Group I, Phase II

   Development Document for Interim
  Final Effuent Limitations Guidelines
                 and
   Proposed New Source Performance
i
           Standards for  the
         SECONDARY COPPER
        SUBCATEGORY OF THE
               COPPER
            Segment of the
       NONFERROUS METALS
         MANUFACTURING
         Point Source Category
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
              FEBRUARY 1975

-------
                                     \       •   1*
                           ERRATA PAGE
                  Secondary Copper Development Document
1.   pp 4, 204 and 205 — change all pH ranges to read
     "pH...Within the range 6.0 to 9.0".

2.   p 103—delete "Jtomonia" from table, change 3rd paragraph
     to read "The control and treatment., .the discharge of
     total suspended solids and heavy (trace) metals can be
     controlled.,." and delete last tWD sentences of 4th
     paragraph beginning "Amionia is considered..."

3.   p 111 - 3rd paragraph, change first sentence to read
     "As set forth....are total suspended solids, copper,
     zinc and oil and grease." and delete sentence beginning
     "An effluent limitation for ammonia—".

-------
          DEVELOPMENT DOCUMENT

                  for

PROPOSED EFFLUENT LIMITATIONS GUIDELINES

                  and

    NEW SOURCE PERFORMANCE STANDARDS

                for the

            SECONDARY COPPER
              SUBCATEGORY
                 of the
             COPPER SEGMENT
                 of the
    NONFERROUS METALS MANUFACTURING
         POINT SOURCE CATEGORY
            Russell E. Train
             Administrator
             James L. Agee
      Assistant Administrator for
     Water and Hazardous Materials
              Allen Cywin
 Director, Effluent Guidelines Division

        George S. Thompson, Jr.
            Project Officer
             November 1974

      Effluent Guidelines Division
Office of Water and Hazardous Materials
  U.S. Environmental Protection Agency
        Washington, D.C.   20460

-------

-------
                          ABSTRACT
This document presents the findings of an extensive study of
the secondary copper smelting industry by the  Environmental
Protection  Agency  for  the  purpose of developing effluent
limitations guidelines  and  standards  of  performance,   to
implement  Sections  304,  306, and 307 of the Federal Water
Pollution Control Act, as amended,

Effluent limitations guidelines contained herein  set  forth
the  degree  of  effluent  reduction  attainable through the
application  of  the  best  practicable  control  technology
currently   available,  and  the  application  of  the  best
available technology economically achievable, which must  be
achieved by existing point sources by July 1, 1977, and July
1, 1983, respectively.  The standards of performance for new
sources  contained  herein  set forth the degree of effluent
reduction attainable through the  application  of  the  best
available   demonstrated   control   technology,  processes,
operating methods, or other alternatives.

The development of data and recommendations in this document
relate to waste  water  generated  in  metal  cooling,  slag
quenching  and granulation, slag milling and classification,
furnace exhaust scrubbing, and electrolytic refining  opera-
tions of the secondary copper smelting industry.

The best practicable control technology currently available,
the  best  available technology economically achievable, and
the best available demonstrated control technology for  each
of  these waste water streams are presented in Section II of
this  report.   The  recommended  effluent  limitations  and
standards of performance corresponding to these technologies
also are presented.

Supporting  data  and  rationale for development of the pro-
posed effluent limitations guidelines and standards of  per-
formance  are contained in this report.

-------

-------
                          CONTENTS

Section                                              Page

 I          CONCLUSIONS                                1

 II         RECOMMENDATIONS                            3

                 Waste Water From Metal Cooling        5
                 Waste Water From Slag Quenching
                   and Granulation                     5
                 Waste Water From Slag Milling
                   and Classification                  5
                 Waste Water From Furnace-Exhaust
                   Scrubbing                           6
                 Waste Water From Electrolytic-
                   Refining Operations                 6

 III        INTRODUCTION                               7

                 Purpose and Authority                 7
                 Methods Used for Development
                   of Effluent Limitations
                   Guidelines and Standards of
                   Performance                         8
                 General Description of the
                   Secondary Copper Industry           9

 IV         INDUSTRY CATEGORIZATION                    37

                 Introduction                          37
                 Objectives of Categorization          37
                 Factors Considered                    37

 V          WASTE CHARACTERIZATION                     55

               Introduction                            55
               Sources of Waste Water                  55
               Characteristics of Waste Water
                 Discharged by Secondary Copper
                 Industry                              58
               Characteristics of Waste Water
                 from Process Streams                  83
                         v

-------
                    CONTENTS (continued)

Section

 VI         SELECTION OF POLLUTANT PARAMETERS

                 Introduction
                 Rationale for Selection of
                   Pollutant Parameters
                 Rationale for Rejection of Other
                   Waste Water Constituents as
                   Pollutant Parameters               109

 VII        CONTROL AND TREATMENT TECHNOLOGY          111

                 Introduction                         111
                 Waste Water From Contact Cooling
                   of Molten Metal                    114
                 Waste Water From Slag Quenching
                   and Granulation                    118
                 Waste Water From Slag Milling
                   and Classification                 125
                 Waste Water From Furnace
                   Exhaust Scrubbing                  131
                 Waste Water From Electrolytic
                   Refining Operations                137
                 Combined Waste Water Streams         145

 VIII       COSTS,  ENERGY, AND NONWATER QUALITY
              ASPECTS                                 151

                 Introduction                         151
                 Basis for Cost Estimation            151
                 Economics of Present Control
                   Practices                          153
                 Economics of Present Treatment
                   Practices                          169
                 Cost Effectiveness of Present
                   Practices                          171
                 Economics of Additional Control
                   and Treatment Processes            184
                 Nonwater Quality Aspects             187
                          VI

-------
                    CONTENTS (continued)

Section                                              Page

 IX         BEST PRACTICABLE CONTROL TECHNOLOGY
              CURRENTLY AVAILABLE—EFFLUENT
              LIMITATIONS GUIDELINES                   189

                 In troduction                          189
                 Industry Category and
                   Waste Water Streams                 190
                 Waste Water From Metal Cooling        191
                 Waste Water From Slag Quenching
                   and Granulation                     193
                 Waste Water From Slag Milling
                   and Classification                  igg
                 Waste Water From Furnace
                   Exhaust Scrubbers                   198
                 Waste Water From Electrolytic
                   Refining Operations                 201
                 Combined Process Waste Water          203
                 Storm Water Runoff                    203
                 Total Costs                           205

 X          BEST AVAILABLE TECHNOLOGY ECONOMICALLY
              ACHIEVABLE—EFFLUENT LIMITATIONS
              GUIDELINES                               207

 XI         NEW SOURCE PERFORMANCE STANDARDS           209

 XII        ACKNOWLEDGMENTS                            211

 XIII       REFERENCES                                 213

 XIV        GLOSSARY                                   215
                              Vll

-------
                          FIGURES

Number                         Title
1,                RAW MATERIAL  AND PRODUCT FLOW
                    DIAGRAM OF  THE SECONDARY COPPER
                    INDUSTRY.                             17

2,                COMPOSITE FLOW DIAGRAM FOR SECONDARY
                    COPPER ALLOY AND SECONDARY COPPER
                    SMELTING AND ELECTROLYTIC REFINING
                    WASTE WATER SOURCES AND TREATMENT.  56

3.                TREND OF EFFLUENT LOADINGS FOR
                    TRACE METALS, COPPER, AND ZINC,
                    AS A FUNCTION OF SUSPENDED SOLIDS
                    FOR SECONDARY ALLOYED AND
                    UNALLOYED COPPER PLANTS.             84

4.                TREND OF THE  TRACE METAL EFFLUENT
                    LOADINGS, AS A FUNCTION OF pH
                    FOR TOTAL DISCHARGE FOR
                    SECONDARY ALLOYED AND UNALLOYED
                    COPPER PLANTS.                       85

5.                GENERALIZED DIAGRAM OF WATER USAGE
                    IN THE COPPER SEGMENT OF THE
                    SECONDARY NONFERROUS METALS
                    INDUSTRY.                             112

6.                CURRENT CONTROL AND TREATMENT
                    TECHNOLOGY  ALTERNATIVES FOR
                    WASTE WATER EFFLUENTS FROM CONTACT
                    COOLING OF  MOLTEN METAL.             115

7.                CURRENT CONTROL AND TREATMENT
                    TECHNOLOGY  ALTERNATIVES FOR
                    WASTE WATER FROM SLAG QUENCHING
                    AND GRANULATION.                     121

8.                CURRENT CONTROL AND TREATMENT
                    TECHNOLOGY  ALTERNATIVES FOR
                    WASTE WATER FROM SLAG MILLING
                    AND CLASSIFICATION.                  127

9.                CURRENT CONTROL AND TREATMENT
                    TECHNOLOGY  ALTERNATIVES FOR
                    WASTE WATER FROM FURNACE EXHAUST
                    SCRUBBING.                            136
                                 vm

-------
11.
12.
13.
14.
15.
16.
17.
18.
19.
   FIGURES  (continued)

        Title

CURRENT CONTROL AND TREATMENT
  TECHNOLOGY ALTERNATIVES FOR
  WASTE WATER FROM ELECTROLYTIC
  REFINING.

END-OF-PIPE WASTE WATER TREATMENT
  FACILITY.

CURRENT CONTROL AND TREATMENT
  TECHNOLOGY ALTERNATIVES FOR
  WASTE WATER FROM CONTACT  COOLING
  OF MOLTEN METAL.

CURRENT CONTROL AND TREATMENT
  TECHNOLOGY ALTERNATIVES FOR
  WASTE WATER FROM SLAG QUENCHING
  AND GRANULATION.

CURRENT CONTROL AND TREATMENT
  TECHNOLOGY ALTERNATIVES FOR
  WASTE WATER FROM SLAG MILLING
  AND CLASSIFICATION.

CURRENT CONTROL AND TREATMENT
  TECHNOLOGY ALTERNATIVES FOR
  WASTE WATER FROM FURNACE  EXHAUST
  SCRUBBING.

CURRENT CONTROL AND TREATMENT
  TECHNOLOGY ALTERNATIVES FOR
  WASTE WATER FROM. ELECTROLYTIC
  REFINING.

COST EFFECTIVENESS OF CONTROL
  AND TREATMENT OF WATER FROM
  MOLTEN METAL COOLING.

COST EFFECTIVENESS OF CONTROL  AND
  TREATMENT OF WATER  FROM SLAG
  QUENCHING AND GRANULATION.

COST EFFECTIVENESS OF CONTROL
  AND TREATMENT OF WATER FROM
  SLAG MILLING AND CLASSIFICATION.
                                                           143
                                                           146
                                                           160
                                                           161
                                                           162
                                                           163
                                                           164
                                                           172
                                                           173
                                                           174

-------
                    FIGURES  (continued)

Number                   Title
20,              COST EFFECTIVENESS  OF CONTROL
                   AND TREATMENT OF  WATER FROM
                   FURNACE EXHAUST SCRUBBING.              175

21.              COST EFFECTIVENESS  OF CONTROL
                   AND TREATMENT OF  WATER FROM
                   ELECTROLYTIC  CELL OPERATION.            176

-------
                           TABLES

                         Title                        Page

              DOMESTIC CONSUMPTION OF PURCHASED
                NEW AND OLD COPPER-BASE SCRAP          10

2. .           TYPES OF COPPER-BEARING SCRAP            18

3*            NOMINAL CHEMICAL SPECIFICATIONS
                FOR BBII STANDARD ALLOYS               36

U.            SMELTERS AND REFINERS OF SECONDARY
                BRASS AND BRONZE AND SECONDARY
                COPPER                                 38

5.            AIR POLLUTION CONTROL PROCESSES USED BY
                SMELTERS AND REFINERS OF  SECONDARY
                BRASS AND BRONZE AND SECONDARY COPPER 46

6.            WATER USAGE BY THE SECONDARY COPPER
                INDUSTRY                               47

7.            WATER USAGE BY SMELTERS AND REFINERS
                OF SECONDARY BRASS AND BRONZE AND
                SECONDARY COPPER                       48

8.            RAW MATERIALS PROCESSED BY  SMELTERS OF
                SECONDARY BRASS AND BRONZE AND
                SECONDARY COPPER                       50

9.            WASTE WATER DISPOSAL PRACTICE  OF THE
                SMELTERS AND REFINERS OF  SECONDARY
                BRASS AND BRONZE AND SECONDARY
                COPPER                                 57

10.           SUMMARY OF WASTE WATER HANDLING
                PRACTICE AND DISPOSITION  USED BY
                SECONDARY COPPER INDUSTRY             59

11.           QUANTITIES OF SELECTED CONSTITUENTS IN
                WATER EFFLUENT FROM SECONDARY COPPER
                INDUSTRY PLANTS IN U. S.               62

12.           CONCENTRATION OF SELECTED CONSTITUTENTS
                IN INFLUENT AND EFFLUENT  WATER,
                SECONDARY COPPER INDUSTRY             66
                                XI

-------
                     TABLES  (continued)

Number                    Title

13.           CONCENTRATION  OF SELECTED CONSTITUENTS
                IN INFLUENT  AND EFFLUENT WATER,
                SECONDARY COPPER INDUSTRY               67

14.           CONCENTRATION  OF SELECTED CONSTITUENTS
                IN .INFLUENT  AND EFFLUENT WATER,
                SECONDARY COPPER INDUSTRY               68
15.           CONCENTRATION  OF SELECTED CONSTITUENTS
                IN INFLUENT  AND EFFLUENT WATER,
                SECONDARY COPPER INDUSTRY               69

16.           CONCENTRATION  OF SELECTED CONSTITUENTS
                IN INFLUENT  AND EFFLUENT WATER,
                SECONDARY COPPER INDUSTRY               70

16A.          VERIFICATION OF CONCENTRATIONS OF SELECTED
                CONSTITUENTS IN INFLUENT AND EFFLUENT
                WATER,  SECONDARY COPPER INDUSTRY        71

17.           CONCENTRATION  OF SELECTED CONSTITUENTS
                IN INFLUENT  AND EFFLUENT WATER,
                SECONDARY COPPER INDUSTRY               72

18.           CONCENTRATION  OF SELECTED CONSTITUENTS
                IN INFLUENT  AND EFFLUENT WATER,
                SECONDARY COPPER INDUSTRY               73

19.           CONCENTRATION  OF SELECTED CONSTITUENTS
                IN INFLUENT  AND EFFLUENT WATER,
                SECONDARY COPPER INDUSTRY               74

20.           CONCENTRATION  OF SELECTED CONSTITUENTS
                IN INFLUENT  AND EFFLUENT WATER,
                SECONDARY COPPER INDUSTRY   .            75

21.           CONCENTRATION  OF SELECTED CONSTITUENTS
                IN INFLUENT  AND EFFLUENT WATER,
                SECONDARY COPPER INDUSTRY               76

22.           CONCENTRATION  OF SELECTED CONSTITUENTS
                IN INFLUENT  AND EFFLUENT WATER,
                SECONDARY COPPER INDUSTRY               77

23.           CONCENTRATION  OF SELECTED CONSTITUENTS
                IN INFLUENT  AND EFFLUENT WATER,
                SECONDARY COPPER INDUSTRY               78
                               XII

-------
                     TABLES  (continued)

Number                    Title
24.           CONCENTRATION OF SELECTED CONSTITUENTS
                IN INFLUENT AND EFFLUENT WATER,
                SECONDARY  COPPER INDUSTRY                 79

25.           CONCENTRATION OF SELECTED CONSTITUENTS
                IN INFLUENT AND EFFLUENT WATER,
                SECONDARY  COPPER INDUSTRY                 80

26.           CONCENTRATION OF SELECTED CONSTITUENTS
                IN INFLUENT AND EFFLUENT WATER,
                SECONDARY  COPPER INDUSTRY                 81

27.           CONCENTRATION OF SELECTED CONSTITUENTS
                IN INFLUENT AND EFFLUENT WATER,
                SECONDARY  COPPER INDUSTRY                 82

28.           CHARACTER OF WASTE WATER FROM AIR
                SCRUBBER AFTER THICKENER
                 (BEFORE CENTRIFUGE AND SETTLING)          89

29.           CHARACTER OF WASTE WATER FROM MOLTEN
                METAL COOLING AND QUENCHING               92

30.           CHARACTER OF WASTE WATER FROM SLAG
                QUENCHING  AND GRANULATION OR SLAG
                MILLING AFTER SETTLING                    94

31.           CHARACTER OF WASTE WATER FROM ELECTRO-
                LYTIC REFINING (TREATED BEFORE
                DISCHARGE)                                 98

32.           CHARACTER OF WASTE WATER FROM NON-
                CONTACT COOLING, PLANT 9                  100

33.           CHARACTER OF WASTE WATER FROM DE-
                MINERALIZER BACKWASHING, PLANT 9          101

34.           CHARACTER OF WASTE WATER FROM PLANT
                RUNOFF,  PLANT 38                          102

35.           WASTE  WATER  HANDLING AND TREATMENT
                PRACTICES  IN THE SECONDARY COPPER
                INDUSTRY                                  113
                                XI11

-------
                      TABLES (continued)

Number                  'Title

36.            EFFECTIVENESS OF THE TREATMENT ALTER-
                NATIVES FOR WASTE WATER FROM MOLTEN
                METAL COOLING                            119

37.            EFFECTIVENESS OF TREATMENT ALTER-
                NATIVES FOR WASTE WATER FROM SLAG
                QUENCH AND GRANULATION                   124

38.             EFFECTIVENESS OF CONTROL AND TREATMENT
                  TECHNOLOGY ALTERNATIVES FOR WASTE
                  WATER FROM SLAG MILLING AND
                  CLASSIFICATION                          130

39.             RESULTS OF SAMPLING WASTE WATER FROM
                  FURNACE EXHAUST SCRUBBING,
                  COMPANY 9                               138

40.             RESULTS OF SAMPLING WASTE WATER FROM
                  FURNACE EXHAUST SCRUBBING, AND
                  MILLING AND CLASSIFYING SLAGS,
                  COMPANY 38                              139

41.             EFFECTIVENESS OF TREATMENT ALTERNATIVES
                  FOR WASTE WATER FROM WET SCRUBBING      140

42.             EFFECTIVENESS OF TREATMENT ALTERNATIVES
                  FOR WASTE WATER FROM ELECTROLYTIC
                  REFINING                                144

43.             EFFECTIVENESS OF END OF PIPE TREAT-
                  MENT OF FACILITY FOR COMBINED
                  PROCESS WASTE WATER                     148

44.             SUMMARY OF CURRENT WASTE WATER CONTROL
                  AND TREATMENT COSTS BY OPERATION
                  AND BY COMPANY                          154

45.             COST EFFECTIVENESS FOR CONTROL AND
                  TREATMENT OF WATER FROM MOLTEN
                  METAL COOLING                           170

46.             COST EFFECTIVENESS FOR CONTROL AND
                  TREATMENT OF WATER FROM SLAG
                  QUENCH AND GRANULATION                  178
                                XIV

-------
                     TABLES  (continued)

Number                 Title
47.            COST EFFECTIVENESS FOR  CONTROL AND
                 TREATMENT OF WATER FROM SLAG MILLING
                 AND CLASSIFYING                         180

48.            COST EFFECTIVENESS FOR  CONTROL AND
                 TREATMENT OF WATER FROM
                 WET SCRUBBING                           181

49.            COST EFFECTIVENESS FOR  CONTROL AND
                 TREATMENT OF WATER FROM ELECTRO-
                 LYTIC CELL OPERATIONS                  183

50.            CONVERSION TABLE                          221
                                XV

-------

-------
                         SECTION I

                        CONCLUSIONS
The  nonferrous  metals  manufacturing point source category
has been divided into the following subcategories:

         (1)  Bauxite refining subcategory
         (2)  Primary aluminum subcategory
         (3)  Secondary aluminum subcategory
         (U)  Primary copper smelting subcategory
         (5)  Primary copper refining subcategory
         (6)  Secondary copper subcategory
         (7)  Primary lead subcategory
         (8)  Primary zinc subcategory

Each subcategory has been found to be  distinctly  different
from   the   standpoints  of  processes  employed,  products
produced, and process waste waters  generated,  as  well  as
other  less  significant  factors.  Effluent limitations and
standards of performance were promulgated on March 26, 19^4,
for the first three subcategories listed above.  Development
documents supporting the  rationale  for  these  regulations
have been published.  This development document presents the
rationale  for  establishing  proposed  effluent limitations
guidelines and standards of performance  for  the  secondary
copper subcategory.

Consideration  of  factors,  such  as age and size of plant,
processes employed, geographic location,  wastes  generated,
and  waste  water treatment and control techniques employed,
supports the categorization of this  industry  as  a  single
subcategory.   The similarities of the wastes produced by the
secondary   copper  alloy  and  secondary  unalloyed  copper
smelting operations and the control and treatment techniques
used by both  to reduce the discharge of pollutants, further
substantiates the treatment of secondary copper smelting  as
a  single subcategory.  The recommended effluent limitations
and standards of performance for specific  facilities   take
into consideration the size of the secondary copper smelting
facility, as well as the mix of different recovery processes
possible within a single plant.

One  conclusion  of this document was that this industry can
achieve the requirements of no discharge  of  process  waste
water  pollutants  to  navigable  waters  for effluents from
metal cooling, slag quenching, slag milling, furnace-exhaust
scrubbing, and electrolytic cell operation by July 1,  1977,
by   the   best  practicable  control  technology  currently

-------
available.  The recommended  level  of  performance  can  be
achieved  by  the  application  of the control and treatment
technologies of pH control, settling, filtering, and recycle
and reuse of water.

It has been  estimated  that  for  the  existing  plants  to
achieve  the  recommended  limitation  of  no  discharge  of
process waste water pollutants  to  navigable  waters  would
require a capital cost and annual operating cost of $538,000
and  $270,000,  respectively.   The  vast  majority of these
costs are  allocated  to  control  of  process  waste  water
effluents at Plant 1.

The  application to existing sources of the above technology
of control and treatment methods will allow the  achievement
of  a  level of performance of no discharge of process waste
water pollutants to navigable waters by July 1, 1983.

Lastly concluded,  the  application  of  the  technology  of
control and treatment methods, cited as the best practicable
control  technology  currently  available,  will  allow  the
achievement of a  level of performance of  no  discharge  of
process  waste  water  pollutants  to navigable water by new
sources.

-------
                         SECTION II

                      RECOMMENDATIONS
In the secondary copper industry, waste water  is  generated
principally   from   five  operations:   cooling  of  molten
unalloyed or alloyed copper, slag quenching and granulation,
slag milling and classification, furnace exhaust  scrubbing,
and  electrolytic  refining.   Each  of  these streams is an
integral part of the total water usage at a given plant  and
each  undergoes  treatment  for pH adjustment and solids re-
moval either separately or jointly before reuse or  recycle.
Water  is consumed in these operations by evaporation and/or
by removal of sludges.

The recommended effluent limitations and standards  of  per-
formance  for  the  five  process waste water streams listed
above are no discharge of  process  waste  water  pollutants
into navigable waters.

Plants in the secondary copper industry are net consumers of
water,  and water storage either in lagoons, basins, holding
tanks, or as part of the cooling circuit is common practice.
Under  certain  conditions,  the  discharge   of   excessive
accumulations  of rainfall may be allowed from point sources
as an exception to the  above  recommended  limitations  and
practices.   This recommendation is based on the recognition
that most plants accumulate  rainwater  runoff  as  part  of
their  overall  water management practice, and variations in
rainfall may exceed the capacity of reasonably well designed
containment or storage facilities.  However, there currently
exists technology within the industry which treats  combined
process  waste  water  streams  by  settling  and filtration
before reuse.  This technology also provides  capability  to
treat  the  discharge  caused  by  excess rainfall before it
enters navigable waters.  Thus, special  provisions  to  the
recommendations made in the proceeding paragraph follow:

    A  process  waste  water  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 waste water 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.

-------
During any calendar month there may be discharged from a
process waste  water  impoundment  either  a  volume  of
process  waste water equal to the difference between the
precipitation for  that  month  that  falls  within  the
impoundment  and  the evaporation within the impoundment
for that month, or, if  greater,  a  volume  of  process
waste  water  equal  to  the difference between the mean
precipitation for  that  month  that  falls  within  the
impoundment  and  the mean evaporation for that month 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).

Any process waste water discharged pursuant to the above
paragraph  shall  comply  with  each  of  the  following
requirements;
                       	Effluent limitations	
   Effluent                              Average of daily
characteristic          Maximum for       values for 30
                         any 1 day       consecutive days
                                         shall not exceed
                         	Metric units  (mg/11
TSS                        50                   25
Cu                          0.5                  0.25
Zn                         10                    5
Oil and Grease             20                   10
pH                      Within the range 7.0 to 10.0
                             English units  (ppm)
Oil and Grease
                               50                   25
                                0.5                  0.25
                               10                    5
                               20                   10
                         	Within the range 7._0 to 10.0	

The   recommended   effluent   limitations   are  considered
achievable by all existing sources by July 1, 1977, inasmuch
as better than 50 percent  of  the  facilities  having  such
waste   streams   are   currently   achieving  the  effluent
limitations.  The recommended limitations are based  on  the
application  of control and treatment technology meeting the
criteria  for  the  best  practicable  control    technology

-------
currently  available, best available technology economically
achievable, and  the  best  available  demonstrated  control
technology,   processes,   operating   methods,   or   other
alternatives.

The technologies on  which  such  effluent  limitations  and
standards  are  based for each type of waste water are given
below.

               Waste Water from Metal Cooling

The best practical control  technology  currently  available
for  waste  water  from  metal cooling is the elimination of
water discharge by recycling and reuse of all water.  Before
recycling, or reuse, the waste  water  must  be  treated  by
adjusting  the  pH,  if  necessary,  to  between  8  and  9,
settling, and filtering to remove solids.  This can be  done
for  the  individual stream or it may be done as part of the
combined process waste water treatment.   Periodic  removal,
dewatering,  and  disposal of sludge from settling basins or
tanks will be necessary.

      Waste Water from Slag Quenching and Granulation

The best practicable control technology currently  available
for  waste  water from slag guenching and granulation is the
elimination of water discharge by recycle or reuse of  waste
water  after  treating the stream to reduce suspended solids
by settling and filtration.  A pH adjustment  to  between  8
and  9,  if necessary, should be done before solids removal.
This could be done on the specific stream or as part of  the
combined process waste water treatment before reuse.

An alternative control method applicable to waste water from
the  quenching  of copper-rich slag would be to air cool the
molten slag in pots and employ mechanical size reduction for
handling and subsequent  recovery  of  the  contained  mecal
content.

      Waste Water from Slag Milling and Classification

The  best practicable control technology currently available
for waste water from copper-rich slag milling and  classifi-
cation  operations  is the elimination of water discharge by
recycle and reuse of all water used after treatment  of  the
stream  by  pH  adjustment to between 8 and 9  (if necessary)
and settling followed by filtration.  This can  be  done  on
the  individual  stream  or  as part of the combined process
waste water treatment before reuse.

-------
A  possible  alternative  method  of  controlling  (actually
eliminating) this process waste water stream at high tonnage
operations  has been identified as the utilization of blast,
cupola,  or  rotary  furnaces  in  place  of   wet   milling
operations.

         Waste Water from Furnace Exhaust Scrubbing

The  best practicable control technology currently available
for waste  water  from  furnace  exhaust  scrubbing  is  the
elimination  of  water  discharge  fay  recycle of all of the
waste water after pH adjustment between  8  and  9  and  the
removal   of   solids   by   settling   and   filtration  or
centrifugation.  This is usually done on the specific stream
and kept separate from the  combined  process  waste  water.
The discharge from the treatment can either be reused in the
scrubbing operation or it can be combined with other process
waste water and then reused in other operations.

     Waste Water from Electrolytic Refining Operations

The  best practicable control technology currently available
for  waste  water  from   electrolytic   refining   is   the
elimination  of  water discharge by treating the waste water
stream so that is is  suitable  for  reuse  in  other  plant
operations.  The treatment consists of the removal of copper
by   cementation   with   iron   metal,   followed  by  lime
neutralization to a pH between 8 and 9 and  sand  filtration
of  the  waste  stream to remove solids.  The discharge from
such a treatment is suitable for reuse in plant water  needs
cited previously.

-------
                        SECTION III
                        INTRODUCTION

                   Purpose and Authority

Section  301(b)   of  the Act requires the achievement by not
later than July 1, 1977, of effluent limitations  for  point
sources,  other  than  publicly owned treatment works, which
are based on the application of the best practicable control
technology   currently   available   as   defined   by   the
Administrator pursuant to Section 304(b) of the Act.

Section  301{b)   also  requires  the acievement by not later
than  July  1,  1983,  of  effluent  limitations  for  point
sources,  other  than  publicly owned treatment works, which
are  based  on  the  application  of  the   best   available
technology  economically  achievable  which  will  result in
reasonable further progress toward the goal  of  eliminating
the discharge of all pollutants, as determined in accordance
with  regulations  issued  by  the Administrator pursuant to
Section 304(b) to the Act.

Section 306 of the  Act  requires  the  achievement:  by  new
sources  of  a Federal standard of performance providing for
the control of the discharge of  pollutants  which  reflects
the   greatest   degree  of  effluent  reduction  which  the
Administrator  determines  to  be  achievable  through   the
application  of  the  best  available  demonstrated  control
technology,   processes,   operating   methods,   or   other
alternatives,   including,  where  practicable,  a  standard
permitting no discharge of pollutants.

Section 304(b) of the  Act  requires  the  Administrator  to
publish within one year of enactment of the Act, regulations
providing  guidelines for effluent limitations setting forth
the degree of  effluent  reduction  attainable  through  the
application  of  the  best  practicable  control  technology
currently available and the  degree  of  effluent  reduction
attainable  through  the  application  of  the  best control
measures  and  practices  achievable,  including   treatment
techniques,  process  and  procedure  innovations, operation
methods, and other alternatives.  The  proposed  regulations
contained  herein  set forth effluent limitations guidelines
pursuant to Section 304 (b) of  the  Act  for  the  secondary
copper   smelting   subcategory  of  the  nonferrous  metals
category.

-------
    Methods Used for Development of Effluent Limitations
          Guidelines and Standards of Performance

The effluent limitations guidelines and  standards  of  per-
formance  recommended herein were developed in the following
manner.  The secondary copper industry,  a  segment  of  the
nonferrous  metals  industry,  was considered by identifying
any potential basis for subcategorizing  the  industry  into
groups  for  the  purpose  of  determining  whether separate
limitations and  standards  would  be  appropriate  for  the
different  subsegments.   Such  possible  categorization was
considered on the basis of water usage, raw materials  proc-
essed, products produced, manufacturing, plant age and size/
and  other  factors.   The  raw waste characteristics of the
waste waters produced were identified.  This  identification
included analyses of (1) the source and volume of water used
in  the  process employed and the sources of waste water and
their points of discharge, and (2) the constituents of waste
waters from operations, which result  in  taste,  odor,  and
color  in  water.   The  constituents  of waste water, which
should be subject to  effluent  limitations  guidelines  and
standards  of  performance  were  identified.   Control  and
treatment technologies applicable  to  each  type  of  waste
water  produced  were  identified  and  these  included both
inplant  and  end-of-process  technologies.   The   effluent
levels  resulting from the application of each treatment and
control technology, as well as the limitations, reliability,
and problems derived from and associated  with  these  tech-
nologies, were also identified.

The  effects  of  the application of technologies upon other
pollution problems including air,  solid  waste,  and  noise
were  identified,  in  order  to establish nonwater environ-
mental impacts.  The energy requirements and  costs  of  the
application of the technologies were identified.

