of the new smelter processes producing gas
streams with high SO2 concentrations, such as the Outokumpu flash
smelter or the Mitsubishi process, offer significant advantages.
The addition of oxygen to the smelting operation can result in
more highly concentrated SC>2 off-gases. Some of these newer
processes, such as the Mitsubishi process, also have the
advantage that the gases from all the furnaces (smelting, slag
cleaning, and converting) can be combined to produce a single gas
stream with an S02 concentration which still permits acid
production.
1356
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - III
PROCESS DESCRIPTION .
The process descriptions which follow concentrate on water uses
and wastewater sources in the acid plant and pretreatment
equipment. Each of the various water and wastewater streams
discussed are present in some or all acid plants. The existence
of any specific waste stream in a particular plant depends on the
specific plant design. These wastewater streams are usually
combined and treated as a single stream, termed "acid plant
blowdown."
The following discussion provides more detailed information on
acid plant processes shown in Figure III-l (page 1362).
Cooling
The temperature of the gas from the pyrometallurgical operation
may be in the range of 400 to 1,200°F, depending upon the
specific operation. Typically, zinc roasters operate around
1,200°F, while the gas exiting a copper converter is about 500°F,
and that from a lead sintering machine is around 800°F.
Molybdenum roasters operate at approximately 900-1,100°F.
Gases from a zinc fluid bed roaster may be sprayed with water
from the dome of the roaster to humidify and cool the gas. A
waste heat boiler may be used, which produces usable steam and
cools the gas stream at the same time. The gases may go through
a humidification chamber, which reduces the temperature and
partially humidifies the gas. The gas is cooled to some extent
by radiation in the ductwork. No wastewater stream is produced
in this cooling step since all the water added is evaporated.
Cleaning
Cleaning is performed to remove particulate matter which may
catalyze undesirable side reactions downstream. Various methods
are used to clean the acid plant feed gas, such as electrostatic
precipitators, baghouses, cyclones, multiple cyclones, wet
scrubbers, and settling chambers. The most common method is
electrostatic precipitators.
Conditioning
In order to produce sulfuric acid of the desired strength, water
vapor must be present in a precise ratio of water to SO2«
Production of 93 percent acid requires about a 1.4 mole ratio of
water to SO2, while 100 percent acid requires a 1.0 mole ratio.
The conditioning or humidification step adds a slight excess of
water to the gas, and the excess is then condensed out. Open and
packed towers or various types of scrubbers may be used for this
process step. Scrubbers are often used in conjunction with a gas
cooling tower to condense the excess water.
This phase of the process serves several purposes: the gas is
further cooled, more of the dust and particulates are removed,
1357
-------
METALLURGICAL ACID PLANT SUBCATEGORY
SECT - III
and the gas is humidified to the proper degree. Since 863 in
contact with water forms 1*2804, the scrubbing liquor becomes a
weak acidf which is usually recirculated with a blowdown (acid
plant scrubber blowdown). A scrubber makeup water stream is also
required.
Mist Precipitation
The gas leaving the conditioning process unit contains acid mist,
as well as particulate matter. This is usually removed in an
electrostatic precipitator, called a mist precipitator. These
units operate at efficiencies of over 98 percent and produce an
acidic wastewater containing toxic metals (mist precipitator
blowdown).
Drying
Drying -towers remove entrained moisture by contact with sulfuric
acid (93 to 98 weight percent). Usually an absorber acid recycle
stream (from the downstream acid production section) is used for
this drying step. The absorbing acid stream becomes slightly
diluted with water during this step. This removed water later
contacts 803 in the absorber to form sulfuric acid.
: '.. ..•,'•'•'•' '» ':'1:'!"t',.'. t ' ;,,;":: ':0i«
Compression
1 • • •• :, , . • • ii ••••.^-, i*,;1?',••.••,>: i.w\
A blower may be required to boost the gas pressure prior to
entering the acid production section of the plant. As the
pressure of the gas stream is increased, water vapor is condensed
and collected as a wastewater.
•j • • "• -:••(. •" :'. ' •' •.''•.- v*;{;,#..•'.::• K,T iJ.',^;/T ,.$
A bearing cooling wastewater stream may be produced in this step
if once-through cooling water is used. This waste stream,
however, is considered nonscope for this regulation and must be
handled on a case-by-case basis by the permit writer.
Acid Production
In the acid production section, the gas containing SC>2 contacts
a vanadium pentoxide catalyst, and the gas is catalytically
oxidized to 803. The sulfur trioxide is then absorbed in 98
percent acid, which becomes more concentrated. Dilute sulfuric
acid or water is added to the recirculating acid, and excess acid
is withdrawn from the system. Oleum (a mixture of 1*2804 and free
303) may also be produced by absorbing the 803 in 98 percent
acid. In oleum production, less water or dilute sulfuric acid is
used to contact the gas, leaving some 862 unconverted. Oleum
typically contains 20 percent 803 and 80 percent of 100 percent
1*2804. The acid plant tail gas contains about 2,000 to 3,000 ppm
SO2 by volume and some entrained acid mist.
' ;. i , I • J-.,mi[ J'1 iliii I •• ,,'il Vlli,:- . - • / •;! " •!' > .' • I
Many sulfuric acid plants must meet an SO2 discharge
concentration limitation which cannot be met by single-contact
acid plants. In many acid plants the gas stream leaving the
absorber is returned to the converter for oxidation of additipnal
1358
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - III
SO2 to 803. The resultant gas stream then flows to a second
absorption tower (not shown in Figure III-l) and is contacted
with 98 percent acid These double-contact acid plants can
produce a final SC>2 concentration in the tail gas of less than
200 ppmv. About half of the metallurgical acid plants in the U.S.
are of the double-contact type. Since the 303 formed in the
first contacting step has been absorbed, the second contacting
favors more complete oxidation of SC-2 than is possible with
single contacting. Overall conversion is on the order of 99.8
percent, rather than the 95.5 to 98.5 conversion achieved in a
single-contact acid plant.
The off-gas from the final absorption tower flows to a mist
eliminator and then is discharged to the atmosphere through a
stack.
The potential water uses and wastewater sources in metallurgical
acid plants are indicated in Figure III-l. The block diagram
shown in Figure III-l is of a typical metallurgical acid plant.
Other gas conditioning, gas cooling, gas cleaning, etc.
technologies may be used instead of or in addition to the ones
shown. Therefore the water uses and wastewater sources shown are
also representations of typical streams, and their occurrences
are functions of the processing equipment in each acid plant.
PROCESS WASTEWATER SOURCES
The principal wastewater sources in the metallurgical acid plants
subcategory are as follows:
1. Acid plant scrubber blowdown,
2. Mist precipitator blowdown,
3. Compression condensate,
4. Box cooler blowdown, and
5. Mist eliminator blowdown.
These wastewater sources have been combined into the single
wastewater stream, acid plant blowdown.
OTHER WASTEWATER SOURCES
There are other wastewater streams associated with the
metallurgical acid plants subcategory. These waste streams may
include bearing cooling water return, steam generator blowdown,
maintenance and cleanup water, and stormwater runoff. These
wastewater streams are not considered as a part of this
rulemaking. EPA believes that the flows and pollutant loadings
associated with these waste streams are insignificant relative to
the wastewater streams selected and are best handled by the
appropriate permit issuing authority on a case-by-case basis.
AGE, PRODUCTION, AND PROCESS PROFILE
1359
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - III
There are 22 metallurgical acid plants in the United States, as
shown in Figure III-2 (page 1363). Ten sulfuric acid plants are
at primary copper plants, three are at primary lead plants, three
are at primary molybdenum plants, and six are at primary zinc
plants. All but one of the plants associated with copper
production are located in Texas or west of Texas. All except for
one of these are zero discharge acid plants. Two of the plants
associated with lead are located in Missouri and both are direct
discharge plants. The other is a zero discharge plant and is
located in Montana. Of the three sulfuric acid plants associated
with molybdenum roasting operations, two arein Pennsylvania and
one is in Iowa. One achieves zero discharge of process
wastewater and two are direct dischargers. The six zinc-related
acid plants are located between Texasarid Pennsylvania. Four are
direct dischargers" and two are indirect dischargers. Table III-l
(page 1361) shows the number of acid plants associated with
copper, lead, molybdenum and zinc, and the discharge status of
these plants.
There are insufficient data to ascertain the age of acid plants
independently of the base metal plants associated with them. Acid
plants are a result of air pollution abatement measures at
existing metal production facilities. Acid plants, due to
corrosive products and materials, have relatively short life
spans. Periodically the acid plant is taken off-line for
maintenance and upkeep. The frequency of maintenance is
dependent on individual plant operating procedures.
Table IIi-2 (page 1361) shows that the acid production range
figures for these plants are fairly evenly distributed among all
categories with acid productions up to 300,000 kkg per year.
All acid plants that provided dcp information use water, and all
but one of these plants generate an acid plant blowdown stream.
In the plant that does not generate a blowdown stream, the water
is evaporated (in-process) during cooling of the smelter off-gas
stream. Other acid plants, through reuse and evaporation
practices, may generate but not discharge acid plant blowdown.
1360
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - III
TABLE III-l
*
SUMMARY OF DISCHARGE STATUS IN THE
METALLURGICAL ACID PLANTS SUBCATEGORY
Discharge Associated Metal Plant
Status Copper Lead Zinc Total
Direct 22 4 8
Indirect 0 0 2 2
Zero 8 1 0_ 9_
Total 10 3 6 19
TABLE II1-2
PRODUCTION RANGE FOR METALLURGICAL ACID PLANTS
Production Range
(kkg/yr 100% ^804) Number of Plants
0 - 50000 2
50001 - 100000 4
100001 - 200000 5
200001 - 300000 5
300001 - Above 3
1361
-------
MEATLLURGICAL ACID PLANT SUBCATEGORY
SECT - III
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1362
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MEATLLURGICAL ACID PLANT SUBCATEGORY
SECT - III
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1363
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - III
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1364
;,: r
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METALLURGICAL ACID PLANT SUBCATEGORY SECT - IV
SECTION IV
SUBCATEGORIZATION
This section summarizes the factors considered during the
designation of the metallurgical acid plants subcategory and its
related subdivisions.
The metallurgical acid plants subcategory was created in the
rulemaking of July 2, 1980 (45 FR 44926) to limit the mass of
toxic pollutants discharged from the production of sulfuric acid
at copper smelters. Only BPT effluent limitations were
established in that rulemaking. As discussed in Section 1, the
initial metallurgical acid plants subcategory included all
operations associated with the manufacture of sulfuric acid at
primary copper plants and included associated air pollution
control (or gas conditioning systems) for sulfur dioxide off-
gases from pyrometallurgical operations. On March 8, 1984 (49 FR
8742), EPA expanded the metallurgical acid plants subcategory to
include the production of sulfuric acid in primary lead and
primary zinc plants and further expanded the coverage to include
sulfuric acid production at primary molybdenum plants in a
rulemaking on September 20, 1985. The 1984 and 1985 rulemakings
promulgated BAT limitations and new source and pretreatment
standards for this subcategory.
FACTORS CONSIDERED IN SUBDIVIDING THE METALLURGICAL ACID PLANT
SUBCATEGORY
EPA examined the 14 factors listed previously to determine if the
metallurgical acid plants subcategory should be subdivided.
Subdivision within the nonferrous metals subcategories allows
separate analysis of distinct wastewater streams. If significant
and distinct wastewater streams which have clearly different
origins can he identified within a subcategory, then segmentation
is indicated. - For the metallurgical.acid plants subcategory,
separation into segments was determined to be unnecessary. For
this subcategory a single all encompassing building block, "acid
plant blowdown," has been designated. The effluent limitations
and standards for the metallurgical acid plants subcategory are
based on analyses of flow and pollutant composition data for the
acid plant blowdown stream.
As discussed in Section III, several wastewater streams are
usually combined to form a single acid plant blowdown stream.
While different acid plants may combine somewhat different
streams to form the acid plant blowdown stream, most of the
wastewater streams which combine to form the acid plant blowdown
stream have similar characteristics with respect to two of the
more important relevant subcategorization factors. These factors
are as follows:
1. Raw materials—most of the wastewater streams which may
1365
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - IV
be combined to form the acid plant blowdown stream are
produced by removing condensates and particulate matter
from gases containing SC>2; and
2. Manufacturing processes—the unit operations (scrubbing,
mist precipitation, compression, etc.) involved in
pretreating the gas and making acid are similar from one
acid plant to another.
Depending on air quality requirements, acid plants may
incorporate a double contact system with the converter to achieve
lower SO2 concentrations of the effluent gas. Although a double
contact acid plant reduces the concentration of SO2* it does not
increase the volume of wastewater generated in an acid plant. A
double contact acid plant recycles the effluent gas stream back
to the converters after absorption for additional conversion of
SO2 to 803 There is no gas conditioning or cleaning required
for gaseous emissions to be recycled. Therefore, the differences
in manufacturing processes of single and double contact acid
plants do not require separate subcategorization.
PRODUCTION NORMALIZING PARAMETERS
The effluent limitations and standards developed in this document
establish mass limits on the discharge of specific pollutant
parameters. To allow these to be applied to plants with various
production levels, the mass of pollutant discharged must be
related^ to a unit of production. This factor is known as the
production normalizing parameter (PNP). Acid plant production is
reported as a percentage of acid contained within the final
product. For example, a plant may report its yearly acid
production as 100 tons of 85 percent sulfuric acid. So that the
wastewater generated within each acid plant can be compared, it
must be related to a common basis suchas 100percent sulfuric
acid production. Data from the 1977 data collection portfolios
indicate that acid plant water use and blowdown correlated better
with acid plant capacity than with actual acid plant production.