This information, as outlined above, was evaluated to deter-
mine   what   levels  of  technology  constituted  the  best
practicable control technology currently available, the best
available technology economically achievable, and  the  best
available  demonstrated  control  technology, processes, and
operating methods, or other  alternatives.   In  identifying
such  technologies,  the  following factors were considered:
the total cost of  the  application  of  the  technology  in
relation  to  the effluent reduction benefits to be achieved
from  such  application,   the   processes   employed,   the
engineering aspects of the application of control techniques
proposed   through   process   changes,   nonwater   quality
environmental impact, and other factors.

-------
Information sources utilized in  this  study  included  pub-
lished literature (references appear in Section XIII), trade
literature,   data   from  four  state  pollution  abatement
offices, and data from the Federal  Water  Pollution  Agency
(R&PP  data  from  six  facilities  were  available and were
used),  Representatives of 44 facilities  of  the  secondary
copper industry were contacted.  These facilities are listed
in  Table  4.   Representatives of 12 facilities were inter-
viewed during plant visits.  The facilities visited included
six facilities that produced essentially pure  copper  as  a
major  product (Companies 8, 9, 12, 17, 32r and 36 listed in
Table 4),  and  six  facilities  that  produced  copper-base
alloys as a major product  (Companies 10, 19, 26, 38, 39, and
41  listed in Table 4).  Analytical verification of effluent
data from two facilities  (Companies 9 and  38) ,  one  copper
and  one  copper-base  alloy,  was  made  to  determine  the
loadings of various inplant  and  end-of-plant  waste  water
sources.

Of    approximately   50   plants  currently  classified  as
secondary copper smelters by the definition given below,  44
plants  were  contacted  in  this  survey.   These 44 plants
consisted  of  37  brass   and  bronze  ingot  producers,  4
producers  of electrolytically refined cathode copper, and 3
producers of fire refined or  semirefined  copper  products.
These secondary copper smelters produced about 24 percent of
the  secondary  copper  or  about  8  percent  of  the total
domestic copper production in 1972.  The  domestic  consump-
tion of copper-base scrap in 1971 and 1972 is shown in Table
1.

In  addition to the 44 facilities contacted and interviewed,
31 plants were contacted as possible secondary  copper  pro-
ducers.   These  31 plants were either improperly classified
as secondary copper producers or are no longer in operation.

    General Description of the Secondary Copper Industry

The secondary copper industry  is  herein  defined  as  that
portion  of  SIC  3341  (Secondary  Smelting and Refining of
Nonferrous Metals) that consists of establishments primarily
engaged in recovering copper metal and  copper  alloys  from
new  and  used  scrap  and  residues from melting operations
(e.g., spills, slags,  skimmings,  etc.).   This  definition
includes  establishments  melting and refining copper alloys
from secondary brass and/or secondary bronze  scrap  sources
to  produce alloyed copper, as well as those melting and re-
fining copper-bearing  scrap  to  recover  principally  pure
copper  (unalloyed copper).

-------
            TABLE 1.  DOMESTIC CONSUMPTION OF PURCHASED NEW AND OLD COPPER-BASE SCRAP,
                      kkg (Cons) IN 1972 AND 1971
Period       	Primary Producers
            New Scrap  Old Scrap
 Secondary Smelters
New Scrap  Old Scrap
      Brass Mills
New Scrap  Old Scrap
Tofal
1971(2)

1972(3)

214,291
(236,263)
237,348
(261,685)
253
(279
246
(272
,784
,806)
,744
,044)
(Copper recovered in
1972

192,022
(211,711) '
. 132
(146
,909
,537)
106,583
(117,512)
100.959
(111,311)
unalloyed and
58,170
(64,135)
277,520
(305,976)
288,218
(317,771)
alloyed form
207,995
(229,322)
568,
(627,
645,
(712,
from
485,
(535,
792
114)
784
000)
24
(27
31
(34
purchased
828
643)
29
(32
,513
,026)
,531
,764)
scrap)
,419
,435)
1,445
(1,593
1,550
(1,709

1,106
(1,219
,483
,697)
,584
,575)

,343
,783)

-------
Secondary  copper smelters and refiners will process primary
sources of copper on occasion, providing  its  cost  is  low
enough.   The  presmelting  treatments, melting and smelting
operations, and  refining  operations  (except  electrolytic
refining)   are common to both bronze and brass and unalloyed
copper production operations.  Water uses  are  similar  and
the  pollutants  contributed by both operations to the waste
water are also similar in origin.

The industry, by  this  definition,  does  not  include  the
collection,  preliminary  grading  and preparation of scrap,
the production of brass or bronze  ingots  from  essentially
virgin  materials, or the recycling of copper-base materials
by  the  fabrication  industry.   The  definition  does  not
include  the  recycling  of  inplant  and purchased scrap by
foundries to pour castings, or the scrap processed by plants
that were primarily designed to process primary copper  ores
or concentrates.

About  70  years ago, the secondary metal industry consisted
of a group of independent  dealers  who  gathered  and  sold
scrap  metals  and  waste materials to a variety of markets.
As the demand for metal products increased, a larger  number
of  sources  of  scrap  were developed and collection became
organized.  Some of the collectors  and  dealers  sought  to
increase   profits  by  remelting  their scrap and producing
commercial ingots.  These  ingots  generally  were  of  poor
quality  by  current  standards.   As  the demand for higher
quality materials developed, the industry  made  efforts  to
improve  its  technology  in  order to improve its products'
quality.  Collecting, sorting, marketing, melting, refining,
and alloying became individual operations, each contributing
to the general advance of  the  total  industry.   Shortages
arising  from World War I forced the use of large quantities
of secondary metals which led  to   general  acceptance  and
stimulated  a rapid growth in the industry,  A similar boost
during World  War  II  increased  the  growth  of  secondary
smelters  and  forced the primary metal producers to consume
more scrap  and  waste  materials.   The  industry  pattern,
developed during the war, continues to exist today.

The  secondary copper industry is the largest of the nonfer-
rous secondary  metal  industries.   It  produces  about  30
percent  of  the total copper consumed in the United States.
The industry  consists  of  dealers  and  collectors,  brass
mills,    primary   smelters   using   scrap   and   mineral
concentrates,  and  secondary  smelters  using  only  scrap.
These plants are found near the source of scrap materials or
near  inexpensive transportation in the Northeastern states,
the East-North Central states, the Pacific Coast  states;  a
                              11

-------
few  plants  are  located  in  the Southern and West-Central
states.  The number of secondary smelters has decreased from
about 75 to less than 50 in the last 15 years. (1)

In 1972, the domestic copper industry produced 3.19  million
kkg  (3.52  million  tons) of copper from primary materials,
and  consumed  1.53  million  kkg  (1.69  million  tons)  of
secondary  copper,  all  on a refined copper basis.  (2)  The
1.53 million kkg  (1.69 million tons)  of secondary copper was
consumed by the following industries:

          Brass mills        - 680,197 kkg
                               (749,942 tons)
                               44 percent

          Primary producers  - 484,092 kkg
                               (533,729 tons)
                               32 percent

          Secondary smelters - 373,349 kkg
                               (411,631 tons)
                               24 percent.

An  estimated  98,000  kkg  (108,000  tons)   of  scrap,  not
included   in   the  above  distribution,  was  consumed  by
foundries,    chemical     plants,     and     miscellaneous
manufacturers. (2)

General Technical Background

To  convert  copper-bearing  scrap and residues from melting
operations into salable secondary brass and bronze ingots or
copper products, alloying additions and impurities  must  be
either  adjusted  to  specifications or reduced to specified
levels, respectively.  To  accomplish  this,  the  secondary
copper  industry  uses  some  recovery  and refining process
steps identical to those of primary copper plants,  as  well
as its own unique processes.

Scrap  is  identified and segregated, often by hand sorting,
according to accepted standard classifications.    Segregated
scrap  metal  and  waste  materials  from melting operations
(residues)  usually require some  preliminary  processing  to
remove both valuable and deleterious associated constituents
(presmelting treatment).

The  common  methods  used for producing secondary metal are
melting,  smelting,  and  alloying.   Operating   techniques
usually  differ from primary metal operations because of the

-------
difference  in  physical  and  chemical  properties  of  the
respective raw materials.

The  technology  of  the  secondary copper industry has been
reviewed by Fine, et al. (U) ,  Spendlove(5)  and others (6-10).
The technology described is general for the entire  industry
and does not imply that each operation is used by all of the
establishments.   In  fact,  variations  in  the  technology
employed by the individual companies are considered by  them
to provide the competitive edge that keeps them in business.
Hence,  much  of the detailed processing information is con-
sidered proprietary.  Overall, the recovery efficiencies  of
all  processes  are  reasonably  high and the quality of the
products meets rigid specifications.

The term "secondary metal"  came  into  use  before  it  had
acquired a singular meaning and still carries some incorrect
connotations  with  those  not familiar with the technology.
"Secondary" pertains only to the origin of the metal and not
its quality.  Secondary metal is produced from  scrap  metal
or  metallurgical  wastes  as contrasted with primary metal,
which is produced from ores.  Secondary metal  is  rerefined
metal returned to the industry after having been used and is
equal in quality to metals made from primary sources.

The  terminology  associated  with the raw materials used in
the secondary  metals  industry  requires  some  definition.
"New  scrap11  refers  to materials produced in manufacturing
plants such as punchings, turnings and borings, defective or
surplus goods, and metallurgical residues,  such  as  slags,
skimmings,  and  drosses,  all of which result directly from
manufacturing operations.  "Old scrap" consists of obsolete,
worn-out, or damaged articles such as automobile  radiators,
pipe,  wire,  bushings,  bearings,  and other materials that
have been in consumer service.  "Home scrap" refers to scrap
that is produced and consumed in the same plant.  "Purchased
scrap" excludes home scrap, but includes  all  new  and  old
scrap  which  has been purchased or has incurred the cost of
transport from one plant to another.  These distinctions are
made for statistical purposes related to  the  economics  of
the secondary metal industry.

Secondary  copper  loses its identity, except statistically,
as it is processed.  It is not possible to determine whether
a copper wire bar  was  derived  from  scrap  charged  to   a
converter, or whether a brass ingot is made from brass scrap
or  virgin  metals.   In the utilization of segregated scrap
there are, however, selected points of entry  of  the  scrap
into  secondary  metal  production,  which  are  set  by the
quality of the scrap with respect  to  its  copper  content.
                               13

-------
Generally,  clean  scrap  consisting of pure copper, such as
copper wire, will enter the  recovery  process  at  a  point
relatively  late  in  the metal refining process, where pure
copper is produced.  If  the  quality  of  the  scrap  (with
respect  to  copper content)  is intermediate due to alloying
constituents, it must  enter  the  refining  process  at  an
earlier  stage,  so  that  these  impurities  can be removed
before a purified  copper  can  be  produced.   Still  lower
grades of raw material must enter the metal refining process
at  the  earliest  steps  of  metal  recovery  such as blast
furnace or  cupola  operations.   Progressively,  through  a
series   of   stepwise  pyrometallurgical  operations,  such
material can end up as pure copper.

The manufacture of secondary brass and  bronze  ingots  from
scrap  and residues usually stops short of the extensive re-
fining necessary to recover pure  copper  from  lower  grade
copper-bearing  scrap  or  residues.  Some refining is prac-
ticed in brass and bronze production operations but  can  be
minimized  with  the  use  of  selectively  sorted  scrap or
residues.  Adjustment of the alloy composition can  be  done
by   dilution   and   alloying,  as  well  as  by  refining.
Therefore, the secondary brass and bronze smelters will  use
some high grade (pure) copper scrap and will compete for its
purchase  with  smelters of pure copper,  conversely, copper
smelters will purchase  intermediate  grade  scrap  for  its
copper   value  and  remove  the  alloying  metals  by  fire
refining.

The early operations in the recovery  of  partially  refined
secondary copper from copper-bearing scrap and residues, and
the recovery of brass and bronze from rhe same type of scrap
and  residues, are very nearly identical.  Operations become
different in the extent of refining,  necessary  to  produce
partially   refined  copper,  as  compared  with  those  for
specification bronze  and/or  brass  alloys.   However,  the
chemistry  for  the  refining  of  brass  and bronze and the
pyrometallurgy necessary to produce partially refined copper
are very similar.   These and other similarities, as well  as
the  differences in the production of the two types of prod-
ucts with respect to waste water generation, are covered  in
the  following sections.  Electrolytic refining is used only
for the refining of copper.  However, this type of  refining
will  be  treated  as  part  of the overall secondary copper
industry, since melting, refining,  and  casting  operations
follow  the  electrolytic refining step in the production of
refined copper by some of the companies surveyed.

In summary, a generalization can  be  made  that  the  ingot
makers   (brass  and  bronze) try to utilize all the elements
                               14

-------
present in their scrap to produce an alloy;  copper  refiners
are  primarily  interested  in  the  recovery  of the copper
content, plus perhaps zinc and precious metals as byproducts
(if present in sufficient amounts).  Both  the  ingot  maker
and  the copper refiner will treat low grade, copper-bearing
waste materials (residues) to recover  the  contained  metal
values.

Process Description

The  recovery  of  copper  or copper-base alloys from copper
bearing scrap metal and residues, that have  been  generated
in the industrial and consumer sectors of the United States,
involves four broad operations;

           (1)  Collecting, sorting, and transporting
               raw materials;
           (2)  Presmelting preparation;
           (3)  Charging, melting, and refining;
           (4)  Pouring or casting the product line.

Collection,  preliminary  sorting,  and transporting are not
considered to be functions of the secondary copper  industry
(as  herein  defined), but rather that of the scrap dealers.
Operations   (2)  through  (4)  above  vary  throughout   the
industry,  resulting  in  variations  in the amount of water
used and waste water generated.

The presmelting treatments of the raw materials  (solids  and
residues)  and  the  melting  and smelting operations  (which
include refining steps) are common to the production of both
brass and bronze ingots and  for  partially  refined  copper
(such  as  black  or blister coppers).  Water uses and waste
water generation are similar in both  types  of  production.
The  cooling  of molten metal after pouring ingots or anodes
is common for brass and bronze  and  for  partially  refined
copper.   In contrast to copper production, brass and bronze
ingots are ready for market and need no further processing.

Partially refined copper  must  be  further  refined  before
marketing,  unless  the  secondary  copper smelter's salable
product is the partially refined  black,  blister,  or  anode
copper.   In  such  cases, refining to high purity copper is
done by  another  company  or  another  plant  of  the  same
company.   Further purification is done by additional smelt-
ing operations  (fire-refined  copper),  or  by  electrolysis
(electrolytic  refined  or  cathode copper), or by both.  To
produce relatively pure cathode copper, cast anodes must  be
electrolytically  refined.   The refined copper cathodes are
melted, deoxidized,  if  necessary,  and  cast  into  copper
                              15

-------
billets  or  cakes.   Copper,  suitable for fabrication into
pipe or tubing, is sometimes made by smelting and  fire  re-
fining  high  quality  copper  scrap  and  casting  it  into
suitable billets.  A generalized flow sheet for the  various
production  options  in  the preparation of brass and bronze
ingots or cathode copper is shown in Figure 1.
Raw Materials
Obsolete consumer  items,  industrial  copper-bearing  scrap
metal  (solids)   and melting wastes (residues)  are the basic
raw materials of the secondary copper industry.  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(2,3) estimates that 6C 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.   The  National  Association  of  Secondary Material
Industries  (Circular NF-73) includes  44  primary  types  of
copper-bearing scrap in their standards.  These designations
are  given  in Table 2. (4)  Segregation of copper-base scrap
into these major categories is done in a preliminary way  by
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  undesirable organic-base constituents, such as
insulation  (plastic and other types),  oil,  grease,  paint,
rubber,  and  antifreeze.   Some  scrap  dealers prepare the
scrap by removing the undesirable nonmetallic materials  and
compacting the scrap metal into bundles.  Additional sorting
and  presmelter treatment of the raw material are often done
by the smelter.   Some smelters do most of  the  pretreatment
steps themselves.  Often, smelters perform recovery of metal
value  from  scrap  or residues on a toll basis for specific
customers.  In such cases, the origin of the scrap fixes its
composition and little, if any,  segregation  or  presmelter
treatment is required before smelting.

No water is used in the segregation and sorting of scrap.
                            16

-------
   'tf .;KAIM: SCKAI-
   R.-flnt'ry Brass
   Scrap (Sla^s
   Pros so s)
                        G>
                                SI.-W
                                Mil i
                                       1W AN1>
                                                                              (Sell or UndfilO
                                                                                BLAST OR CDUPOLA
                                                                                MELTISO FURNACE
INTERMEDIATE  ^RADE SCRAP
(5)Tc:al " 37 Classifications,  eg.
   Cortposltion Or Red Brass
   Railroad Car Journals
   Yellow Brass
   Cartridge Cases
   Auto Radiators
   Bronzes (Aluminum, Manganese,etc)
                                                BRIQLtTTIN
                                                DRYING
                                                BURNING
                                                HAGSETIC-
                                                SEPARATIOS
                                                                              Residues  to
                                                                              Low Grade Scrap
                                   Sludges  to Prt:c.
                                   Met.  RPCOV, Low
                                   Oradt Scrap or
                                                                   R* si Jut's to Low Crade Scrap
 ©  No.  1 Coppi-r Wir.
         1 Heavy Co
    -TSo.  2 Copp. r  Wire
    LJ-O.  2 Hc.ivy Copper

          Coppt-r
       Figure 1.   Raw material  and  product  flow diagram
                       of  the secondary  copper industry.
                                              17

-------
                                                          (4)
                   TABLE 2.   TYPES  OF COPPER-BEARING SCRAP
Number                            Designation
  1           No.  1 copper wire
  2           No.  2 copper wire
  3           No.  1 heavy copper
  4           No.  2 heavy copper
  5           Light copper
  6           Refinery brass
  7           Copper-bearing scrap
  8           Composition or red brass
  9           Red-brass composition turnings
 10           Genuine babbitt-lined brass bushings
 11           High-grade,  low-lead bronze solids
 12           Bronze papermill wire cloth
 13           High-lead bronze solids and borings
 14           Machinery or hard red-brass solids
 15           Machinery or hard brass borings
 16           Unlined standard red car boxes (clean journals)
 17           Lined standard red car boxes (lined  journals)
 18           Cocks and faucets
 19           Mixed brass  screens
 20           Yellow brass scrap
 21           Yellow brass castings
 22           Old  rolled brass
 23           New  brass clippings
 24           Brass shell  cases without primers
 25           Brass shell  cases with primers
 26           Brass small  arms and-rifle shells,  clean fired
 27           Brass small  arms and rifle shells,  clean muffled (popped)
 28           Yellow brass primer
 29           Mixed new nickel-silver clippings
 30           New  nickel-silver clippings and  solids
 31           New  segregated nickel-silver clippings
 32           Old  nickel silver
 33           Brass pipe
 34           Nickel-silver castings
 35           Nickel silver turnings
 36           Yellow-brass rod turnings
 37           Yellow-brass rod ends
 38           Yellow brass turnings
 39           Mixed unsweatcd auto radiators
 40           Admiralty brass condenser tubes
 41           Aluminum brass condenser tubes
 42           Muntz metal  tubes
 43           Plated rolled brass
 4-;           Mangane.SL- bronze solids

-------
presm^lting Treatment

Before  scrap,  in the forms of solids (metal)  and residues,
is used by the smelter, some type of  pretreatment  is  per-
formed.   Additional sorting is often done by the smelter to
attain tighter control of the  alloy  constituents  and  the
copper  content.   In  addition,  metallic  and  nonmetallic
contaminants are removed before the scrap is  compacted  for
easy handling.  The type of presmelting treatments used will
depend  on  the  type  of  scrap being processed.  These are
discussed in detail below.
Stripping Process.  Insulation and lead  sheathing  are  re-
moved   from  electrical  conductors,  such  as  cables,  by
specially designed stripping machines or by hand.

Essentially no atmospheric emissions or  liquid  wastes  are
generated  by this process.  However, significant quantities
of  solid  wastes  are  produced.   These   wastes   consist
primarily of organic materials, such as plastics, paper, and
other  materials  used  as  protective  coverings  on copper
scrap.  The lead is sold, reclaimed, or  used  in  producing
copper-base  alloys.  The organic solid wastes are reclaimed
or disposed of by burning or landfill.
Briguetting  Process.   Compressing  bulky  scrap,  such  as
borings,  turnings,  tubing,  thin  plate,  wire screen, and
wire, into small bales densifies  the  scrap,  permits  more
compact  storage,  and  makes for easier handling and faster
melting.   Oxidation  of  the   metal   is   also   reduced.
Briquetting  is  carried  out  by  compacting the scrap with
hydraulic presses.

Essentially no  atmospheric  emissions,  liquid  wastes,  or
solid wastes are generated during this process.
Si?e  Reduction  Process.   Large thin pieces of scrap metal
are reduced in size by pneumatic cutters,  electric  shears,
and/or manual shearing.  Tramp iron liberated from the scrap
is  removed  from  the  shredded  product magnetically.  The
iron-free products are usually briquetted for easy handling.
Shredding is also employed 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.

-------
Large  solid  scrap pieces must be reduced in size to permit
ease of handling and charging.  This is done by sledging  or
sowing.

When  treating bulky metal items, the process produces small
quantities of atmospheric emissions, consisting of dusts  of
approximately the same composition as the metal,  collection
of  the  dust  via cyclones or baghouses permits recovery of
the  metal  value.   When   insulation   is   present,   the
nonmetallic portion is separated from the metallic fraction.
The  metal  fraction  is  recovered, while the insulation is
either  reclaimed  or  becomes  a  solid   waste   that   is
incinerated  or disposed of in a landfill.  Water is used in
the shredding operation for equipment cooling.
Crushing Process.  Previously dried, brittle,  spongy  turn-
ings,  borings,  and long chips are processed in hammermills
or ballmills.  After crushing, tramp iron  is  removed  mag-
netically.   Dust  particles  consist  of dirt, organic com-
pounds, finely divided metal, and  undefined  solid  wastes.
Such  areas  may  or  may  not  be hooded with dust recovery
provisions.  Water use in the crushing operation is  limited
to occasional equipment cooling.
Drying Process.  Borings, turnings, and chips from machining
are  covered  with cutting fluids, oils, and greases.  These
contaminants are removed in the drying  process,  where  the
scrap  is  heated in, for example, 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
sulfinated  and  chlorinated  hydrocarbons.   Therefore, the
gaseous emissions are composed of  sulfur  oxides,  hydrogen
chloride,   hydrocarbons,  and  other  combustion  products.
Particulate matter in the atmospheric emissions is soot and,
possibly, metallic fumes.  Essentially no  solid  or  liquid
wastes are generated by the process.

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.
However,  this  technique  does not remove the sulfur oxides
and chloride emissions.  Wet scrubbing may  be  employed  to
remove these gases from the exhaust.
                              20

-------
Burning	Process.    Much  of the scrap is covered with paper
and   organic   polymer   insulation,   such   as    rubber,
polyethylene,  polypropylene,  or  polyvinyl  chloride.  The
contaminants, not removed by stripping, are removed from the
scrap by the burning process using furnaces, such as muffles
and rotary kilns.

The burning process is a potential source of  air  pollution
problems,  because of the organic contaminants in the scrap.
In addition  to  the  combustion  products  such  as  carbon
dioxide  and  water, the emissions may contain such gases as
phthalic anhydride and hydrogen chloride from the burning of
polyvinyl  chloride.    Fluorocarbon   insulation   releases
hydrogen  fluoride  when  burned.   Many  of these gases are
highly toxic and  corrosive.   Water  may  be  used  in  wet
scrubbers to remove these emissions.
Sweating	Process.   Scrap  containing  low  melting  point
materials, such as radiators,  journal  bearings,  and  lead
sheathed  cables, can be sweated to remove babitt, lead, and
solder as valuable byproducts, which  would  otherwise  con-
taminate  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 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 babbit, 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 provisions  for  solder,  lead,
and/ or babbit recovery.

Atmospheric  emissions  consist  of  variable  quantities of
fumes and combustion products  originating  from  antifreeze
residues,  soldering  fluxes,  rubber  hose remains, and the
fuel used to heat the sweat furnace.  Wet scrubbers are used
by some smelters to control these emissions.  No other water
is used in sweating operations.
Residue  Concentration  Processes.   Most  of  the   smaller
smelters  concentrate  the  copper values in slags and other
                              21

-------
residues, such as drosses, skimmings, spills, and sweepings,
before   charging   the   concentrates   into    rotary   or
reverberatory   furnaces.    Slags   are  normally  crushed,
screened through a coarse screen to remove trash  and  lumps
of  copper, pulverized with a ball mill, and concentrated on
a table classifer.  The concentrate usually contains  70  to
90  percent  copper  or  copper  alloy,  and  the gangue, or
depleted slag, contains four or five percent  copper  alloy.
The  depleted  slag is usually retained at the plant site as
landfill.  One of the  smelters  surveyed  charges  residues
containing  about 30 percent copper or greater directly into
their rotary furnace.  Lower grade residues are  wet  milled
and concentrated by gravity and table classifiers.

The   concentration   of   residues   by  wet  grinding  and
classifying requires large  volumes  of  water.   The  water
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 Briguetting.    Most    smal1
brass  and  bronze ingot makers 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 slags or residues
must be agglomerated before charging to  prevent  them  from
being  blown  out  of  the stacks.  The fine portions of the
copper rich slags or other residues are pellitized by adding
water  and  some  binder,  if  necessary,  and  rolling  the
material  in  a  disk  or  drum pellitizer until most of the
fines are in the form of small marble size pellets.   A  few-
plants  are evaluating roll briquetting equipment to produce
small pillow shaped briquettes of the fine slag or  residue.
The  fine  material  is  mixed  with a small amount of resin
binder and some water before it is briquetted.

Although small amounts of water are  used  in  the  process,
waste water is not generated in this operation.
Blast Furnace or	Cupola	Process.   These  operations  were
not considered to be  part  of  the  presmelting  treatment.
They  are, however, discussed in detail below in the section
on smelting processes.
                               22

-------
Summary  of	Water  Uses  in	Scrap  Preparation.         The
literature  indicates  that  water  is  used occasionally in
hammer mills, used to strip the insulation from copper wire,
and in wet milling  and  concentrating  copper  from  copper
slags.   Water  was  found  to  be  used only in wet milling
operations in the smelters surveyed..

Water is also reported in  the  literature  to  be  used  in
systems  employing leaching to recover copper from low grade
residues or  slags  or  in  air  cleaning  systems  for  the
incinerators or sweating furnaces, if these systems employed
water  in  any  gas  cleaning  process.   None of the plants
surveyed reported water use for these purposes.
Smelting Low Grade Scrap and Residues
Drosses, slags, skimmings, and low grade  copper  and  brass
scrap   (those  badly  mixed  or  containing  high  levels of
impurities)  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 product of cupola or blast furnace melting (black copper
or  cupola  melt)  generally  is  a  mixture  of  copper and
variable amounts of most of  the  common  alloying  elements
such  as  tin,  lead,  zinc,  nickel,  iron, phosphorus, and
sometimes arsenic, antimony, aluminum, beryllium,  chromium,
manganese,  silicon,  precious metals, or other elements.  A
matte is also formed when sufficient sulfur  is  present  to
form  a  complex  copper-iron-nickel-lead  sulfide.  Similar
mixtures may be obtained with other  melting  furnaces  when
the scrap charge materials are not segregated.

Under  I960 market conditions, the minimum profitable copper
content for the charge was about 30 percent.  In  1973,  the
market  conditions  make it profitable to charge with as low
as 10 percent copper content material.  The charge 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,  briquetting,  or sintering to reduce losses in
the stack gas.  Limestone and millscale 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.
                               23

-------
During  the  cupola   and  blast furnace processes, metallic
constituents (copper alloys  and  copper)   melt,  while  the
limestone and iron (and aluminum, silicon, etc,) 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.

A typical slag  from  a  blast  furnace  has  the  following
approximate composition:

                              Percent
                    FeO         29
                    CaO         19
                    SiO2        39
                    Zn ~        10
                    Cu          0.8
                    Sn          0.7

Collected dusts contained:

                              Percent
                    Zn         58-61~
                    Pb         2-8
                    Sn         5-15
                    Cu         0.5
                    Sb         0.1
                    Cl         0,1 - .5

The  product  metal composition, as well as the materials in
the slag and dusts, will vary with the materials charged.


Blast Furnace.   The  blast  furnace  is  a  vertical  shaft
furnace  with  a sealed top.  This furnace is used to reduce
copper compounds, as well as to melt metal  and  form  black
copper  or  a  copper  matte  and a slag.  Charges of copper
alloys, compounds, residues, and slags are fed  into the  top
of  the furnace through a double bell, gas seal arrangement,
along with coke for fuel, and fluxes.  The top  gases may  be
cleaned and burned as a source of fuel  (e.g., to preheat the
blast).   The blast air is blown in through tuyeres near the
bottom of the shaft.  Either molten metal or matte and  slag
are  tapped  intermittently.   Water use in the operation is
discussed in the section on cupolas.

                              24

-------
Cupola Furnaces,   Cupola  furnaces  are  similar  -to  blast
furnaces  in  design.   Both  furnaces are refractory lined,
vertical shaft furnaces charged  from  the  top  with  coke,
scrap  metal,  copper rich slag, and flux, and fired with an
air blast that is blown in through tuyeres near  the  bottom
of  the  shaft.   The  cupola  may be tapped continuously or
intermittently for metal and/or slag.  Normally, cupolas are
used only to melt metal and slag;  whereas,  blast  furnaces
are  used  to  reduce copper bearing oxides or other residue
compounds.  Cupolas normally use  less  fuel  (coke)  and  a
lower temperature blast than do blast furnaces.  The exhaust
gases  from the cupola do not contain enough calorific value
to be utilized as a fuel.

The tuyeres and lower shell portion of both  blast  furnaces
and  cupolas  are  normally  water cooled.  Large volumes of
water are required for cooling the walls and  tuyeres.   The
water  normally  is  recirculated.  The water pollutants are
mainly thermal and salts in cooling rower blowdown.  The air
emissions from blast furnaces and cupolas  are  contaminated
and  must  be  cleaned  either with baghouse filters or high
energy  water  scrubbers  to  meet  regional   air   quality
standards.   If  water  scrubbers  are  used, then the waste
water must be treated  before  it  can  be  recirculated  or
discharged.  At some plants, large volumes of water are used
to  quench  and  granulate copper-poor  (depleted) slags from
the smelting  operation.   This  creates  waste  water  that
requires treatment prior to discharge.
Converters.   The  process  of  conversion  in the secondary
copper industry can be done in furnaces  called  converters,
which  are  specifically  designed for that operation, 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;
whereas, the high sulfur content in primary copper serves as
the fuel.

With the use of converters or converter-oriented operations,
the copper value in  badly  mixed  alloys  is  reclaimed  by
oxidizing  most  of  the  alloying elements and removing the

-------
oxides as a slag.  Molten metal is occasionally 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 and/or green  wood
inserted in 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.

Air emissions from converter type operations are severe  and
air   pollution   control   devices,   such   as  baghouses,
electrostatic  precipitators,  or  scrubbers,  are   usually
employed.  When wet scrubbers are used to control emissions,
the   waste   water   is  treated  before  recirculation  or
discharge.  Waste water may also be generated  if  water  is
used  for  granulation  of  the  hot  converter slags formed
during the operation.  The converter slags  contain  copper,
which  is  usually  recovered  in  cupola or blast furnaces.
Water used to cool and condition the gases for electrostatic
precipitators and baghouses is discharged as steam.

Crucible Furnaces.  Crucible furnaces are  refractory  lined
cylindrical  furnaces with a vertical axis.  The crucible is
supported by  a  refractory  stool  in  the  center  of  the
furnace.   The  furnaces are heated by the combustion of gas
or oil in the annular space between  the  crucible  and  the
refractory  wall.   This indirect firing prevents contact of
the combustion products with the charge.  Crucible  furnaces
are  generally  used to melt small quantities of clean scrap
to produce special alloys.  No water is used in this type of
furnace operation.