Thus, the production normalizing parameter is the production
capacity of sulfuric acid on a 100 percent acid basis.
1366
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METALLURGICAL ACID PLANT SUBCATEGORY SECT - V
SECTION V
WATER USE AND WASTEWATER CHARACTERISTICS
This section describes the characteristics of wastewater
associated with the metallurgical acid plants subcategory. Data
used to quantify wastewater flow and pollutant concentrations are
presented, summarized, and discussed. The contribution of
specific production processes to the overall wastewater discharge
from metallurgical acid plants is identified whenever possible.
The two principal data sources used in the development of these
limitations and standards were the data collection portfolios and
field sampling results. Data collection portfolios contain
information regarding wastewater flows and production levels.
Data gathered through comments on the proposed mass limitations
and Section 308 requests are also principal data sources.
In order to quantify the pollutant discharge from metallurgical
acid plants, a field sampling program was conducted. Wastewater
samples were collected in two phases: screening and
verification. The first phase, screen sampling, was to identify
which toxic pollutants were present in wastewaters from
production of the various metals. Screening samples were
analyzed for 128 of the 126 priority pollutants and other
pollutants deemed appropriate. (Because the analytical standard
for TCDD was judged to be too hazardous to be made generally
available, samples were never analyzed for this pollutant. There
is no reason to expect that TCDD would be present in
metallurgical acid plant wastewaters). A total of 10 plants were
selected for screen sampling in the nonferrous metals
manufacturing category. A complete list of the pollutants
considered and a summary of the techniques used in sampling and
laboratory analyses are included in Section V of Vol. 1. In
general, the samples were analyzed for three classes of
pollutants: priority organic pollutants, priority metal
pollutants, and criteria pollutants (which includes both
conventional and nonconventional pollutants). A verification
sampling effort was conducted at one primary zinc plant between
proposal and promulgation. Acid plant blowdown was one of the
waste streams sampled.' The Agency believed additional process
and wastewater data were needed to better characterize the
primary zinc subcategory. Also, sampling was conducted at one
metallurgical acid plant associated with primary molybdenum
roasting operations as a part of nonferrous metals manufacturing.
As described in Section IV of this supplement, the wastewaters
from metallurgical acid plants in primary copper, primary lead,
primary molybdenum, and primary zinc plants (and wastewaters from
SO2 off-gas conditioning or control operations) are all included
in the single wastewater stream termed "acid plant blowdown" in
this document.
1367
-------
METALLURGICAL ACID PLANT SUBCATEGORY
SECT - V
WATER USE AND WASTEWATER DISCHARGE RATES
Two flow-to-production ratios for each acid plant were calculated
using information supplied in the data collection portfolios. The
two ratios, water use and wastewater discharge flow, are
differentiated by the flow value used in calculation. Water use
is defined as the volume of water required per ton of sulfuric
acid capacity (on a 100 percent acid basis) and is therefore
based on the sum of recycle and makeup flows. Wastewater flow
discharged after pretreatment or recycle (if these are present)
is used in calculating the production normalized flow—the volume
of wastewater discharged from a given process to further
treatment, disposal, or discharge per ton of 100 percent acid
capacity. Differences between the water use and wastewater
discharge flow rates result from recycle or evaporation. The
production capacity values used in the calculation correspond to
the production normalizing parameter, PNP, as discussed in
Section IV.
.. • ,, • . • ;, ..' . . '.I',, i I III |||| I ||M
The two water-to-production ratios for each acid plant are shown
in Table y-1 (page 1371). This table also gives the percent
recycle, which is calculated from these two ratios.
Since the data collection portfolios have been collected, the
Agency has learned that two primary zinc plants, one primary lead
plant, and one primary copper plant have closed or no longer
produce these metals. Flow and production data (when available)
for these plants are presented in this section and in the
remainder of this document. Although these plants are currently
not operating, these data are an integral part of the BAT
effluent limitations because as representative processes their
information remains relevant in determining what constitutes best
available technology. Therefore, it is necessary to present this
information so that the BAT limitations are documented.
WASTEWATER CHARACTERISTICS
In order to quantify the concentrations of pollutants present in
the blowdown stream from acid plants, wastewater samples were
collected at eight plants. Diagrams indicating the sampling
points are shown in Figures V-l through V-8 (pages 1381 - 1388).
These diagrams also indicate some of the ways in which different
wastewater sources are combinedto produce the acid plant
blowdown stream.
The acid plant blowdown stream sampling data is presented in
Table V-2 (page 1372). Where no data is listed for a specific
day of sampling, the wastewater samples for the stream were not
collected. If the analysis did not detect a pollutant in a waste
stream, the pollutant was omitted from the table. The method by
which each sample was collected is indicated by number, as
follows:
1 one-time grab
2 24-hour manual composite
1368
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - V
3 24-hour automatic composite
4 48-hour manual composite
5 48-hour automatic composite
6 72-hour manual composite
7 72-hour automatic composite
The data tables include some samples measured at concentrations
considered not quantifiable. The base-neutral extractable, acid
extractable, and volatile organics are generally considered not
quantifiable at concentrations equal to or less than 0.010 mg/1.
Below this concentration, organic analytical results are not
quantitatively accurate; however, the analyses are useful to
indicate the presence of a particular pollutant. The pesticide
fraction is considered honquantifiable at concentrations equal to
or less than 0.005 mg/1. Nonquantifiable results are designated
in the tables with an asterisk (double asterisk for pesticides).
The detection limits shown on the data tables are not the same as
published detection limits for these pollutants by the same
analytical methods. The detection limits used were reported with
the analytical data and hence are the appropriate limits to apply
to the data. Detection limit variation can occur as a result of
a number of laboratory-specific, equipment-specific, and daily
operator-specific factors. These factors can include day-to-day
differences in machine calibration, variation in stock solutions,
and variation in operators.
The statistical analysis of data includes some samples measured
at concentrations considered not quantifiable. Data reported as
an asterisk are considered as detected but below quantifiable
concentrations, and a value of zero is used for averaging.
Priority organic, nonconventional, and conventional data reported
with a "less than" sign are considered as detected, but not
further quantifiable. A value of zero is also used for
averaging. If a pollutant is reported as not detected, it is
excluded in calculating the average. Finally, priority metal
values reported-as less than a certain value were considered as
not detected and a value of zero is used in the calculation of
the average. For example, three samples reported as ND, *, and
0.021 mg/1 have an average value of 0.010 mg/1. The averages
calculated are presented with the sampling data; these values
were not used in the selection of pollutant parameters.
As discussed in Section III, the acid plant blowdown stream is
normally a combination of several streams related to the
manufacture of sulfuric acid from SO2 off-gases from
metallurgical operations. Typical potential components of this
stream include:
1. Acid plant scrubber blowdown,
2. Mist precipitator blowdown,
3. Compression condensate,
4. Box cooler blowdown, and
5. Mist eliminator blowdown.
1369
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - V
The acid plant blowdown stream sampling data given in Table V-2
are used in Section VI to determine which pollutants should be
considered for regulation. The sampling data in Table V-2
indicate that the acid plant blowdown stream contains treatable
concentrations of several metals (such as antimony, arsenic,
cadmium, chromium, copper, lead, mercury, nickel, selenium,
silver, and zinc), and suspended solids. The pH data indicate
either acidic op basic wastewaters depending on the stream
sampled. Priority organicswere found at measurable
concentrations in some streams.
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1370
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - V
TABLE V-l
WATER USE AND WASTEWATER DISCHARGE FLOW RATES
FOR METALLURGICAL ACID PLANTS
(1/kkg (gal/ton) of 100% H2SO4 Capacity)
Wastewater
Water Use
Plant Code
206 Cu
285 Cu
284 Pb
7001 Cu
4503 Cu
283 Zn
278 Zn
213 Cu
211 Cu
216 CU
279 Zn
212 Cu
281 Zn
214 Cu
282 Zn!
60 Cu
290 Pb
280 Pb!
280 Zn!
4201 Cu
288 Cu
9060 Zn
6310 Zn
Discharge
1/kkg (gal/ton)
NOTES: NR
INC
*
459
NR
INC
(110)
NR
60690 (14550)
62190 (14910)
140000 (33560)
175500 (42080)
1468 (352)
82280 (19730)
NR
4487 (1076)
NR
35800 (8580)
6540 (1570)
NR
195500
19052
8609
NR
INC
NR
NR
(46870)
(4570)
(2064)
Percent
1/kkg (gal/ton)
331.9(80)
745.5(179)
748.9(180)
1214 (291)
1306 (313)
1351
1386
1468
1481
2145
2394
4196
4904
5470
6213
6238
6249
6457
15840
3362
505
NR
(324)
(332)
(352)
(355)
(514)
(563)
(1006)
(1176)
(1310)
(1490)
(1496)
(1498)
(1548)
(3798)
(806)
(121)
Recycle
100
NR
INC
NR
98
98
99
99
0
98
NR
47
NR
86
0*
NR
97
67
25
NR
INC
NR
NR
= Data not reported in dcp.
= Inconclusive data reported in dcp.
= 100% Evaporation
= Plant closed or no longer operating acid plant,
1371
-------
METALLURGICAL ACID PLANT SUBCATEGORY
SECT - V
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1372
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METALLURGICAL ACID PLANT SUBCATEGORY
SECT - V
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METALLURGICAL ACID PLANT SUBCATEGORY SECT - V
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1374
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METALLURGICAL ACID PLANT SUBCATEGORY
SECT - V
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METALLURGICAL ACIDPLANT SUBCATEGORY
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METALLURGICAL ACID PLANT SUBCATEGORY SECT - V
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1377
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METALLURGICAL ACID PLANT SUBCATEGORY
SECT - V
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METALLURGICAL ACID PLANT SUBCATEGORY
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METALLURGICAL ACID PLANT SUBCATEGORY SECT - V
Discharge
FIGURE V-l
SAMPLING SITES AT PRIMARY LEAD PLANT B
1381
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - V
Tap tf
Sanitary
'-•sees
Plant
Runoff
Contact/
Noncontact
Cooling Wattr
Regenerate
Wastes from
Dcfflineralizer
Process H.O
from ZnO and
ZnS Leaching
Purification and
Electrolytic
Vastewater
Lab and
Pilot Plant
Activities
Acid Plant
Roaster
Scrubber
Mist
Precipitators
Lagoon
Mix Tank Lime
and Polymer
Addition
0.1149
MOD
Clarifier
JO.766 MGD
Discharge
FIGURE V-2
SAMPLING SITES AT PRIMARY ZINC PLANT I
...... I"1
1382
:":*v ;i;Sflf:: I
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - V
Acid Plant
aseous Emissions
rom Roaster
Roaster Scrubber
Mist
Pr«cipicators
Preleach
Filtrate
Boiler
Slowdown
0.43
MOT
Equalization
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Neutralization
And Lime
Mixing
Vacuum Filtrate
Clarlfier
Final
Settling
Two Ponds
Underflow to
Vacuum Filter
Then to Landfill
MGD
Discharge
FIGURE V-3
SAMPLING SITES AT PRIMARY LEAD PLANT C
1383
-------
METALLURGICAL ACID PLANT fiUBCATEGORY SECT - V
Cicy Water
Roaster
Scrubber
Boiler
Slowdown
Acid Plane
,•' ,i'!, ' i1!" ', 'liiri''"!1
'i ,'"' ."III'!,' '' ',ll!il,'|lii|l!l '".' 'Ill
FIGURE V-4
SAMPLING SITES AT PRIMARY ZINC PLANT D
1384
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - V
siag
Granulation
So neontact
Cooling
6.134 MOT
Concentrator
Acid Plan:
Converter
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Mis:
PreclBisator
Acid Plane tZ
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Q.45M WO
Mixing
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Discharge
—————____^—____™_____________ Recycle
FIGURE V-5
SAMPLING SITES AT PRIMARY COPPER SMELTING AND REFINING PLANT C
1385
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - V
Xoncontact
Cooling
Water
Acid Plane
Bagbouse
Spray
VOA Blank
Source Water
Discharge
FIGUREV-6
SAMPLING SITES AT PRIMARY COPPER SMELTER PLANT B
1386
-------
Source
Hkcarr
Bfccce
EEaie
SIootfowiE
0. QOS7S
HGH
Bcuafc W«r«ir
SZE
: a,02Q6:ft gflSS
Aooxfc
CLmmafnf
Tknfc
finodc
Cbnd «na«cc
Sump SmmZ,
ifacer-
Haute
f Hirer C««cfc
Hump- Seal.
Wkcec Fori—
32%
(J.Q2SS HOE
ff.OZSS
0,0336 SES-
2ZS. \
satciort
wftEE-
time
Clarifies
Discharge
330E
SSMEE3JES SZTES &T- ESIMSSl" ZUSO
G
1387
-------
METALLURGICAL ACID PLANT SUBCATEGORYSECT - V
Source Water
Acid
Plant
Slowdown
Other
NFM Wastewater
69
781
Pressure
Filter
H2S
Molybdenum
"to Roaster
Pressure
Filter
.^.Selenium
to Storage
782
Lime.