Induction  Furnaces.   Induction   furnaces   are   electric
furnaces  heated  by either high  or low frequency induction
heating techniques.  Furnace sizes range from a  few  pounds
to several tons.  Small furnaces are used to melt and refine
precious  metals  recovered  from  slimes  from electrolytic
refining.  Intermediate  sizes  are  used  to  melt  special
alloys or high purity materials.  The intermediate sizes may
be lift-out crucible furnaces.  Larger sizes may be used for
general melting and refining.  A small amount of meral fumes
may  be  vented  to  the  air  cleaning  system.   induction
                           26

-------
furnaces and their power  sources  are  water-cooled.    This
noncontact  cooling  water is usually of good quality and is
recirculated after cooling or discharged without treatment.

Summary	of  Water  Usage  in Melting Furnaces.         Large
volumes  of  water  are  generally  used  to  water cool the
outside of the lower section of blast furnaces  or  cupolas.
Large volumes of water are also used to quench and granulate
slag from these furnaces, when this method of handling slags
is employed.  Both of these large volumes of water generally
are  recirculated  for  economic  reasons.   Water  used  to
granulate slags would be expected to  be  contaminated  with
soluble and insoluble materials in the slag.

Large  volumes of water are used by some plants when wet air
pollution control equipment is used instead of dry  baghouse
equipment.   The  water  is  used  in wet caps which must be
followed by high  or low energy  scrubbers.   The  water  is
normally  recirculated  for economic reasons.  Contamination
is always severe, because the water will contain all of  the
pollutant  materials  originally  in  the  air, such as zinc
oxide and other alloying metal oxides.

Large amounts of water are used  in  induction  furnaces  to
cool  the  induction  coils  (or  inductors) and to cool the
electrical power source.  This water, since it  is  employed
in   noncontact   cooling,   is   not  contaminated,  except
thermally.

Appreciable amounts of water are used to cool the  doors  of
some  reverberatory  or  rotary furnaces.  This water is not
contaminated, except thermally.

No water is used with fuel-fired crucible furnaces.

Smelting and Alloying Intermediate Grade Copper Based Scrap
Copper based scrap metals, intermediate grade  copper  metal
scrap,  black and/or 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
refining is usually small, if the scrap is well sorted.   If
                             27

-------
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 reduced
or removed by chemical reaction with oxygen.  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 employed in refining vary
with the type of furnace, the types of scrap in the  charge,
and the experience and training of the personnel, as well as
the type of product being produced.

The  chemicals  used  in refining are air or oxygen-enriched
air and solids employed to  modify  the  slag  cover  or  to
modify   (and  alloy) the melt.  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,
and  in  the  refining  of zinc-rich copper alloy scrap, the
loss of zinc is unavoidable.  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 layer on the surface of the melt,
since the oxides have a lower density than the metal.  These
oxides combine with the slag cover, which is  usually  added
to  aid  in  the removal of the oxidized impurities.  Fluxes
and silica or glass are added to control the fluidity of the
molten slag cover.  The slag cover protects the molten metal
surface from unwanted oxidation and  reduces  volatilization
of  zinc.  The slag cover is maintained between 6.4 and 12.7
mm thick (0.25 to 0.50 inch), depending on the type of  melt
being processed.

Borax,  slaked  lime or hydrated lime, glass or silica, soda
ash, rasorite, and/or 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 smelter is
anhydrous rasorite, a sodium borate  flux   (Na^B^O?),  which
has great affinity for metal oxides and siliceous materials.
Its  fluidity can be easily adjusted and the quantities used
are about 2 to 3 percent by weight of the charge.
                                28

-------
To deoxidize 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  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.
Reverberatory Furnace Operations.  The reverberatory furnace
is a rectangular boxlike structure, refractory  lined,  that
uses  direct  firing  to  heat  the charge by conduction and
radiation.  The furnace is charged either through  the  top,
through  side  doors, or, occasionally, through the flue and
may be stationary or tilting.  Water is  sometimes  used  to
cool the doors on the reverberatory furnace.

Stationary reverberatory furnaces have capacities ranging up
to  250  tons  of  metal  per charge.  Tilting reverberatory
furnaces  are  somewhat  smaller.   These  are   the   basic
production  units  for  large runs of the more common copper
base alloys.  The furnace is charged with scrap metal at the
start of the heat and at  intervals  during  the  melt  down
period.   The  fuel is normally natural gas or oil.  The air
may be enriched with oxygen or  preheated  to  increase  the
melting  rate.   The bath of metal in the hearth is normally
coated with a thin layer of fluxed slag to protect  it  from
oxidation  and  volatilization.   Air  pollution  control is
practiced on the exhausts from smelting furnaces.  when  wet
air pollution controls are used, a waste water is generated.

The  metal  produced  in  a  reverberatory  furnace can be a
specification brass or bronze alloy that has undergone  some
refining, followed by alloying.  It can also be a blister or
a refined copper.  Slags removed from reverberatory furnaces
                               29

-------
contain  copper  values,  which  are  recovered in cupola or
blast furnaces.  Slags produced by  small  secondary  plants
are  sold  to  larger  secondary smelters or even to primary
smelters equipped to recover the metal value.   Waste  water
is  generated  when  water  is  used  for reverberatory slag
quenching or granulation.


Rotary  Furnace-   Rotary  furnaces  are  refractory  lined,
barrel  shaped  furnaces,  that are fired with gas or oil in
one end, and exhaust the  combustion  products  through  the
opposite  end.   The  furnaces  rotate either 360 degrees or
back and forth through 180 degrees or less during operation.
The furnaces can  be  either  tilting  or  nontilting.   The
charging,  alloying,  fluxing,  and  sampling procedures are
similar to those used in the  reverberatory  furnace.   This
type  of furnace is the basic melting unit for smaller heats
of copper base materials.  Water is used  in  this  type  of
furnace operation for noncontact cooling of bearings.  Waste
water  is also generated when slags from rotary furnaces are
quenched or granulated with water*  When wet  scrubbers  are
used  in  the  control  of emissions from rotary furnaces, a
waste water, that requires treatment before recirculation or
discharge, is generated.
Refining High Grade Copper Scrap
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 are also produced for
making copper base alloys.  Fire refining is only  partially
completed  when  the  metal  is  to  be cast 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.
Eire  Refining.   Part of the secondary copper production at
some (but not all) plants is fire refined by blowing air  or
oxygen  through  the  molten metal to remove excess zinc and
iron in a reverberatory or rotary  furnace.   Most  metallic
impurities,  including  lead, tin, and zinc, are undesirable
                           30

-------
impurities  in  high  purity  copper   products.     In   the
production  of essentially pure copper products,  the blowing
is continued until essentially all of  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
deoxidized 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.
Skimming.   After a heat of copper alloy has been refined in
a reverberatory or rotary furnace, it is analyzed,  adjusted
in   composition  if  necessary,  adjusted  to  the  desired
temperature, and skimmed to remove the slag  containing  the
impurities.  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.  Waste
water  is  generated  in  plants  that  use wet crushing and
concentrating.
Electrolytic Refining.  Several  secondary  copper  smelters
practice  electrolytic  refining in order to produce a high-
purity  cathode  copper.   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  cathodes  are  removed
periodically  from  the  electrolytic  cells,  are washed to
remove adhering acid, and are  then  melted  and  cast  into
fine-shape  castings,  such as wire bar and billets.  Having
been  greatly  reduced  in  size  during  the   electrolytic
                               31

-------
process,  the  used  anodes  are  removed from the cells and
remelted into new anodes.   If  nickel  is  present  in  the
anodes, as is the case at Plant 1, 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,
wherein 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 byproduct.  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.   One  domestic  secondary
copper facility.  Plant  1,  performs  on-site  recovery  of
precious metals.

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 blowing 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  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/or  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 casess a
waste water is generated.
Pouring and Casting of Final Product
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
                             32

-------
of  billets,  cakes, wire bars, wire rod, and ingots.   Water
use in each product line is considered separately.


Brass  and  Bronze  Ingot.   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/or storage in tanks
or ponds.  The waste water is discharged  periodically  into
streams  or sewers to permit the storage tanks to be cleaned
of charcoal and mold wash sludges containing some metals  or
their oxides*

Black  and  Blister  Copper.   Black copper  (or cupola melt)
produced from blast or cupola 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 employed to cast  pigs,
sows,  or  other  shapes.  Shot is produced by quenching the
molten black copper in water after a stream  of  the  molten
materials  has  been  broken  up  into  droplets  with  high
pressure air and water.  Waste water is  generated  only  in
shot  production.  Blister copper production may also be out
of phase with  subsequent  reduction  operations  due  to  a
                               33

-------
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.  Waste water containing residual mold
wash and some metal oxide scale is  generated.   The  quench
tank water is usually cooled and stored for reuse.
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  direct  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.   In each case, only noncontact cooling water
is generated, and this is cooled and recirculated.

Waste water, that is generated in  casting  finished  copper
shapes,   is   primarily   noncontact  cooling  water.   The
production  of  wire  bar  and   ingots   does   produce   a
contaminated waste water.
                              34

-------
Products
Brass  and Bronze.  The types of copper-base alloys produced
by ingot makers are the basic 31 standard alloys (listed  in
Table  3), produced by members of the Brass and Bronze Ingot
Institute.  Hundreds of  other  specialty  alloys  are  also
produced.(7)
Refined  Copper.  Although some smelters of copper will sell
black, blister, and/or anode copper as  their  end  product,
the  major  volume  is in the various grades of fire refined
and electrolytic refined copper.  The end use of  the  metal
will  specify  the  purity  required.   Tubing,  pipe, etc.,
require less pure copper than that required  for  electrical
conductors  used  in  power  transmission  or  communication
equipment.  Typical  grades  of  refined  copper  are  tough
pitch, deoxidized, electrolytic, and oxygen free.
                               35

-------
TABLE 3.   NOMINAL CHEMICAL SPECIFICATIONS FOR BBII STANDARD ALLOYS
Alloy Classification
1A
IB
2A
2B
2C
3A
3B
3C
3D
3E
4A
4B
5A
5B

6A
6B
6C
7A
8A

Tin bronze
Tin bronze
Leaded tin bronze
Leaded tin bronze
Leaded tin bronze
High-lead tin
bronze
High-lead tin
bronze
High-lead tin
bronze
High-lead tin
bronze
High-lead tin
bronze
Leaded red brass
Leaded red brass
Leaded semired
brass
Leaded semired
brass
Leaded yellow brass
Leaded yellow brass
Leaded yellow brass
Manganese bronze
Cu,
88.
88.
88.
87.
87.
80 .
83.
85.
78.
71.
85.
83.
81.
76.
72.
67.
61.
59.
%
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Sn, 70
10.0
8.0
6.0
8.0
10.0
10.0
7.0
5.0
7.0
5.0
5.0
4.0
3.0
2.5
1.0
1.0
1.0
1.0
Pb,
1.
1.
1.
10.
7.
90
15.
24.
5.
6.
7 .
6.
3.
3.
1.
1.
%
5
0
0
0
0
0
0
0
0
0
0
5
0
0
0
0
Zn,
70
Fe,
7, Al, 70 Ni, 70
Si, 70 Mn, 70
2.0
4.0
400
4.0
200
3.0
1.0
5.0
7.0
9.0
15.
24.
29.
37.
37.
0
0
0
0
0




1.




0 0.6




0.5
High-strength manganese
bronze
57.
5



39.
0
1.
0 1.0
1.5
8B High-strength manganese

8C

9A
9B
9C
9D
10A
10B
11A

11B

12A
12B
bronze
64,
0



24.
0
3.
0 5.0
3.5
High-strength manganese
bronze
Aluminum bronze
Aluminum bronze
Aluminum bronze
Aluminum bronze
Leaded nickel brass
Leaded nickel brass
Leaded nickel
bronze
Leaded nickel
bronze
Silicon bronze
Silicon brass
64.
88.
89.
85.
81.
57,
60.

64.

66.
88.
82.
0
0
0
0
0
0
0

0

5
0
0





200
3.0

4.0

5.0







9,
5.

40

1.







0
0

0

5


24.




20.
16.

8.

2.
5.
14.
0




0
0

0

0
0
0
3.
3.
1.
4.
4.






1.

0 5.0
0 9,0
0 10.0
0 11=0 2.0
0 11.0 4.0
12.0
16.0

20.0

25.0
5

3.5


0.5
3.0






4.0 1.5
4.0
                             36

-------
                         SECTION IV

                  INDUSTRY CATEGORIZATION

                        Introduction

This  section  describes  the  scope of the secondary copper
industry.  Included are technical  discussions  of  the  raw
scrap  materials  used,  methods of production, and products
produced.  Possible methods of subcategorizing this industry
into  discrete  units  for  separate  waste  treatment   and
effluent limitations guidelines are also discussed.

                  . v
                Objectives of Categorization
The  objective  of  industry  categorization is to establish
recommended   effluent   limitations   and   standards    of
performance,  which are specific and uniformly applicable to
a given category.  Categorization, therefore,-  involves  the
identification   and  examination  of  the  factors  in  the
industry, which might effect categorization in terms of  the
recommendations to be developed.
                     Factors considered

A  study was made of the secondary copper industry, covering
such factors as raw materials used, product line,  processes
employed,  water usage, plant age, plant location, and plant
capacity.  Forty four plants, out of an  estimated  50  were
surveyed   (about  90  percent).  Of the total, 37 were brass
and bronze ingot producers,  and  seven  were  producers  of
refined  copper.  Twelve plants were visited by interviewing
teamsr six in each product line.

The results of the survey indicate that the secondary copper
industry  should  be  considered  as  a   single   category.
Rationale for this judgment is given below.
Results of the Industry Inventory
Some  of  the information obtained in the industry survey of
the 44 plants is tabulated in Table 4.  This table  contains
information  on 37 brass and bronze ingot producers, such as
to their  production  or  capacity,  the  number  of  people
employed, products, water use, and waste water treatment and
                              37

-------
TABLE 4.    SMELTERS AND REFINERS OF SECONDARY BRASS AND BRONZE AND SECONDARY COPPER

             (Summary of survey including water use and wastewater treatment
               and disposition)


Metric Quench
(Short) Air Molten
Company Employees Tons /Mo Product Cleaning Metal
1 1,800 15,SOO OFHC Wet, dry, Yes
(17,500) copper & electro-
Water Use

Electro-
Cooling lytic
Yes
Yes
static
2 23 725 BB ingots
(800)

3 169 3,630 (b'BB ingots
(4,000)

^4 40 455-680 BB ingots
03 (500-750)

5 60 180-225 BB ingots
(200-250)

6 120 814 BB ingots
(900)

7 40 225 BB ingots
(250) 9,the/
Nonferrous
Metals
8 900 3,175 Cathode
(3,500)
3,630 Tubular
(4,000
Dry Yes


Dry No


Dry Yes


None No


Dry Yes
(Quench and

Plans Yes
dry

Wet Yes

(Quench and

No


Yes,
reverb.
door
No


No


Yes
granulate

Yes


Yes

granulate

No


No


No


No


No
slags)

No


Yes

slags)


Liters
(Gallons)
/Day
(33M) City &
Bay
City water
~ 11,360
( " 3,000)
Small amount
city

Small amount
city

Well
91,000
(24,000)
136,000
(36,000)
City
?
Lake
/ \
7.6M
(2M)


Water Treatment
and Remarks
NoneJ discharged
into bay

None, discharged
into sewers

None discharged


Settling^ discharged
to sanitary sewer
once a year
None, discharged
into sewers .

Settling basin, re-
circulated, discharge*
to sewer.
Nonej discharged into
the lake

Settling tanks, then
1.7 M gal/day dis-
charged to city
sewers

-------
                                       TABLE 4.   (continued)
Metric
(Short)
Company Employees Tons/Mo Product
9 180 l,360(b) Cathode
(1,500) copper
10 125 2,270 BB ingots
(2,500)
11 200 2,270 BB ingots
(2,500)
12 s 200 2,720 Cathode
(3,000) copper

Water Use
Air Quench Electro-
Cleaning Ingots Cool ing lytic
Wet and
dry
(Quench and
Drv
(Quench and
Electro-
static
dry
Drv
Yes Yes Yes,
no dis-
granulate slags ) charge
Yes Yes No
granulate slags)
Ye s No No
(Wet milling
of slags)
Ye s Ye s Ye s

Liters
(Gallons)
/Day
16M
(4.2M)
329,000
(87,000)
545,000
(144,000)
2.73M
(720,000)
Water Treatnent
and Remarks
No discharge
normally; overflow
to river
None discharged;
all filtered and
recirculated
None discharged,
recycled
All recycled, with
discharge from lake
13


14



15
 60
120
125
 455  BB ingots      Dry      Yes     No       No
(500)             (Wet crushing and concentrating slags"
 410  BB ingots
(450)
 320  Other metals
(350)
 495  BB  ingots
(545)
 445  White metals
(490)
  45  Zinc alloys
 (48)
Dry       Yes    Yes      No       53,000
                                  (14,000)  City
                                    8,700
                                   (2,300)  Well
Dry      Yes     Yes      No      170,300
                                  (45,000)
(new plant)

Recirculated;
settling tank

None; dis-
charged to  city
sewers

Recycled^ dis-
charged to sewer

-------
TABLE 4. (continued)
Metric
(Short)
Company Employees Tons/Mo
16 248 665
Salary-85 (734)
Hourlv-163 555
(610)
190
(212)
17 • 150 l,JdO
(1 ,500)
18 100 1.80
^ (200)
o
19 31 360-455
(400-500)
20 50 N.A.
Water Use

Air Quench Electro-
Product Cleaning Ingots Cooling lytic
BE ingots Dry Yes Yes No
Lead solder
& Babbit
zinc
particles
Black & Wet No res No
blister and
copper dry (Quench and granulate slags
and quench copper shot)
BB ingots Wet Yes No No
BB ingots Dry Yes No No
B B ingo t s D r v Ye s Ye s No
(Electro-
static)

Liters
(Gallons)
/Day
439,000
(116,000)


220,000
(58,000)
7
62,500
(16,500)
7
City &
Ground

Water Treatment
and Remarks
Settling; recycled;
discharged to
sewer


Scrubber water
filtered and re-
circulated, no
discharge
Recycled into the
lagoon; no discharge
Settling tanks then
to sewers
None discharged; all
recirculated
21
22
(No  data supplied,  3 plants)
All water into
sanitary sewers
                                        n    n
23
                       II    II      M

-------
                                      TABLE  4.   (continued)
Metric
(Short)
Company Employees Tons/Mo.
24 150 l,815Cb)
(2,000)
25 890 815
(900)
26 60 570
(625)
27 15 45
(50)
th
_J
28 100-150 (?)
29 ? 55
(60)
30 15 225
(250)

Air Quench
Product Cleaning Ingots
BB ingots Dry ifes
BB castings Dry Yes
(on order)
BB ingots Wet Yes
BB ingots Dry Yes
Ag, Au
(?) Drv No
BB
BB ingots Wet Yes
(non-
contact)
BB ingots Dry Yes
(90%
complete)
Water Use
Liters
Electro- (Gallons)
Cooling lytic /Day
No No Unknown,
River
No No ?
Well
Yes No 1.14M
(300,000)
No Yes ?
(evaporated) City
No No 1.87M
(495,000)
No No ?
No No City
Water Treatment
and Remarks
Settling tanks;
discharged into
sewers
No treatment; dis-
charge to a stream)
small amount
New treatment plant
starting up; 80% of
water discharged to
a stream now
No treatment; dis-
charged to city sewers
very small amount
Claimed no water used
for copper-base alloy
None discharged
Settled; dis-
charged to city
sewers, very small
31
  90    BB ingots      None     Yes      No
(100)   shot     (Water used  to make shot)
No
amount
None discharged;
all recycled

-------
TABLE 4.
Metric
(Short)
Company Employees Tons /Mo . Product
32 750 3,630 Wire bar,
(4,000) rod
33 25 245 BB ingots
(270)

•^ Cb)
1X1 34 30 1,J6(T BB ingots
(1,500)
35 15 320 BB ingots
(350)
36 40 2,720 Copper
(3,000) billets

37 25 360 BB ingots
(4001
(continued)
Water Use
Liters
Air Quench Electro- (Gallons)
Cleaning Ingots Cooling lytic /Day
Electro- Yes Yes No 1.14M
static (non- (300,000)
(wet and contact)
dry)
Dry Yes No No ?
City

Dry Yes No No 7,600
(2,000)
Wet No No No ?
City
None Yes Yes No 102,000
(27,000)

Wet Yes No No 950
(250)


Water Treatment
and Remarks
Direct to harbor
now; $1.5 ir.ill
installation
completed in
1973
Settled; dis-
charged to city
sewers
None1, discharged
into city sewers
None discharged;
recycled
Only boiler water
discharged', all
other noncontact
water recycled
Recirculatedj 100
g/week discharged
in the yard

-------

Metric
(Short)
Company Employees Tons/Mo.
38 40 225
(250)

39 70 910
(1,000)


40 250/300 455-815
(500-900)

£ 41 85 1,000(C)
(1,100)

42 40 680
(750)

43 275/325 1,815
(2,000)


44 20 225
(250)


S 1
TABLE 4. (continued)


Product
BB ingots


BB ingots



BB ingots
Al, Pb,
Zn
3B ingots,


BB ingots


BB ingots,
other
metals

BB ingots



Water Use

Air Quench Electro-
Cleaning Ingots Cooling lytic
Wet Yes Yes No
(Wet grinding and classification
of slags)
Wet and dry Yes No No
(Wet grinding and classification
of slags)
(Quench and granulate slags)
Dry Yes No No
(electro-
static)
Dry Yes No No
(Wet grinding and classification
of slags)
Dry Yes Yes No


Wet Yes Yes No
(3 units)
(Wet grinding and classification
0? slags)
Dry Yes Yes No
(907.
complete)

i *•

Liters
(Gallons)
/Day
91,000
(24,000)
City
142,000
(37,500)


?
City &
Well
45,500
(12,000)

City


Wells
76,000
(20,000)

?
Wells




Water Treatment
and Remarks
All recirculated


No discharge
normal lyj settling
pond overflow to
river
Settling tank;
discharged to
city sewers
Settling pond then
discharged into
storm sewers
Settling tank;
discharged into
sewers
None discharged;
all recirculated
except ingot quencl

None discharged; .
all process water
softened and
recycled
(a)  M = million.
(b)  Capacity not  average production.
(c)  Includes nickel production.

-------
disposition.   Water uses noted are in air cleaning, cooling
or quenching molten metal, equipment  cooling,  electrolytic
refining,  quenching  and  granulation  of  slags,  and  wet
milling and classification of slags.

Of  the  seven  secondary  copper  producers,  four  produce
electrolytically  refined  cathode  copper, two produce fire
refined copper, and one produces incompletely refined  black
and blister copper.  Electrolytically refined cathode copper
is suitable for the production of the highest quality copper
products,  such as pipe, tubing, or high conductivity copper
wire.  Fire refined copper may be  capable  of  meeting  the
specifications  for  pipe  or  copper  wire,  but  generally
contains more impurities than cathode copper.  Black copper,
the crude product from cupola  or blast furnace rr.elting, and
blister  copper,   a   semirefined   copper   product   from
converters,  must  be  further  refined.   Brass  and bronze
ingots are used as raw materials in foundries or fabricating
plants to produce brass or bronze products.

Industry Profile

From the information given in Table 4, the following listing
summarizes the distribution of plants exhibiting some of the
relevant   features   to   be   considered   in    potential
subcategorization of the industry*

          Feature                No. of Plants     (Percent),

- Current Production
     (or Capacity)
    kkg per month

        Less than 50                  13             (33)
          50-100                       9             (23)
         101-300                      13             (33)
         301-1000                      4             (1C)
         Over 1000               .      1              (3)

- Product Line
    Copper-base alloys                37             (84)
    Fire refined copper                2              (5)
    Electrolytic copper                4              (9)
    Black or blister copper            1              (2)

- No. of Employees
        Less than 50                  13             (33)
          50-100                       9             (23)
         1C1-300                      13             (33)
         301-1000                      4             (10)
                               44

-------
         Over 1000                     1             (3)

- Plant Age, Years
    Copper-base alloys
            <10                        3            <10)
           10-25                       8            (26)
           26-40                      10            (32)
           >40                        10            (32)

    Refined copper
           <10                         2            (29)
           10-25                       0
           26-40                       3            (43)
           >40                         2            (29X

Air   pollution  control  systems,  in  use  by  the  plants
surveyed, are compiled in Table 5.  Air pollution control is
used on blast or cupola furnaces, on reverberatory or rotary
furnaces, and  on  some  sweat  furnaces.   One  plant  also
controls   fugitive  dust  in  the  plant.   Of  rhe  plants
surveyed, 52 percent use dry air pollution control.  Most of
the plants using wet  air  pollution  control  employ  total
recycle of the waste water.

Water  usage  by  the  industry  was estimated from the data
supplied in the survey and is summarized in Table 6 for each
segment of  the  industry.   The  brass   and  bronze  ingor
producers use, on the average, less water per kkg of product
than  do  the refined copper producers.  There are, however,
plants that are exceptions in each segment.

The specific processes in which water is used and the source
of the process water as determined from the survey are given
in Table 7.  Almost all of the plants use water  for  molten
metal  contact  type  cooling, and about 50 percent of those
surveyed use municipal water.
Factors
Factors taken into  consideration  for  subcategorizing  the
secondary  copper  industry include raw materials processed,
products produced,  processes  employed,  plant  age,  plant
size,  air pollution control techniques, and plant location.
Application of each of these categorization factors leads to
uncertainties in  subcategorization,  as  described  in  the
following rationales.
                               45

-------
TABLE 5.   AIR POLLUTION  CONTROL  PROCESSES  USED BY SMELTERS AND REFINERS
            OF SECONDARY BRASS  AND BRONZE AND SECONDARY COPPER
                                            Number of Plants (Percent)
 Control Process
Brass and Bronze   Copper
         Combined
 Plants Surveyed
 Only Dry Air-Pollution  Control
 (Electrostatic)
 Only Wet Air-Pollution  Control
 Both Types of Air-Pollution  Control
 No Air-Pollution Control
 No Data Supplied
       37
       21 (57)

        7 (21)
        1 (31
        ^ (ID
        3
  7
2 (29)

1 (14)
4 (57)
1 (14)
  0
  44
23 (52)
 8 (20^
 "? 0.11
 s  (ii)
                                 46

-------
TABLE  6.  WATER USAGE  BY  THE  SECONDARY COPPER INDUSTRY
1/Kkg
Company Code Metal
Gal/Ton
(Metal)
Brass and Bronze Production
5
6
10
11
14
15
16
14
26
34
37
38
39
41
43





Refined Copper
1
8
9
12
17
32
36





13,480
5,040
4,350
7,200
2,570
5,190
9,340
4,600
60,000
170
80
12,130
4,680
1,370
1,260
Companies = 15
Max 60,000 1/kkg
Min 80 1/kkg
Ave 8,760 1/kkg
(2,100 gal/ ton)
Production
235,850
33,500
356,000
30,100
4,850
9,400
1,130
Companies = 7
Max 356,000
Min 1,130
Ave 95,800 1/kkg
(23,000 gal/ ton)
(3,200)
(1,210)
(1,040)
(1,730)
(620)
(1,240)
(2,240)
(1,100)
(14,400)
(40)
(20)
(2,910)
(1,120)
(330)
(300)






(56,530)
(8,000)
(85,200)
(7,200)
(1,160)
(2,260)
(270)





                             47

-------
TABLE 7,   WATER USAGE BY SMELTERS AND REFINERS OF SECONDARY
            BRASS AND BRONZE AND SECONDARY COPPER
Number of Plants (Percent)
Brass
Water Usage
No Water Use
Wet Air Pollution Control
Ingot Cooling (Contact)
No Information Supplied
Furnace and Equip Cooling (Noncontact)
S lag Quench and Granulation
Wet Milling and Classification of Slag
Electrolytic Refining
Water Sources
City
Well
Surface
City and Well
Surface and City
Not Given
and Bronze

1
8
30
4
13
4
6
0

16
6
1
3
1
6
Copper

0
5
7

7
4
0
4

2
1
1
1
2
0
Combined

1(2)
13 (30)
37 (84)

20 (45)
8(16)
6 (14)
4 (9)

18 (41)
7 (16)
2 (5)
4 (9)
3 (7)
6 (14)
                              48

-------
Raw  Materials*   The  principal  groupings of raw materials
used in the secondary copper  industry  are  (1)   low  grade
scrap (residues), (2) intermediate grade scrap (solids) F and
(3)  high  grade  scrap  (solids).   The  scrap is purchased
primarily for its copper content.   Each establishment is one
of these scrap sources.  However,  there  are  establishments
that  use all three grades.  Although brass and bronze ingot
makers can produce their products  from  intermediate  grade
scrap,  some   use  low  grade scrap and most use high grade
scrap.  Categorization of the industry into those operations
that process residues  (low grade scrap) and  those  that  do
not   may  be  possible.   However, as shown by Table 8, the
industry is evenly split along these lines.  This  split  is
true  for  both the brass and bronze and the copper segments
of the industry.   Moreover, residues are processed either by
wet milling and classification  or  in  a  blast  or  cupola
furnace,    which    would    tend    to    complicate   any
subcategorization based on this distinction.  Therefore,  on
the  basis  of raw materials, a single category remains most
suitable for recommending effluent limitations.

Products.  Subcategorization of the  industry into producers
of brass and bronze ingots and  producers of refined  copper
was   considered.    However,   in  the  comparison  of  the
metallurgical steps involved in   (1)   converting  the  scrap
material  into  brass  and bronze ingot with (2)  those steps
used in producing refined copper,   the  differences  in  the
steps  are  only  in  the  degree  of  refining necessary to
produce the end product.  Therefore, a single  category  for
brass   and  bronze ingot producers and producers of refined
copper is supported.

There is one fact about the  products  of  secondary  copper
installations  that  complicates  the  entire categorization
picture.  Many of the plants surveyed not. only  have  copper
or  copper-base  alloys  as products, but also recover white
metals, such as lead, babbit,  and  solder  and,  at  -times,
refine  secondary  aluminum  at  the same location.  In such
circumstances, it was concluded that if  the  major  tonnage
output  was  a copper or a copper base alloy, then the plant
should be  considered  as  part  of  this  secondary  copper
industry category.

Cathode  copper,  produced  by  electrolytic  refining, is  a
product of only the producer of refined copper  and  not  of
the  producer  of  brass  and  bronze  ingot  and,, thus, was
considered as a basis for subcategorization.  Only  four  of
the seven copper refiners produced cathode copper, while the
remaining   three   produced   only   fire  refined  copper.
Moreover,  those  companies  that  produce  cathode   copper
                               49

-------
 TABLE  8.    RAW MATERIALS PROCESSED BY SMELTERS OF SECONDARY
              BRASS AND BRONZE AND SECONDARY COPPER
                                    	Number of Plants_(Percent)	
  Raw Materials Processed           Brass and Bronze    Copper     Combined
Solids (Scrap Metal Only)      •         17  (46)           3  (43)     20  (45)
Residues (Slags, Drosses, etc.), Only    0                0           0  (0)
Bach Solids and Residues                17  (46)           4  (57)     21  (48)
No Data Supplied                         3  (8)            0           3  (7)
                                     50

-------
produce  their anodes by fire refining low  and intermediate
grade scrap.   The refining technique differs from brass  and
bronze  ingot  production only in the extent of refining and
the possibility of byproduct recovery (i.e.,  NiSO4,  CuSO4,
slimes or precious metals).

As   a   generalization,  more  water  is  employed  in  the
production of refined copper than in the production of brass
and bronze ingots.  The ingot producers use  an  average  of
8,760  1/kkg  (2,100 gal/ton), while refined copper producers
use an average of 95,800 1/kkg (23,000  gal/ton).   Specific
water  uses  for the companies surveyed in each product line
of the industry are given in Table 6.  There  are,  however,
plants producing copper that use less water than some of the
plants producing ingots  (compare Companies 9, 17, 32, and 36.
with  Companies  5,  16,  34,  and  38) .   Because  of  such
variations in water use for each product  line  and  because
these  figures do not relate to waste water discharge  {since
much of the process water  is  recycled),  subcategorization
based on water usage is not practical.

These  considerations  of the products of the industry, when
related to processes used to  manufacture  them,  support  a
single  category  for  establishments  producing  brass  and
bronze  ingots,  those  producing  various  grades  of  fire
refined copper, and those producing electrolytically refined
copper products.
Processes.   The  main  processes  for  conversing  scrap'to
copper or copper-base  alloys  are    (1)  presmelting  scrap
preparation,    (2)  charging  and  melting  the  scrap,   (3)
refining the melt, and  (U) pouring and casting  end  product
shapes.

Scrap  preparation  procedures employed on solids are common
to the industry.  Residue scrap, primarily copper-rich slag,
is wet milled and classified to recover metal value  by   six
of  the 17 brass and bronze smelters  processing residues  (35
percent) .  The remainder  (65 percent) use  blast  or  cupola
furnaces  for  metal  recovery.   All of the copper smelters
employ melting for metal recovery from residues.   The  fact
that  no smelter processes residues alone  (see Table 5),  but
also processes solids by methods  common  to  the  industry,
supports establishment of a single category.

Methods  used  in  charging  and in the melting of the scrap
metal are common to the industry.  Methods  of  pouring   and
casting  of the end product are also  common to the industry.
                               51

-------
Both process aspects support the establishment of  a  single
category.

In  the refining process, the manufacture of secondary brass
and bronze ingots from  scrap  and  residues  usually  stops
short  of  the  extensive refining necessary to recover pure
copper from the same raw material.   The  refining  that  is
done  in  the  brass  and  bronze segment of the industry is
chemically identical  (metallurgically)  to that done in fire
refining in the copper segment of the industry, and  similar
types  of  pollutants  will  end  up  in  the  waste  water.
Therefore, the differences in the extent of fire refining do
not   warrant   subcategorization   and   do   support   the
establishment of a single category.

The anodes used in electrolytic refining are produces of -the
fire  refining  process.   The  waste water generated by the
electrolytic process, such as spent electrolyte and  cathode
washing   water,  is  relatively  small  in  volume  and  is
classically reused for nickel  sulfate  and  copper  sulfate
byproduct recovery or as make-up to the electrolyte circuit.
One  secondary  copper electrolytic refinery sells its spent
electrolyte.  Another electrolytic refinery uses  barometric
condensers  for  the  production  of nickel sulfate from its
electrolyte purge.  Entrainment of  process  materials  into
the   noncontact  water  of  the  barometric  condensers  is
minimized by  the  usage  of  well-maintained,  cieintrsinruent
devices.  This same plant is the only known secondary copper
facility  which  is  currently  practicing  precious  metals
recovery from collected electrolytic slimes.  A  very  small
volume  of  process waste water (on the order of 23 cu m/oay
(6,000 gpd)  is generated during  precious  metals  recovery,
some  of  which  is currently impounded in lined ponds while
the remainder is discharged.  Since electrolytic refining at
secondary copper facilities produces very small  volumes  of
process  waste  water  and since most, of this flow is either
reused, sold,  or,  as  with  the  situation  of  barometric
condenser   water,   segregated   as  a  noncontact  source,
subcategorization is not considered to be warranted  on  the
basis of the existence of this process.

Plant	Age.    The  average  age of secondary copper industry
plants is estimated to t>e about 32 years.  The oldest of the
brass  and bronze ingot plants has been in existence for  75
years,  while  the  newest plant has been in operation for  5
years  (average age is 33  years).   The  oldest  ana  newest
plants in the refined copper segment have been operating for
67  and  3  years,  respectively   (average age is 31 years).
From the survey, there appears to be no  connection  between
either  the  age of the plant and the character of the waste
                              52

-------
water  or  any  ability  to  treat waste water.   Some of the
oldest plants have updated  facilities  for  production  and
have retrofitted waste water treatment facilities.

Air  Pollution Control Methods.   More than 52 percent of the
plants surveyed  use  dry  air  pollution  control   systems,
primarily baghouses.  About 30 percent are employing wet air
pollution  control systems, primarily high energy scrubbers.
In both cases they are being employed primarily  to  recover
the  byproduct  metal  oxides  (mostly  zinc  oxide)  emitted
during pyrometallurgical operations.

The raw waste water generated by a plant using wet scrubbers
would be expected to have different characteristics than one
not employing  a  wet  air  pollution  control  system.   In
practice,  total  recycle  of  scrubber water is employed to
assure recovery of the metal oxides, and such plants  should
be   able   to   meet   recommended   effluent  limitations.
Therefore,  establishment  of  a   separate   category   for
facilities  employing  wet  air pollution control systems is
not warranted.

Plant Location.  Secondary copper smelters are located close
to their supply of raw material.   Thus, most  of  them  are
located  within,  or  bordering  on, large urban areas.  New
scrap originates from manufacturing  plants  located  within
the  large  population  centers.  Large amounts of old scrap
also originate from the same population centers.

Plants near urban centers use municipal  water  sources  and
discharge  their  waste  water  to  municipal sanitary sewer
systems  (about 45 percent of those  surveyed).   Recommended
effluent   limitations   will   apply   to  such  facilities
eventually, and may require installation at  some  of  those
plants  of  waste water processing facilities at or adjacent
to the plant site.  In those cases where  there  is  limited
land  available,  such  a requirement will entail additional
considerations in the assessment of the economic  impact  of
the  recommended  effluent  limitations control or treatment
technique.  However, there exist operating  plants  in  such
urban  areas  where  the  recommended  control and treatment
technologies have been implemented.  In view of demonstrated
achievement of the recommended limitations by some plants in
urban locations, the industry  is  considered  as  a  single
subcategory on the basis of geographic location.
                            53

-------

-------
                         SECTION V

                   WASTE CHARACTERIZATION


                        Introduction
The  sources  of  waste  water  within  the secondary copper
industry are set forth  in  this  section.    The  kinds  and
amounts  of  waste  water  constituents are identified.  The
characteristics  of  raw  waste  water  are  presented   for
facilities  for  which  such data were available or could be
determined.    In   some   cases,   treated   streams    are
characterized.   Stream mixing before discharge or treatment
often   did   not   permit    specified    process    stream
characterization.   In  such  cases,  the  net  loading  was
determined from  differences  in  inlet   and  outlet  water
characteristics obtained during sampling.7     '  :     • ---...,-.

                   Sources of; Waste_Water

The  secondary  copper industry generates waste water in the
following processes or operations:

          o  Scrubbers as air pollution control
             equipment;
          o  Ingot, anode, shot, or billet casting
              (metal cooling);
          o  Slag granulation, slag milling, and
             slag classification;
          o  Electrolytic'refining cells;               ......
          o  Equipment cooling;
          o  Mixed streams from various combinations
             of processes.

These processes are presented as a composite flow diagram of
water use in Figure 2.  In a specific plant, waste water may
not be generated in all of these  processes.   For  example,
waste  water  from  electrolytic  cells  is not generated by
plants producing only brass and  bronze  ingot.   Mixing  of
waste   water  streams  before  treatment  or  discharge  is
practiced by many of the plants.  A  summary  of  the  waste
water disposal techniques practiced by the industry is given
in  Table  9.   One fourth of the plants surveyed claimed no
discharge of waste water, while 45 percent  discharged  into
municipal  sanitary  sewer systems and 27 percent discharged
into streams or storm sewers.  Runoff water was found to  be
discharged into streams or storm sewers  (68 percent).
                               55

-------
                                                                                      Hater Source
I  POTABLE   .
  TREATMENT'

X
I  SANITARY  1
i  USES      u
I  PRIMARY
|  AND
•  SECONDARY
1  TREATMENT
U - , __
ui
en
SPRAY
AND/OR
QUENCH
COOLING
OF
MOLTEN
METAL

,


EQUIPMENT
AND
NON-
CONTACT
COOLING
OF
MOLTEN
METAL




SLAG
GRANULATION





SLAC
MILLING
AND
CLASSIFYING



                                                                                           MELTING AND REFINING
                                                                                           FURNACE EXHAUST
                                                                                           SCRUBBING
                                                                                                      ENTRAINMENT
                                                                                                      SEPARATOR
                                                                                 pH Adjustment
                                                                                 NaOH, Ca(OH)  ,N1I
                                                                                           PRIMARY SOLIDS REMOVAL
                                                                                           SETTLERS AND THICKENERS
                       Various Combinations  of  Wastewaters  ©(©,©, and @
                       are Cooled and DischarRcd  Into Settling Tanks or Ponds
                       from Which Thty May Bt> Discharged or Reclrculated.On
                       Occasions (?),<£()> and  rdary  cxpper smeltinrr

-------
           9-  KASTE :EBS
               CF SECONDARY BRAES AND EPCNZE AND SECCHQAKT COPPER
   Wastewater
   Disposition

No Discharge Reported
   Lagoon or Pond
Sanitary Sewers
Streams or Storm Sewers
No Data Supplied
      Number of Plants  (Percentage)
Brass and Bronze

    10 (27)
     4 (11)
    19 (51)
     7 (19)
     1 (3)
         Combined
1 (14)    11 (25)
1 (141      5 (11)
1 (14>    20 (45)
5 (71)    12 (27)
0 (0)       1 (2)
   Runoff Water
   Disposition
Sanitary Sewer
Storm Sewer
Lagoon, Pond
Stream
No Data Supplied
     1 (3)
    24 (65)
     2 (V>
     3 (8)
     7 (19)
1 (14)     2  (5)
2 (29i    26  (59)
2 (29'i     4  (9)
1 (14)     4  (9)
1 (141     8  (18)
                                      57

-------
The  handling  of  the  process  waste  water  by the plants
surveyed before discharge is shown  in  Table  10.   Of  the
plants  surveyed, 25 percent did not treat their waste water
before discharge, while 14 percent  provided  some  form  of
treatment.  The remaining 59 percent practiced water conser-
vation by recycling a major portion of their process water.
         Characteristics of Waste Water Discharged
                by Secondary Copper Industry
The  characteristics  of waste water discharged by plants in
the secondary copper  industry  were  obtained  from  permit
applications made to the Corps of Engineers under the Refuse
Act  Permit  Program  (RAPP  data),  from State environmental
agencies,  from the  companies  directly,  and  by  contract
sampling  teams.  These data, along with flow and production
or  capacity  information  for  each  plant,  were  used  to
determine  effluent  loadings  for each plant for which data
were available.

Waste water from most of the operations received some treat-
ment before being discharged.  Water from venturi  scrubbers
was  found  to  always  be treated to remove the bulk of the
suspended  solids.   The  treated  water  may  be   recycled
completely  or  may be mixed with other waste water streams.
Water from ingot cooling, slag granulation, or slag  milling
was  always  settled  before being recycled or released to a
mixed waste water stream.   Waste  water  from  electrolytic
cells  was  treated  to  remove the copper, neutralized, and
filtered before being released to waste water mixed streams.
Backwash waste  water  from  softeners  or  boiler  blowdown
usually  was  treated  in  a  settling  pond  before  it was
released.  Cooling water was  normally  cooled  in  a  tower
before being recycled or released to a mixed stream.

After  preliminary treatment, mixed streams  were discharged
to  city  sewers  or  surface  waters,  recycled  with  some
discharge  to  streams  or  sewers,   or  recycled  with   no
discharge.  Some plants recirculated all of their water with
no  discharge.   Others  recirculated  all of the water with
only periodic discharge during  heavy  rains.   Still  other
plants  recycled  with a continuous discharge, or discharged
all of their waste water on a once-through basis.
                              58

-------
TAHIE 10.  SUW&BY CF WASTE WfiTER HANDLING PRftCnOET
           DISPOSITION tJSED BY SECOtTtfVES* ttlTER INDUSTRY
Number of Plants (Percentage)
No Water Use
No Treatment, Discharge to
Stream
Sewer
Treat, Discharge to
Stream
Sewer
Recycled, No Discharge
Recycled, Some Discharge to Stream
Periodic
Continuous
Recycled, Some Discharge to Sewer
Periodic
Continuous
Brass
1

2
8

1
4
10

3
1

5
2
and Bronze Copper
(3)

(6)
(24)

(3)
(ID
(29)

(9)
(3)

(14)
(6)
0

1
0

1
0
1

2
1

0
1


(14)


(14)

(14)

(29)
(14)


(14)
Combined
1

3
8

2
4
11

5
2

5
3
(2)

(7)
(18)

(5)
(9)
(25)

(ID
(5)

(11)
(7)
                           59

-------
Effluent Loadings
The  waste waters from the several potential sources usually
are joined into a common reservoir  or  outfall.   The  RAPP
data,  characterizing  such  outfalls,  and  other data that
characterize the waste water consist  of  analytical  deter-
minations  of the concentrations of waste water constituents
in mg/1.  The concentrations can be  converted  to  effluent
loadings  in  kilograms of pollutant per kkg, kg/kkg (pounds
per ton, Ib/ton), of copper or copper base alloy produced by
the following equation:

   Effluent Loading = C x F x K/P kg/kkg metal
                       (Ib/ton metal)

   where

             C = concentration of
                 pollutant in mg/1;

             F = stream flow in I/day (gal/day);

             p = production in kkgs
                 metal/day (tons/day);

             K = constants used in conversion
                 to obtain the proper units

                 (a)  10~6 kg x 1/mg

                 (b)  4.1722 x 10~6 tons x
                      1/mg x gal

                 (c)  8.345 x 10~6 Ib x 1/mg x
                      gal.

Precise loading calculations involving the determination  of
the total weights of constituent into and out of a plant are
impractical  to  calculate,  since  water  balances were not
established from the data used.  For  such  situations,  the
difference  in the discharge concentration less that present
in the intake was used to give a  net  concentration  change
which,  in turn, was used to calculate the net loadings.  In
cases of water effluent loadings  for  specific  plant  unit
operations,  such  estimates could be made, and the loadings
reflect the total weight of  pollutant  produced,  less  the
total weight of the constituent in the intake water.
                            60

-------
Plant. Data
Actual  effluent  loadings  were  calculated  from  effluent
concentration and  flow  data  obtained  for  the  companies
listed  in  Table  11.   The  original data from which these
effluent loadings were calculated are presented in Tables 12
through 27.  In those cases where  data  were  obtained  for
several  separate  discharges  from a single plant, separate
tables are given for each pipe.  The  effluent  loading  was
calculated  for  each constituent from each pipe and totaled
to obtain the overall effluent loadings given in  Table  11.
The   net  concentrations  were  determined  for  the  total
discharge, where more than one pipe was  used  to  discharge
process water.

Some  generalizations can be made about the plants listed in
Table 11.  The  waste  waters  from  Plants  1  and  8  were
discharged  with a minimum of treatment.  When the RAPP data
from  Plant  1  were  obtained,  ammonia  was  used  for  pH
adjustment of scrubber water, and then total waste water was
discharged with no recirculation.  Plant 8 discharges into a
joint  treatment  plant, also with no recirculation.  Of the
plants listed, Plants 1  and  8  had  the  highest  effluent.
loadings.   Both  use  wet  air cleaning and produce cathode
copper.  Plant 9, which  performs  operations  identical  to
Plants 1 and 8, recirculates most of its water and effects a
reduced  loading  in  total  trace  metals.   Plant  12 also
performs electrolytic refining of  anodes  produced  at  the
plant,  but  uses dry air pollution control on its furnaces.
The plant recycles all of the water from a  lake,  which  is
pretreated  before use.  This effluent loading is the lowest
of the copper producers for total trace metals.

Plant 43 and Plants 26 and 39 are examples of  copper  alloy
producers  that  practice  typical  and  extremes  in  water
management.  All three practice wet  air  pollution  control
that  uses  a  closed water circuit, with makeup water being
added to replenish that lost by evaporation.  The water used
for ingot cooling and slag granulation is  discharged  after
once-through  use  by  Plant 26, while Plant 39 recirculates
such streams continuously, with makeup water being furnished
by runoff and wells.  Plant 43  also  performs  milling  and
classifying  of  slag at the plant site.  Plant 39 mills and
classifies at a remote site.

Table 11 contains data on brass and bronze smelters   (Plants
26, 39, and 43), and copper smelters and refiners  (Plants 1,
8,  9,  12,  and 32).  To determine whether any variation in
                         61

-------
          TABLE 11 .  QUANTITIES OF SELECTED CONSTITUENTS IN WATER EFFLUENT
                      FROM SECONDARY COPPER INDUSTRY PLANTS IN U. S.
                      kg/kkg  (Ib/ton) of Metal Produced
Plant 1 (Net)
Flow, I/day 120.5 x 106
Flow, (gal/day) . (31.85 x 106)
Production, metric tons/day 529 (Cu)
Production, (tons/day) (583)
Conc.(a>

Alkalinity
COD, mg/1
Solids
Diss. Solids
Susp. Solids
Total Vol. Solids
Nitrate
Kjeldahl Nitrogen
Ammonia (as N)
Phosphorus
Sulfate
Chloride
Cyanide
Fluoride
Aluminum
Antimony
Arsenic
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Selenium
Silver
Sodium
Tin
Zinc
Oil and Grease
Phenols
Surfactants
mg/1
91.0
9.44
40.0
-
44.72
179
0.507
38.20
37.36
0.906

13.06

0.158
0.252
0
0.0036

0.0284

0

8.18

1.82


0.0019


0.097


2.436
1.801


kg/kkg
19.96
2.15
9.11
-
10.24
67.66
0.115
8.70
8.51
0.206

29.76

0.0363
0.0098
NLC
0.0009

0.0063

NLC

0.651

0.415


0.0009


0.022


0.555
0.419


(Ib/ton)
(39.92)
(4.30)
(18.2)
-
(20.48)
(135.3)
(0.229)
(17.39)
(17.02)
(0.412)

(59.45)

(0.0726)
(0.020)

(0.0018)

(0.0126)



(1.302)

!0.830)


'o.oois;


(0.044,1


(1.110)
(0.838.)


Plant 8
(Net)
7,721,000
(2,040,000)
326.5 (Cu)
(360)
Cone.,
mg/1 kg/kkg
266 6.278

503 11.895
142 3.351
141 3.334



1.3 0.031


64 1.510

0.71 0.017

0.49 0.116






3.9 0.092
43.25 1.021
1.5 0.035



2.6 0.061




5.15 0.127



-
(Ib/ton)
(12.493)

(23.79)
(6.702)
(6.668)



(0.062)


(3.005)

(0.034)

(0.231)






(0.183)
(2.032)
(0.070)

-

(0.121)

"


(0.243)



PH
6.95
7.0
                                            62

-------
 TABIE 11.  (continued)
Plant 9 (Net)
Flow • I/day;
Flow (gal/day)
Production .metric tons/day
Production (tons/day)
Cone.
mg/1
Alkalinity 427.5
COD, mg/1
Solids
Diss. Solids MOO
Susp. Solids 22
Total Vol. Solids
Nitrate
Kjeldahl Nitrogen
Ammonia (as N)
Phosphorus 2.0
Sulfate
Chloride 550.6
Cyanide
Fluoride
Aluminum
Antimony
Arsenic
Boron
Cadmium 0.055
Calcium
Chromium
Cobalt
Copper 0.175
Iron 0.12
Lead 1 . 8
Magnesium
Manganese
Mercury 0.0017
Nickel 0
Selenium
Silver
Sodium
Tin
Zinc 4.15
Oil and Grease
Phenols
Surfactants
851,600
(225,000)
46.5 (Cu)
(50)
Cone.
kg/kkg (Ib/ton) mg/1
8.019


35.64 (71.28)
0.413 (0.825) 9




0.0375 (0.0750)

10.328 (20.657)



0.01


0.00103 (0.00206)

0

0.00328 (0.00657) 0.27
0.00225 (0.00450)
0.0338 (0.0675) 0.04

e c
3.2x10° (6.4xlO'5)
NLC 0 . 02

0


0.0778 (0.156) 0.74


,
Plant 12 (Net)
817,600
(216,000)
78 (Cu)
(86)

kg/kkg (Ib/ton)




0.126 (0.251)










l.lxlO'4 (2elxlO-4)




NLC

. 0.0028 (0.0056)
i 1,
4.2xHT4 (8.4x10^)


2.1xlO-4 (4.2xlO~4)

NLC


0.0078 (0.0155)



9.4
7.4
              63

-------
                                  TABLE 11.  (continued)
 Flow  I/day
 Flow (gal/day)
 Production  metric tons/day
 Production (tons/day)
Alkalinity
COD,  mg/1
Solids
Diss. Solids
Susp. Solids
Total Vol.  Solids
Nitrate
Kjeldahl Nitrogen
Ammonia  (as N)
Phosphorus
Sulfatc
Chloride
Cyanide
Fluoride.
Aluminum
Antimony
Arsenic
Boron
Cadnii um
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesia::;
Manganese
Mercury
Nickel
Sol em" urn
Silver
Sodium
Tin
Zinc
Oil and •,"
Phenols
Si.ir.fnc t:r>;: ts
Plant 26 (Net)
605,600
(160,000
33.3 (Alloy)
(36.8)
Conc.;
mg/1
104 
-------
                                   TABLE U.   (continued)
Plant 39 (Net)
Flow I/day
Flow (gal /day)
Production (.metric tons/day
Production (tons /day)


Alkalinity
COD, mg/1
Solids
Dias. Solids
Susp. Solids
Total Vol. Solids
Nitrate
Kjeldahl KlCm^cn
Ammonia (as ;•;)
Phosphorus
Sulfate
Chloride
Cyanide
Fluoride
Aluminum
Antimony
Arsenic
Boron
Cadmium
Calcinra
Chromium
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Nichol
So1] onium
Silver
Sodium
Tin
Zinc
Oi I and urc-aso
Phenol s
Surfactants
PH



Cone .,
mg/1
174
27
297
233
64
31
0.10

0.053


39

35
0.250
0.0005
0.012
0.010
0.004

0.01

0.20

0.05

0.00007


0.010
0

0.08


0.135
8.9
3,075
(1,000)
43.5 (Alloy)
(48)

kg/kkg (Ib/ton)
0.051 (0.030)
0.002 (0.004)
0.026 (0.052)
0.020 (0.041)
0.0056 (0.0112)
0.0027 (0.0054)
8.7xlO'6 (17.4xlO~6)

4.6xlO"6 (9xlO~6)


0.0034 (0.0068)

0.0031 (0.0062)
2xlQ-5 (4xlO~5)
4xKT8 (8xlO-8)
IxlO"6 (2xlO~6)
9xlO'7 (2xlO"6)
3xlO'7 (6xlO~7)

9xlO'7 (2xlO~6)

1.7xlO"5 (3.4xlO"5)
.
4.4xlO"6 (9xlO~6)

6xlO'9 (1.2xlO-8)


9xlO'7 (2xlO"6)
NLC

7xlO'6 (1.4xlO"5)


1.2xlO"5 (2.4xlO"5)

Plant 43 (Gross)
75,700
(20,000)
61.9 (Alloy)
(62.8)
Cone .,
mg/1 kg/kkg
448 0.0548

1,160 1.419
1,020 1.247
140 0.171












0.0833 0.0001


0.066 8xlO"5

3.376 0.004
1.972 0.002
4.337 0.0053


0.164 0.0002




17.83 0.022



8.24




(Ib/ton)
(0.110)

(2.838)
(2.495)
(0.342)












(0.0002)


(1.6x10-^)

(0.008)
(0.004)
(0.011)


(0.0004)



1
(0.044)




(a)   Net concentrations are for combined process-water discharge,
(b)   Gross Concentration,
(c)   NLC - No Loading Calculable.
                                            65

-------
         TftBLE 12.   CONCENTRATION 0? SELECTED CONSTITUENTS IN INFLUENT
                     AND EFFLUENT WATER, SECONDARY COPPER INDUSTRY^)
                     (PLANT 1, PIPE 001)

          Volume:   6.81 x 106 I/day (1.80 x 106 gal/day)
          Operations:  Heat exchange and barometric condensers
          Production:  529 kkg/day (583 tons/day)

Constituent
Alkalinity
BOD
COD
Total Solids
Diss. Solids*
Susp. Solids
Total Vol. Solids
Nitrate, N
KjeldahlsNitrogen
Ammonia (as N)
Phosphorus (as P)
Chloride
Fluoride
Aluminum
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Silver
Zinc
Oil and Grease
PH
Temp (Win),C(F)
Temp (Sum), C(F)
Intake.
mg/1
110
3.7
395
21,724
21,689
34.8
1,832
0.62
3.7
3
0.25
13,000
1.26
0.01
<0.05
0.008
0.070
0.020
0.768
0.40
< 0.001
0.30
0.170
2.0
6.6
15(59)
24(75)
Discharge
mg/1
95
3.9
562
20,032
19,960
72
2,196
0.23
5.2
1.8
0.23
13,000
1.36
0.039
0.05
0.008
0.070
0.020
1,30
0.356
< 0.001
0.220
0.30
2.7
6.7
22(71)
29(84)
Net Cone.
mg/1
75
0.2
167
-1,692
1,729
37.2
364
-0.39
1.5
1.2
-0.2
0
0.10
0.029
0
0
0
0
0,532
-0.044
0
-0808
0.13
0.7



Net 1
kg/kkg
0.19
0.003
2.15
NLC^
NLC
0.48
4.69
NLC
0.019
NLC
NLC
NLC
0.0013
0.0004
NLC
NLC
NLC
^LC
0.007
NTLC
NLC
NLC
0.002
0.009



jO ad ing
(lb/ton)
(0.38)
(0.005)
(4.30)

(0.96)
(9.34)

(0.038)



(0.0026)
(0.0008)




(0.014)



(0.0036)
(0.018)



(a)   Source:   FAPP data (1972).

(b)   NLC = no loadings calculable,
                                       66

-------
TABLE 13. CONCENTRATION OF SELECTED CONSTITUENTS IN INFLUENT
AND EFFLUENT WATER, SECONDARY COPPER INDUSTRY^
(PLANT 1, PIPE 002)
Volume: 64.5 x 10 I/day (17.05 x 106 gal/day)
Operations: Surface condenser in power house, filter backwash
water, Zeolite softener, regenerating solution,
boiler blowdown water, noncontact cooling, and
storm drains
. Production: 529 kkg/day (583 tons/day)
Constituent
Alkalinity
BOD
COD
Total Solids
Diss. Solids
Susp. Solids
Total Vol. Solids
Nitrate
Kjeldahl Nitrogen
Ammonia (as N)
Phosphorus (as P)
Chloride
Fluoride
Aluminum
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Silver
* Zinc
Oil and Grease
PH
Temp (Win),C(F)
Temp (Sum),C(F)
Intake,
mg/1
110
3.7
395
21,724
21,689
34.8
1,832
0.46
3.7
3.0
0.25
13,000
1.26
0.01
< 0.05
< 0.008
0.070
0.02
0.768
0.50
< 0.001
0.30
0.17
2.0
6.6
15(58.6)
24(75.1)
Discharge»
mg/1
112
3.7
291
21,514
21,476
38
2,106
0.40
4.5
3.4
0.25
12,000
1.43
0.054
< 0.05
0.011
0.104
0.02
4.932
1.953
0.0017
0.481
2.517
4.9
6.8
25(75.6)
32(88.8)
Net Cone.,
mg/1
2
0
-104
-210
-213
3.2
274
-0.6
0.8
0.4
0
-1,000
0.17
0.44
0
0.003
0.034
0
4.164
1.453
0.0007
0.181
- 2.347
2.9



Net Loading
kg/kkg
0.24
NLC
NLC
NLC
NLC
0.39
33.4
NLC
0,098
0.049
NLC
NLC
0.021
0.0054
NLC
0.0004
0.004
NLC
0.509
0.177
9xlO~5
0.022
0.286
0.354



(Ib/ton)
(0.48)




(0.78)
(66.8)

(0.196)
(0.098)


(0.042)
(0.011)

(0.0008")
(0.0082)

(1.016)
(0.354)
(l.SxlO"4)
(0.044)
(0.572)
(0.707) .



(a)   Source:  RAPP data (1972),
(b)   NLC =  no loadings  calculable,
                                       67

-------
          TABLE 14.  CONCENTRATION OF SELECTED CONSTITUENTS IN INFLUENT
                     AND EFFLUENT WATER, SECONDARY COPPER INDUSTRY(a)
                     (PLANT 1, PIPE 003)
          Volume:  49.2 x  106 I/day  (13 x  106  gal/day)
          Operations:  Cooling and granulation of  slag,  fume  scrubbing,
                       ammonia pH  control
          Production:  529 kkg/day  (583 tons/day)

Constituent
Alkalinity
BOD, 5 -day
COD
Total Solids
Diss. Solids-
Susp, Solids
Total Vol. Solids
Nitrate
Kjeldahl Nitrogen
Ammonia (as N)
Phosphorus (as P)
Chloride
Fluoride
Aluminum
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Silver
Zinc
Oil and Grease
PH
Temp (Win),C(F)
Temp (Sum),C(F).
Intake,
mg/1
110
3.7
105
21,724
21,689
34.8
1,832
0.46 ' .
3.7
3
.75
13,000
1.76
0.010
0.05
0.008
0.07
0.02
0.768
0.50
0.001
0.3
0.17
2
6.6
15(59)
24(75)
Discharge,
mg/1
370
1.0
61
21,822
21,687
135
2,150
1.7
96
94
2.47
13,320
1.41
0.048
0.05
0.013
0.095
0.02
15.282
3.054
0.003
0.22 .
3.043
2.6
7.18
25(77)
34(94)
Net Cone..
mg/1
210
-2.7
-44
98
-2
100.2
318
1.24
92.3
91
2.22
320
0.15
0.038
0
0.005
0.025
0
14.514
2.554
0.002
-0.08
2.873
0.6



Net
kg/kkg
19.53
NLC
NLC
9.11
NLC
9.37
29.57
0.115
8.58
8.46
0.206
29.76
0.014
0.004
XLC
0.0005
0,0023
NLC
0.1350
0.238
0.0002
NLC
0.267
0.056



Loading
(Ib/ton)
(39.02)

(18.20)

(18.621)
(59.072)
(.229)
(17.14)
(16.897)
(0.412)
(59.45)
(0.028)
(0.008)

(0.0009)
(0.0045)

(2.697)
(0.475)
(0.0009)

;0.533)
(0.112)



(a)   Source - RAPP data.
(b)   NLC = no loadings calculable
                                       68

-------
               TABLE 15.   CONCENTRATION OF CONSTITUENTS IN INFLUENT AND
                           EFFLUENT WATER, SECONDARY COPPER INDUSTRY
                           (PLANT 8)

               Discharge to joint treatment plant
               Volume:  7,721,000 I/day (2,040,000 gal/day)
               Operations:  Furnace exhaust scrubbers, cast anode coolinj
               Production:  326.5 kkg/day (360 tons/day)

Constituent
Alkalinity
BOD, 5 -day
COD
Solids
Diss. Solids
Susp, Solids
Ammonia
Chloride
Fluoride
Aluminum
Antimony
Copper
Iron
Lead
Nickel
Zinc
pH
Temp (Win), C(F)
Temp (Sum), C(F)
Intake (fe)
me/1
154
0
23
373
538
55
0.8
36
0.69
1.5
0.03
0.1
6.147
0.5
0.4
1.05
7.3
12(53)
12(53)
. Discharge/
mg/1
420
0
23
876
680
196
2.1
100
1.4
0.5
0.52
4.0
49.4
2.0
3.0
6.2
7.0
NR(d)
NR
Net Cone..
me/1
266
0
0
503
142
141
1.3
64
0.71
-1.0
0.49
3.9
43.253
1.5
2.6
5.15



Net
ke/kkg
6.278,
NLC'C'
NLC
11.895
3.351
3.334
0.031
1.510
0.017
NLC
0.116
0.092
1.021
0..35
0.061
0.127



Loading
(Ib/ton)
(12.493)


(23.79)
(6.702)
(6.668)
(0.062)
(3.005)
(0.034)

(0.231)
(0.183)
(2.032)
(0.070)
(0.121)
(0.243)



(a)   Source:   RAPP data; municipal water source data,

(b)   Average  of city and well intake.