Lime Pit
NaOH
Rainfall
67
Settling
Ponds
Non-Scope
Streams
68
Discharge
to "Creek"" "
FIGURE V-8
SAiyiPLING SITES AT PRIMARY MOLYBDENUM PLANT B
1388
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - VI
SECTION VI
SELECTION OF POLLUTANTS
This section examines chemical analysis data presented in Section
V and discusses the selection or exclusion of pollutants for
potential limitation. Each pollutant selected for potential
limitation is discussed in Section VI of Vol. 1. That discussion
provides information about where the pollutant originates (i.e.,
whether it is a naturally occurring substance, processed metal,
or a manufactured compound); toxic effects of the pollutant in
humans and other animals; and behavior of the pollutant in POTW
at the concentrations expected in industrial discharges.
The discussion that follows describes the analysis that was
performed to select or exclude pollutants for further
consideration for limitations and standards. Pollutants will be
selected for further consideration if they are present in
concentrations treatable by the technologies considered in this
analysis. The treatable concentrations used for the priority
metals were the long-term performance values achievable by lime
precipitation, sedimentation, and filtration. The treatable
concentrations used for the priority organics were the long-term
performance values achievable by carbon adsorption.
As discussed in Section V, EPA collected wastewater
characterization data from several plants, during the rulemaking
process. The waste streams sampled were from acid plants
associated with all four metal types. The same pollutants
selected for further consideration for limitation at proposal
have been selected for promulgation with the addition of the
nonconventional pollutants fluoride and molybdenum for molybdenum
acid plants only.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETERS
This study examined samples from metallurgical acid plants for
three conventional pollutant parameters (oil and grease, total
suspended solids, and pH) and the nonconventional pollutant
parameters fluoride and molybdenum.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETERS SELECTED
The conventional and nonconventional pollutant parameters
selected for limitation in this subcategory are as follows:
Molybdenum (for molybdenum acid plants only)
Fluoride (for molybdenum acid plants only)
Total suspended solids (TSS)
pH
Molybdenum was detected in all four .samples of acid plant
1389
-------
METALLURGICAL ACID PLANT SUBCATEGORY
SECT - VI
blowdown collected at a primary molybdenum roasting facility.
The observed concentrations range from 1.69 to 8.38 mg/1. The
Agency also received extensive data with comments submitted on
the nonferrous metals manufacturing rulemaking which show that
molybdenum may typically be present inmolybdenum acid plant
blowdown in concentrations as high as 80 mg/1. Because these
concentrations are significantly higher than the level achievable
with available treatment, molybdenum is selected for limitation
in this subcategory for molybdenum acid plants only. See Section
X for a discussion on the treatment effectiveness level .for
molybdenum.
, 'I .Hbiiii:,1' 1'W i
Fluoride was detected in all three samples of acid plant blowdown
collected at a primary molybdenum roasting facility. The
observed concentrations ranged from 25 to 720 mg/1. Because
these concentrations are significantly higher than the 14.5 mg/1
achievable with available treatment, fluoride is selected for
limitation in this subcategory for molybdenum acid plants only.
The total suspended solids concentration in11 samplesranged
from 10 to 23,740 mg/1. All of these values are above the 2.6
mg/1 concentration attainable by available treatment. Further-
more, most of the methods used to remove toxic metals do so by
converting these metals to precipitates. Meeting a limitation on
total suspended solids also ensures that sedimentation to remove
precipitated toxic metals has been effective. For these reasons,
total suspended solids are selected for further consideration for
limitation.
Acid plant wastewater varied widely in pH, from 0.6 to 11.5. Many
harmful effects may be caused by extreme pH values, or by rapid
changes in pH. Therefore, pH is selected for further
consideration for limitation.
PRIORITY POLLUTANTS
The frequency of occurrence of the priority pollutants in the raw
wastewater samples taken is presented in Table VI-3 (page 1400).
The raw wastewater samples from five streams 88, 89, 209, 212,
321, and 781 are considered in the frequency of occurrence count.
These streams contain raw wastewaterfromprocesses associated
with the metallurgical acid plants sub'categpry' and include the
data collected by the Agency after proposal at one primary zinc
metallurgical acid plant and one primary molybdenum acid plant.
Other streams from which raw wastewater wassampled contained
acid plant wastewater, however these streams also contained
wastewater associated with other subcategories(lead, copper, or
zinc). These samples are not considered inthe frequency of
occurrence count. The data in the frequency of occurrence table
provide the basis for the consideration ofspecific pollutants,
as discussed below. , , ^ i^i.ii. : ': „ ; , , , :
PRIORITY POLLUTANTS NEVER DETECTED
The priority pollutants listed in Table VI-1(page 1396) were not
1390
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - VI
detected in any wastewater samples from this subcategory;
therefore, they are not selected for consideration in
establishing limitations.
PRIORITY POLLUTANTS NEVER FOUND ABOVE THEIR ANALYTICAL
QUANTIFICATION CONCENTRATION
The priority pollutants listed in Table VI-2 (page 1398) were
never found above their analytical quantification concentration
in any wastewater samples from this subcategory; therefore, they
are not selected for consideration in establishing limitations.
PRIORITY POLLUTANTS PRESENT BELOW CONCENTRATIONS ACHIEVABLE BY
TREATMENT
Berylliunr and cyanide are not selected for consideration in
establishing limitations because they were not found in any
wastewater samples from this subcategory above concentrations
considered achievable by existing or available treatment
technologies.
Beryllium was found above its analytical quantification
concentration in two of 15 samples with concentrations of 0.01
mg/1 and 0.002 mg/1. Both of these values are below the 0.20
mg/1 treatable concentration. Therefore, beryllium is not
selected for limitation.
Cyanide was found. above its analytical quantification
concentration in two of 13 samples with concentrations of 0.033
mg/1 and 0.032 mg/1. Because both of these values are below the
treatable concentration of 0.047 mg/1, cyanide is not selected
for limitation.
PRIORITY POLLUTANTS DETECTED IN A SMALL NUMBER OF SOURCES
The pollutants listed below were found in only a small number of
sources within the subcategory and-their occurrence is uniquely
related to only those sources. Therefore, the following
pollutants were not selected for limitation in this subcategory.
6. carbon tetrachloride
13. 1,1-dichloroethane
22. parachlorometa-cresol
23. chloroform
38. ethylbenzene
44. methylene chloride
66. bis(2-ethylhexyl) phthalate
78&81. anthracene&phenanthrene
85. tetrachloroethylene
86. toluene
127. thallium
Although these pollutants were not selected for consideration in-
establishing nationwide limitations, it may be appropriate, on a
case-by-case basis, for the local permit writer to specify
1391
-------
METALLURGICAL ACID PLANT SUBCATEGORY
SECT - VI
effluent limitations.
Carbon tetrachloride was present above its treatable
concentration in two of 11 samples collected from three plants.
Because it was detected at onlyoneplant, indicating the
pollutant is probably site-specific, carbon tetrachloride is not
selected for limitation.
1,1-Dichloroethane was found above itsanalytical quantification
concentration in just one of 11 "samples collected atthree
plants. The reported concentration, 0.18 mg/1, is above 0.01
mg/1, which is considered achievable by available treatment.
Because it was found at only one plant, indicating the pollutant
is probably site-specific, 1,1-dichloroethane is not selected for
limitation.
Parachlorometa-cresol was detected above its treatable
concentration in two of five samples collected. The reported
concentrations were 0.045 mg/1 and 0.042 mg/1. Both samples
containing parachlorometa-cresol were from the same acid plant
blowdown raw wastewater stream. TWO other streams did not
contain this pollutant. Therefore, this pollutant is considered
site-specific so it is not selected for limitation.
Chloroformwas found above its treatable concentrationintwoof
11 samples. This pollutant was detected in six other samples
below the analytical quantification level. Chloroform, a common
laboratory solvent, is not attributable to specific materials or
processes associated with acid plants. Since the possibility of
sample contamination is likely, chloroform is not selected for
limitation.
Ethylbenzene was detected in only one of 11 samples collected
from three plants. The value reported was 0.049 mg/1. Because
it was treatable in only one sample, indicating the pollutant is
probably site-specific, ethylbenzene is not selected for
limitation.
Methylene chloride was found above its treatable concentration in
three of 11 samples, at concentrations of 0.016, 0.224, and 0.23
mg/1. This pollutant is not attributable to specific materials
or processes associated with acid plants; however, it is a common
solvent used in analytical laboratories. Since the possibility
of sample contamination is likely, methylene chloride is not
selected for limitation. : ^
Dichlorobromomethane was found in only one of 11 samples. The
detected concentration, 0.014 mg/1, is slightly above the
treatable concentration. Also, dichlprpbromome^thane was not
found in two other samples from the 'sa'me^slire'a'tru". Since it was
found in only one of five raw wastewater streams sampled, it can
be considered site-specific. For these reasons, this pollutant
is not selected for limitation.
Bis(2-ethylhexyl) phthalate was found above its analytical
1392
-------
METALLURGICAL ACID PLANT SUBCATEGORY
. SECT - VI
quantification concentration in six of 11 samples. The maximum
concentration observed was 0.193 mg/1. The presence of this
pollutant is not attributable to materials or processes
associated with the metallurgical acid plant subcategory. It is
commonly used as a plasticizer in laboratory and field sampling
equipment. EPA suspects sample contamination as the source of
this pollutant. Therefore, bis(2-ethylhexyl) phthalate is not
selected for limitation.
Anthracene and phenanthrene (analyzed together for eight samples)
were found above their analytical quantification concentrations
in one of 11 samples collected from three plants. The single
sample was also above the treatable concentration (0.010 mg/1).
Since they were treatable in only one sample', indicating that
these pollutants are probably site-specific, anthracene and
phenanthrene are not selected for limitation.
Tetrachloroethylene was detected in six of 11 samples collected
from three plants. Five of the six samples had concentrations
below the analytical quantification limit. The reported
concentration was 0.011 mg/1, which is slightly above the
treatable concentration. Therefore, tetrachloroethylene is not
selected for limitation.
Toluene was found above its analytical quantification
concentration in only one of 11 samples. The reported toluene
concentration, 0.057 mg/1, is above 0.010 mg/1, which is
considered achievable by available treatment. However because
it was found at only one plant, indicating the pollutant is site-
specific, toluene is not selected for limitation.
Thallium was found above its analytical quantification
concentration in three of 15 samples. In only two of the samples
was the thallium concentration above its treatable concentration
of 0.34 mg/1, and these two were both in the same stream at only
one plant. Therefore, thallium is not selected for limitation.
TOXIC POLLUTANTS SELECTED FOR CONSIDERATION IN ESTABLISHING
LIMITATIONS
The toxic pollutants listed below were selected for further
consideration in establishing limitations for this subcategory.
The toxic pollutants selected are each discussed following the
list.
114.
115.
118.
119.
12O.
122.
123.
124..
125.
126.
antimony
arsenic
cadmium
chromium
copper
lead
mercury
nickel
selenium
silver
1393
-------
&CIB PEfilll!
SEEK — ¥1
128. zinc
Antimony was detected above Its treatable concentration fll.47
»g/l) in four of 15 samplesr ranging from 3.4 to 51
Qiaiierefprep antimony is. selected far further consideration
limitation. " ' ' '
for
Arsenic was
concentration
4*300 mg/1.
consideration
. /f
Cadmium was
concentration
to. 42.13
cons ideration
found in- concentrations above its treatable
£O-34 mg/lj| in Ifl of 15 samples ranging from 1.5 to
Bierefore^ arsenic is selected for further
for limitation.
.• •.;..' '" ;. ,,'ii it * ,'; •, •;> ::Ai= .!; ;,- j;,;'.,.. i;,;•;;;!S is!,-a1^msmi•;• ;„-:•"'- *;":v;:; ts -:•/«; *i;• > jL.• i.*,: 5k! I
found in concentratiO'ns afeowe, its treatafile
£0 .CI49I mg/l| in' ICToE 15 saffipl.es ranging front §'.7
Skerefore,, cadaiaK is selected, far
far If«f tation.
C3Btrc3imicEtt was found in concentrations afaoiVfe its treatable
concentration C&-&7 mgf/L| in seYen, of 15 saa^les ramginig froffi
ff.ffiff to""i3..W'mg/i. T&erefofejr "cferoittiuffi. is selected far fartfser
consideration for limitation:.
Clipper was fo^raad in,- coraeentrations a&ewre its treafeaiile
concentration CO'.Jff mg/1! in 12 out of 15 samples ranging froai
1.5' to Sat"'' rag/1. Tn-ereforer capper is selected for fartfeer
consideration for
Eead was ..... ^' found,
concentration '"
'
in ' concentrations abowe
£ts
........... : ..................... treafslile
rangi'ng ...... from ........ §.1"' .......... to
pg/l.' i&erefore^ lead is 'selected fSsr fnrtiier consideration
for limitation. , [[[ [ [[[ [ [[[ ',.