(c)   NLC « no loadings calculable.

(d)   NR = not reported.
                                       69

-------
             T.ABLE 16.   CONCENTRATION OF CONSTITUENTS IN INFLUENT AND
                         EFFLUENT WATER,  SECONDARY COPPER INDUSTRY^
                         (PLANT 9, PIPE —)

             Volume:   851,600 I/day (225,000 gal/day)
             Operations:   Flue gas scrubbing, slag granulation, cast anode
                          cooling, noncontact cooling, softener backwash
             Production:   45.4 kkg/day (50 tons/day)

Constituent
Alkalinity
BOD, 5 -day
Diss. Solids
Susp. Solids
Hardness
Phosphorus (as P)
Chloride
Cadmium
Calcium
Copper
Iron
Lead
Mercury
Nickel
Zinc
pH
Temp (Win),C(F)
Intake.
mg/1
246.24

450

324.9

32.49

226

0.33




7.1
14(57)
Discharge,
mg/1
673.74
5.0
2,350
22
61.6
2.0
583.11
0.055
17
0.175
0.45
1.80
0.0017
0
4.15
9.4
NR
Net Cone.
mg/1
427.5
5.0
1,900
22
-263.3
2.0
550.62
0.055
-209
0.175
0.12
1.8
0.0017
0
4.15


Net
kg/kkg
8.019
0.0938
35.64
0.413
NLc(b)
0.0375
10.328
0.00103
NLC
0.00328
0.00225
0.0338
3.2xlO'5
NLC
0.0778


Loading
(Ib/ton)
(16.038)
(0.187)
(71.28)
(0.825)

(0.0750)
(20.657)
(0.00206)

(0.00657)
(0.00450)
(0.0675)
(6.4xlO~5)

(0.156)


(a)   Source:   Plant data, intake water; State Environmental Agency,
     discharge water from lagoon (1973)0

(b)   NLC = no loadings calculable,,

(c)   NR = not recorded.
                                         70

-------
   TABUS  I6h.   VERIFICATION OF CONCENTRATIONS  OF  CONSTITUENTS  IN  INFLUENT AND
                EFFLUENT WATER, SECONDARY COPPER INDUSTRY (^
                 (PLANT  9, PIPE—)

                Volume:  851,600  I/day  (225,000 gal/day)
                Operations:  Flue  gas scrubbing, slag  granulation,  cast anode
                             cooling, noncontact cooling,  softener backwash,
                             electrolytic refining
                Production:  45.4  kkg/day  (50  tons/day)

Constituent
Alkalinity
COD
Solids
Diss. Solids
Susp. Solids
Phosphorus
Cyanide
Antimony
Arsenic
Boron
Cadmium
Copper
Iron
Lead
Manganese
Mercury
Nickel
Zinc
Oil and Grease
pH
Intake,
rng/1
223
4.1
440
398
42
0.046
0.003
0.063
> 0.001
0.087
0.013
0.004
* 0.005
0.210
0.538
0.00048
0.009
0.448
>1
7.93
Discharge;
me/1
194
15.2
1286
1259
27
0.029
0.003
0.095
>.001
2.465
0.089
0.048
>0.005
0.148
0.426
;» o.oooi
0.019
0.672
>1
8.32
Net Cone ,;
me/1
-29
11.1
846
861
-15
-0.017
0
0.032
0
2.378
0.076
0.044
0
-0.062
-0.111
-0.00038
0.010
0.224
0

Net
kg/kke
NLC(b)
0.208
15.87
16.15
NLC
NLC
NLC
0.0006
NLC
0.0446
0.00143
0.00083
NLC
NLC
NLC
NLC
0.00019
0.0042
NLC

Loading
(Ib/ton)

(0.416)
(31.74)
(32.30)



(0.0012)

(0.0892)
(0.00286)
(0.00166)




(0.00038)
(0.0084)


(a)   Source:   Average of two daily composites by sampling team (10/29/-10/30, 1974

(b)   NLC = no loadings calculable.
                                       71

-------
             JEABI£ 17.  CONCENTRATION  OF  CONSTITUENTS  IN  INFLUENT AND
                        EFFLUENT WATER, SECONDARY  COPPER  INDUSTRY(a)
                         (PLANT  12)

            Discharge  to  lake
            Volume:  817,600 I/day  (216,000  gal/day)
            Operations:   Slowdown of cooling tower,  noncontact cooling cast
                          anode  cooling, slag granulation,  electrolytic
                          refining
            Production:   78 kkg/day (86 tons/day)

Constituent
Alkalinity
BOD, 5 -day
COD
Solids
Diss. Solids
Susp. Solids
Nitrate
Kjeldahl Nitrogen
Chloride
Aluminum
Antimony
Chromium
Copper
Lead
Nickel
Silver
Zinc
Oil and Grease
PH
Temp (Win), C(F)
Temp (Sum), C(F)
Intake,
mg/1
22
16
29
30
40
3
0.10
1.85
8
0.4


6.4
7.6
14(57)
22(72)
Discharge Net Cone.
mg/1 mg/1



12 9


0.1 0.01
0 0
0.27 0.27
0.04 0.04
0.02 0.02
0 0
0.74 0.74
7.4(8.7-6.1)
27(80)
28(82)
Net
kg/kkg



0.126


0.00011
NLC
0.0028
0.00042
0.00021
XLC
0.0078

Loading
(Ib/ton)



(0.251)


(0.00021)
(0.0057)
(0.00084)
(0.00042)
(0.0155)

(a)   Source:   RAPP data,  intake water; Company data, weekly average of daily
     composite of discharge water.

(b)   NLC - no loadings calculable.
                                          72

-------
          TABLE 18.   CONCENTRATIONS OF SELECTED  CONSTITUENTS  IN  INFLUENT
                     AND EFFLUENT WATER, SECONDARY  COPPER INDUSTRY(a>
                     (PLANT  26, PIPE 001)

        Volume:  6.05 x 105  I/day  (1.60 x  105  gel/day)
        Operations:  Ingot cooling and noncontact cooling,  furnace exhaust scrubbing
        Production:  33.3 kkg/day  (36.8 tons/year)

Constituent
Alkalinity
BOD, 5 -day
COD
Solids
Diss. Solids
Susp. Solids
Total Vol Solids
Hardness
Nitrate (as N)
Kjeldahl Nitrogen
Ammonia (as N)
Phosphorus (as P)
Sulfate (as S)
Bromide
Chloride
Cyanide
Fluoride
Aluminum
Antimony
Arsenic
Boron
Cadmium
Calcium
Ch rom ium
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Selenium
Silver
Sodium
Tin
Titanium
Zinc
Oil and Grease
Phenols
PH
Temp (Win.),C(F)
Temp (Sum},C(F)
Intake ,
mg/1



160



132-171




21.5

7.0-11.0

1.0
0.0003




33.6
-6
3x10 °
0

11.7





4.3





8.5
13(55)
13(55)
Discharge ,
mg/1
104
29.0
306.3
275.5
260.5
15.0
86.0
145.8
0.58
0.13
NF(c)
0.29
60.9
0.32
22.7
NF
1.45
.44
NF
NF
NF
NF
47.6
0.02
0.560
0.89
1.50
4.8
NF
NF
XT
0.004
NF
60.8
NF
NF
0.30
8.5
NF
8.5
-
29(84)
Net Cone.;
mg/1



115.5



13.8
0.58
0.13
0
0.29
39.4
0.32
15.7
0
0.45
0.44
0
0
0
0
14
0.02
0.560
0.89
1.5
-6.9
0
0
0
0.004
0
56.5
0
0
0.30
8.5
0



Net
kg/kkg



2.079



0.248
0.010
0.002
NLC^ °>
0.005
0.709
0.006
0.283
NLC
0.008
0.008
NLC
NLC
NLC
NLC
0.252
0.0004
o.oio
0.016
0.027
NLC
NLC
NLC
NLC
NLC
NLC
1.017
NLC
NLC
0.005
0.153
NLC



Load ins
(Ib/ton)



(4.137)



(0.494)
(0.020)
(0.004)

(0.01)
(1*418)
(0.012)
(0.563)

(0.016)
(0.016)




(0.501)
(0.001)
(0.020)
(0.032)
(0.057)






(2.034)


(0.010)
(0.305)




(a)   Source:  RAPP data; plant data (J.y/1)

(b)   NLC - no loading calculable.

(c)   NF - not found.     j

-------
           TABU" 19,  CONCENTRATIONS OF SELECTED  CONSTITUENTS  IN  INFLUENT
                      AND EFFLUENT WATER, SECONDARY COPPER  INDUSTRY^
                      (PLANT 32, PIPE 001)

         Volume:  227,000 I/day  (60,000 gal/day)
         Operation:  Contact cooling of molds  (lead alloy)
         Production:  149.7 kkg/day (165 tons/day)

Constituent
Alkalinity
BOD, 5 -day
COD
Solids
Diss. Solids
Susp. Solids
Total Vol Solids
Nitrate
Kjeldahl Nitrogen
Ammonia (as N)
Phosphorus (as P)
Chloride
Fluoride
Aluminum
Antimony
Arsenic
Calcium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Sodium
Tin
Zinc
Oil and Grease
Phenols
Surfactants
PH
Temp (Win), C (F)
Temp (Sum), C(F)
Intake;
mg/1
15
0
19
90
58
14
44
1.75
1.54
0.05
0.02
14
1.16
0.020
0
0
0.0075
o.oio
0
0.40
0
5.0
0.05
0
0
0.35
25
0
0.10
4.1
0.04
0.6
6.85
14(58)
16(60)
Discharge,
mg/1
118
30
63
37.2
242
52
116
4.46
7.28
0.4
1.67
119
0.58
0.240
0
0
.053
.065
5.310
18.250
6.390
13.5
0.675
0.001
0.050
5.52
100
0.10
3.75
9.7
0.09
1.24
6.8
21(69)
22(71.6)
Net Cone.,
mg/1
103
20
44
232
184
38
72
2.67
5.74
0.35
1.65
105
-0.58
0.220
0
0
0.046
0.055
5.310
17,85
6.390
8.5
0.670
0.001
0.050
5.17
75
0.10
3.65
5.6
0.05
0.64



Net
kg/kkg
0.156
0.030
0.067
0.352
0.279
0.058
0.109
0.0041
0.0086
0.0005
0.0025
0.159
NLc(b>
0.0008
NLC
NLC ,
7.0xlO~i?
7.0x10
0.0161
0.0271
0.0097
0.0129
0.0010 ,
— t~l
1.5x10
7.6x10
0.0079
0.114
0.00015
0.0056
0.0085
7.6x10
0.00097



Loading
(Ib/ton)
(0.313)
(0.061)
(0.134)
(0.704)
(0.558)
(0.155)
(0.218)
(0.0082)
(0.0172)
(0.0011)
(0.005)
(0.319)

(0.0007)

-4
(1.4x10 ,)
(1.4x10" )
(0.0322)
(0.0542)
(0.0194)
(0.0258)
(0.0020)
(3.0x10" )
(1.5x10)
(0.0158)
(0.227)
(0.0003)
(0.112)
(0.0169),
(1.5x10""")
(0.00193)



(a)   Source:   RAPP data.
(b)   NLC = no loadings calculable.
                                       74

-------
          TABLE 20.   CONCENTRATION OF SELECTED CONSTITUENTS IN INFLUENT
                      AND EFFLUENT WATER, SECONDARY COPPER INDUSTRY(a)
                      (PLANT 32, PIPE 004)

         Volume:   189,250 I/day (50,000 gal/day)
         Operations:   Continuous casting of copper rod, drawing oil coolinj
                      and oxide scale removal with sulfuric acid
         Production:   149.7 kkg/day (165 tons/day)

Constituent
Alkalinity
BOD, 5-day
COD
Solids
Diss. Solids
Susp. Solids
Total Vol Solids
Nitrate (as N)
Kjeldahl Nitrogen
Ammonia (as N)
Phosphorus (as P)
Sulfide (as S)
Chloride
Fluoride
Aluminum
Antimony
Arsenic
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Silver
Tin
Zinc
Oil and Grease
Phenols
PH
Terop (Win,),C(F)
Temp (Sum),C(F)
Intake.
mg/1
15
0
19
90
58
14
44
1.75
1.54
0.05
0.02
0.1
14
1.16
0.02
0
0
0
0.0075
0.01
Q
0
0.4
0
0.005
0.05
0
0
0
0
0.10
4.1
0.04
6.85
14(58)
16(60)
Discharge
mg/1
124
75
230
1,240
700
490
316
6.2
4.2
2.33
0.07
0.1
422
1.2
O.U2
0
0
0.003
0.042
0.04
0.008
1.3
9.87
0.350
0.04
0.0075
0.0005
0.425
0.0025
0
2.5
12.3
0.08
6.8
18(65)
21(69.8)
Net Conc.^
mg/1
109
75
211
1,150
642
476
272
4.45
2.66
2.28
0.05
0
408
0,04
0
0
0
0.003
0.0345
0.03
0.008
1.3
9.47
0.350
0.035
-0,0425
0.0005
0.425
0.0.025
0
2.4
8.2
0.04



Net
kg/kkg
0.138
0.095
0.267
1.459
0.812
0.602
0.344
0.056
0.003
0.003
6xlO~5
NLC^ ^
0.005
5xlO"5
NLC
NLC
NLC
5xlO'6
c
5x10°
1.1x10''
0.0017
0.012
0.0005
5xlO"5
NLC
6xlO"7
0.0006
3xlO"6
NLC
0.003
0.010
5xlO"5



Loading
(Ib/ton)
(0.276)
(0.190)
(0.534)
(2.908)
(1.624)
(1.204)
(0.688)
(0.0112)
(0.007)
(0.006)
(IxlO'4)

(0.010)
(9xlO~5)



(1x10-5)
(IxlO-4)
(1x10 )^
5 (2.2xlO"D)
(0.0034)
(0.024)
(0.0009)
(IxlO-4)
£
(1.2xlO~°)
(0.0012)
(6xlO~6)

(.006)
(0.021)
(9xlO-J)



(a)   Source:   RAPP data.
(b)   NLC = no loadings calculable.
                                     75

-------
             .'--TIxLE  ;>]..   CONCENTRATIONS OF CONSTITUENTS  IN INFLUENT AND
                         EFFLUENT WATER, SECONDARY  COPPER INDUSTRY(a)
                         (PLANT 32, PIPE 005)

            Volume:   113,555 I/day  (30,000 gal/day)
            Operations:   Flue gas wash, remove  fly  ash
            Production;   147.7 kkg/day (165  tons/day)

Constituent
Alkalinity
BOD
COD
Solids
Diss. Solids
Susp. Solids
Total Vol Solids
Nitrate
Kjeldahl Nitrogen
Ammonia (as N)
Phosphorus (as P)
Sulfide (as S)
Chloride
Fluoride
Aluminum
Antimony
Arsenic
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Silver
Sodium
Zinc
Oil and Grease
Phenols
Surfactants
pH
Temp (Win),C(F)
Temp (Sum),C(F)
Intake,
mg/1
15
0
19
90
58
14
44
1.75
1.54
0.05
0.02
0,1
14
1.16
0.02
0
0
0
0.0075
0.010
0
0.4
0
0.005
0.050
0
o
\J
Oa35
0
25
0.1
4.1
0.04
0.6
6.85
14(58)
16(60)
Discharge
mg/1
6
8
62
154
74
48
90
3.25
2.24
0.99
0.02
0.1
21
1.1
0
0
0
0
0.0085
0.020
0.10
0.35
0.8
0.0055
0.050
0.0005
0
1.75
0
17
0.125
9.1
0.10
1.32
4.8
43(110)
45(113)
Net Cone.,.
mg/1
-9
8
43
64
16
44
46
1.5
0.7
0.94
0
0
7
-0.06
-0.02
0
0
0
0.001
0.01
0.1
-0.05
0.8
0.0005
0
0.0005
0
0.040
0
-8
0.025
5.0
0.06
0.72



Net
kg/kkg
NLC 
-------
             T&BLE 22.  CONCENTRATION  OF  CONSTITUENTS  IN INFLUENT AND
                        EFFLUENT WATER, SECONDARY  COPPER INDUSTRY^
                        (PLANT  32,  PIPE 006)

           Volume:  435,275  I/day  (115,000  gal/day)
           Operations;  Polyvinyl  chloride  insulation  incineration scrubber,
                        plated  precious metal  recovery(b)
           Product:   149.7 kkg/day  (165 tons/day)

Constituent
Alkalinity
BOD, 5 -day
COD
Solids
Diss. Solids
Susp. Solids
Total Vol. Solids
Nitrate
Kjeldahl Nitrogen
Ammonia (as N)
Phosphorus (as P)
Sulfate (as S)
Sulfide (as S)
Chloride
Fluoride
Aluminum
Antimony
Arsenic
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Mercury
Nickel
Potassium
Silver
Sodium
Titanium
Zinc
Oil and Grease
Phenols
PH
Temp (Win.),C(F)
Temp (Sum,),C(F)
Intake,
mg/1
15
0
19
90
58
14
44
1.75
1.54
0.05
0.02
0.6
0.1
14
1.16
a, 02
0
0
0
0.0075
0.01
0
0
0.4
0
5.0
0
0
0.35
0
25
0
0.10
4.1
0.04
6.85
14(58)
16(60)
Discharge,
mg/1
80
2
37
148
112
16
92
3.65
2.24
0.1
0.02
3.2
0.1
43
1.16
0.09
0
0
0
0.0085
0.01
0.380
0.5
0.35
0.05
5.5
0.0005
1.05
1.25
0.005
44
0.010
0.975
13.9
0
3.2
29(84)
31(87)
Net Cone.,
mg/1
65
2
18
58
54
2
48
1.9
0.07
0.05
0
2.6
0
29
0
0.07
0
0
0
0C001
0
0.380
0.5
-0.05
0.05
0.5
0.0005
1.05
Oe9
0.005
19
0.01
0.875
9.8
-.04



Net
kg/kkg
0.189
0.0058
0.0524
0.169
0.157
0.0058
0.140
0.0055
0.0020
0.00015
NLC
-------
    1 TABLE 23.   CONCENTRATIONS OF CONSTITUENTS IN INFLUENT AND EFFLUENT WATER,
                 SECONDARY COPPER. INDUSTRY^
                 (PLANT 32, PIPE 008)

    Volume:   37,850 I/day  (10,000 gal/day)
    Operations:  Spraytower for electrostatic precipitator, cooling  and washing
                 flue gases from metal furnaces
    Production:  27.2 kkg/day (30 tons/day)

Constituent
Alkalinity
BOD 5-day
COD
Solids
Diss. Solids
Susp, Solids
Total Vol Solids
Nitrate (as N)
Kjeldahl Nitrogen
Ammonia (as N)
Phosphorus (as P)
Sulfide (as S)
Chloride
Fluoride
Aluminum
Antimony
Arsenic
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Magnes ium
Manganese
Mercury
Nickel
Potassium
Silver
Sodium
Zinc
Oil and Grease
Phenols
Surfactants
PH
Temp (Win.), C(F)
Temp (Sum), C(F)
Intake,
TOR /I
15
0
19
90
58
14
44
1.75
1.54
0.05
0.02
0.1
14
1.16
0.02
0
0
0
00010
0
0
0.4
0
0.05
0.05
0
0
0.35
0
25
0.1
4.1
0.04
0.1
6.85
(58)
(60)
Discharge,
me/1
16
2
38
200
no
68
79
4.82
3.64
0.72
0.46
0.1
64
1.1
0.04
0
o
0.003
0.020
0.750
10.6
1.375
0.350
0.10
0.10
0.0005
0.750
6.86
0.025
44
4.0
4.6
0
0.32
6.8
(72)
(75)
Net Conc._
mfc/1
1
2
19
110
52
54
34
3.07
2.1
0.67
0.44
0
50
-0.06
0.02
0
0
0.003
0.01
0.25
10.6
1.475
0.350
0.05
0.05
0.0005
0.750
6.51
0.025
19
3.9
0.5
-0.04
0.22



Net
ke/kke
0.001
0.003
0.026
0.153
0.072
0.075
0.047
0.004
0.003
0.0009
0.0006
NLC
0.070
NLC
3xlO"5
NLC
NLC
4xlO'6
IxlO"5
0.0003
0.015
0.002
0.0005
7xlQ"5
7xlO~5
6xlO~7
0.001
0.009
3x10"^
0.026
0.005
0.0007
NLC
0.0003



Loading
(Ib/toti)
(0.002)
(0.006)
(0.052)
(0.306)
(-0.144)
(0.150)
(0.094)
(0.009)
(04006)
(0,0018)
(0.00X7)

(0.014)

(6x1 O'5)


(8xlO~6)
(2xlO-5)
(0.0006)
(0.03)
(0.004)
(0.001)
(IxlO"4
(IxlO"4)
(IxlO"6)
(0.007)
(0.018)
(6xlO~5)
(0.052)
(0,010'»
(0,0014)

(0.0006)



(a)   Source:  RAP? data.
(b)   NLC =  no loadings calculable.
                                    78

-------
            TABIE 24.    CONCENTRATION OF CONSTITUENTS IN INFLUENT AND
                         EFFLUENT WATER, SECONDARY COPPER INDUSTRY*-3'
                         (PLANT 32, PIPE 009)

            Volume:   37,850 I/day (10,000 gal/day)
            Operations;   Noncontact cooling water, cooling tower blowdown
                         (cold side)
            Production:   149.7 kkg/day  (165 tons/day)

Constituent
Alkalinity
BOD, 5-day
COD
Solids
Diss . Solids
Susp. Solids
Total Vol. Solids
Nitrate (as N)
Kjeldahl Nitrogen
Ammonia (as N)
Phosphorus (as P)
Sulfate (as S)
Sulfide (as S)
Chloride
Fluoride
Aluminum
Antimony
Arsenic
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Silver
Sodium
Tin
Titanium
Zinc
Oil and Grease
Surfactants
PH
Temp (Win-),C(F)
Temp (Sum).C(F)
Intake.
mg/1
15
0
19
90
58
14
44
1.75
1.54
0.05
0.02
0.6
0.1
14
1.16
20
0
0
0
7.5
0.010
0
0
0.40
0
5
0.050
0
0
0.35
0
25
0
0
0.100
4.1
0.60
6.85
14(58)
16(60)
Discharge,
mg/1
18
0
26
116
82
26
68
1.0
2.38
0.02
0.08
1.2
0.1
21
1.2
20
0
0
0
7.5
0.015
0
0.225
0.350
0.425
5
0.025
0.0005
0
0.35
0.005
25
0
0.010
0.065
3.9
0.62
6.85
23(73)
24(75)
Net Conc.y
mg/1
3
0
7
20
24
12
24
-0.75
0.84
-0.03
0.06
0.6
0
7
0.084
0
0
0
0
0
0.005
0
0.225
-0.05
0.425
0
-0.025
0.0005
0
0
0.005
0
0
0.010
-0.035
-0.2
0.02



Net
kg/kkg
0.0008
NLC ^b'
0.0018
0.0051
0.006
0.003
0.006
NLC
0.0002
NLC
2xlO~5
2xlO'4
NLC
0.0018
2xlO'5
NLC
NLC
NLC
NLC
NLC
1.3xlO"6
NLC
5.7xlO~5
NLC
0.0001
NLC
NLC
1.3xlO~7
NLC
NLC
1.3xlO'6
NLC
NLC
2.5xlO~6
NLC
NLC
5xl.O'6



Loading^
(Ib/ton)
(0.0016)

(0.0036)
(0.010)
(0.012)
(0.006)
(0.006)

(0.0004)

(4xlO-f)
(2xlO"4)

(0.0036>
(4x10-5)





(2.6xlO~6)

(llxlO'5)

(0.0002)


(2.6xlO~7)


' (2.6xlO~6)


(5xlO~6)


(IxlO'5)



(a)   Source:   RAPP data.
(b)   NLC = no  loadings  calculable.
                                     79

-------
           TABIE 25.     CONCENTRATION  OF CONSTITUENTS  IN INFLUENT AND
                         EFFLUENT WATER,  SECONDARY COPPER INDUSTRY^
                         (PLANT  32,  PIPE  010)

           Volume:  643,000  I/day (170,000  gal/day)
           Operations:   Noncontact  cooling  water, cooling tower blowdown
                         (hot side)
           Production:   149.7 kkg/day  (165  tons/day)

Constituent
Alkalinity
BOD, 5 -day
COD
Solids
Diss. Solids
Susp. Solids
Total Vol. Solids
Nitrate (as N)
Kjeldahl Nitrogen
Ammonia (as N)
Phosphorus (as P)
Sulfate (as S)
Sulfide (as S)
Chloride
Fluoride
Aluminum
Antimony
Arsenic
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Silver
Sodium
Tin
Titanium
Oil and Grease
Surfactants
PH
Temp (Win),C(F)
Temp (Sum.),C(F)-
Intake/
mg/1
15
0
19
90
58
14
44
1.75
1.54
0.05
0.02
0.6
0.1
14
1.16
0.020
0
0
7.5
0.010
0
0
0.400
0
5
0.050
0
0
0.35
0
25
0
0
4.1
0.6
6.85
14(58)
16(60)
Discharge^
rng/1
18
1.0
26
116
82
26
68
1.0
2.38
0.02
0.08
1.2
0.1
21
1.2
0.020
0
0
7.5
0.015
0
0.225
0.350
0.425
5
0.025
0.0005
0
0.35
0.005
25
0
0.010
3.9
0.62
6.85
29(84)
30(86)
Net Conc.f
rag/1
3
1
7
26
24
12
24
-0.75
0.84
-0.03
0.06
0.6
0
7
0.04
0
0
0
0
0.005
0
0.225
-0.050
0.425
0
-0.025
0.0005
0
0
0.005
0
0
0.010
-0.2
0.02



Net Loading
kg/kkg
0.013
0.004
0.030
0.117
0.104
0.052
0.104
/!_ \
NLC(b->
0.0036
NLC
2.6xlO'4
0.0026
NLC
0.030
1.7xlO'4
NLC
NLC
NLC
NLC
2xHT5
NLC
9.7xlO"4
NLC
0.0018
NLC
NLC
2.1xlO"6
NLC
NLC
2xlO'5
NLC
• NLC
4.3xlO'5
NLC
8.6xlO-5



db/day)
(0.026)
(0.008)
(0.060)
(0.234)
(0.208)
(0.104)
(0.208)

(0.0072)
/
(5.2x10"^)
(0.0052)

(0.060)
(3.4xlO~4)




(4xlO-5)

(1.9xlO"3)

(0.0037)


(4.2xlO-6)


(4xlO-5)


(8.6xlO~5)

(1.7xlO'4)



(a)   Source:   RAPP data.
(b)   NLC =  no  loadings  calculable.
                                     80

-------
      TABLE 26.   CONCENTRATIONS  OF  CONSTITUENTS  IN  INFLUENT  AND  EFFLUENT WATER,
                  SECONDARY  COPPER INDUSTRY^
                '  (PLANT  39,  PIPE 002)

     Volume:   3,785  I/day (1,000  gal/day)(b)
     Operations:   Ingot  cooling and  quench,  slag  granulation,  plant  runoff,
                  furnace exhaust scrubbing
     Production:   43.5 kkg/day (48 tons/day)

Constituent
Alkalinity
BOD
COD
Solids
Diss. Solids
Susp. Solids
Total Vol Solids
Nitrate (as N)
Nitrite
Kjeldahl Nitrogen
Ammonia (as N)
Chloride
Fluoride
Aluminum
Antimony
Arsenic
Boron
Cadmium
Chromium
Copper
Lead
Mercury
Silver
Sodium
Zinc
Surfactants
Chlorinated
Hydrocarbons
Pesticides
pH
Temp (Win. ), C(F)
Temp (Sum), C(F)
Intake:
nig/1
266
8
24
483
424
59
123
0
0.004
1.07
0.038
52











592





7.6
5.6 (42)
7 (45)
Discharge.
mg/1
440
22.2
51
780
657
123
154
0.10
0
0.80
0.091
91
35
0.250
0.00050
0.012.0
0.010
0.004
0.010
0.200
0.050
0.00007
0.010
588
0.080
0.135

0.001
0.001
8.9
7 (45)
29 (85)
Net Conc.y
mg/1
174
14.2
27
297
233
64
31
0.10
-0.004
-0.27
0.053
39
35
0.250
0.00050
0.012
0.010
0.004
0.010
0.20 •
0.050
0.00007
0.010
0
0.080
0.135

0.001
0,,001



Net Loading
kg/kkg
0.0151
0.001
0.002
0.026
0.020
0.0056
0.0027
8.7xlO~u
NLC1-0-1
NLC
4.6xlO"6
0.0034
0.0031
2xlO"5
4x10'^
IxlO'6
9xlO"7
3xlO'7
9xlO"7
1.7xlO~5
4.4xl(T6
6x10-9
9xlQ-7
NLC
7x10-6
1.2x10-5

9xlO'8
9xlO~8



(Ib/ton)
(0.030)
(0.002;
(0.004)
(0.052)
(0.041)
(0.0112)
(0.0054)
(17.4xKT6)


(9xlO~6)
(0.0068)
(0.0062)
(4x10-5)
(SxlO'8)
(2xlO~6)
(2xlO~6)
(6xlO-7)
(2xlO-6)
(3.4xlO~5)
(9xlO-6)
(1.2xlg-B)
(2xlO~6)

(1.4xlO"5)
(2.4x10-5)

(2xlO~7)
(2xlO~7)



(a)   Source;   RAPP data.

(b)   Company  estimates rainfall watershed into recirculating pond exceeds
     evaporation by 3785  I/day (1000 gal/day) and varies seasonally.
(c)   NLC -  no  loadings  calculable.
                                     81

-------
            TABLE 27.    CONCENTRATION OF CONSTITUENTS IN INFLUENT AND
                        EFFLUENT WATER, SECONDARY COPPER INDUSTRY(a^
                        (PLANT 43) Lagoon outfall

           Volume:  75,700 I/day (20,000 gal/day)
           Operations:   Ingot cooling, slag milling, noncontact cooling,
                        furnace exhaust scrubbing, slag quench
           Production:   61.9 kkg/day  (68.2 tons/day)

Constituents
Alkalinity
Solids
Diss. Solids
Susp. Solids
Boron
Chromium
Copper
Iron
Lead
Nickel
Zinc
Intake, Discharge,
rag/1 (k) mg/1
448
1160
1020
140
0.0833
0.066
3.376
1.792
4.337
0.164
17.834
Gross Cone.,
mg/1




0.083
0.066
3.376
1.792
4.337
0.164
17.834
Gross
kg/kkg
0.0548
1.419
1.247
0.171
0.0001
8xlO"5
0.004
0.002
0.0053
0.0002
0.022
Loading
Clb/ton)
(0.110)(c)
(2.838)
(2.495)
(0.342)
(0. 0002V ^
(1.6x10-^)
(0.008)
(0.004)
(0.011)
(0.0004)
(0.044)
pH
                                  8.24
(a)   Source:   State Environmental Agency (1973).

(b)   Intake is  nonpotable  well  water;  no analysis,

(c)   Gross Loadings Only.
                                      82

-------
the  waste  water  characteristics  based  on  product  line
exists, the effluent loading  values  for  suspended  solids
from  Table  11  were  plotted as a function of the combined
trace metals, copper, and zinc effluent loading  values  for
all of the plants (Figure 3).   There is considerable scatter
in  the  data,  resulting  from plant to plant variations in
water management practice and from the fact  that  the  data
represent  both net: and gross effluent loadings.  The number
of metals that were summed to make up  the  combined  metals
also  varies  from  plant  to  plant because of insufficient
analytical data.  Despite  this,  a  reasonable  correlation
exists between the suspended solids discharged and the total
metals   and   copper.    For  zinc,  there  is  a  parallel
correlation, but it is  slightly  displaced  from  that  for
copper  and  total  metals.   This correlation indicates that
plants providing a means for reduction of  suspended  solids
also have reduced total metals in the effluent.

With  respect  to  the  characteristics  of waste water from
copper base  alloy  producers  and  producers  of  secondary
copper,  the  correlation  exists  for both types of plants,
suggesting similarities in the  constituents  in  the  waste
water.   The  plot  of  the data for Plant 26 shows a slight
displacement from the trend lines.  This could be  explained
by the large amount of water used by the plant, 60,000 1/kkg
(14,000  gal/  ton)  on a once-through basis as compared with
the average for the  copper  alloy  producers,  8,700  1/kkg
(2,100 gal/ton) (see Table 6).  The data points for Plant 39
are  slightly  displaced  below  the  trend  line  since the
plant's discharge of waste water is reduced  by  good  water
management to that of rainfall exceeding  evaporation.

The  discharges from the plants listed in Table 11 also vary
in pH, which  affects  the  combined  trace  metal  effluent
loading.  To establish a correlation between these two waste
water  characteristics,  the  combined  trace metal effluent
loading was plotted against pH   (Figure  4}.   There  is  an
apparent correlation between the two parameters.  The curves
suggest  that  at  the  higher  pH  values,  the total metal
effluent loading is lower.  The two sets of curves  show  no
separation  of  plants  based  on product line, since copper
alloy  producers  are  among  both  sets  of  points.    The
existence of two sets of trend lines is due to the variation
of the number of metals that make up the "total trace metal"
effluent loading.
    Characteristics of Waste Water from Process Streams
The contributions of each of the processes shown in Figure 2
                          83

-------
                                                                                    Combined Trace Metals,
                                                                                                 (-•
                                                                                                 =•1
CO
            OJ
p     J


£'  S' o
Fj  O  Mi

"' "   (D
QJ  fy  i-ti
1—'  W  Ml

O  iU  C

^  Ml 3
         0
     }-•  r tl HI

     ^  S  i?
     >5  -3  «
     '"  (D  ft
     «
            n
                                                                                    Zn or Cu Loading

-------
10
                    pH of Discharge
  Figure 4.   Trend of the trace jnetal effluent loadings,  as a
              function of pH of tctal discharge for secondary

              alloyed and unalloyed copper plants.
                    85

-------
to the overall waste water loading in the  secondary  copper
industry  are  not  readily  broken out from plant discharge
data because of stream mixing.  Sampling teams were sent  to
selected  plants  to  characterize  raw  waste  water  being
generated  from  each  process,   wherever   feasible.    The
variability  of  the scrap material being processed during a
30- day operation makes the data from  short  term  sampling
excursions indicative only of the characteristics of the raw
waste water.
Waste Water from Air Pollution Control
Most  smelters  of  secondary brass and bronze and secondary
copper employ some form of air pollution control.    The  air
cleaning  equipment  may  be either baghouse filters (dry or
water spray cooled),  which produce no waste water, or it may
be high energy venturi type scrubbers, which  require  large
quantities  of  water  for their operation.  Sometimes, both
types are employed at the same facility.  These two types of
equipment are used in  conjunction  with  most  melting  and
refining operations.   For hydrocarbon type exhausts, such as
the  emissions  from driers used to remove oil from turnings
during pretreatment,  afterburners are used  to  control  the
smoke  and hydrocarbon content.  Electrostatic precipitators
are also used by a  small  percentage  of  the  smelters  in
conjunction with wet and/or dry systems.

A  breakdown  of the air pollution control processes used by
the smelters of secondary brass  and  bronze  and  secondary
copper smelters, surveyed in this program, is given in Table
5.  Fifty two percent use only dry air pollution control, 20
percent use only wet air pollution control, while 11 percent
use both.  Abour 15 percent use electrostatic precipitators,
which, for the establishments surveyed, are not cleaned with
water.   Dusts,  smoke,  and fumes are removed from exhausts
from the following industry operations:

          Cupola  or blast furnace melting,
          Reverberatory furnace operation,
          Converter operation,
          Pouring and casting.

Cupola  and blast furnace operations, used to recover  metal
values  from  copper   (or  brass  and  bronze) rich slags or
residues, produce large  quantities  of  particulate  matter
from dusty charge materials, such as fine slags, fine fluxes
of  silica  sand,  limestone,  or fluorspar, and coke ash or
coke breeze, as well as metal oxide fumes.   Some  smoke  is
                          86

-------
also produced from the combustion of coke  and organic wastes
in the charge materials.   Metal  oxide  fumes  are   produced
from  zinc,   lead,  and  other volatile metal impurities,  if
they are present in the charge.

Reverberatory  and  rotary  furnaces  produce  some   smoke,
particularly if oil-fired or if the charge is not pretreated
to  remove  organic  wastes.   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.   Borax  is  almost  always present as one of the
flux constituents.

Exhausts from converters contain metal oxides of all of   the
metals  present,  including some copper oxide and the oxides
of sulfur, phosphorus, or other nonmetals  that were  present
in  the  original  melt.    When wet scrubbing is used, these
constituents will be contained in the water as suspended  or
dissolved solids.

A  considerable  amount  of  zinc  oxide and some lead oxide
fumes are formed during  the  pouring  of   molten brass  or
bronze  alloys  that  contain  these volatile metals.  Their
fume  is  generally  collected  along  with  the  combustion
exhaust  gases  and  directed to the air cleaning equipment.
Casting of molten refined  copper  does  not  produce  metal
oxide  fumes,  since  zinc  or  lead  are  not present  or are
present in such  low  concentrations  in  partially   refined
copper   (anode  or  blister  copper)  that  very low partial
pressures are exerted.

Wet air scrubbers remove  from  90  to  99  percent   of   the
entrained solids.  Most of these solids are removed  from the
scrubber  water  by means of thickeners, centrifuges,  and/or
filters, and  the  clarified  water  is  pumped  to   cooling
towers,  holding  tanks,  or ponds and recycled.  Some  bleed
off water from the tower is discharged to  a holding  tank  or
pond   before   recycle.   The  sludge  collected  from   air
scrubbing operations during brass and bronze  smelting   will
contain  over 50 percent zinc  (as zinc oxide) and one  to two
percent lead as its oxide.  The sludge  recovered  from   wet
air  scrubbing during the refining of copper by blowing  will
contain up to four  percent  copper  as  oxide  and  varying
amounts  of  zinc  and lead, depending on the grade  of  scrap
that entered the melt.  Waste water discharged from settling
ponds or tanks would be expected to contain suspended solids
of about the same  composition,  on  a  dry  basis,   as   the
sludge.   In addition, the waste water would contain most of
the soluble constituents originally in the feed  water  plus
                        87

-------
the  additions  of borax, metal borates,  lime, and soda ash,
when these materials are used as furnace fluxes.  The pH  of
the  water  is  normally  adjusted to above seven with lime,
ammonia, or caustic before being recycled, when polymer  and
organic laden material is charged.

The amount of water used in wet air pollution control  is  a
function   of   the   exhaust   gas   flow   rates  and  the
characteristics of the pollutants being removed, as well  as
the  type  of  scrubber being employed.  High energy venturi
scrubbers, typical of the industry, use  from  150  to  4540
liters  per  minute  (40  to  1200  gal per minute), with an
average of about 1230 liters per minute   (325  gpm).   Large
plants   employ  about  three  such  units  to  control  air
emissions, primarily from reverberatory or rotary  furnaces.
Due  to  evaporative  losses,  about 12 percent of the water
used  in  scrubbing  is  new  make  up  water.   Spray  type
scrubbing  towers  are  also  employed  by  the  industry to
control emissions from  cupola  furnaces.   The  volumes  of
water used in these systems could not be determined, but are
assumed to be equal to those used in high energy systems.

Reliable  data  on the composition of the raw waste water or
circulating water from air scrubbers  on  secondary  smelter
operations  were  not  available.   The  compositions of the
waste waters from two smelters sampled (Plant  9  and  Plant
38)  are  shown  in  Table 28.  The loadings were determined
from differences in the concentration of inlet- water to  the
scrubber  and  the  outlet from a thickener that follows the
scrubber in the treatment circuit.  Appropriate  corrections
were   made  for  evaporation  of  water  (approximately  20
percent).

The data in Table 28 are as close to characterization of raw
waste water from furnace exhaust scrubbing as  was  possible
to  obtain  during sampling of Plants 9 and 38.  The samples
were taken at the  thickener  overflow.   At  Plant  9,  the
thickener  also receives underflow from a centrifuge used to
remove zinc oxide sludge, which contributes to its suspended
solids loading.  At Plant 38, the thickener did not  receive
a  recycle  from  the  centrifuge.   The  loadings of total,
suspended, and dissolved solids were greater for Plant 9   (a
copper  producer)  than  for  Plant  38  (an alloy producer).
This would be expected because  of  the  greater  amount  of
blowing  necessary  to  remove  impurities  in  the  furnace
charge.  Effluent loadings in wet scrubber water in Plant  9
also  occur  for boron, cadmium, and zinc, with a very small
gain in mercury also being observed.

-------
                         TABLE 28.   CHARACTER CF WASTE WATER FROM AIR SCRUBBER AFTER
                                    THICKEMER (Before centrifuge and settling)
Plant 38 

Product
kkg/day
ton/day
Water flow,
I/day
Constituent
Alkalinity
COD
Solids,Total
Solids, Diss.
Solids, Susp.
TOC
Phosphorus
Cyanide
Antimony
Arsenic
Boron
Cadmium
Copper
Iron
Lead
Manganese
Mercury
Nickel
Zinc
Oil and Grease
PH
Intake
Cone . ,
mg/1
Alloy
9.7
10.7

22,800(c>

79
—
306
5
301
-.
0.01
0.06
<0.1
<0.02
0,002
<0.05
0.06
0.21
0.11
0.20
<0.001
<0.1
<0.1
--
7.2

Cone . ,
mg/1




19,000

44
295
6669
2465
, 4201
530
<0.01
0.06
3.9
1.3
5.7
3
280
20.7
1802
2.1
0.005
3
1517
164
7.1
Discharge

Loading
kg/kkg






NLC
0.578
12.344
4.817
7.521
1.038
NLC
0
0.0076
0.0026
0.011
0.006
0.548
0.040
3.565
0.004
1 x 10"6
0.006
2.971
0.321

(Ib/ton)






(NLC)
,(1.156)
(24.688)
(9.634)
(15.042)
(2.076)
(NLC)
0
(0.0152)
(0.0052)
(0.022;
(0.012)
a. 096)
(o.oso;
(7,130)
(0.008)
(2 x KT6)
(0.012)
(5.942)
(0.642)

Intake
Cone . ,
mg/1
Copper
45.3
50

7>086,000
-------
In the waste water from furnace exhaust scrubbing  at  Plant
38,  effluent  loadings for all of the trace metals,  as well
as for the three forms of solids, were obtained.  The  trace
metal  effluent  loadings  from Plant 38 are less for boron,
cadmium, and mercury than  those  from  Plant  9,  but  have
calculable  loadings  for  nickel,  manganese,   lead,  iron,
copper, arsenic, and antimony.

The net effect of subsequent solids removal treatment  after
pH  adjustment,  with caustic or lime has been determined and
is described in Section VII.

In summary, the large volumes of water necessary to  operate
wet  air  scrubbers  makes recirculation of the water, after
the bulk of solids have been removed an economic  necessity.
The settled sludge consists mostly of zinc oxide and is sold
by  most  smelters.  Some form of settling is always used to
aid cooling when  the  volumes  of  water  are  large.   The
recirculation  of water concentrates dissolved solids.  This
has caused a seasonal problem in one plant (Plant  39),  but
other  plants  recirculate all of the scrubber water with no
apparent problems.
Waste Water from Molten Metal Cooling
Water is used by 37 of the 44 plants surveyed to cool molten
metal cast into ingots,  shot, and anodes by  direct  contact
cooling  methods.   The metal is solidified by spray cooling
or partial immersion of the mold and then quenched in tanks.
Finished refined  copper  shapes  are  usually  prepared  by
cooling  the  molten  metal by noncontact cooling techniques
and then quenching the solidified  metal  with  clean  water
(usually  municipal) to limit staining of the metal surface.
Contact cooling waste water is normally settled and recycled
after cooling, generally as  a  mixed  stream.   It  may  be
discharged  after  settling.  Contact cooling water employed
to  quench  cool  the  finished  refined  copper  shapes  is
frequently  recycled, after passing through heat exchangers,
which use cooled, recirculated process water.

Smooth brass and bronze ingots must cool slowly 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.  In a typical
operation, 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 immersed in a tank of water during  the
                        90

-------
second  portion  of  the  conveyer travel;  and,  finally,  the
solidified ingot is discharged into a quenchtank  of  water.
Part  of  the  charcoal burns during the ingot travel on  the
conveyer.  The unburned charcoal and charcoal ash all end up
in  the  cooling  water.   This  charcoal  and  sludge   are
periodically  cleaned  out  of the quenching tanks,  settling
tanks, and ponds or cooling  towers.   The   water  from  the
settling tank may be recirculated or discharged.

In  addition  to  the  charcoal  and charcoal ash,  the water
pollutants associated with direct metal  cooling  are  small
amounts  of  metal oxides from the ingot surface, refractory
mold wash (calcium phosphate), and  dust  from  the  smelter
floor.  Charcoal is not used when casting copper anodes,  but
the  mold wash is employed and the wash ends up in the waste
water.  Oil and grease,  used  to  lubricate  the  automated
casting  and  conveying  system,  appears  in  cooling waste
water.

The generation of cooling wasre water is intermittent during
daily operations at a plant.  The period of  operation  will
vary  with the capacity of the mold line and the capacity of
furnaces containing the finished metal.  In some  operations
casting  may  require  only  2  to 2.5 hours, while in large
installations, casting can be continuous for an 8 to 10-hour
period.  The liters of water used to cool a kkg ranges  from
6500  to  420  1/kkg   (1550 to 100 gal/ton) with the average
being about 2400 1/kkg  (570 gal/ton).

Reliable data on the composition of the raw waste  water  or
circulating  water  from ingot or anode cooling in secondary
copper smelters were not available.  The compositions of the
waste waters from ingot or anode  cooling  in  two  smelters
(Plant  9  and Plant 38} sampled are shown in Table 29.  The
loadings were calculated from differences in the  inlet  and
outlet concentrations of the recirculated water.

Waste  water,  originating  from  molten  metal  cooling and
quenching during the production of anodes  and  copper-alloy
ingot, gains only small amounts of pollutants.  The effluent
loadings  for  the  operation,  to  a  large  part,  are not
calculable, since net concentration  changes  are  negative.
Plant   9   is   the   only   copper   smelter  among  those
characterized.  Plants  26,  38,  and  39  are  copper-alloy
producers.   The  effluent  loadings for copper range from a
negative value to 0.01 kg/kkg for Plant 26.   Zinc  effluent
loadings  range from a negative value to 0.022 for Plant 43.
Of  further  significance,  cyanide,  mercury,  and  cadmium
loadings  were  not  apparent.   Oil  and  grease  from mold
                         91

-------
                                                          29.  CHftRKTER Of VRSTE WKTER FRCM (CLTEN MBTftL COOLING AND QUENCHING



                                                                           (Cross and/or Net  Loadings)
Company




Product
kkg/day
(ton /day)
Flow,
1/dav
(gal /day)
Constituent
Alkalinity
COD
Solids lot.il
Solids, Hiss.
Solids, Susp.
TOC
Phosphorus
Cyanide
Antimony
Arsenic
Boron
Cadninum
Chromium
Copper
Iron
Lead
Manganese
Mercury
Nickel
Zinc
Oil and Crens
PH
(a) Includes
(b) NLC = no
26 iGroai)
Intake Discharge
Cone,, Cone., Loading
mg/1 mg/1 kg/kkg (Ib/ton)
Alloy
27. i
(30)

755,000 605,600
(199,500) (160,000)

104 2.316 (4.632)

160 275.5 1.687 (3.374)



0.29 0.006 (0.012)
SF (0.040)
1.50 0.034 (0.068)
NF
NF
NF
0.30 0.007 (0.014)
,• -- 8.5 0.189 (0.378)
8.5
some equipment cooling in discharge.
loading calculable .

Intake
Cone.,
mg/1




29,500
( 7,800)

79
--
306
301
5
--
0.01
0.06
<0.01
tt.02
0.002
0.05

0.60
0.21
0.11
0.20
^.001
•U.I
,•0.1
--
7.2


38
(Net)
bv Code




43 (Gross)
Dl3Charge(a)
Cone. ,
mg/1




18,200
( 4,800)

56.67
25.0
207.3
192.63
14.67
9.33
0.183
0.057
0.1
<0.0!
0.047
<0.05

1.067
0.633
0.5
0.133
:.001
0.1
0.4
22.33
7.87


Loading
kg/kkg
Allov
9.7
(10.7)




NLC
0.047
NLC
NLC
0.012
o.ois(c)
0.0003
NLC
0.0002
NLC
0.0001
NLC

0.0001
0.0006
0.0006
NLC
NLC
0.0002
0.0007
0.042(c>



Intake
Cone . ,
(Ib/ton) mg/1








(0


(0
(0
(0

(0

(0


(0
(0
(0


(0
(0
(0










--
.094)
--
--
.024)
.036)
.0006)

.0004)

.0002) .
--
--
.0002)
.0012)
.0012)


.0004)
.0004)
.084)




Cone . ,
mg/1




75,700
(20,000)

448.8
--
U60
1020
140





0.0833
0
0.066
3.376
1.792
4.337


0.164
17.834

8.9


Discharge

Loading
kg/kkg'
Alloy
61.9
<68.2)




0.549

1.419
1.247
0.171





0.0001
NLC
0.0001
0.004
0.002
0.0053


0.0002
0.022




(Ib/ton)







(1.098)

(2.838)
(2.494)
(0.342)





(0.0002)

(0.0002)
(0.008)
(0.004)
(0.0106)


(0.0004)
(0.044)




Intake
Cone . ,
mg/1







170
23.2
1294
64
1231

0.029
0.005
0.142
.-o.ooi
2.46
0.111

0.098
<0.005
0.297
0.325
•33.0004
0.024
1.492
<\
8.3



9 (Net)
Discharge
Cone., Loading
mg/1 kg/kkg " (Ib/ton)
Copper
"45.3
(50)

3,000,000
(792,000)

182 0.795 (1.59)
11.2 NLC
1238 NLC
31 NLC
1208 NLC

0.023 NLC
0.005 NLC
0.126 NLC
<0.001 NLC
2.35 NLC
0,098 NLC

0.069 NLC
<0.007 NLC
0.223 NLC
0.372 0.003 (0.006)
<0.0002 NLC
0.019 NLC
0.821 NLC
<1 0
8.3


(c) Cross loading.
(d) Net loading.
(e) Casting
(f) NF = not
time estimated ;it 'i hours.
found .




















Source:   Plants 26 and 43,  RAPP and State  Environmental Agencies; Plants 38 and 9 sampling excursions,

-------
conveyers is present.  Lead and iron are also added  to  the
waste  water.   The concentrations in the discharge do vary.
Plants 26 and 38 cool ingots with municipal water on a once-
through basis and the discharge concentrations are less than
that  of  Plant  43,   which  recycles  part  of  the  water.
However, the loadings for Plant 43 are intermediate to those
of Plants 26 and 38.
Waste Water from Slag Granulation and Slag Milling and
Classification
Slag   covers   on  reverberatory  or  rotary  furnaces  are
generally raked-off before the furnace is tapped.  This slag
will contain a variety of  materials,  including  slags  and
fluxs  that  have  been added, rasorite (a borax flux)f soda
ash, lime, silica or glass, sand, and about 10 to 30 percent
copper or alloy.  The copper content must be recovered,  and
this  is  done  either  by melting down the entire slag in a
cupola or blast furnace or by milling  and  classifying  the
slags  into  a  waste  gangue  material  and  a  copper-rich
concentrate.

When cupolas or blast furnaces are employed to  recover  the
copper  values  from  reverberatory or rotary furnace slags,
the bulk of the copper-rich slag is normally  screened,  and
the  fine  slag  is  pelletized.   The coarse chunks and the
pellets of slag are charged into the cupola or blast furnace
along with other scrap copper, coke, and fluxes.  The charge
is melted and two products are tapped, a copper alloy  (black
copper or cupola melt) and a waste or  depleted  slag   that
contains about one to two percent copper.  The waste slag is
normally  granulated  with  water  sprays, while it is still
molten, and transported with a flow of water in a trough  or
pipe  to the slag storage area.  The water used to granulate
the slag normally goes to settling ponds and cooling towers,
and is then recirculated.  It contains some fine  solids  of
the  granulated slags and a part of the soluble constituents
of the slag.  Reliable data  on  the  composition  of  waste
water  or  circulating  water from slag quenching operations
were not available.  The composition of the  slag  quenching
water  from  one secondary smelter, Plant 9, was sampled and
the results are given in Table 30.

An alternative slag treatment method  consists  of  grinding
the  slag  and separating the copper values from the bulk of
the slag by classification methods.  Generally, the slag  is
crushed,  ground  in  ball  mills, and classified with table
concentrators to produce a copper product containing   80  to
                          93

-------
                                                      TABLE 30.   diAH/iCmi OF WAS1E Wffl-ER FRCM SLAG QUENCHING AND GKANUIATION

                                                                 OR SLAT, MIILINT, AFTER SETTLING
                                                                             (Grosa  and/or Net Loading)
Company by Code
9 (Hct)(a) 11 (GroSR)(b>

Product
kkti/day
(ton/day)
Water flow
(gal/day)
Constituent
Alkalinity
COD
Solids, rot.!]
Solids, dias.
Sol ida , aiinp.
roc
Phosphorus
Cyanide
Antimony
Arsenic
Boron
Cadmium
Copper
Chromium
Iron
Lead
Manganese
Mercury
Nickel
Zinc
Oil and Grease
pH
Intake
Cone . ,

Cone . ,
lUsi.-h.ti Hi

l.o.-uling
kn/kkn
(Ib/ton)
,'Mlt
(792,000)

170
23.2
L294
64
U'll

0.029
0.005
0.142
13.001
2.46
0.111
0.098

0.005
0.297
0.325
D.0004
0.024
1 . 492
•1


190
25.3
1620
3 3d
1284

0.031
0.004
0.111
0.001
2. 60
0.067
0.071

0.007
o.i1):?
0.399
"0.0003
0.030
0.62?
•1
8.32

1 . 32 5
0.1J9
21.589
18.013
1.510

0.0001
NLC(e>
NLC
NLC
0.001
NLC
NLC

NLC
NLC
0.0005
NLC
KLC
NLC
WLC


(2.650)
(0.278)
(43.18}
f.16.03)
(7.020)

(0.0002)



(0,001)





(0.001)





Intake
Cone . , Cone , ,
mg/1 mg/1
1) i s o h .1 r f> e

I ,o ,1 d i n R
kfc/kkg
(Ib/ton)
Intake
Cone . ,
A_l lpv_
108
(119)
545,400
(144,100)

2965
--
3900
.,
630


Sp(d)



0.11
19.79
0.120
13.0
23.0


0.35
80.35

9.8

14.976

19.695

3.182


--



0.0006
0.100
0.001
0.066
0.116


0.002
0.631



(29.95)

(39.39)

(6.364)






(0.0012)
(0.20)
(0.002)
(0.132)
(0.232)


(0.004)
(1.262)



71.33
18.333
421.3
387.67
33.67
63.3
0.293
0.053
<0.1
•35.02
0.667
0.067
12

1.833
5.333
0.467
<0.001
0.133
6,0
11.0
7.4
38 (Ne

Cone. ,
rag/1
!t) 00
DiacharRe


Loading
kg/kkg
(Ib/ton)
Alloy
9.7
(10.7)
72,670
(19,200)

104.67
22.67
6456
2953.7
3502.3
268.67
0,403
0.163
2.867
<0.02
6.0
1.683
1250

163.667
916,67
43,33
0.012
18.0
983.33
23.333
8.53

0.250
0.032
45.210
19.224
25.986
1.539
0.001
0.001
0.021
KLC
0.040
0.012
9.275

1.212
6.835
0.321
0.001
0.134
7.322
0.092


(0.50)
(0.064)
(90.42)
(38.45)
(51.97)
(3.078)
(0.002)
(0.001)
(0.042)

(0.080)
(0.012)
(18.55)

(2.424)
(13.67)
(0.642)
(0.002)
(0.268)
(14.64)
(0.184)


Intake
Cone , ,
mg/1
39 (N
let) 00

Olacharge
Cone . ,
rag/1
Loading
kg/kkg
(Ib/ton)
Alloy
43.5
(48)
662,400 617,000
(175,000) (163,000)

685


1,754
21,605

1,0





0.10

13
0.9
0.05


0.16
0
9.35

733


1,852
22 ,980

1.0





0.11

14
1.0
0.05


0.17
0
9.55

0.681


1.39
326

BLC





0.00014

0.0142
0.0014
NIC


0.00014
NLC


(1.36)


(2.78)
(652)







(0.00028)

(0.0284)
(0.0028)



(0.00028)


(a)  Slag granulation.
(b)  Slag milling.
(c)  Estimated time for granulation 6 hr/day.
(d)  NF = not found.
(e)  NLC - no loading calculable.

Source:  Plants 11 and 39 State Environmental Agencies; Plants 9 and 38  sampling  excursions.

-------
90  percent  of  the  copper  alloy  and a gangue waste slag
material containing 4 or 5 percent of the copper alloy.  The
slag gangue is discarded at the plant site  and  the  copper
concentrate is remelted in reverberatory or rotary furnaces.
Milling  and  concentrating are generally wet operations and
the waste water normally  goes  to  settling  ponds  and  is
recirculated.

The  characteristic of waste water from slag granulation and
the wet milling and classification should be similar,  since
materials  from  nearly identical sources are being treated.
Once the waste water from slag granulation has  been  cooled
to  ambient  conditions,  there  is  net expected to be much
difference between the two.  In both cases, coarse insoluble
fused slags settle rapidly to  leave  a  residual  level  of
suspended  solids.   Therefore,  characterization  is on the
supernatant water from settling tanks and/or ponds.

Reliable data on the composition of waste water or  recircu-
lating  water from slag granulation were not available.  The
composition of  circulating  water  from  slag  milling  was
available,  and this is shown in Table 30 for Plants 11, 38,
and 39.  Also  included  are  the  characteristics  of  slag
granulation  waste  water  from Plant 9.  Data for Plants 38
and 9 were obtained by sampling teams.

In the milling and classifying  of  slag  to  recover  metal
value  and  the  quenching  and  granulation of molten slag,
water contacts the glass-like refractory materials based  on
silica-sodium  borate  or  lime-silica-iron  oxide  systems.
Hydrolysis of the slags leads to  discharges  with  high  pH
values,  ranging from 9.8 to 8.3.  The other characteristics
of slag treatment waste water are high levels  of  suspended
solids  that  usually  are  reduced  by settling.  The heavy
(trace) metal components of the  slags,  which  are  usually
tied  up  as part of the oxide slag, apparently are soluble,
since  antimony,  cadmium,  copper,  chromium,  iron,  lead,
manganese,  nickel,  and  zinc  are  in the supernatant.  In
addition, boron loadings exist whenever a borax flux is used
and is usually  associated  with  slags  from  copper  alloy
production.   The  heavy(trace) metal effluent loadings from
the molten slag granulation operation  would  appear  to  be
less  than  those from the milling of cooled slag from brass
and bronze ingot producers.  However, the  effluent  loading
of dissolved salts for both types of operations is about the
same, 36 to 38 kg/kkg.

Plant   38   employs  a  closed  loop  in  the  milling  and
classifying operation, but the reservoir is  a  mixed  waste
                          95

-------
water  stream.   Samples  at  Plant  38  were  taken   before
settling of the effluent from wet milling  and  classifying,
and   this  accounts  for  the  inordinately  high loadings
obtained.  This discharge could be characterized  as   a  raw
waste  water.   After  being  mixed  with  cooling water and
settled scrubber water and being passed through  two   ponds,
the  water has characteristics of the intake water.  Oil and
grease is picked up during wet milling of slag, but  is  not
present in molten slag granulation.
Waste Water from Electrolytic Cells
Electrolytic  cells  in tank houses are used to refine anode
copper into high purity cathode copper.  The anodes are cast
in metal molds from, fire refined  copper.   The  electrolyte
solution  consists  of  demineralized  makeup  water,  copper
sulfate,  and  sulfuric  acid.    Normally,   the  electrolyte
solution  is  continuously circulated through thickeners and
filters to remove  solids  and  recycled  back  through  the
electrolytic  cells.   The  cells  operate hot, so that some
makeup water is required.  The makeup water  normally   comes
from  the  boiler condensate in the steam lines used to heat
the cells.   Most of the  makeup  water  is  generally   added
during  the daily washdown of salts,  accumulated at the tops
of the cells through evaporation.

The slimes, periodically  cleaned  out  of  the  cells,  are
filtered  out  of  the electrolyte and are normally sold for
the recovery of  precious  metals  and  rare  elements  when
present in sufficient amounts.   Otherwise,  it is recycled to
the   furnaces.    Only  Plant  1  performs  precious   metal
recovery, and the process waste water generated during  this
recovery  is very small in volume.  Plants 8, 9, and 12 sell
the slimes for their precious metal content.

In the event that the efficiency of copper metal  deposition
on   the   cathode  falls  below  that  of  the  dissolution
efficiency, the concentration of copper in  the  electrolyte
solution has built to a level,  where the conductivity  of the
solution  decreases  to less than the optimum range for good
electrical energy utilization.   In such cases, the amount of
copper in the electrolyte must be  reduced  in  one  of  two
ways.   A bleed stream is stripped of copper either by  higher
voltage    electrolysis    in   a   separate   cell    (i.e.,
electrowinning),   using  nonconsumable  lead   or   titanium
electrodes,  or it is removed by cementation with iron.  The
spent electrolyte, in either case, must be treated before it
can be discharged.
                        96

-------
Normally,  all  of  the  electrolyte is recirculated.  Waste
electrolyte resulting from spills, leaks, or repair of cells
must be treated before it is discharged.  Waste  electrolyte
is  first  treated  with  iron  to  cement  out  the copper,
neutralized, filtered, and discharged to the  holding  pond.
The  spent electrolyte may be sold and/or treated by others.
The elements, such as arsenic,  tellurium,  selenium,  etc.,
normally   associated   with   primary  copper  electrolytic
refining effluents, are usually not found in the electrolyte
from secondary copper refining, since the scrap has  already
undergone refining (when it was initially produced to remove
these  elements).   Silver,  platinum,  gold, etc., may find
their way into slimes from old  scrap.   However,  they  are
usually  present in low concentrations.  Except for Plant 1,
nickel buildup in the spent electrolyte is also kept to  low
levels,  since it too is no longer associated with copper or
copper scrap grades except through retention in  old  scrap.
Plant   1   uses  the  high  nickel  content  in  its  spent
electrolyte to produce NiS04_.