'-. , ii!;I ! ' ' • . • • • ' ' . ' ' : ' :.!'•; «' •; j; : • ' • • •:;": '; '. >' • • -i ..... ...... ;'!"! :":*'; > ' ...... K 'fmifiiiiftf;1', : >•„! •: '• :' .i '« s> >i IS HSWKi ! S'lii ' ...... (ffe .; i'S'B: ...... I9U If i'J ,,
- , ,..•'.., "; !if . . . • "'',,: ; '• ' 1, , .;..•,:••:, ; • , 'ff. • V! t, : -*; J V, ' '! ' I . "niii; ' :iS J:«K' tiii^^^^^^^^^^^^^^^^^^^^^^^ ..... Ii ;i"- H- '',••:',': KJ&ffl S^mmm; M. isf i .
-------
IkCID
SBBEKHSBORX
SECT -
was foimcl ±n CDneentxatlons above 3.ts
•Concentration JB.23 mg/13 in 12 »ut of 15 samples ranging from
2,35 too 512 mg/1, Tlierefore^ zinc Is selected for furtliex
for limitation,
1395
-------
V 'i : - V , ' ,'Vv !, • i ••,.;,; ""':*"i m^A 'I1;' !*' "St-i;1 ;,: i.^'Ji^KV*^;'. '
METALLURGICAL ACID PLANT SUBCATEGORY SECT - VI
-',!J!* ;,,"it' IM.'tl'/VB iW SUKHUMI
TABLE VI-1
•.. ".'i1 1. , , , Mil n,: J, F :, * ,
TOXIC POLLUTANTS NEVER DETECTED
2. acrolein
3. acrylonitrile
5. benzidene
7. chlorobenzene
8. 1,2,4-trichlorobenzene
9. hexachlorobenzene
12. hexachloroethane
16. chloroethane
17. DELETED
18. bis (2-chloroethyl) ether
19. 2-chloroethyl vinyl ether (mixed)
20. 2-chloronaphthalene
21. 2,4.6-trichlorophenol
24. 2-chlorophenol
25. 1,2-dichlorobenzene
26. l/S-dichlprobenzene
27. 1,4-dichlorobenzene
28. S/S'-dichlorobenzidine
30. 1,2-trans-dichloroethylene
31. 2,4-dichlorophenol
32. 1,2-dichloropropane
33. 1,3-dichloropropylene
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. 1,2-diphenylhydrazine
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. bis(2-chloroisopropyl) ether
43. bis(2-chloroethoxy) methane
45. methyl chloride
46. methyl bromide
50. DELETED
52. hexachlorobutadiene
53. hexachlorocyclopentadiene
57. 2-nitrophenol
58. 4-nitrophenol
59. 2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
6.1. N-nitrosodimethylamine
63. N-nitrosodi-n-propylamine
72. benzo(z)anthracene
77. acenaphthylene
79. benzo(ghi)perylene
.
m
1396
-------
METALLURGICAL ACID PLANT SUBCATEGORY
SECT - VI
TABLE VI-1 (Continued)
TOXIC POLLUTANTS NEVER DETECTED
82. dibenzo(a,h)anthracene
83. indeno(l,2,4-cd)pyrene
88. ' vinyl chloride
89. aldrin
95. alpha-endosulfan
97. endosulfan sulfate
113. toxaphene
116. asbestos
129. 2,3,7,8-tetrachlorodibenzo-p-dioxin
1397
-------
METALLURGICAL ACID PLANT SUBCATEGORY
SECT - VI
TABLE VJ-2
,' • •' : ' : ••••• '',•' ' . ' I.; ' I
TOXIC POLLUTANTS NEVER FOUND ABOVETHEIR ANALYTICAL
QUANTIFICATION CONCENTRATION
1. acenaphthene
4. benzene
10. 1,2-dichloroethane
11. 1,1,1-trichloroethane
14. 1,1,2-trichloroethane
15. 1,1,2,2-tetrachloroethane
29. 1,1-dichloroethylene
34. 2,4-dimethylphenol
39. fluoranthene
47. broraoform
49. DELETED
51. chlorodibromomethane
54. isophorone
55. naphthalene
56. nitrobenzene
62. N-nitrosodiphenylamine
64. pentachlorophenol
65. phenol
67. butyl benzyl phthalate
68. di-n-butyl phthalate
69. di-n-octyl phthalate ,
70. diethyl phthalate
71. dimethyl phthalate
73. benzo(a)pyrene (3,4-benzopyrene)
74. 3,4-benzofluoranthene
75. benzo(k)fluoranthene (11,12-benzofluoranthene)
76. chrysehe
80. fluorene
84. pyrene
87. trichloroethylene
90. dieldrin
91. chlordane (technical mixture and metabolites)
92. 4,4'-DDT
93. 4,4'-DDE(p,plDDX)
94. 4,4'-DDD(pfp'TDE)
96. b-endosulfan-Beta
98. endrin
99. endrin aldehyde
100. heptachlor
101. heptachlor epoxide
1398
-------
METALLURGICAL ACID PLANT SUBCATEGORY
SECT - VI
TABLE VI-2 (Continued)
TOXIC POLLUTANTS NEVER POUND ABOVE THEIR ANALYTICAL
QUANTIFICATION CONCENTRATION
102.
103.
104.
105.
106.
107.
108.
109.
110.
111.
112.
a-BHC-Alpha
b-BHC-Beta
r-BHC (lindane) -Gamma
delta-BHC
PCB-1242 (Arochlor
PCB-1254 (Arochlor
PCB 1221 (Arochlor
PCB-1232 (Arochlor
PCB-1248 (Arochlor
PCB-1260 (Arochlor
PCB-1016 (Arochlor
1242)
1254)
1221)
1232)
1248)
1260)
1016)
(a)
(a)
(a)
(b)
(b)
(b)
(b)
(a), (b) Reported together
1399
-------
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METALLURGICAL ACID PLANT SUBCATEGORY SECT - VI
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METALLURGICAL ACID PLANT SUBCATEGORY
SECT - VI
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1403
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METALLURGICAL ACID PLANT SUBCATEGORY SECT - VI
THIS PAGE INTENTIONALLY LEFT BLANK
1404
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - VII
SECTION VII
CONTROL AND TREATMENT TECHNOLOGIES
The preceding sections of this supplement discussed the sources,
flows, and characteristics of metallurgical acid plant
wastewater. This section gives the technical basis for the
existing BPT effluent limitations, indicates the treatment
technologies which are currently practiced, and summarizes the
treatment options which have been examined as part of this
analysis.
TECHNICAL BASIS OF BPT
As mentioned in Section III, EPA promulgated best practicable
control technology currently available (BPT) effluent limitations
guidelines for the metallurgical acid plants subcategory of the
nonferrous metals category on July 2, 1980. The technology basis
for the 1980 BPT effluent limitations was treatment of acid plant
wastewater by precipitation and flocculation with lime and
polymers, followed by sedimentation.
The production normalizing parameter for the 1980 BPT was tons of
100 percent H2SO4 capacity (rather than production). The BPT
wastewater flow rate was determined to be 6,079 1/kkg (1,457 gal/
ton) at 100 percent equivalent sulfuric acid capacity.
The 1980 BPT effluent limitations applied only to metallurgical
acid plants associated with primary copper plants. Also, the
pollutants selected for regulation were TSS, copper, cadmium,
lead, zinc,, and pH. As discussed in Section VI, additional
pollutants are now considered for limitation in the revised
limitations and standards.
The' only change to the promulgated BPT limitations for the
metallurgical acid plants subcategory is the inclusion of
sulfuric acid plants associated with primary lead, primary
molybdenum, and primary zinc plants. Also, limitations for the
pollutants molybdenum and fluoride are added for molybdenum acid
plants only and iron co-precipitation is included as part of the
BPT technology basis for molybdenum acid plants to control
discharges of molybdenum. As with primary copper acid plants,
associated wastewater generated by air pollution control (or gas
conditioning systems) for sulfur dioxide off-gases from
pyrometallurgical operations at these plants are also included as
part of the acid plant blowdown.
CURRENT CONTROL AND TREATMENT PRACTICES
As described in Section III, there are 22 metallurgical acid
plants associated with primary copper, primary lead, primary
molybdenum, and primary zinc plants in the U.S. Ten acid plants
are associated with primary copper plants, three are associated
1405
-------
METALLURGICAL ACID PLANT SUBCATEGORY
SECT - VII
with primary lead plants, three are associated with primary
molybdenum plants, and six are associated with primary zinc
plants.
In these primary metals plants, the metals are usually produced
from sulfideores. In the production sequence,sulfur oxides are
released in the pyrometallurgical processes of roasting,
sintering, smelting, or converting.
After the hot gases have been subjected to waste heat recovery
and primary particulate control, the gasesare usuallytreated
with an open scrubbing tower (or one scrubber performing both
operations of preconditioning and scrubber) and a mist
precipitator (for final particulate and 863 removal). Due to a
build-up of salts in the scrubbing liquor, a blowdown may be
necessary.
In areas of net evaporation, this wastewateris usually impounded
and evaporated. Other control measures are reuse and
minimization of the amount of blowdown.Four plants indicated
cooling towers were used in treating acid plant blowdown.
Although the functions of these cooling towers in the treatment
systems were not indicated, many of the plants may be using
cooling towers to cool the wastewater stream prior to reuse or
discharge. Some plants may be concentrating the wastewater
stream with their cooling towers.
."• ; •' :" : • '../,'•' •*"'!:'"'l:''.-'ft,:.' ' : It',. :!$*•. .'.:%y^'•.•'*'•:'. :•"";• **''l:l;
Using the acid plant blowdown for cooling hot gases from other
processes, feeding the blowdown into fluid bed roasters, or using
the blowdown for ore concentrating arethree possible reuse
schemes. One plant reports that it uses its blowdown for ore
concentrating after sedimentation. The amount of acid plant
blowdown can be minimized by using efficient primary particulate
control devices. This minimizes the loadcarried to acid plant
scrubbers, thus minimizing required blowdown.
I '• '. • •'.'• 'I , • . ,; •• III I
As discussed in Section' V, wastewater associated with-
metallurgical acid plants subcategory is characterized by the
presence of the toxic metal pollutants and suspended solids. The
raw (untreated) wastewater data for specific sources as well as
combined waste streams is presented in Section V. Generally,
these pollutants are present in each of the waste streams at
treatable concentrations, so these waste streams are commonly
combined for treatmentto reduce the concentrations ofthese
p'ollutants. Construction of one wastewater treatment system for
combined treatment allows plants to take advantage of economies
of scale and, in some instances, to combinestreams of differing
alkalinity to reduce treatment chemical requirements. Ten plants
in this subcategory currently have combined wastewater treatment
systems, nine have lime precipitation and sedimentation, and two
have lime precipitation, sedimentation, andfiltration. One of
the plants with lime precipitation and sedimentation has
preliminary treatment consisting of sulfide addition and
filtration. As such, three options have been considered for the
promulgated BAT, BDT, and pretreatment in this subcategory, based
flit! i!
'ii Ft" ;;,:ii. .MI Hi1:;.
1406
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METALLURGICAL ACID PLANT SUBCATEGORY SECT - VII
on combined treatment of these compatible waste streams.
CONTROL AND TREATMENT OPTIONS
Based on an examination of the wastewater sampling data, three
control and treatment technologies that effectively control the
pollutants found in metallurgical acid plants smelting
wastewaters were selected for evaluation for copper, lead/ zinc,
and molybdenum- metallurgical acid plants since proposal. On
March 18, 1985, the Agency published a Notice of Data
Availability which revised the three proposed options to include
iron coprecipitation for molybdenum acid plants to achieve
discharge limitations for molybdenum. These technology options
are discussed below. Other treatment technologies considered at
proposal include activated alumina adsorption (Option D) and
activated carbon adsorption (Option E). These technologies were
not selected for evaluation because they are not applicable to
the metallurgical acid plants subcategory. Although arsenic was
found in process wastewaters at treatable concentrations,
activated alumina technology was not selected because it is not
demonstrated in the nonferrous metals manufacturing category, nor
is it clearly transferable. Since no toxic organic pollutants
were selected for consideration for limitation in this
subcategory, activated carbon technology is not applicable.
OPTION A
Option A for the metallurgical acid plants subcategory is
equivalent to the BPT control and treatment technologies. The
BPT end-of-pipe treatment scheme consists of chemical
precipitation and sedimentation. Iron co-precipitation is also
included for molybdenum acid plants. This technology is included
to control discharges of molybdenum. Chemical precipitation and
sedimentation consists of lime addition to precipitate metals
followed by gravity sedimentation for the removal of suspended
solids, including the metal precipitates.
OPTION B
Option B for the metallurgical acid plants subcategory consists
of all the requirements of Option A (lime precipitation and
sedimentation) plus in-plant reduction of process wastewater
flow. Iron co-precipitation is also included for molybdenum acid
plants. This technology is included to control discharges of
molybdenum. Water recycle is the control mechanism for flow
reduction.
OPTION C
Option C for the metallurgical acid plants subcategory consists
of Option B (lime precipitation, sedimentation, and in-process
flow reduction) with the addition of sulfide precipitation, and
multimedia filtration. The technology basis for the one primary
copper plant and all primary molybdenum plants is in-process flow
reduction, sulfide precipitation, pressure filtration, lime
1407
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METALLURGICAL ACID PLANT SUBCATEGORY SECT - VII
precipitation, sedimentation, arid multimedia filtration. Iron
co-precipitation is also part of the technology basis for primary
molybdenum acid plants. This technology is included to control
discharges of molybdenum. For the zinc and lead plants, the
technology basis is in-process flow reduction, lime precipitation
and sedimentation, sulfide precipitation and sedimentation, ~~*
multimedia filtration.
and
Multimedia filtration is used to remove suspended solids,
including precipitated metals, below the level attainable by
gravity sedimentation. The model filter is of the gravity,
mixed-media type, although other forms of filters such as rapid
sand filters or pressure filters would perform satisfactorily.
The addition of filters also provides for consistent removal
during periods of time when there are rapid increases in flows or
loadings of pollutants to the treatment system.
i,1!1: iSii'S • I
,' ,!|,, 'iMlillii'11 ' 111'.'1* "I
I I
.I.i'.'i ' i iiillii.-;1"'!
1408
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METALLURGICAL ACID PLANT SUBCATEGORY SECT -''VI11
'SECTION VIII
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS
This section describes the method used to develop the costs
associated with the control and treatment technologies discussed
in Section VII for wastewaters from metallurgical acid plants.
The energy requirements of the considered options as well as
solid waste and air pollution aspects are also discussed.
In Section VI of this supplement, several pollutants and
pollutant parameters are selected for further consideration for
limitation for the metallurgical acid plants subcategory. These
pollutants or pollutant parameters include several toxic metals,
total suspended solids, and pH. Metals are most economically
removed by chemical precipitation, sedimentation, and filtration.
The recycle of acid plant blowdown through holding tanks or
cooling towers may also be added as a preliminary flow reduction
measure which decreases the discharge flow and results in the
concentration of pollutants in the effluent stream. Treatment of
a more concentrated effluent introduces the possible economic
benefits associated with treating a lower volume of wastewater.
TREATMENT OPTIONS COSTED FOR EXISTING SOURCES
As discussed in Section III of this supplement, metallurgical
acid plants are located on-site at primary copper, lead,
molybdenum, and zinc smelters.. Three treatment options have been
considered for promulgation for the metallurgical acid plants
subcategory. These options are summarized below and are
schematically presented in Figures X-l through X-4 (pages 1431 -
1434).
OPTION A
Option A for the metallurgical acid plant subcategory consists of
lime precipitation and sedimentation end-of-pipe treatment
technology. Iron co-precipitation is included in Option A for
molybdenum acid plants. This technology is included to control
discharges of molybdenum.
OPTION B
Option B for the metallurgical acid plant subcategory requires
flow reduction measures consisting of the recycle of acid plant
blowdown through holding tanks or cooling towers if cooling is
required, and end-of-pipe treatment consisting of lime
precipitation and sedimentation, and iron co-precipitation for
molybdenum acid plants.
OPTION C
Option C for the metallurgical acid plant subcategory requires
1409
-------
PLSJ3T
- V±ll
flow reduction measures consisting of the recycle of acid plant
blowdown, through holding"tanks""and cooling towers.., and end—of—
pipe treatment technology consisting of lime precipitation and
sedimentation, sulfide precipitation, iron co-precipitation for
molybdenum acid plants, and multimedia filtration.
Cost Methodology
a detailed ,„ discussion of , the,, methodology used to develop the
compliance "costs Is presented" in'Section" ictll of Vol. 1. Plant— •
by-plant compliance costs have beenestimated for the nonferrous
metals manufacturing category and are presented in the
administrative record supporting thisregulation. The costs
developed for the final regulation are presented in Tables VIII—1
and VIII—2 Jpage 1414J for the direct and indirect dischargers,
respectively. ^ | ^ ^ ^
Each of the "major assumptions used to""develop compliance "costs"as
presented in Section VIII of Vol. 1. However, each subcategory
contains a unique set of waste streams requiring certain
subcategory-specific assumptions todevelopcompliance costs.
Four major assumptions are discussed briefly below.
|1) Flow reduction of" £he'acifl plant blowlown''ls ''accomplished "
using '" cooling towers, ' ' JVnnual '" 'costs associated with
maintenance and chemicals, to prevent biological growth.,
corrosion, and" scale "formation ajnsT 'Included' 'In the estimated
compliance costs," xf" a"'plant "currently recycles acid plant
blowdown, capital costs"of the recycle equipment |cooling
tower, piping, and pumpsj were not Included in the
compliance costs.
(2) Sludge generated by the sulfide precipitation and
sedimentation process at the primary zinc and primary lead
facilities was considered hazardous waste for disposal
purposes. mt the one primary copper facility and all
primary molybdenum facilities^- sludge generated by the
sulfide precipitation and pressure filtration process was
also considered hazardous waste.
(3)
Because the compliance costs represent incremental costs an
acid plant may be expected to incur in complying with this
regulation, annual costs for iaplace treatment used to
comply with promulgated BPT regulations in the primary zinc
and primary lead subcategories are also not included in this
regulation.
The cost of treating acid plant blowdown from acid
plants in the primary copper, primary zinc, and primary
lead subcategories is determined by flow-weighting
appropriate costs. The entire cost of cooling towers
for flow reduction of the acid plant blowdown is attributed
to the metallurgical acid plants subcategory. Costs for
sulfide precipitation and settle are attributed to the
metallurgical acid subcategory for primary copper and
141D
-------
, lea* plants. Seelfide precipitation costs - ' are-
apportioned feetweea t&e prfiraary zinc and metallurgical acid,
SEE&categories oa a flow—weigfeted &asis. Compliance cost
estimates for t&e two primary moly&denEEHt metallurgical acid.
plants were developed by costing separate treatment
to treat: acid plant; frlowdawau
HQKWATER
Honwater qpal.£fe.y iaqpacfcSr specific to fcfee
pEaztts sra&categary,, Inctii3lEEg emergy
and air poILttfciaa are eiiseassecl below.
fefee
for ^eteEȣiEine| fe&e eaergy regplresEHsenitrs for
\rarians-. opfetoras • Is. dlscasse^l is Sections. ¥Z11 of t&e General,
BocuBEeEife. Eaergy re«jEi£reBier£ts for tfee fc&ree options
are estimated , afc 1,158 •H!f-&r/yr-r Ir158 Mr-fcr/yrr an.^
1.746 MSf-fer/yr for Q&ti&aai'&r B, amel C»- respectively . CJptiam C
represEerets- less tfieetit .cme'perceat af a topical- plaas.fc's'elecferieai
, Et Is therefore eoEEdiHieel tbafe t&e e0er regpiremezEts of"
t&e treatBBeat options eKmsidiere«I will feawe mo sigaif ic^ist
total plant energy
front
Slttdges will necessarily coataiiE
of toxie metal, pollutants. Wastes generated
-shelters ara^: refiners are enrreatly
regsilatioa &y Jkct. of Coogfress f Kesonree CoKser^atioffi and
fict CBaESail ' Seetiom 3OOl(b}- €onsegiaeffitlyr sludg
frcfflE treating primary iaefastries* wraste^ater,
«etallurc|ical aeicl plants wastewaterr are. aot presently
ta regulafciatt as nazardatES wastes.
T&e tec&aology &asis for t&e metallurgical acid
sra&c^tegory includes stflifi^e precipitation for 'tfee control of
various toxie metals- " Tbe a^eracy &elie^es sludge generated:
tferoogfe SEElf i^e pcecipitatiott faa^ seclisaeatatioiE or pressure
filtration| will &e classified as feazardoHs .
costs of liazar^i^is waste disposal were considered in t&e
analysis for t&is saficategory fin spite of t&e ciErremt
and: regtElatiom esemptiouj because stilf ide will aot form metal
&ydrox:ides t&at resist leac&ing. S&e casts of feazardons waste
disposal were determined to fee economically ac&iewaljle, Mowewer,
lime sludges are not expected to Eie hazardous. ^E&e Agency
estimates t&at t&e metallurgical acid plants sn&category will
generate 5
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METALLURGICAL ACID PLANT SUBCATEGORY SECT - VIII
• , '" • ",1,, ,•!!,"'. i,,'1! Illli 'iillillll'jJl'iii ,', .'"' ' ' , ," , ' 'i, , l'1,1'1 ',',!,' ,•!:'„',, " 'I' 'i' , ,"i.,,'I'lil'
are no existing BPT limitations in place which cover discharge of
pollutants from molybdenum acid plants.
If these wastes should be identified or are listed as hazardous,
they will come within the scope of RCRA's "cradle to grave"
hazardous waste management program, requiring regulation from
the point of generation to point of final disposition. EPA's
generator standards would require generators of hazardous
nonferrous metals manufacturing wastes to meet containerization,
labeling, recordkeeping, and reporting requirements; if plants
dispose of hazardous wastes off-site, they would have to prepare
a manifest which would track the movementofthe wastesfrom the
generator's premises to a permitted off-site treatment, storage,
or disposal facility. See 40 CFR 262.20 45 PR 33142, May 19
1980) as amended at 45 FR 86973 (December 31, 1980). The
transporter regulations require transporters of hazardous wastes
to comply with the manifest system to assure that the wastes are
delivered to a permitted facility. See 40 CFR 263.20 45 33151
(May 19, 1980), as amended at 45 FR 86973 (December 31, 1980).
Finally, RCRA regulations establish standards for hazardous waste
treatment, storage, and disposal facilities allowed to receive
such wastes. See 40 CFR Part 464 46 FR 2802 (January 12, 1981),
47 FR 32274 (July 26, 1982).
Even if these wastes are not identified as hazardous, they still
must be disposed of in compliance with the Subtitle D open
dumping standards, implementing 4004 of RCRA. (See 44 FR 53438
September 13, 1979). The Agency has calculated as part of the
costs for wastewater treatment the cost of hauling and disposing
of these wastes.
AIR POLLUTION
There is no reason to believe that any substantial air pollution
will result from implementation of chemical precipitation,
sedimentation, sulfide precipitation, and multimedia filtration.
These technologies transfer pollutants to solid waste and do not
involve air stripping or any other physical process likely to
transfer pollutants to air. Minor amounts of sulfur may be
emitted during sulfide precipitation, and water vapor containing
some particulate matter will be released in the drift from
cooling towers, however, the Agency does not consider this impact
to be significant.
.1412
• . ,
IL"H! i; IILiI IliLL !', ,"i' „}*(„ "n, !!'
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - VIII
TABLE VIII-1
COST OF COMPLIANCE FOR THE
METALLURGICAL ACID PLANTS SUBCATEGORY
Option
B
C
Direct Dischargers
(March, 1982 Dollars)
Capital Cost
1,460,000
2,480,000
Annual Cost
1,522,000
2,040,000
TABLE VII1-2
COST OF COMPLIANCE FOR THE
METALLURGICAL ACID PLANTS SUBCATEGORY
Option
B
C
Indirect Dischargers
(March, 1982 Dollars)
Capital Cost
16,100
161,000
Annual Cost
19,300
84,500
1413
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METALLURGICAL ACID PLANT SUBCATEGORYSECT"-VI1I
•' j
lH'itillTIK,1, "IUI ..... "I ..... '
.1 -I;''-' iJ'.'...'i." I'Jis" JV.
-ii • .'.•." i'h" «*'«.»*'
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• ...... ';! .......... ;::',S,S;|! ..... ''i ..... ill!": ..... ;'
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'ji,i:, ',i-\ , f ...... !|ii;,' ItfV
i,:1*'1 v»ii,',;ii liii"1;
THIS PAGE INTENTIONALLY LEFT BLANK
1414
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METALLURGICAL ACID PLANT SUBCATEGORY SECT - IX
SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
EPA promulgated BPT effluent limitations for the metallurgical
acid plants subcategory on July 2, 1980, as Subpart I of 40 CFR
Part 421. The provisions of this subpart apply to process
wastewater discharges resulting from or associated with the
manufacture of by-product sulfuric acid at primary copper
smelters, including any associated air pollution control or gas-
conditioning systems for sulfur dioxide off-gases from
pyrometallurgical operations. On March 8, 1984, EPA expanded BPT
for the metallurgical acid plants subcategory to include sulfuric
acid plants associated with primary lead and primary zinc
smelting operations as part of the promulgated rulemaking for
nonferrous metals manufacturing. The effluent limitations for
the lead and zinc acid plants are identical to those promulgated
for primary copper acid plants.
EPA has since expanded the applicability of the BPT limitations
for metallurgical acid plants to include primary molybdenum acid
plants. On March 18, 1985, EPA published a Notice of Data
Availability which stated that, in addition to expanding the
applicability, EPA was proposing to modify the existing BPT
effluent limitations to include limitations for the pollutants
molybdenum and fluoride for molybdenum acid plants only.
The effluent limitations established by BPT for the metallurgical
acid plants subcategory are based on chemical precipitation and
sedimentation treatment technology with the addition of iron
coprecipitation preliminary treatment for primary molybdenum acid
plants as shown in Figure IX-1 (page 1419). The limitations are
based on a production normalized wastewater discharge rate of
6,079 1/kkg of 100 percent sulfuric acid production capacity.
The promulgated BPT limitations are shown in Table IX-1 (page
1418)-.
The Agency has finalized its proposals that metallurgical acid.
plants at primary lead, primary molybdenum, and primary zinc
plants be included in the metallurgical acid plants subcategory
originally established for copper smelting acid plants. This new
subcategorization is based both on the similarity of acid plant
operations (regardless of the metal smelted), and the similarity
of the wastewater matrices (confirmed by comparison of raw
wastewaters). BPT limitations for the modified metallurgical
acid _plants subcategory are identical to those already
established for primary copper acid plants with the exception
that limitations for molybdenum and fluoride are provided for
molybdenum acid plants.