The boiler feed  water  associated  with  electrolytic  cell
refining  is  normally  demineralized  or  softened, and the
backwash water from the treatment will contain the  ions  in
the  source  water,  but  at higher concentrations.  Boilers
normally will be blown  down  daily,  and  this  water  will
contain  the  concentrated  salts  that  were  in the charge
water.

Data on the waste water from the  electrolytic  cells  after
the  treatment described above, are given in Table 31.  This
waste water would not be expected to contribute much to  the
total  water  flow through the outfall, since such discharge
occurs only during  breakdown  in  the  cell  house.   Those
plants that discard spent electrolyte precede discharge with
at  least  cementation  with  iron  to remove copper values.
Plant 8 discharges this  solution  into  a  joint  municipal
treatment  plant  after  cementation,  and  the  mixed waste
stream has a pH of 7  (see Table 11).  The high iron effluent
loading is consistent with  such  treatment  to  reduce  the
copper and acid values.

Noncontact Cooling Water
Large  amounts  of water are used at times to cool doors and
frames of furnaces, to cool power transformers  and  furnace
coils  or  inductors  in  induction furnace melting, to cool
bearings, to externally cool the ducts of baghouses used  in
air pollution control, and to cool the shells and burners of
                          97

-------
    TftBIE  34.  CHARftCIER OB W*STE W&ER FEW PUM.T RUNOFF, PIAITT 38

               Discharge to River
      Volume:   unknown (a, b). (-
-------
                         SECTION VI

             SELECTION OF POLLUTANT PARAMETERS

                        Introduction
The  waste water constituents, which have been determined to
be present in the process  waste  waters  of  the  secondary
copper  industry  in  sufficient quantities to warrant their
control and treatment, are as follows:

         Total suspended solids
         Ammonia
         Copper
         Zinc
         Oil and grease
         PH

This section provides the rationale for  the  selection,  as
well as the rejection, of pollutant characteristics for this
subcategory.
                 Rationale for Selection of
                    Pollutant Parameters
The  control and treatment technologies discussed in Section
VII describe the current practices by the industry which are
used to treat and control  the  selected  pollutants.   From
these  discussions,  it  was concluded that the discharge of
total suspended solids, heavy (trace)  metals,  and  ammonia
can  be  controlled  by  pH  adjustment and suspended solids
removal.

Setting effluent limitations on copper  and  zinc,  the  two
principal  pollutant metals in process waste waters from the
secondary copper industry, and specifying a  pH  range  will
in-turn  limit  the  other trace metals found in these waste
waters.  Such metals include aluminum, magnesium,  antimony,
cadmium,  chromium,  cobalt,  iron, lead, manganese, mercury
(through absorption), nickel, silver, and tin.   Ammonia  is
considered  as  a  significant  pollutant  parameter,  since
certain plants are controlling the  pH  of  their  discharge
with ammonia.  When this is done, the heavy metal hydroxides
are solubilized by metal ammonia complex-ion formation.

There  is  an  optimum  pH  for precipitation of each metal,
which results in its greatest reduction  by  solids  removal
                          103

-------
(settling  or  filtration).   The pH selected for the mixture
of metals associated with the secondary copper industry is a
compromise between the maximum removal of copper  and  zinc,
as  hydroxides,  and  that  suited  for  maximum  removal of
cadmium, lead, antimony, tin, and  other  metals  associated
with  the  raw scrap metal source.  Coprecipitation of these
heavy metal hydroxides with copper and zinc  hydroxide  (and
also  aluminum,  iron,  and magnesium hydroxide, if they are
present in the  waste  water)  at  a  pH  at  which  optimum
coprecipitation  occurs  is  used  in  good  water treatment
practice.  Therefore, an appropriate pH adjustment  followed
by  solids  removal  will  reduce  all  the metals to levels
consistent  with  the  best  control  technology   currently
available.  Because of the variability of the composition of
the  raw material entering the process, the consideration of
each of the metals as a significant pollutant  parameter  is
not practicable.

pH, Acidity and Alkalinity

Acidity  and  alkalinity  are  reciprocal terms.  Acidity is
produced  by  substances  that  yield  hydrogen  ions   upon
hydrolysis  and  alkalinity  is  produced by substances that
yield hydroxyl ions.  The terms "total acidity"  ana  "total
alkalinity" are often used to express the buffering capacity
of  a  solution.   Acidity  in  natural  waters is caused by
carbon dioxide mineral acids, weakly dissociated acids,  and
the  salts  of  strong  acids and weak bases.  Alkalinity is
caused by strong bases and the salts of strong alkalies  and
weak acids.

The term pH is a logarithmic expression of the concentration
of  hydrogen  ions.  At a pH of 7, the hydrogen and hydroxyl
ion concentrations are essentially equal and  the  water  is
neutral.   Lower  pH  values  indicate  acidity while higher
values indicate alkalinity.   The relationship between pH and
acidity or alkalinity is not necessarily linear or direct.

Waters with a pH below 6.0  are  corrosive  to  water  works
structures,   distribution  lines,  and  household  plumbing
fixtures and can thus  add  such  constituents  to  drinking
water  as  iron,  copper,  zinc,  cadmium,  and  lead.   The
hydrogen ion concentration can affect  the  "taste"  of  the
water.   At a low pH, water tastes "sour".  The bactericidal
effect of chlorine is weakened as the pH increases,  and  it
is  advantageous  to  keep  the pH close to 7.  This is very
significant for providing safe drinking water.

Extremes  of  pH  or  rapid  pH  changes  can  exert  stress
conditions  or  kill  aquatic  life  outright.   Dead  fish.
                           104

-------
associated algal blooms, and  foul  stenches  are  aesthetic
liabilities  of  any  waterway.   Even moderate changes from
"acceptable" criteria limits of pH are deleterious  to  some
species.   The  relative  toxicity  to  aquatic life of many
materials  is  increased  by  changes  in  the   water   pH,
Metalocyanide  complexes  can  increase  a  thousand-fold in
toxicity with a drop of 1,5 pH units.  The  availability  of
many  nutrient  substances  varies  with  the alkalinity and
aciditye  Ammonia is more lethal with a higher pH.

The  lacrimal  fluid  of  the  human  eye  has   a   pH   of
approximately  7.0  and  a deviation of 0.1 pB unit from the
norm  may  result  in  eye  irritation  for   the   swimmer.
Appreciable irritation will cause severe pain.

Total Suspended Solias

Suspended   solids   include   both  organic  and  inorganic
materials.  The inorganic components include sand, silt, and
clay.  The  organic  fraction  includes  such  materials  as
grease, oil, tar, animal and vegetable fats, various fibers,
sawdust,  hair,  and  various  materials from sewers.  These
solids may settle out rapidly and bottom deposits are  often
a  mixture  of  both  organic  and  inorganic  solids.  They
adversely affect fisheries by covering  the  bottom  of  the
stream  or lake with a blanket of material that destroys the
fish-food bottom fauna  or  the  spawning  ground  of  fish.
Deposits  containing  organic  materials  may deplete bottom
oxygen  supplies  and  produce  hydrogen   sulfide,   carbon
dioxide, methane, and other noxious gases.

In  raw  water  sources for domestic use, state and regional
agencies generally specify that suspended solids in  streams
shall  not  be  present  in  sufficient  concentration to be
objectionable  or  to  interfere   with   normal   treatment
processes.   Suspended  solids  in  water may interfere with
many industrial processes, and cause foaming in boilers,  or
encrustations  on  equipment exposed to water, especially as
the temperature rises.  Suspended solids are undesirable  in
water  for  textile  industries,  paper and pulp, beverages,
dairy  products,  laundries,  dyeing,  photography,  cooling
systems,  and  power plants.  Suspended particles also serve
as  a  transport  mechanism   for   pesticides   and   other
substances,  which  are  readily  sorbed  into  or onto clay
particles.

Solids may be suspended in water for a time, and then settle
to the bed of the stream or lake.  These  settleable  solids
discharged   with   man's   wastes   may  be  inert,  slowly
biodegradable materials, or rapidly decomposable  substances.
                         105

-------
While in suspension, -they  increase  the  turbidity  of  the
water,    reduce   lignt   penetration,   and   impair   the
photosynthetic activity of aquatic plants.

Solids in suspension are  aesthetically  displeasing.   When
they  settle  to  form sludge deposits on the stream or lake
bed, they are often much more damaging to the life in water,
and they  retain  the  capacity  to  displease  the  senses.
Solids,  when  transformed  to  sludge  deposits,  may  do a
variety of damaging things, including blanketing the  stream
or  lake  bed  and  thereby destroying the living spaces for
those benthic organisms  that  would  otherwise  occupy  the
habitat.   When  of  an  organic  and therefore decomposable
nature, solids use a portion or all of the dissolved  oxygen
available  in  the  area.  Organic materials also serve as a
seemingly inexhaustible  food  source  for  sluageworms  ana
associated organisms.

Turbidity  is  principally  a measure of the light absorbing
properties of suspended solids.  It is frequently used as  a
substitute  method of quickly estimating the total suspended
solids when the concentration is relatively low.

Ammonia

Ammonia is a common product of the decomposition of  organic
matter.   Dead  and  decaying animals and plants, along with
human and animal  body  wastes,  account  for  much  of  the
ammonia  entering  the aquatic ecosystem.  Ammonia exists in
its nonionized form only at higher pH levels and is the most
toxic in this state.  The lower the  pH,  the  more  ionized
ammonia  is  formed and its toxicity decreases.  Ammonia, in
the presence of dissolved oxygen, is  converted  to  nitrate
(NO^)   by  nitrifying  bacteria.  Nitrite (NO2), which is an
intermediate product between ammonia and nitrate,  sometimes
occurs  in quantity when depressed oxygen conditions permit.
Ammonia can exist in  several  other  chemical  combinations
including ammonium chloride and other salts.

Nitrates   are   considered   to   be  among  the  poisonous
ingredients of mineralized waters,  with  potassium  nitrate
being  more  poisonous than sodium nitrate.   Excess nitrates
cause   irritation   of   tne   mucous   linings   of    tne
gastrointestinal  tract  and  the  bladder;  the symptoms are
diarrhea and diuresis,  and  drinking  one  liter  of  water
containing 500 mg/I of nitrate can cause such symptoms.

Infant methemoglobinemia, a disease characterized by certain
specific  blood  changes and cyanosis, may be caused by high
nitrate concentrations  in  the  water  used  for  preparing
                       106

-------
feeding  formulae.   While  it  is still impossible to state
precise concentration limits, it has been widely recommended
that water containing more than 10 mg/1 of nitrate  nitrogen
(NO3-N)  should  not be used for infants.  Nitrates are also
harmful in fermentation processes and can cause disagreeable
tastes in beer.  In most natural waters,  the  pH  range  is
such  that  ammonium  ions   (NH4+) predominate.  In alkaline
waters, however, high concentrations of  un-ionized  ammonia
in undissociated ammonium hydroxide increase the toxicity of
ammonia  solutions.   In streams polluted with sewage, up to
one half of the nitrogen in the sewage may be in the form of
free ammonia, and sewage may carry up to 35  mg/1  of  total
nitrogen.  It has been shown that at a level of 1.0 mg/1 un-
ionized  ammonia,  the ability of hemoglobin to combine with
oxygen  is  impaired  and  fish  may  suffocate.    Evidence
indicates that ammonia exerts a considerable toxic effect on
all  aquatic life within a range of less than 1.0 mg/1 to 25
mg/1,  depending  on  the  pH  and  dissolved  oxygen  level
present.

Ammonia   can  add  to  the  problem  of  eutrophication  by
supplying nitrogen through   its  breakdown  products.   Some
lakes  in warmer climates, and others that are aging quickly
are  sometimes  limited  by  the  nitrogen  available.   Any
increase will speed up the plant growth and decay process.

Copper

Copper  salts  occur in natural surface waters only in trace
amounts, up to about  0.05   mg/1,  so, 'that  their  presence
generally  is the result of  pollution!  This is attributable
to the corrosive action of the water  ion  copper  and  brass
tubing,  to  industrial effluents, and frequently to the use
of copper compounds for the  control of} undesirable  plankton
organisms.

Copper  is not considered to be a cumulative systemic poison
for  humans, but it can cause symptoms  of  gastroenteritis,
with  nausea  and  intestinal irritations, at relatively low
dosages.  The limiting factor in  domestic water supplies  is
taste.    Threshold   concentrations   fl>r  taste  have  been
generally reported in the range of 1.0-t.O mg/1  of  copper,
while  as  much   as   5-7.5   mg/1  makeslthe water completely
unpalatable.
The   toxicity   of   copper   to   aquatic  organisms   varies
significantly,   not only with the speciet, but also' with the
physical   and   chemical  characteristics!  of   thei   water,
including    temperature,  hardness,   turlidity,  and  carbon
dioxide content.   In hard   water,  the  -bxicity  of  copper
                          107

-------
 salts  is reduced by the precipitation of copper carbonate or
 other  insoluble compounds.  The sulfates of copper and zinc,
 and  of  copper  and  cadmium are synergistic in their toxic
 effect on fish.

 Copper concentrations less than 1 mg/1 have been reported to
 be toxicr particularly in soft water, to many kinds of fish,
 crustaceans,   mollusks,    insects,    phytoplankton    and
 zooplankton.   Concentrations  of  copper,  for example, are
 detrimental  to  some  oysters  above  0.1  ppm.    Oysters,
 cultured  in  sea  water  containing 0.13-0.5 ppm of copper,
 deposited the metal in their bodies and became  unfit  as  a
 food substance.

 Oil and Grease

 Oil  and grease exhibit an oxygen demand.  Oil emulsions may
 adhere to the gills of fish or coat  and  destroy  algae  or
 other  plankton.   Deposition of oil in the bottom sediments
 can  serve  to  exhibit   normal   benthic   growths,   thus
 interrupting the aquatic food chain.  Soluble and emulsified
 material  ingested  by fish may taint the flavor of the fish
 flesh.  Water soluble components may exert toxic  action  on
 fish.   Floating oil may reduce the re-aeration of the water
 surface and in conjunction with emulsified oil may interfere
 with photosynthesis.  Water insoluble components damage  rhe
 plumage  and  coats  of  water  animals  and fowls.  Oil and
 grease  in  a  water  can  result  in   the   formation   of
 objectionable  surface  slicks preventing the full aesthetic
 enjoyment of the water.

 Oil spills can damage the surface of boats and  can  destroy
 the aesthetic characteristics of beaches and shorelines.

 Zinc

Occurring  abundantly  in  rocks  and  ores, zinc is readily
 refined into a stable pure metal and is used extensively for
 galvanizing, in alloys, for electrical purposes, in printing
 plates, for 'dye manufacture and for  dyeing  processes,  and
 for  many other industrial purposes.  Zinc salts are used in
 paint   pigments,    cosmetics,    Pharmaceuticals,    dyes,
 insecticides,  and  other  products  too  numerous  to  list
 herein.  Many of these s£ilts  (e. g., zinc chloride  and  zinc
 sulfate)   are  highly  soluble  in  water; hence it is to be
 expected that zinc might occur in  many  industrial  wastes.
On  the  other  hand,  some zinc salts  (zinc carbonate, zinc
oxide, zinc sulfide) are insoluble in water and consequently
 it is to be expected tha^t some zinc will precipitate and  be
removed readily in most natural waters.
                         108

-------
In  zinc  mining  areas,  zinc  has  been found in waters in
concentrations as high as 50 mg/1  and,  in  effluents  from
metal-plating works and small-arms ammunition plants, it may
occur  in  significant  concentrations.  In most surface and
ground waters, it is present only in trace  amounts.   There
is  some  evidence  that zinc ions are adsorbed strongly and
permanently on silt, resulting in inactivation of the zinc.

Concentrations of zinc in excess of 5 mg/1 in raw water used
for drinking water supplies cause an undesirable taste which
persists through conventional treatment.  Zinc can  have  an
adverse effect on man and animals at high concentrations.

In  soft  water,  concentrations of zinc ranging from 0.1 to
1.0 mg/1 have been reported to be lethal to fish.   Zinc  is
thought  to  exert  its  toxic  action  by forming insoluble
compounds with the mucous that covers the gills,  by  damage
to the gill epithelium, or possibly by acting as an internal
poison.   The  sensitivity  of  fish  to  zinc  varies  with
species, age and condition, as well as with the physical and
chemical characteristics of the water.  Some acclimatization
to the presence of zinc  is  possible.   It  has  also  been
observed  that  the effects of zinc poisoning may not become
apparent  immediately,  so  that  fish  removed  from  zinc-
contaminated to zinc-free water  (after 4*6 hours of exposure
to  zinc) may die 48 hours later.  The presence of copper in
water  may  increase  the  toxicity  of  zinc   to   aquatic
organisms,  but  the  presence  of  calcium  or hardness may
decrease the relative toxicity.

Observed values for the distribution of zinc in ocean waters
vary widely.  The  major  concern  with  zinc  compounds  in
marine  waters  is  not one of acute toxicity, but rather of
the long-term sub-lethal effects of the  metallic  compounds
and  complexes.   From  an  acute  toxicity  point  of view,
invertebrate marine animals seem to be  the  most  sensitive
organisms  tested.   The  growth  of  the  sea  urchin,  for
example, has been retarded by as little as 30 ug/1 of zinc.

Zinc sulfate has also  been  found  to  be  lethal  to  many
plants, and it could impair agricultural uses.
        Rationale for Rejection of Other Waste Water
            Constituents as Pollutant Parameters
Chemical  oxygen  demand,  COD,  is  associated with organic
materials present in the discharges.   Control  of  oil  and
grease  indirectly  controls  this  parameter.   The  use of
                          109

-------
charcoal in ingot manufacture contributes to this parameter,
but charcoal can  be  removed  along  with  other  suspended
solids.  Charcoal has some beneficial effects on waste water
because  of  its  ability to absorb pollutants, which can be
removed as part of sludge.

Cyanide, arsenic, selenium, and phenols  were  found  to  be
absent  or  of  such  low  concentrations  as  to  make them
pollutionally  insignificant.    Fluoride   was   found   in
concentrations  up  to  35  mg/1;  however,  this  is at the
practicable limit attainable by current treatment technology
in which lime addition is employed.  When lime is used, some
reduction could be  expected  along  with  suspended  solids
removal.

Calcium,  sodium,  nitrate, and chloride are usually present
as part of the dissolved salts,  for  which  no  practicable
treatment   currently   is   available  for  decreasing  the
concentrations of these constituents further.

Sulfate, phosphorus,  aluminum,  magnesium,  and  boron  are
partially  removed when lime treatment and pH adjustment are
employed for the reduction of metal pollutants.   Therefore,
as the metal loadings of zinc and copper are controlled, the
loadings of antimony, cadmium, chromium, cobalt, iron, lead,
manganese,  mercury   (through  absorption),  nickel, silver,
tin, aluminum and magnesium will be decreased.
                             110

-------
                        SECTION VII

              CONTROL AND TREATMENT TECHNOLOGY


                        Introduction

The .control and treatment technologies  that  are  currently
being  used  for  reducing  discharge of pollutants in waste
water from  contact  cooling  of  molten  metal,  from  slag
granulation, from slag milling and classifying, from furnace
exhaust  scrubbing, and from electrolytic cell operation are
discussed in this section.  The discussion includes a  range
of  treatment  alternatives  for  each  type  of waste water
stream.  Alternative control technologies that  could  limit
or eliminate the effluent originating from the processes are
identified.

In  the context of this report the term "control technology"
refers to any practice applied in order to reduce the volume
of waste water discharged.  "Treatment technology" refers to
any practice applied to a waste water stream to  reduce  the
concentration of pollutants in the stream before discharge.

As  set forth in Section VI, the constituents of waste water
from the secondary copper industry that are to be considered
as  pollutants  of  significance  and  for  which   effluent
limitations  are  to  be  recommended  are  total  suspended
solids, copper, zinc, oil and grease,  and  ammonia.   These
pollutants   in  the  discharge  water  originate  from  the
operations of wet scrubbing on melting and refining  furnace
exhausts,  slag  milling  and  classifying  to recover metal
values, molten slag quenching and granulation,  and  contact
cooling  of  molten metal.  A minor source of polluted waste
water originates from electrolytic refining cell operations.
An  effluent  limitation  for  ammonia  is  recommended   to
discourage  its  use  for pH adjustment of process water.  A
diagram illustrating those operations in which water is used
in the production of refined copper and copper alloy  ingots
is  presented  in  Figure  5.  In addition to the operations
already  cited,  water  is  used  for  equipment  and  other
noncontact  cooling  operations  and for sanitation.  Runoff
water at some plants can end  up  as  part  of  the  process
water.

The  waste  water  handling  practices currently used by the
plants surveyed are given in Table 35.  Of the 43 plants for
which information was obtained, 25  percent  of  the  plants
claim  no  discharge  of  water,  34  percent  of the plants
                         111

-------
                                                                                    Water  Source
  POTABLE
          1
  TREATMENT '
I	1
    r.
          1
I  SANITARY  I
,
           ,
r
I PRIMARY
( AND
, SECONDARY
" TREATMENT
L  _ , _ _
SPRAY
AND/OR
QUKNCH
COOLING
OF
MOLTEN
METAL









EQUIPMENT
AND
NON-
CONTACT
COOLING
OF
MOLTEN
METAL











SLAG
GRANULATION




















SLAG
MILLING
AND
CLASSIKYINC



1


                                                                                         MELTING AND  REFINING
                                                                                         FURNACE EXHAUST
                                                                                         SCRUBBING
                                                                              pH  Adjustment
                                                                              NaOH,  Ca(OH)2,NH
                   Various Combinations of Wastt'waterB  (3),©,©, and  ©
                   • re Cooled and Discharged Into Settling Tanks  or Ponds
                   from Which They May Be Discharged  or Reclrculated On
                   OccaalonB ©,©,and  (Ql  are also  Combined  and then
                   Discharged or Recycled
                                                                                         PRIMARY SOLIDS RKMOVAL
                                                                                         SETTLERS AND THICKENERS
                                                                                                                                                        Backwash
                                                                                                                           pH Adjustment
                                                                                                                           NaOH, Ca(OH)
                                                                                                                                                                   Runoff Water
                                                                                                                       Slowdown


-------
          TABLE 35.  WASTE WATER TRFATMFMT AND HANEUNK PRACTICES
                     JH TilE SECONDARY COPPER INDUSTRY
Number (Percent)                                               Number of
   of Plants                Types of Practices                  Plants

  11       25     No Discharge of Wastewater Claimed
                   Recycle	„	11
                     Settling Pond(s)	    2
                     Settling Tank(s)	    4
                     pH Adjustment,  Settling Tank,  Filtration.    2
                     Unknown (assume at least holding tank
                       that must be  cleaned periodically)...    3
  15       34     Recycled With Discharge
                   Continuously. „ 	  5
                     Settling Tank(s)	    2
                     Settling Pond(s)	    1
                     Settling Ponds  and Tanks	    1
                     pH Adjustment,  Tanks and Filtration ...    1
                   Periodically	10
                     Settling Pond(s)	    1
                     Settling Tank(s)	    7
                     Settling Ponds  and Filtration 	    1
                     Settling Tank and Pond and Filtration . .    1
  17       39     Discharge With No Recycle
                   Treated 	  6
                     Settling Tank •  •  •	    4
                     Settling Pond	    1
                     pH Adjustment,  Settling and Filtration. .    1
                   No Treatment  ....  0 ...  0	„ 11
                             113

-------
recycle with discharge either continuously or  periodically,
and 39 percent discharge with no recycle.

      Waste Water From Contact Cooling of Molten Metal

Of  the 44 plants surveyed, 38 (86 percent)  water-cooled the
cast ingots or anodes.  Two of the  plants  used  noncontact
cooling  water.   The  other four plants that air cool their
molten metal product are small -tonnage producers.

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 me smooth surface requested by
certain customers.  Ingot mold lines are quire 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 ingots1  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 water contains a small amount of metal  oxide  from
the  ingot  surface,  refractory  mold wash,  lubricants, and
dust  from  the  smelter  floor.   These  contaminants   are
observed  as  loadings  of  suspended  solids, heavy  (trace)
metals, and oil and grease.

Current treatment and control alternatives employed  by  the
industry for the reduction of water use and the reduction of
pollutants  are  diagrammed  in Figure 6.  Various levels of
technology are indicated, ranging from no  treatment  before
discharge  to  various  types  of solids removal that enable
total reuse of water either for molten metal cooling  or  in
other  process  streams.   In the diagram, the complexity of
the water treatment alternatives increases from 1, which  is
no  treatment, to 6, which can be operated with no discharge
of waste water.

Identification of Control Alternatives

The amount of waste water generated in molten metal  cooling
can  be  reduced  by  recirculation  and cooling.  If for no
other reason than economy, this is the practice used by  the
                         114

-------
               Water Source



SPRAY SPRAY
AM)/OR AMD/OR
rjl'EXCH QUITCH
f.om.INi; COOLING
OF Of
"fjf.TKS MOLTKN
MtTAL METAL






















1
SPRAY
AND/OR
QUENCH
COOLING
OF
MOLTEN
METAL
1
PRIMARY
SOI. IDS
REMOVAL

























PRIMARY
SOLIDS
REMOVAL

|
0 tud uetf







4
sludg




CLARIFICATION


1


Other
Process — ^
Water
1




















SPMY
AND/OR
QUENCH
COOLING
OF
MOLTEN
METAL
1
m-









•
COOLIMG
TOWER













SPRAY
AND/OR
(JUENCU
COOLING
OF
MOLTEN
METAL
1

»_

1 1

e9 | slu'U.' s
bl tlWl IIWI1
1 Oilier


Other
Water

MIXED
I'llOCl'.SS
WATER
RESERVOIR


MIXKI)
PROCESS
WATER
RESERVOIR








Discharge Recycle Recycle
Wdter Wattr
Or Or
Discharge Discharge








Water








MIXBn
1'ROCKSS
WATER


iiX TENDED
SIITTI.IN^;
AN'!)











1





























SPRAY
AND/OR
QUENCH
COOLING
OF .
MOLTEN
METAL


















MIXED
PROCESS
WATP.R


SETTLING
AND
COOLING





a— Other Procc'sa
Water

^


r
sludges Backwash
i
H FILTRATION










Recycle Recycle Recycle
Watur Water Water
Or Or Or
Disc large Disc large Discharge
           ©
©
6.  Current treatment and control  technology alternatives for
    waste water from contact cooling  of molten metal.

-------
industry.   Only  one  plant  (Plant  26)   discharged  water
directly from molten metal cooling, but  it  is  planned  to
recirculate  this process stream.  The amounts of pollutants
added to  the  stream  could  be  reduced  significantly  if
noncontact  cooling  were  used  instead of contact cooling.
The use of water could be eliminated if air cooling  of  the
molten metal were employed.  However, such a method would be
suited for only low tonnage producers of specialty alloys.

Air. Cooling of Molten Metal.  Air cooling of molten metal is
employed  only  by  small tonnage specialty alloy producers.
It is also  used  for  the  casting  of  blister  copper  in
graphite  molds  when such material is to be shipped or when
production of refined copper is  out  of  phase  with  blast
furnace and converter operation.

Air  cooling  is  not  employed  in  the production of large
tonnage metal for several reasons.  The casting  line  would
be inordinately long (or large), requiring a large number of
molds  to  allow  the  metal  to  cool enough to be handled.
Maintenance would be higher because of the longer  conveyer,
the  added  heat  load  on equipment and lubricants, and the
need for added blower motors.   Air  cooling  would  greatly
reduce the rate of finished metal production from levels now
possible    with   cooling   methods   using   water.    Its
applicability, except in special cases, is doubtful.

Honcontact Cooling of Molten Metal.  Refined  copper  shapes
such  as  billets  and  cakes  and  partially refined copper
(anodes and ingots)  are  solidified  by  noncontact  cooling
through  the molds.   This is also true for some copper alloy
ingot  production.   However,  in  both  cases  the  current
practice requires that the metal be finally contact quenched
with  additional  water to permit handling at the end of the
casting line.  If only noncontact cooling were employed, the
quantity and types of pollutants added to the cooling  water
would  be  reduced  from those added during contact cooling;
however,  all  other  conditions  remaining  constant,   the
production  rate  would be reduced from present levels.  The
effluent from noncontact cooling can be recirculated with  a
minimum  of  treatment  and would require only makeup  water
and a bleed stream to limit salt  (dissolved solids)  buildup
that could plug water passages.  The pollutant loading would
not   be  expected  to  be  different  from  those  loadings
determined for other noncontact  cooling  operations  or  as
makeup   water for other plant operations.  Such utilization
would  require  increased   water   storage   capacity   and
recirculation capability, as well a longer or larger casting
line.   The  complete  conversion  of the entire industry to
                         116

-------
noncontact cooling of metal would not be practical since  it
would require extensive retrofitting.

Recirculation   After Treatment.   The  practice of treating
and recirculating contact cooling water to limit  water  use
and  discharge  is  practiced  by  59  percent of the plants
surveyed.  The pollutant  loadings  resulting  from  contact
cooling  of molten metal are minor relative to other process
streams,  and  with  solids  removal  by   settling   and/or
filtration,  the  water  can  be  reused, with makeup  water
being added to replace the amount evaporated.  The volume of
the discharge can be reduced  to  no  discharge  of  process
waste  water  or  to  very  low  levels, even in cases where
rainwater runoff enters the reservoir used  to  contain  the
water (Plant 39, Table 27).

Control alternatives illustrated in Figure 6 as Alternatives
5  and  6  (with slight variations) are used by six of the 12
plants visited  in  this  survey.   The  most  sophisticated
installations  required  for  reuse  are storage pond and/or
cooling tower capacity, associated plumbing, sand filters, a
reservoir,  and  capability  for  backwashing  of   filters,
Maintenance would primarily be in the area of sludge removal
every  six months.  Pump and filter maintenance requirements
are claimed to be negligible.  The advantage of  Alternative
6  is  that  in the event of flooding due to heavy rain, the
discharge  would  be  one  that  is  settled  and  filtered.
Ordinarily  no  water is discharged from the closed circuit.
The system, being an end-of-pipe type of treatment for mixed
process waste waters which upgrades the water for reuse,  is
suited  for  treatment of waste water from slag granulation,
slag milling and classifying, and noncontact cooling as well
as that from contact cooling of molten metal.
Identification of Treatment Alternatives

The waste water from the contact  cooling  of  molten  metal
requires  treatment  to  reduce  the  pollutants  of oil and
grease and suspended solids, as well  as  pH  adjustment  to
reduce  the  heavy  (trace)  metals in solution.  This holds
true for  once-through  and  recirculated  water  use.   The
adjustment  of  pH  can come from the addition of an alkali,
such as sodium  hydroxide  or  lime.   The  water  may  also
increase  in  pH  if  waste  water  from slag granulation is
combined with the contact  cooling  water,  because  of  the
hydrolysis  of some of the constituents of the alkaline slag
generated during fluxing.  In copper alloy  production,  ash
left  after  charcoal  placed  on the ingot has burned away,
also hydrolyses to increase the pH  of  the  cooling  water.
                         117

-------
For  reasons  cited  earlier, ammonia should not be employed
for pH adjustment.

The effectiveness of Alternative's 3, 4, and  5  (Figure  6)
for  the  reduction  of the pollutant parameter loadings for
suspended solids, copper, zinc,  and  oil  and  grease  from
those  calculated  for  a  once  through  operation  (1)  is
indicated in Table,36.  There is reasonable  correlation  of
reduced  loadings  with  the level of treatment. The loading
levels for Alternative 5 are exceptionally low  because  the
discharge  from Plant 39 was estimated to be only the amount
of runoff in excess of that lost by evaporation and to be  a
relatively  small flow.  Alternative 6 illustrated in Figure
6, is used by Plant 10, and  no  discharge  of  waste  water
occurs  except when runoff water is in excess of evaporation
{no analyses available).