The modified BPT effluent limitations have the potential for
double counting of zinc acid plants for BPT because EPA is not
recommending modification of the primary zinc BPT limitations to
1415
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - IX
11111111 ' ' , ' »i"! :.!i;, 1|"1'i. .:'': III I I II I gill
,,l,i ' : • ' '» i ' n »!i"! , ' ' i „;, '|iy I I II II I
eliminate the acid plant portion of those limitations. The
justification for this approach is that EPA believes existing
permits probably reflect BPT for the combined discharge of_ zinc
smelting and acid plant operations. It is believed that existing
permits at these plants will be modified to reflect the BAT
requirements where there is no such double counting. Therefore,
this apparent inconsistency should not have any actual effect on
existing permits. The potential for double counting is not a
factor in primary lead because EPA is changing the technology
basis for BPT and will eliminate acid plants in the modified BPT.
Similarly, all potential double counting of zinc acid plants will
be eliminated as part of the recommended BAT, NSPS and PSNS
effluent limitations and standards for the primary zinc
subcategory.
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
There is no cost associated with expanding the current BPT
regulationto include primary zinc andprimary lead acid plants
because all of the direct discharging primary lead and primary
zinc metallurgical acid plants currently have BPT technology in
place. '"
The costs incurred by the two direct discharging primary
molybdenum acid plants are not included in this document because
they are based on information which has been claimed to be
confidential. Implementation of the expanded BPT by the two
direct discharging primary molybdenum acid plants would result in
the annual removal of 4,432 kilograms of priority metals, 19,687
kilograms of molybdenum, and 27,849 kilograms of fluoride.
1416
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METALLURGICAL ACID PLANT SUBCATEGORY SECT - IX
TABLE IX-1
BPT EFFLUENT LIMITATIONS FOR THE
METALLURGICAL ACID PLANT SUBCATEGORY
Acid Pant Slowdown BPT
Pollutant or
Pollutant Property
Maximum, for
Any One Day
Maximum for
Monthly Average
(Ib/million Ibs) of 100 percent sulfuric acid capacity
Cadmium
Copper
Lead
Zinc
Fluoride1
Molybdenum1
Total Suspended Solids
pH
0.180
5.000
1 800
3.600
212.800
Reserved
304.000
Within the range of
O.Q90
2 000
0.790
0.900
121.000
Reserved
152.000
6.0 to 9.0
LFor molybdenum acid plants only.
1417
-------
ACEB PUSHIf SOBCSTEHOiKZ" SECT? —
S*
E-EO
E«n
Pt^t
OKI
KtPt
HO ft
lit
Of rf
1418
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - X
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
The effluent limitations which must be achieved by July 1, 1984,
are based on the best control and treatment technology used by a
specific point source within the industrial category or
subcategory, or by another industry where it is readily
transferable. Emphasis is placed on additional treatment
techniques applied at the end of the treatment systems currently
used for BPT, as well as reduction of the amount of water used
and discharged, process control, and treatment technology
optimization.
The factors considered in assessing best available technology
economically achievable (BAT) include the age of equipment and
facilities involved, the process used, process changes, nonwater
quality environmental impacts (including energy requirements),
and the costs of application of such technology (Section 304 (b)
(2)(5) of the Clean Water Act). At a minimum, BAT represents the
best available technology economically achievable at plants of
various ages, sizes, processes, or other characteristics. Where
the Agency has found the existing performance to be uniformly
inadequate, BAT may be transferred from a different subcategory
or category. BAT may include feasible process changes or
internal controls, even when not in common industry practice.
The required assessment of BAT considers costs, but does not
require a balancing of costs against effluent reduction benefits
(see Weyerhaeuser v. Costle, 590 F.2d 1011 (D.C. Cir. 1978)).
However, in assessing the proposed BAT, the Agency has given
substantial weight to the economic achievability of the
technology.
TECHNICAL APPROACH TO BAT
The Agency reviewed a wide range of technology options and
evaluated the available possibilities to ensure that the most
effective and beneficial technologies were used as the basis of
BAT. To accomplish this, the Agency elected to examine three
technology options which could be applied to copper, lead,
molybdenum and zinc metallurgical acid plants as BAT options and
which would represent substantial progress toward reduction of
pollutant discharges above and beyond progress achieved by BPT.
On March 18, 1985, the Agency published a Notice of Data
Availability which revised the three proposed options to include
iron co-precipitation for molybdenum acid plants to control
discharges of molybdenum.
In summary, the treatment technologies considered for the
metallurgical acid plants subcategory are:
Option A (Figure X-l, page 1431) is based on
1419
-------
flu,I*! i1"!1 ,, ' 'i,,'i ' JIB'1" ii'liif,, |, S!!,i"!!|
METALLDRGICAL ACID PLANT SUBCATEGORY SECT - X
illllli |"i|"ii|"i:|i;: '!'i'l"l|l|lnii|< i|:!li!l!|!lll '"'i'lli « \W'f 1' ' II "'fll'llll'l' IIU i"'" ll'ililiililllll,1 IS'.!:* I', i' I,1'1" Til I'l'HII! i'',»,: Illlihl I'mlP' ill i':'l Illllr! lii|llllliiimill, 'illlii I
'ft'',1,1 ';" ,,'!"'']',i|||i' ,f,,' ,,,,11:11,l. '"i,,|, inn;' '|,'; i!,,||:',, ,jf n| 11,; i : ||" ;;•,',: ' My ft ,,'iiVj, :•, JjVli W, I, Pi |l'|i" I",ill |
1 I'"1 ,' i'!i,l!,'"!if"i ':': /itWii;,"'! iJllllfi"1 III'I'"!,:,!!! 1
o Chemical precipitation and sedimentation
o Iron co-precipitation for molybdenum acid plants
Option B (Figure X-2, page 1432) is based on
o Chemical precipitation and sedimentation
o In-process flow reduction
b Iron co-precipitation for molybdenum acid plants
•:!l i ' ' ' • ; ' '' ,1'' h, ''I:1" ll''1'' ' ' " ,'"11" '"«
Option C (Figure X-3f page 1433) is based on
o Chemical precipitation and sedimentation
o In-process flow reduction
o Sulfide precipitation and sedimentation for lead and zinc
acid plants
o Sulfide precipitation and pressure filtration preliminary
treatment for one copper acid plant and all molybdenum
acid plants
o Iron co-precipitation for molybdenum acid plants
o Multimedia filtration
The three options examined for BAT are discussed in greater
detail below. The first option considered is the same as the BPT
treatment and control technology. The second and third options
each represent substantial progress toward the prevention of
pollution above and beyond the progress achievable by BPT.
OPTION A
II, V
Option A for the metallurgical acid plants subcategory is
equivalent to BPT, which includes end-of-pipe treatment of
chemical precipitation and sedimentation. Chemical precipitation
and sedimentation consists of lime addition to precipitate metals
followed by gravity sedimentation forthe removal of suspended
solids including metal precipitates. Iron co-precipitation is
also included for molybdenum acid plants to control discharges of
molybdenum (see Figure X-l, page 1431).
OPTION B "' ^ ^ ^ ' ' ". _ ' ,,. [..',,',.^",.,l', ." . . ] "..~'[ ' .,'! , ,1',;"',
Option B for the metallurgical acid plants subcategory consists
of all the requirements of Option A (lime precipitation and
sedimentation) plus in-plant reduction of process wastewater flow
Iron co-precipitation is also included for molybdenum acid plants
to control discharges of molybdenum (see Figure X-2, page 1432).
Flow reduction measures, including in-process changes, result in
the concentration of pollutants in other effluents. Treatment of
a more concentrated effluent allows achievement of a greater net
pollutant removal and introduces the possible economic benefits
associated with treating a lower volume of wastewater.
"I ' • • '.•.'•",• , ''•:., ". ... J ...I.,!!' I I
Methods used,in Option B to reduce process wastewater discharge
rates include recycle or reuse of the acid plant blowdown waste
1420
!'i!r ..... . :• "
^^^ '
.iiiiii: X:!,,!!),!". ...... liil Kv b iiiC!:'! ...... HE- Sis
i
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - X
stream. As discussed in Section IX, the acid plant blowdown
stream is composed of any process wastewater discharges resulting
from or associated with the manufacture of by-product sulfuric
acid at primary copper, primary lead, and primary zinc" smelters.
Any associated air pollution control or gas-conditioning systems
for sulfur dioxide off-gases from pyrometallurgical operations at
these plants (roasting, sintering, and converting) are also
included as a constituent of the acid plant blowdown stream.
Recycle of the acid plant blowdown is achieved through coolinq
towers or holding tanks.
OPTION C
Option C for the metallurgical acid plants subcategory consists
of _all control treatment requirements of Option B (lime
precipitation, sedimentation, and in-process flow reduction) plus
sulfide precipitation (followed by sedimentation), and multimedia
filtration technology added at the end of the Option B treatment
scheme. Sulfide precipitation is added to reduce cadmium, zinc,
and other priority metal concentrations below concentrations
achievable with lime and settle. For lead and zinc acid plants,
sulfide precipitation and sedimentation is added after lime
precipitation and sedimentation (see Figure X-3, page 1433). For
one copper acid plant and all molybdenum acid plants, sulfide
precipitation and pressure filtration are added before lime
precipitation and sedimentation. Iron co-precipitation is also
part of the technology basis for molybdenum acid plants. This
technology is included to control discharges of molybdenum (see
Figure X-4, page 1434).
Multimedia filtration is used to remove suspended solids,
including precipitates of metals beyond the concentrations
attainable by gravity sedimentation. The filter suggested is of
the gravity, mixed media type, although other forms of filters,
such as rapid sand filters or pressure filters, would perform
satisfactorily.
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
As one means of evaluating each technology option, EPA developed
estimates of the pollutant removal estimates and the compliance
costs associated with each option. The methodologies are
described below.
POLLUTANT REMOVAL ESTIMATES
A complete description of the methodology used to calculate the
estimated pollutant removals achieved by the application of the
various treatment options is presented in Section X of the
General Development Document. The pollutant removal estimates
have been revised from proposal based on comments and new data,
however, the methodology for calculating pollutant removals was
not changed. The data used for estimating pollutant removals are
the same as those used to revise compliance costs.
1421
-------
METALLURGICAL ACID PLANT SUBCATEG6RYgECT L x
Sampling data collected during the field sampling program were
used to characterize the major waste streams considered for
regulation. At each sampled facility, the sampling data were
production normalized for each unit operation (i.e., mass of
pollutant generated per mass of product manufactured). This
value, referred to as the raw waste, was used to estimate the
mass of toxic pollutants generated within the metallurgical acid
plants subcategory. By multiplying the total subcategory
production for a unit operation by the corresponding raw waste
value, the mass of pollutant generated for that unit operation
was estimated.
i,!,!' „ , 1,1 '!•! Ml, , ,|, ' '"' i , !: ijirj'iij,! ' "fir , I , , ,, ,• : ' ,ii.;, 'i ''Pi r. „ ' '" ' "IV , " !' ., ''.'i,1 ,'.,;
The volume of wastewater discharged after the application of each
treatment option was estimated for each operation at each plant
by comparing the actual discharge to the regulatory flow. The
smaller of the two values was selected and summed with the Bother
.plant flows. The mass of pollutant discharged was then estimated
by multiplying the achievable concentration values attainable
with the option (mg/1) by the estimated volume of process
wastewater discharged by the subcategory. The mass of pollutant
removed is the difference between the estimated mass of pollutant
generated within the subcategory and the mass of pollutant
discharged after application of the treatment option. The
pollutant removal estimates for the direct dischargers in the
metallurgical acid plants subcategory are presented in Table X-l
(page 1429).
COMPLIANCE COSTS
• ' • • . i
1 • •• '•.,'.. i i .
Compliance costs presented at proposal were estimated using cost
curves, which related the total costs associated with
installation and operation of wastewater treatment technologies
to plant process wastewater discharge. EPA applied these curves
on a per plant basis, a plant's costs—both capital, and
operating and maintenance—being determined by what treatment it
has in place and by its individual process wastewater discharge
(from dcp). The final step was to annualize the capital costs,
and to sum the annualized capital costs, and the operating and
maintenance costs, yielding the cost of compliance for the
subcategory.
; ' ••:••'.''.•• ' ;< h .':!••'.,•: '.•,-' • .'•'.i^'
Since proposal, the cost estimation methodology has been changed
as discussed in Section VIII of this supplement and in Section
VIII of Vol. 1. A design model and plant-specific information
were used to size a wastewater treatment system for each
discharging facility. After completion of the design, capital
and annual costs were estimated for each unit of the wastewater
treatment system. Capital costs rely on vendor quotes, while
annual costs were developed from the literature. The compliance
costs for direct dischargers are presented in Table VIII-1 (page,
1414) .
BAT OPTION SELECTION - PROPOSAL
For proposal, EPA selected Option C t'wfiich includes lime
1422
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - X
# •
precipitation, sedimentation, in-process flow reduction, and
multimedia filtration) as the basis for BAT in the metallurgical
acid plants subcategory.
Option F, which included reverse osmosis, is not demonstrated in
the subcategory and is not clearly transferable from another
subcategory or category and therefore was eliminated from
consideration.
BAT OPTION SELECTION - PROMULGATION
The complete technology basis for this subcategory consists of
in-process flow reduction through recycle and end-of-pipe lime
and settle, sulfide precipitation (followed by sedimentation),
and multimedia filtration technology for lead and zinc acid
plants. For one copper acid plant and all molybdenum acid
plants, the technology basis is in-process flow reduction,
sulfide precipitation, pressure filtration, lime precipitation,
sedimentation, and multimedia filtration. The technology basis
for molybdenum acid plants also includes iron co-precipitation to
control discharges of molybdenum.
Extensive self-monitoring data were submitted through the
comments for the primary-lead, primary zinc, primary copper, and
metallurgical acid plant subcategories. The data were analyzed
statistically for comparison with the combined metals data base.
In addition, design and operating parameters for the treatment
systems from which the data were collected was solicited through
Section 308 authority. Of the seven plants submitting data, the
Agency has determined that data from three of the plants should
not be used to establish treatment because of design or
operational deficiencies. However, three other plants may be
well operated and, of these, the two primary zinc plants appear
to have problems complying with the proposed zinc limitations
(possibly due to high influent zinc concentrations or to ammonia
interferences). The remaining plant, from the primary lead
subcategory, appears to have difficulty meeting the proposed
limit for cadmium. Although there were indications that the
plants might not be operating their treatment systems optimally,
the coefficient of variability for treated effluent was higher
than for influent, and the influent was more variable than would
be expected. The Agency as a conservative measure assumed that
additional treatment (sulfide precipitation) is necessary to meet
the proposed limits.
The last of the seven plants submitting data is from the primary
copper subcategory and was found to be operating its treatment
system at pH 12 to optimize arsenic removal. At pH 12, metals
removal for pollutants other than arsenic decreases due to the
increased solubility of metals at higher pH levels. Therefore,
the Agency believes effluent data from this plant are not
appropriate to determine treatment performance for other plants
without this problem. After examining the arsenic values of the
raw materials used by plants in the copper smelting subcategory,
the Agency believes that this one plant is the only discharger
1423
-------
METALLURGICAL ACID PLANT SUBCATEGORYSECT - X
experiencing arsenic concentrations frequently over 100 mg/1 in
the raw wastewater.
However, the Agency believes the addition of sulfide
precipitation, in conjunction with multimedia filtration, will
achieve the treatment performance values as proposed based on the
lower solubility of metal sulfides (I.e., lower than metal
hydroxides) as well as performance data for this technology on
inorganic chemical wastewaters. (Sulfide precipitation
technology is discussed fully in SectIonVII of Vol. 1.
Application of the promulgated BAT mass limitations will result
in the removal of an estimated 145,000 kg/yr of priority
pollutants generated. The final BAT effluent mass limitations
will remove 2,120 kg/yr of priority metals over the intermediate
BAT option considered, which lacks filtration. Bothoptions are
economically achievable. EPA believes that the incremental
removal justifies selection of filtration as part of BAT mocfel
technology. Filtration is demonstrated at two metallurgical acid
plant facilities, while sulfide precipitation is demonstrated at
five plants in the nonferrous metals manufacturing category
(phases I and II). The estimated capital investment cost of BAT
is $2.5 million (March, 1982 dollars) and the estimated annual
cost is $2.0 million.
FINAL AMENDMENTS TO THE REGULATION
After promulgation, petitioners questioned the data on which the
treatment effectiveness concentration for'" molybdenum removal is
based. As a part of a settlement agreement,thepetitioners
agreed to install iron coprecipitation, the model technology, on
all of the molybdenum-bearing wastestreams at their facilities
regulated under this subcategory and to provide operating data to
the Agency. EPA agreed to consider these data in anyrulemaking
to propose new molybdenum limits. In the interim, EPA agreed to
propose to suspend the molybdenum ilm'Ita't'i'ohsMn the previously11
promulgated BPT and BAT limitations, NSPS and PSNS for this
subcategory. EPA would then recommend interim limits for use in
permits on a Best Professional Judgment (BPJ) basis. Interim
limits, based on a monthly average treatment effectiveness of 30
mg/1 and a daily maximum of 60 mg/1, were established which will
be effective until April 30, 1988. At that time, if . no full-
scale data are available, EPA will establish limits based on the
results of a bench-scale iron coprecipitation data obtained under
the supervision of the Agency.
WASTEWATER DISCHARGE RATES
As discussed in Section III, the principal wastewater sources in
the metallurgical acid plant suj.)Ca£ggOry include acid plant
scrubber blowdown, mist precipitation blowdown, box cooler
blowdown, and mist elimination blowdown. These wastewater
sources have been combined into a single wastewater stream,
referred to as acid plant blowdown.
, ,' 1424
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - X
The proposed BAT discharge rate for metallurgical acid plant
wastewater was 2,554 1/kkg (612.5 gallons/ton) of 100 percent
sulfuric acid production capacity. This is the allowance
promulgated for BAT. This value represents the best existing
practices of the subcategory, as determined from the analysis of
the dcps. Individual water use and discharge rates from the
plants surveyed are presented in Section V of this supplement for
the acid plant blowdown streams. At proposal, 20 of the 21
metallurgical acid plants for which dcp information was available
reported an acid plant wastewater stream. Seven of these plants
recycle greater than 86 percent of their acid plant wastewater.
The BAT discharge rate was based on the average discharge rate of
the plants with greater than 86 percent recycle (refer to Section
VII of Vol. 1.) The plant with 100 percent recycle was not
included in the average.
Revised discharge flows were submitted by two plants after
proposal. These data supported the proposed flow allowance. The
Agency*- received no data demonstrating that the proposed BAT flow
allowance should be changed.
As part of the proposal, dcps were received from the three
molybdenum acid plants. Data from these dcps were used to
calculate production normalized flows for these plants. Because
these flows are consistent with the rate promulgated for copper,
lead, and zinc acid plants, the Agency decided not to revise the
BAT discharge rate and to use this rate for molybdenum acid
plants.
REGULATED POLLUTANT PARAMETERS
In implementing the terms of the Consent Agreement in NRDC v.
Train, Op. Cit., and 33 U.S.C.C1314 (b)(2)(A and B) (1976), the
Agency placed particular emphasis on the priority pollutants. The
raw wastewater concentrations from individual operations and the
subcategory as a whole were examined to select certain pollutants
and pollutant parameters for consideration for limitation. This
examination and evaluation, presented in Section VI, concluded
that 13 pollutants and pollutant parameters are present in
metallurgical acid plant wastewaters at concentrations that can
be effectively reduced by identified treatment technologies.
(Refer to Section VI.)
However, the cost associated with analysis for priority metal
pollutants has prompted EPA to develop an alternative method for
regulating and monitoring priority pollutant discharges from the
nonferrous metals manufacturing category. Rather than developing
specific mass effluent limitations and standards, for each of the
priority metals found in treatable concentrations in the raw
wastewaters from a given subcategory, the Agency is promulgating
effluent limitations only for those pollutants generated in the
greatest quantities as shown by the pollutant removal estimate
analysis. The Agency is promulgating effluent mass limitations
to control the discharge of five priority metal pollutants
1425
-------
METALLURGICAL ACIE> PLANT SUBCATEGORY SECT - X
present at all types of metallurgical acid plants. Since acid
plants are operated in conjunction with primary lead, primary
copper, primary molybdenum and primary zinc plants, the
pollutants selected for limitation in those subcategories are
selected for limitation in the metallurgical acid plants
subcategory. Therefore, certain regulated pollutants may not be
present at a specific acid plant. For example, arsenic may not
be found at primary zinc acid plants, but mass limitations are
established to control arsenic at primary copper acid plants.
The pollutants selected for specific limitation are listed below:
115
118
120
122
128
arsenic
cadmium
copper
lead
zinc
fluoride (molybdenum acid plants only)
molybdenum (molybdenum acid plants only)
By establishing limitations and standards for certain toxic metal
pollutants, dischargers are expected to attain the same degree of
control over priority metal pollutants as they would have been
required to achieve had all the priority metal pollutants been
directly limited.
This approach is justified technically since the treatment
effectiveness concentrations used for lime precipitation and
sedimentation technology are based on optimized treatment for
concomitant multiple metals removal.Thus, even though metals
have somewhat different theoretical solubilities, they will be
removed at very nearly the same rate in a lime precipitation and
sedimentation treatment system operated for multiple metals
removal. Filtration as part of the technology basis is likewise
justified because this technologyremovesmetals non-
preferentially.
The priority metal pollutants arsenic, cadmium, copper, lead
^i«^. =^Q end-*; final i w limited to ensure the control of
These
and
zinc are specifically limited to ensure the control of the
excluded priority metal pollutants. These pollutants are
indicatorsof the performance of the treatment technology.
Molybdenum is not considered to be an indicator pollutant and is
specifically limited only at molybdenum acid plants.
The following' priority pollutants are excluded" From limitation ""on
the basis that they are effectively controlled by the limitations
developed forarsenic, cadmium, copper,lead and zinc:
114.
119.
123.
124.
125.
126.
antimony
chromium
mercury
nickel
selenium
silver
1426
liiiilililiiilllililiililtliilliiijililllliiiii^lililll'llljlliiillllflillliniij
-------
METALLURGICAL ACID PLANT SDBCATEGORY SECT - X
EFFLUENT LIMITATIONS
The concentrations achievable by application of the BAT are
explained in Section VII of Vol. 1 and summarized there in Table
VII-21. The molybdenum treatment effectiveness values in that
table have been questioned by Petitioners and EPA has agreed in
a settlement agreement to temporarily suspend the molybdenum
limits pending the development of new data.
The achievable concentrations (both one day maximum and monthly
average values) are multiplied by the BAT normalized discharge
rate for acid plant blowdown, 2,554 1/kkg (612.5 gallons/ton), to
calculate the mass of pollutant allowed to be discharged per mass
of 100 percent sulfuric acid production capacity. As discussed
in Section IV, 100 percent sulfuric acid capacity is used rather
than actual production. Use of capacity results in a better
correlation between the comparison of water usage rates when they
are production normalized. The results of these calculations in
milligrams of pollutant per kilogram of 100 percent sulfuric acid
production capacity represent the BAT effluent limitations and
are presented in Table X-2 (page 1430) for the metallurgical acid
plant subcategory. Table X—2 also presents the discharge
allowances which would have been established for the unregulated
priority pollutants if they had been specifically regulated. This
information may be used by permit writers when developing permits
for combined wastes or when additional specific regulation of
these pollutants should become appropriate.
1427
-------
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METALLURGICAL ACID PLAISTT SUBCATEGORY SECT „..-,X
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1428
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - X
TABLE X-2
BAT MASS LIMITATIONS FOR THE
METALLURGICAL ACID PLANTS SUBCATEGORY
Acid Plant Slowdown BAT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of 100 percent
equivalent sulfuric acid capacity
Antimony
*Arsenic
*Cadmium
Chromium
* Copper
*Lead
Mercury
Nickel
Selenium
Silver
*Zinc
*Fluoride1
*Molybdenum1
4.929
3.550
0.511
0.945
3.269
0.715
0.383
1.405
2.094
0.741
2.605
89.390
Reserved
2.196
1.583
0.204
0.383
1.558
0.332
0.153
0.945
0.945
0.306
1.073
50.820
Reserved
*Regulated Pollutant
•'•For molybdenum acid plants only.
1429
-------
METALLURGICAL ACID PLANT SUBCATEGORY
SECT - X
-------
METALLURGICAL ACID PLANT SUBCATEGORY
SECT - X
I
X
-------
METALLURGICAL ACID PLANT SUBCATEGORY
SECT - X
11
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1432
-------
METALLURGICAL ACID PLANT SUBCATEGORY
SECT - X
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1433
-------
METALLURGICAL ACID PLANT SUBCATEGORYSECT -X
,, , , ,,' i' i"l ilL • , l • 'i|.'i'ii,'' ' . "i'r ,,,!.'
:•";: "'!' 'ill, ,.'.( 1 11 '":»l ..i.1" '
THIS PAGE INTENTIONALLY LEFT BLANK
' ' "''' '
1434
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - XI
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
The basis for new source performance standards (NSPS) under
Section 306 of the Act is' the best available demonstrated
technology (BDT). New plants have the opportunity to design the
best and most efficient production processes and wastewater
treatment technologies without facing the added costs and
restrictions encountered in retrofitting an existing plant.
Therefore, Congress directed EPA to consider the best
demonstrated process changes, in-plant controls, and end-of-pipe
treatment technologies which reduce pollution to the maximum
extent feasible.
This section describes the technologies for treatment of
wastewater from new sources, and presents mass discharge
standards of regulated pollutants for NSPS based on the selected
treatment technology.
TECHNICAL APPROACH TO BDT
All of the treatment technology options applicable to a new
source were previously considered for the BAT options. Three
options were considered for BDT for copper, lead, zinc, and
molybdenum metallurgical acid plants. On March 18, 1985, the
Agency published a Notice of Data Availability which revised
these three options to include iron co-precipitation for
molybdenum acid plants to control discharge of molybdenum. The
options considered for BDT are identical to the BAT options
discussed in Section X. In-process flow reduction required under
Option B is based on a- recycle ratio obtained by averaging
discharge rates from plants that recycled 86 percent or more of
their acid plant blowdown. The treatment technologies considered
for BDT are:
OPTION A
o Chemical precipitation and sedimentation
o Iron co-precipitation for molybdenum acid plants
OPTION B
o Chemical precipitation and sedimentation
o In-process flow reduction
o Iron co-precipitation for molybdenum acid plants
OPTION C
o Chemical precipitation and sedimentation
1435
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - XI
o In-process flow reduction
o Sulfide precipitation (and sedimentation or pressure
filtration)
o Iron co-precipitation for molybdenumacid plants
o Multimedia filtration
Partial or complete reuse or recycle of wastewater is an
essential part of Options B and C. Reuse or recycle can precede
or follow end-of-pipe treatment.
BDT OPTION SELECTION
111 • i is » i, n1 •' '» ', ;,i • '||,|i,,ii|i' ,, ,; ' '• n'•;, i . • ,, 1, , , iiii,,ii:, , i,;:11"!', r Jllll'i MI ,,, ;:i, \u•,>'...
EPA is promulgating that the best available demonstrated
technology for the metallurgical acid plants subcategory be equal
to BAT. The best demonstrated technology consists of lime
precipitation, sedimentation, in-process flow reduction, sulfide
precipitation, sedimentation or pressurefiltration, iron
coprecipitation for molybdenum acid plants, and multimedia
filtration. EPA has not found that new plants could achieve any
additional flow reduction beyond that proposed for BAT.
REGULATED POLLUTANT PARAMETERS
The Agency has no data that suggest that the pollutants found in
treatable concentrations in processes within new sources will be
any different than with existing sources. Accordingly,
pollutants selected for specific limitation under NSPS, in
accordance with the rationale of Sections VI and X, are identical
to those selected for BAT. The conventional pollutant parameters
TSS and pH are also selected for limitation.
NEW SOURCE PERFORMANCE STANDARDS
The promulgated NSPS discharge flow for acid plant blowdown is
the same as the promulgated BAT discharge flow. See Section X
for a discussion of the molybdenum.treatment effectiveness value
and effluent limitations. The acid plant blowdown discharge flow
is 2,554 ?/kicg (612 gallons/ton). The mass of pollutant allowed
to be discharged per mass of product is calculated by multiplying
the achievable treatment concentration (mg/1) by the normalized
wastewater discharge flow (1/kkgj. The BDT achievable treatment
concentrations are identical to the BAT ".^achievable, tfeatment
concentrations. New source performance standards, as determined
from the above procedure are shown in Table Xl-1 (page 1437) for
the acid plant blowdown stream.
,i'J'i ' ''ifiiiii,*!1, i
•*• flit"1
1436
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - XI
TABLE XI-1
NSPS FOR THE METALLURGICAL ACID PLANT SUBCATEGORY
Acid Plant Slowdown NSPS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of 100 percent
equivalent sulfuric acid capacity
Antimony
*Arsenic
*Cadmium
Chromium
* Copper
*Lead
Mercury
Nickel
Selenium
Silver
*Zinc
*Fluoride1
*Molybdenum1
*TSS
*pH Within
4.929
3.550
0.511
0.945
3.269
0.715
0.383
1.405
2 094
0.741
2.605
89.390
Reserved
38.310
the range of 7.5 to 10.0 at all
2.196
1.583
0.204
0.383
1.558
0.332
0.153
0.945
0.945
0.306
1.073
50.820
Reserved
30.650
times
*Regulated Pollutant
molybdenum acid plants only.
1437
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - XI
THIS PAGE INTENTIONALLY LEFT BLANK
1438
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - XII
SECTION XII
PRETREATMENT STANDARDS
Section 307(b) of the Act requires EPA to promulgate pretreatment
standards for existing sources (PSES), which must be achieved
within three years of promulgation. PSES are designed to prevent
the discharge of pollutants which pass through, interfere with,
or are otherwise incompatible with the operation of publicly
owned treatment works (POTW). The Clean Water Act of 1977
requires pretreatment for pollutants, such as heavy metals, that
limit POTW sludge management alternatives. Section 307(c) of the
Act requires EPA to promulgate pretreatment standards for new
sources (PSNS) at the same time that it promulgates NSPS. New
indirect discharge facilities, like new direct discharge
facilities, have the opportunity to incorporate the best
available demonstrated technologies, including process changes,
in-plant controls, and end-of-pipe treatment technologies, and to
use plant site selection to ensure adequate treatment system
installation. Pretreatment standards are to be technology-based,
analogous to the best available technology for removal of toxic
pollutants.
This section describes the control and treatment technologies for
pretreatment of process wastewaters from existing sources and new
sources in the metallurgical acid plant subcategories.
Pretreatment standards for regulated pollutants are presented
based on the selected control and treatment technology.
TECHNICAL APPROACH TO PRETREATMENT
Before proposing pretreatment standards, the Agency examines
whether the pollutants discharged by the industry pass through
the POTW or interfere with the POTW operation .or its chosen
sludge disposal practices. In determining whether pollutants
pass through a well-operated POTW, achieving secondary treatment,
the Agency compares the percentage of a pollutant removed by POTW
with the percentage removed by direct dischargers applying the
•best available technology economically achievable. A pollutant
is deemed to pass through the POTW when the average percentage
removed nationwide by well-operated POTW meeting secondary
treatment requirements, is less than the percentage removed by
direct dischargers complying with BAT effluent limitations
guidelines for that pollutant. (See generally, 46 Fed. Reg, at
9415-16 (January 28, 1981).)
This definition of pass through satisfies two competing
objectives set by Congress: (1) that standards for indirect
dischargers be equivalent to standards for direct dischargers,
while at the same time, (2) that the treatment capability and
performance of the POTW be recognized and taken into account in
regulating the discharge of pollutants from indirect dischargers.
The Agency compares percentage removal rather than the mass or
1439
-------
METALLURGICAL ACID PLANT SUBCATEGORY SECT - XII
concentration of pollutants discharged because the latter would
not take into account the mass of pollutants discharged to the
POTW from non-industrial sources nor the dilution of the
pollutants in the POTW effluent to lower concentrations due to
the addition of large amounts of non-industrial wastewater.
PRETREATMENT STANDARDS FOR EXISTING AND NEW SOURCES
Options for pretreatment of wastewaters are based on increasing
the effectiveness of end-of-pipe treatment technologies. All
inplant changes and applicable end-of-pipe treatment processes
have been discussed previously in Sections X and XI. The
treatment options for PSES and PSNS are the same as the options
discussed in Section X. A description of each option is presented
in Section X.
Treatment technologies used for the PSES and PSNS options are:
11 '"! '" '" ,,, "f1'1 ' iii i
Option A
o Chemical precipitation and sedimentation
o Iron co-precipitation for molybdenum acid plants
Option B
o Chemical precipitation and sedimentation
o In-process flow reduction
o Iron co-precipitation for molybdenum acid plants
Option C " " ' "
o Chemical precipitation and sedimentation
o In-process flow reduction
o Sulfide precipitation (and sedimentation or pressure
• filtration) •
o Iron co-precipitation for molybdenum acid plants
o Multimedia, filtration v
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
The industry cost and pollutant removal estimates of each
treatment option were used to determine the most cost-effective
bption. The methodology applied in calculating pollutant
reduction benefits and plant compliance costs is discussed in
Section X.
1 ,,,,,, , , .... ' ", ' i] ,
Table XII-1 (page 1443) shows the pollutant removal estimates for
the one indirect discharger. Compliance costs are presented in
Table VIII-2 (page 1414).
PSES AND PSNS OPTION SELECTION
EPA did not propose PSES for metallurgical acid plants_ in the
proposed rulemaking for nonferrous metals manufacturing even
though there is one existing indirect discharging metallurgical
!>',:;*;
1440
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METALLURGICAL ACID PLANT SUBCATEGORY , SECT - XII
acid plant. At proposal, it was estimated that this plant
currently discharged less pollutants than would be allowed under
PSES because its wastewatet discharge rate was much less than
that allowed. The revised removal estimates, however. Vindicate
that the PSES technology will remove 367 kg/yr of priority metals
over current discharge estimates. The Agency has, therefore,
decided to promulgate PSES for metallurgical acid plants^
EPA is promulgating PSES equal to BAT for this subcategory.
Promulgation of PSES for the metallurgical acid plant subcategory
will prevent pass-through of cadmium and zinc. The revised
pollutant removal estimates indicate that PSES will remove 12,400
kg/yr of the priority metals generated. , The final , PSES
limitations will remove 330 kg/yr priority pollutants over the
intermediate option, which lacks filtration. Since both options
are economically achievable and both prevent pass-through, the
Agency is promulgating PSES equal to BAT.... Implementation of the
promulgated PSES will result in an estimated capital cost of
$0.161 million (March, 1982 dollars) and an estimated annual cost
of $0.085 million (March, 1982 dollars).
The technology basis for promulgated PStiS is identical to NSPS
and BAT, which are based on lime precipitation, sedimentation,
in-process flow reduction, sulfide precipitation and
sedimentation, iron co-precipitation for molybdenum acid plants,
and multimedia filtration. EPA has not , identified any
demonstrated technology that provides better pollutant removal
than PSNS technology. The wastewater discharge rate for the acid
plant blowdown stream is the same for PSNS and BAT. The Agency
believes that no additional flow reduction is feasible for new
sources because the only other flow reduction technology, reverse
osmosis, is not demonstrated nor is it clearly transferable to
the nonferrous metals manufacturing category.
REGULATED POLLUTANT PARAMETERS
The pollutants selected for limitation under PSES are cadmium and
zinc. Since the one indirect discharging metallurgical acid
plant is found at a primary zinc facility, only those pollutants
associated with primary zinc were evaluated for pass-through.
This analysis indicated that copper and lead would not pass
through a well-operated POTW with secondary treatment. With PSES
technology, it was estimated-that 33 percent of the pollutants
would be removed. A POTW, however, would remove 58 percent of
the copper and 48 percent of the lead.
Metals may be toxic to the biological system, pass, through
largely untreated, or limit sludge management alternatives due to
the metals that are removed with the sludge. PSES prevent the
pass-through of cadmium and zinc.
Pollutants selected for limitation under PSNS, in accordance' with
the rationale of Sections VI and X, are identical to those
selected for specific limitation for BAT. PSNS prevent the pass-
through of arsenic, cadmium, copper, lead, zinc, molybdenum and
1441
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METALLURGICAL ACID PLANT SUBCATEGORY SECT - XII
fluoride.
PRETREATMENT STANDARDS
The PSES and PSNS discharge flow for acid plant blowdown is the
same as the BAT discharge flow of 2,554 liters per metric ton
(612.5 gallons/ton) of 100-percent sulfuric acid capacity. See
Section X for a discussion of the molybdenum treatment
effectiveness value and effluent limitation. The mass of
pollutant allowed to be discharged per mass of product is
calculated by multiplying the achievable treatment concentration
(mg/1) by the normalized wastewater discharge flow (1/kkg). The
PSES arid PSNS achievable treatment concentrations are identical
to BAT and NSPS achievable treatment concentrations and are
presented in Table VII-21 of Vol. 1. Pretreatment standardsfor
existing and new sources, as determined from the above procedure
are shown in Tables Xll-2 and XII-3 for the acid plant blowdown
stream.
Mass-based standards are promulgated for the metallurgical acid
plant subcategory to ensure that the standards are achieved by
means of pollutant removal rather than by dilution. They are
particularly important since the standards are based upon flow
reduction; pollutant limitations associated with flow reduction
cannot be measured by any other way but as a reduction of mass
discharged.
1442
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METALLURGICAL ACID PLANT SUBCATEGORY
SECT - XII
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METALLURGICAL ACID P*LANT SUBCATEGORY SECT? - XII "
TABLE XI1-2
PSES FOR THE METALLURGICAL ACID PLANTSUBCATEGORY
Acid Plant Slowdown PSES
Pollutant Maximum for Maximum for
or Pollutant Property Any One Day Monthly Average
mg/kg (Ibs/million Ibs) of 100 percent sulfuric acid
capacity
Cadmium
Zinc
0.511
2.605
0.204
1.073
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1444
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METALLURGICAL ACID PLANT SUBCATEGORY SECT - XII
TABLE XII-3
PSNS FOR THE METALLURGICAL ACID PLANT SUBCATEGORY
Acid Plant Slowdown PSNS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
rag/kg (Ib/million Ibs) of 100 percent
equivalent sulfuric acid capacity
Antimony
*Arsenic
* Cadmium
Chromium
* Copper
*Lead
Mercury
Nickel
Selenium
Silver
*Zinc
*Fluoride1
*Molybdenum1
4.929
3.550
0.511
0.945
3.269
0.715
0.383
1.405
2.094
0.741
2.605
89.390
Reserved
2.196
1.583
0.204
0.383
1.558
0.332
0.153
0.945
0.945
0.306
1.073
50.820
Reserved
*Regulated Pollutant
1For molybdenum acid plants only.
1445
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METALLURGICAL ACID PLANT SUBCATEGORY SECT - XII
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'
1446
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METALLURGICAL ACID PLANT SUBCATEGORY SECT' -' XIII'•"r
SECTION XIII
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY
EPA is not promulgating best conventional pollutant control
technology (BCT) for the metallurgical acid plants at this time.
1447
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METALLURGICAL ACID PLANT SUBCATEGORY SECT - XIII
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'1 I"
V-'vK'.ll'iiiV;:.: '.« •••[.:S!J W*m 1
1448
•frU.S. GOVERNMENT PRINTING OFFICE: 1969-625-946
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