      Waste Water From Slag Quenching and Granulation

Slag  covers  on  reverberatory  or  rotary   furnaces   are
generally raked off before the furnace is tapped.  This slag
will  contain  a  variety of materials including rasorite (a
borax flux), soda ash, lime, silica sand, and up to about 30
weight percent copper or alloy.  The copper content of  this
slag must be recovered.

To aid in the recovery, molten slags raked from the furnaces
are  quenched  with  high  velocity  water  jets, which also
granulate the material to ease handling.  The water used for
the granulation of reverberatory or a rotary  furnace  slags
drains from the slag into a pond or basin for settling.  The
drained slag can then be processed in one of two ways:

      (1)  The slags are comminuted by grinding in
           ball mills, screened, and the metal
           value separated from the slag by table
           classification.
      (2)  The granulated slags, which may originate
           from dry crushing as well as from water
           granulation, along with other low-grade
           copper scrap, are charged into a cupola
           or blast furnace.  Aside from molten
           alloy, molten slag is also obtained.  This
           depleted (waste) slag is normally
           granulated with water sprays while it
           is still molten and transported with
           a flow of water in a trough or pipe to
           a slag storage area.  The water used
           to granulate the slag goes to settling
           ponds or cooling towers and is usually
           recirculated.
                          118

-------
           TABLE 36.   EFFECTIVENESS OF THE TREATMENT ALTEPNRT3VES FOR
                      WASTE WZiTER FRCM MOLTEN MTTTAL COOLING


Loading
, kg/kkg metal produced (or lb./
Treatment Alternative
Pollutant
Parameter
Susp. solids
Cadmium
Copper
Lead
Mercury
Nickel
Zinc
PH
Table Referenced
1
Plant
26
1.69
NF(a)
0.010
0.034
NF
NF
00007
8.5
V-21
3
Plant
38
0 = 012
NLC
OoOOl
0.006
NR
0.0002
0=0007
7.9
V-21
Plant
43
0.171
NLC
00004
0.0053
NR
0.002
0.022
8.9
V-21
4
Plant
12
0.126
NR(C)
0.0028
0.0042
NR
0.00021
0,0078
8.3
V-9
1000 lb)
5
Plant
39
000056
3 x 10"7
1.7 x 10"5
4,4 x 10~6
6 x 10"9
NR
7 x 10~6
8.9
V-18
(a) NF - not found.
(b) NLC = no loading calculable.
(c) NR = not reported in  analytical data.
                          119

-------
The waste water from both copper-rich slag and depleted slag
granulation contains some fine solids of the granulated slag
and  part of the soluble constituents of the slag.  Normally
the pH of the waste  water  is  between  8  and  10  due  to
hydrolysis of the basic metal oxides present in the slag.

Of  the  44 plants surveyed, eight  (18 percent) use water to
quench and granulate slags.  Only   four  of  the  37  copper
alloy producers (11 percent) quench copper-rich slags, while
four  of the seven cathode copper producers (57 percent) use
water for this purpose on  depleted  slags.   The  remaining
copper alloy producers either air cool slags or ship them in
the  form  of  cast slag pots to large scale processors, **ho
treat the material for metal recovery  in  cupola  or  blast
furnaces.   The  depleted  molten   slags  from  these latter
recovery operations are, however, granulated with water.

The current control and  treatment  technology  alternatives
for  waste  water  from  slag  quenching and granulation are
illustrated in Figure 7.  The  simplest  is  Alternative  1,
which  represents heaping the slag  slurry on a pile with the
waste water draining to a discharge.  This is  not  done  by
any  of the plants visited.  Such a stream was characterized
by a  sample  team,  however.   Alternatives  2,3,4,  and  5
illustrate   varying   degrees   of  treatment  and  control
technology for solids  removal.   Alternatives  3,4,  and  5
will, in effect, treat the waste water to a quality suitable
for  recycle.   Alternative  3  is  being  operated  in a no
discharge mode by Plant 10 when evaporation exceeds  runoff.
Alternatives 4 and 5 bleed part of  the waste water stream.
Identification of Control Alternatives

The  amount  of  waste water generated in slag quenching and
granulation can be  reduced  with  recirculation.   Such  an
approach  is  being  employed by the industry.  Since excess
water is needed to quench the slag and to form and transport
a slurry, the water could  not  be  effectively  metered  to
reduce  the  amount used or discharged.  The use of water to
granulate slags to make  them  easier  to  handle  and  make
disposal  more  convenient  could be eliminated if the slags
were collected in slag pots and cooled in  the  air.   Those
slags  with high levels of solid-metal value would then have
to be crushed so that they can be charged into hammer  mills
or  directly  into ball mills for wet milling operations.  A
lesser amount of crushing will be required if the slag is to
be charged into a cupola or blast furnace for the purpose of
                         120

-------
                                  TZT
0
                                       C "0 O
                                       si i ri
                                       rt O 3"
e


^
r
i
_ t
*
SB M -B £ -0 £

> !« m T (n
t-1 >< to



^— 1





? S B £

H




-






.


0
.^ 	

,

c
<5 o
«; o
•z,
o

%—

n O 33
•X C- 1-1
f O P
r •-;



r. >-o «
> 3 P! >
x P: o
H
O





-------
recovering metallic copper value.  The molten depleted slags
formed during blast or cupola  furnace  operation  could  in
turn  be  cast into pots for ultimate disposal.  Granulated,
depleted slag is sold by some  of  the  smelters  and  wpuld
require continued use of water for its production.

Air  Cooling  and Mechanical Size Reduction.  Slag covers on
reverberatory or rotary furnaces  are  generally  raked  off
before  the  furnace  is  tapped.   The  slag will contain a
molten mixture of a variety of  materials,  including  slag-
occluded  metal  and  flux materials that have been added to
the melting furnace.

Copper-Rich Slag.  A common practice  used  by  most  copper
alloy  producers to eliminate the use of water is to collect
this copper-rich slag in inverted  cone-shaped  thick  metal
pots about one meter (1.1 yard)  or larger  in diameter.  The
slag  is  cooled  in the pot without the use of water and is
eventually transported in the pot to  the  copper-rich  slag
storage  pile,  where  it is dumped.  Slag from this pile is
also treated to reclaim the  copper  values  either  by  the
smelter  or  it  is sold to another secondary copper smelter
for reclaiming.  Therefore, the use of air cooling  followed
by  mechanical  size  reduction  as a control alternative to
copper-rich slag quenching would seem warranted.

Copper-Poor Slag.  Another source of slag  is  generated  by
the industry.  This slag, which is copper-poor, is generated
by some smelters that reclaim the metal content of their own
slag and purchased copper.  This is done by melting the slag
along  with other copper-base scrap and residues in a cupola
or  a  blast:  furnace.    The  copper-rich  slag,  which   is
relatively  friable,  is  crushed and screened and the fines
pelletized.  The course chunks and the pelletized  slag  are
charged  into  the  cupola  or blast furnace.  The charge is
melted and two products are tapped, a copper alloy and waste
or depleted slag that contains 1 to 2 percent  copper.   The
waste slag is normally granulated with water spray.

Waste  water  from  depleted  or  waste  slag  quenching and
granulation could be  completely  eliminated  by  collecting
this  molten,  depleted slag in inverted, cone-shaped, thick
metal pots while it is being tapped from the  furnace.   The
slag  would be cooled in the pots, transported in the pot to
the waste slag pile, and dumped.  It should  be  noted  that
none of the plants visited handled their depleted slags from
cupolas  or blast furnaces in slag pots.  Depleted slags are
granulated with water to make them easier to  transport  and
handle.   In  this  form  they  have more end uses than just
landfill.  In addition the granulated slags may be easier to
                         122

-------
dispose of as ballast or fill than the large  chunks  formed
in  slag  pots.   Therefore,  the  use  of  air  coaling and
mechanical size reduction as an alternative to depleted slag
granulation is not warranted.

Recirculation  After	Treatment.  Recirculating waste  water
from  slag  quenching  and  granulation  after treatment for
solids removal is practiced by all of the  plants  presently
granulating  slags.   There  are variations in the extent of
solids removal  and  the  need  for  discharge.   These  are
discussed  in  more  detail  in  the  treatment alternatives
section  that  follows.   Of  the  control   and   treatment
alternatives  given  in  Figure  7, Alternative 3 provides a
means of treating all of the waste water for total  recycle.
Solids  are  removed  by  settling and filtration before the
water is recycled for reuse for slag granulation  and  other
processes.   This  treatment  alternative  was  discussed in
detail in the previous section of the  report  dealing  with
contact cooling water.

Identification of Treatment Alternatives

The  waste  water from molten slag quenching and granulation
requires treatment to reduce suspended solids and associated
heavy metals.  The pH of the waste water has been  found  to
be  between  8  and  10,  which aids in the reduction of the
soluble heavy metals.  In most operations, the pH reaches an
equilibrium value due to hydrolysis of  basic  metal  oxides
and  salts  in  the  slag.   In  mixed  process  waste water
operations, sufficient reaction occurs to maintain a pH near
8.5 for the mixed stream.  If needed, the pE  of  the  mixed
process  waste  water  is  usually  adjusted  with  lime  or
caustic.

Solids removal  technology,  illustrated  in  Figure  7,  is
usually by means of settling and cooling towers  (Alternative
5}, mixed process stream settling  (Alternative 4), and mixed
process stream settling and filtration  (Alternative 3).  The
effectiveness   of  these  alternative  treatments  for  the
reduction of pollutant parameters is indicated in Table  37.
The  raw  waste  water from slag granulation was sampled and
characterized  in Plant 9  (see Table 30).  No loadings  could
be calculated because the discharge concentrations were less
than  the  intake  concentrations.  The intake warer used in
the quenching operation was recycled,  mixed  process  waste
water   contained   in  a  lagoon.   For  this  reason,  the
concentrations of the slag quenching waste water  are  given
to  enable  a  qualified  comparison  to be made.  In such a
situation, where large amounts of steam are evaporated, some
concentration of pollutants should occur; however, since the
                             123

-------
slags as a source of black  copper  for  the  production  of
fire-refined  copper  or  anodes  for  electrolytic refining
operations.

The current control and  treatment  technology  alternatives
used  for  waste  water from slag milling and classification
are shown schematically  in  Figure  8*   Alternative  1  £s
direct  discharge  of the effluent without any treatment and
is not practiced by any of  the  plants  surveyed.   Primary
solids removal before discharge  (Alternative 2)  is practiced
by one plant.  The remaining plants recycle the slag milling
waste   water  after  various  degrees  of  solids  removal.
Alternative 5 is in an entirely closed-loop with a  constant
reuse of the water and is practiced by Plant 11.

Identification of Control Alternatives

Recovery  of  the  metallic  content of copper-rich slags is
technically possible without the use of water.   This  could
be  done  by  dry milling.  It is being accomplished by melt
agglomeration in a blast or rotary furnace.  The waste water
discharge from wet milling  operations  can  be  reduced  or
eliminated   by  recirculation  of  the  waste  water  after
treatment.

Dry  Milling and Concentrating.  Slags can be milled dry and
concentrated by screening out the  coarser,  more  malleable
metal  fraction  from  the  finer, more friable slag oxides.
This approach is not being  used  by  the  secondary  copper
industry,  but  is  being  used  in  the  secondary aluminum
industry.  The operation would be expected to  be  extremely
dusty  and  would  require extensive dust control equipment.
Because of the composition of the slag, the dust could  pose
an added occupational hazard.  Dry milling and concentrating
is not a currently viable alternative to wet milling because
of   the   lack  of  technological  development  within  the
secondary copper industry.

Recovery of Metal by Melting.  An  approach  that  is  being
employed  to  recover  the metallic content from copper-rich
slags by the processors of large volumes of  such  materials
is  by  melting,  either  in blast or cupola  furnaces or in
specially designed rotary furnaces (specifically  Plant  9).
In  such operations, the large pieces of slag are reduced in
size by impacting with a heavy  weight   (crane  and  wrecker
ball) .   The  fine  portion  of  the  slag  is pelletized by
grinding damp, fine slag and forming pellets in one  of  two
ways:

      (1)  Pellets are formed in a rotating disk
                              126

-------
HILLING
  r._J
                          PHIMAKY

                          SOI. 111S

                          KLMOVAL
                      bluds..'
  ©
DiuclxarKe



  ©
                                                iludge
                                                          Discharge
                                                                                     Discharge
©
©
                           Firure 8.   Current cor.tir?!  ar-.:! tro^tr^ent technolfxry alternatives
                                        for wasto victor  fron  si?--* m.i llln^ arxl  classification.

-------
                   TABIE 38.  KFn;eriVFM;ss or CCNTROI. AND TTOVTMEWT TECHNOIJOGY ALTERNATIVES
                              FOR i5\STE W&IEK PRCK SLAG MILLING AIJD CLASSIFICATION
CO
O
Loadings ,
Pollutant
Parameters
Susp. solids
Cadmium
Copper
Lead
Mercury
Nickel
Zinc
Oil & grease
pll
Table
Referenced

1.
Plant
38(a)
25.99
0.012
9.275
6.835
0.001
0.134
7.322
0.092
8.53
V-22



Plant
39 (a)
326
NR(d)
0.11
0.0014
NR
NR
0.00014
NLC
9.55
V-22

kg/kkg metal produced (or lb/1000 lb aietal)
Treatment Alternative
2
Plant
11
3.182
0.006
0.10
0.116
NR
0.002
0.631
NR
9.8
V-19

3
Plant
43 (b)
1.247
NR
0.004
0.0053
NR
0.0002
0.022
NR
8.24
VII-6(a>

4
Plant Plant
0.266 Recycle,
seasonal
discharge
0.095
0.042
NLC
-------
                                                 Water Source
Dlj chirg*
                        Sludge
                 Recycle Water
                      Or
                   Discharge
                                                                      Othgr
                                                                      Process
                                                                      Water
                                                       Process
                                  „,  .
                                  Sludge
                                                   Backwash
Recycle Water
    Or
  Discharge
Bleed  Recycle Water
         Or
       Discharge
                                                                                                Sludge
                                                                                                  Slowdown
              Fioure 7.  Current  control  arc! tr-amer.t  techrx-logy alternatives
                            for v.-aste water  frcr n.1 -.•;  mx;r>chir.g ard  oranulaticn.

-------
recovering me-tallic copper value.  The molten depleted slags
formed during blast or cupola  furnace  operation  could  in
turn  be  cast into pots for ultimate disposal.  Granulated,
depleted slag is sold by some  of  the  smelters  and  would
require continued use of water for its production.

Air  Cooling  and Mechanical Size Reduction.  Slag cover's on
reverberatory or rotary furnaces  are  generally  raked  off
before  the  furnace  is  tapped.   The  slag will contain a
molten mixture of a variety of  materials,  including  slag-
occluded  metal  and  flux materials that have been added to
the melting furnace.

Copper-Rich Slag.  A common practice  used  by  most  copper
alloy  producers to eliminate the use of water is to collect
this copper-rich slag in inverted  cone-shaped  thick  metal
pots about one meter (1.1 yard)  or larger  in diameter.  The
slag  is  cooled  in the pot without the use of water and is
eventually transported in the pot to  the  copper-rich  slag
storage  pile,  where  it is dumped.  Slag from this pile is
also treated to reclaim the  copper  values  either  by  the
smelter  or  it  is sola to another secondary copper smelter
for reclaiming.  Therefore, the use of air cooling  followed
by  mechanical  size  reduction  as a control alternative to
copper-rich slag quenching would seem warranted.

Copper-Poor Slag.  Another source of slag  is  generated  by
the industry.  This slag, which is copper-poor, is generated
by some smelters that reclaim the metal content of th-ir own
slag and purchased copper.  This is done by melting the siag
along  with other copper-base scrap and residues in a cupola
or  a  blast  furnace.    The  copper-rich  slag,  which   is
relatively  friable,  is  crushed and screened and the fin^s
pelletized.  The course chunks and the pelletizea  slag  are
charged  into  the  cupola  or blast furnace.  The charge is
melted and two products are tapped, a copper alloy and waste
or depleted slag that contains 1 to 2 percent  copper.   The
waste slag is normally granulated with water spray,

Waste  water  from  depleted  or  waste  slag  quenching and
granulation could be  completely  eliminated  by  collecting
this  molten,  depleted slag in inverted, cone-shaped, thick-
metal pots while it is being tapped from the  furnace.   The
slag  would be cooled in the pots, transported in the pot to
the waste slag pile, and dumped.  It should  be  noted  that
none of the plants visited handled their depleted slags from
cupolas  or blast furnaces in siag pots.  Depleted slags are
granulated with water to nake them easier to  transport  and
handle.   In  this  form  they  have nore end uses than just
landfill.  In addition the granulated slags may be easier to
                         122

-------
dispose of as ballast or fill than the large  chunks  formed
in  slag . pots.   Therefore,  the  use  of  air  cooling and
mechanical size reduction as an alternative to depleted slag
granulation is not warranted.

Recirculation  After	Treatment.   Recirculating waste  water
from  slag  quenching  and  granulation  after treatment for
solids removal is practiced by all of the  plants  presently
granulating  slags.   There  are variations in the extent of
solids removal  and  the  need  for  discharge.   These  are
discussed  in  more  detail  in  the  treatment alternatives
section  that  follows.   Of  the  control   and   treatment
alternatives  given  in  Figure  7, Alternative 3 provides a
means of treating all of the waste water for total  recycle.
Solids  are  removed  by  settling and filtration before the
water is recycled for reuse for slag granulation  and  other
processes.   This  treatment  alternative  was  discussed in
detail in the previous section of the  report  dealing  with
contact cooling water.

Identification of Treatment Alternatives

The  waste  water from molten slag quenching and granulation
requires treatment to reduce suspended solids and associated
heavy metals.  The pH of the waste water has been  found  to
be  between  8  and  10,  which aids in the reduction of the
soluble heavy metals.  In most operations, the pH reaches an
equilibrium value due to hydrolysis of  basic  metal  oxides
and  salts  in  the  slag.   In  mixed  process  waste water
operations, sufficient reaction occurs to maintain a pH near
8.5 for the mixed stream.  If needed, the pK  of  the  mixed
process  waste  water  is  usually  adjusted  with  lime  or
caustic.

Solids removal  technology,  illustrated  in  Figure  7,  is
usually by means of settling and cooling towers  (Alternative
5), mixed process stream settling  (Alternative 4), and mixed
process stream settling and filtration  (Alternative 3).  The
effectiveness   of  these  alternative  treatments  for  the
reduction of pollutant parameters is indicated in Table  37.
The  raw  waste  water from slag granulation was sampled and
characterized in Plant 9  (see Table 30).  No loadings  could
be calculated because the discharge concentrations were less
than  the  intake  concentrations.  The intake water used in
the quenching operation was recycled,  mixed  process  waste
water   contained   in  a  lagoon.   For  this  reason,  the
concentrations of the slag quenching waste water  are  given
to  enable  a  qualified  comparison  to be made.  In such a
situation, where large amounts of steam are evaporated, some
concentration of pollutants should occur; however, since the
                             123

-------
            TABLE 37.  EFFECTIVENESS OF TREATMENT ALTERNATIVES
                       FOR V&STE VJKCER FRai SLAG QUENCH AND
                       GRANULATION

Loading
, kg/kkg (cone, mg/1) metal produced (or Ib/
Treatment Alternative 1000 Lb)
Pollutant
Parameter
Susp. solids



Cadmium

Copper

Lead

Mercury

Nickel


Zinc

1
Plant
9
3.51
(1284)

(a)
NLC
(0.067)
NLC
(0.071)
NLC
(0.192)
NLC
«0.003)
NLC
(0.03)

NLC
(0.622)
4
Plant
39
0.0056
(64)

-7
3 x 10 '
(0.004)
1.7 x 10"3
(0.20)
4.4 x 10~6
(0.05)
6 x 10~9
(0.0007)
NR

-6
7 x 10
(0.080)
523
Plant Plant Plant
12 17 10
0.126 Recycled, Recycled,
(12) no dis- seasonal
charge discharge
(b)
NR

0.0028
(0.27)
0.0042
(0.04)
NR

0.0021
(0.02)

0.0078
(0.74)
Oil and grease
pH
  Table
    Referenced
                   NLC
           NR
           NR
                       .,3
V-22
V-18
(a) NLC = rfo loading calculable.
(b) NR  = not reported in analytical data.
                           124

-------
waste water percolates through the slag pile, some reduction
of pollutants might occur on the surface and interstices  of
the  granulated  slag.   There  are  no  analytical  data to
substantiate this, but it would appear to be plausible.

In Alternative 4, in which a periodic discharge occurs  when
rain-water  accumulation  exceeds  evaporation, the apparent
loadings are very low because the daily discharge volume was
estimated from annual data.  For  comparison,  however,  the
concentrations   of   the   pollutant  parameters  are  also
presented  to  illustrate  the  values  in  the   discharge.
Alternative  5,  in  which the waste water undergoes primary
solids removal followed by a cooling tower that  requires  a
bleed stream discharge, is intermediate in its effectiveness
in removal of the pollutant parameters cited.

      Waste Water From Slag Milling and Classification

Copper-rich  slag that has been granulated or cast into slag
pots is processed by wet grinding and classification methods
to recover metal values.  Generally, the copper-ricn slag is
crushed, ground in ball mills, and screened  and  classified
with   table  concentrators  to  produce  a  copper  product
containing 80 to 90 percent of the copper alloy and a gangue
containing about 4 to 5 percent of copper alloy.   The  slag
gangue  (tailings) is discarded and the copper concentrate is
remelted  in  reverberatory or rotary furnaces.  The milling
and concentrating are generally wet operations.

A large flow of water is used in the  concentrating  of  the
slags.   The water will contain suspended solids, because of
the fine product produced during milling, and a  portion  of
the  soluble constituents of the slag.  The  waste water goes
to a  settling  pond  and  is  recycled  by  most  companies
performing slag milling and classifying.

The  waste  water from the milling of copper-rich slag has  a
high pH due to hydrolysis of the basic metal oxides  derived
from  the  melting furnace flux contained in the slag  cover.
It also contains suspended solids and soluble  heavy   metals
that are present in the slag.

Only  six   (14  percent)  of  the 44 plants  surveyed process
copper-rich slags by wet milling and all are  copper   alloy-
ingot producers.  Of  the remaining 38 plants, 15 use furnace
processes for the recovery of copper alloy metal from  slags.
The  rest   (23)  sell  these slags to other  plants for their
recoverable metal content.  Refined copper producers usually
have the capability to treat such slags in a blast  furnace,
and  purchase  much of this material.  These plants use such
                           125

-------
slags as a source of black  copper  for  the  production  of
fire-refined  copper  or  anodes  for  electrolytic refining
operations.

The current control and  treatment  technology  alternatives
used  for  waste  water from slag milling and classification
are shown schematically  in  Figure  8.   Alternative  1  is
direct  discharge  of the effluent without any treatment and
is not practiced by any of  the  plants  surveyed.   Primary
solids removal before discharge (Alternative 2)  is practiced
by one plant.  The remaining plants recycle the slag milling
waste   water  after  various  degrees  of  solids  removal.
Alternative 5 is in an entirely closed-loop with a  constant
reuse of the water and is practiced by Plant 11.

Identification of Control Alternatives

Recovery  of  the  metallic  content of copper-rich slags is
technically possible without the use of water.   This  could
be  done  by  dry milling.  It is being accomplished by melt
agglomeration in a blast or rotary furnace.  The waste water
discharge from wet milling  operations  can  be  reduced  or
eliminated   by  recirculation  of  the  waste  water  after
treatment.

Dry  Milling and Concentrating.  Slags can be milled dry and
concentrated by screening out the  coarser,  more  malleable
metal  fraction  from  the  finer, more friable slag oxides.
This approach is not being  used  by  the  secondary  copper
industry,  but  is  being  used  in  the  secondary aluminum
industry.  The operation would be expected to  be  extremely
dusty  and  would  require extensive dust control equipment.
Because of the composition of the slag, the dust could  pose
an added occupational hazard.  Dry milling and concentrating
is not a currently viable alternative to wet milling because
of   the   lack  of  technological  development  within  the
secondary copper industry.

Recovery of Metal by Melting.  An  approach  that  is  being
employed  to  recover  the metallic content from copper-rich
slags by the processors of large volumes of  such  materials
is  by  melting,  either  in blast or cupola  furnaces or in
specially designed rotary furnaces (specifically  Plant  9).
In  such operations, the large pieces of slag are reduced in
size by impacting with a heavy  weight   (crane  and  wrecker
ball).   The  fine  portion  of  the  slag  is pelletized by
grinding damp, fine slag and forming pellets in one  cf  two
ways:

      (1)  Pellets are formed in a rotating disk
                             126

-------
              iLLim;
to
-J
                                                                    Discharge
                                                                                              Discharge
                                                                                                                          Sludqa
              CD
©
                                      Fioure 8.  Current control  arr1. tr'-^tpent technolfyn/  alternatives
                                                  for '-'asto v^.t-jer  from. s.U''~ r-.illin^ and classification.

-------
                   TABI£ 38.  UTTCTIVENLSS or CCNTROL AND TREATMENT TECIE«JQGY ALTERNATIVES
                              FOR \5\STE WATER FRCK SLAfi MILLING AiJD CLASSIFICATION
LJ
O
Loadings ,
Pollutant
Parameters
Susp. solids
Cadmium
Copper
Lead
Mercury
Nickel
Zinc
Oil & grease
PH
Table
Referenced

1.
Plant
38 (a)
25.99
0.012
9.275
6.835
0.001
0.134
7.322
0.092
8.53
V-22



Plant
39 (a)
326
NR
0.11
0.0014
NR
NR
0.00014
NLC
9.55
V-22

kg/kkg metal produced (or lb/1000 lb metal)
Treatment Alternative
2
Plane
11
3.182
0.006
0.10
O.H6
NR
0.002
0.631
NR
9.8
V-19

3
Plant
43 (b)
1.247
NR
0.004
0.0053
NR
0.0002
0.022
NR
8.24
VII-6(a>

4
Plant Plant
0.266 Recycle,
seasonal
discharge
0.095
0.042
NLC
0.001
0.047
0.087
7.4


5
Plant
ll(c)39(b)
Recycle,
no
discharge









           (a)  Plants 10, 38, and 39 do not discharge normally;
                Data on Plant 38 from sampling excursion.

           (b)  Mixed process wastewater.

           (c)  Plant 11:  data for Alternative 3 taken before Alternative 5 technology installed

           (d)  Not recorded in analytical  data,.

           (e)  NLC - no  loading calculable.

-------
                             Water Source








to













SLAG
QUENCH
AJJD
GRANULATION












1












1
Dli ch«rga























SLAG
QUENCH
AND
GRANULATION















PRIMARY
SOLIDS
REMOVAL







*





















Sludge



•




Recycle Water


Or

Discharge











1
sue
QUENCH
AND
GRANULATION

SLAG






QUENCH
AND


(JKANUIATIOtJ

MIXED
PKCCE'JS
WATER-
RESERVOIR

PRIMARY
SOLIDS
RFMO'ML

1
Process 	 I
Water f




MIXED
PROCESS
^_ Other Process WATER-
Water PRIMARY
~* SO LI OB
,*J „, , ._ . REMOVAL
eludga Sludge *
Backwash |
*— | FILTRATION] 	 ' J
i
1
1
1
1
*
L_












— H


















»


1
















SLAG
QUENCH
AND
UUASULATlOti













PRIMARY
SOLIDS
REMOVAL

T~
Sludge



' .
Recycle Water Bleed Recycle Water
Or
Discharge





Di

Or
scharge











COOLING

i


















Blowdowo Recycle



Water
Or
Discharge
Fioure  7.   Current control,  arc treatment  techrjc-lxxy alternatives
            for waste water  frcr ^.V1:; Blenching ^rd arariulation.

-------
recovering metallic copper value.  The molten depleted slags
formed during blast or cupola  furnace  operation  could  in
turn  be  cast into pots for ultimate disposal.  Granulated,
depleted slag is sold by some  of  the  smelters  and  woulci
require continued use of water for its production,

Air  Cooling  and Mechanical Size Reduction.  Slag covers on
reverberatory or rotary furnaces  are  generally  raked  off
before  the  furnace  is  tapped.   The  slag will contain a
molten mixture of a variety of  materials,  including  slag-
occluded  metal  and  flux materials that have been added to
the melting furnace.

Copper-Rich Slag.  A common practice  used  by  most  copper
alloy  producers to eliminate the use of water is to collect
this copper-rich slag in inverted  cone-shaped  thick  metal
pots about one meter (1.1 yard)  or larger  in diameter.  The
slag  is  cooled  in the pot without the use of water and is
eventually transported in the pot to  the  copper-rich  slag
storage  pile,  where  it is dumped.  Slag from this pile is
also treated to reclaim the  copper  values  either  by  the
smelter  or  it  is sold to another secondary copper smelter
for reclaiming.  Therefore, the use of air cooling  followed
by  mechanical  size  reduction  as a control alternative to
copper—rich slag quenching would seem warranted.

Copper-Poor Slag.  Another source of slag  is  generated  by
the industry.  This slag, which is copper-poor, is generated
by some smelters that reclaim the metal content of their own
slag and purchased copper.  This is done by melting the slag
along  with other copper-base scrap and residues in a cupola
or  a  blast  furnace.    The  copper-rich  slag,  which   is
relatively  friable,  is  crushed and screened and the fines
pelletized.  The course chunks and the pelletized  slag  are
charged  into  the  cupola  or blast furnace.  The charge is
melted and two products are tapped, a copper alloy and waste
or depleted slag that contains 1 to 2 percent  copper.   The
waste slag is normally granulated with water spray.

Waste  water  from  depleted  or  waste  slag  quenching and
granulation could be  completely  eliminated  by  collecting
this  molten,  depleted slag in inverted, cone-shaped, thick
metal pots while it is being tapped from the  furnace.   The
slag  would be cooled in the pots, transported in the pot to
the waste slag pile, and dumped.  It should  be  noted  that
none of the plants visited handled their depleted slugs from
cupolas  or blast furnaces in slag pots.  Depleted slags are
granulated with water to make them easier to  transport  and
handle.   In  this  form  they  have more end uses than just
landfill.  In addition the granulated slags may be easier to
                         122

-------
dispose of as ballast or fill than the large  chunks  formed
in  slag  pots.   Therefore,  the  use  of  air  cooling and
mechanical size reduction as an alternative to depleted slag
granulation is not warranted.

Recirculation  After	Treatment.   Recirculating waste  water
from  slag  quenching  and  granulation  after treatment for
solids removal is practiced by all of the  plants  presently
granulating  slags.   There  are variations in the extent of
solids removal  and  the  need  for  discharge.   These  are
discussed  in  more  detail  in  the  treatment alternatives
section  that  follows.   Of  the  control   and   treatment
alternatives  given  in  Figure  7, Alternative 3 provides a
means of treating all of the waste water for total  recycle.
Solids  are  removed  by  settling and filtration before the
water is recycled for reuse for slag granulation  and  other
processes.   This  treatment  alternative  was  discussed in
detail in the previous section of the  report  dealing  with
contact cooling water.

Identification of Treatment Alternatives

The  waste  water from molten slag quenching and granulation
requires treatment to reduce suspended solids and associated
heavy metals.  The pH of the waste water has been  found  to
be  between  8  and  10,  which aids in the reduction of the
soluble heavy metals.  In most operations, the pH reaches an
equilibrium value due to hydrolysis of  basic  metal  oxides
and  salts  in  the  slag.   In  mixed  process  waste water
operations, sufficient reaction occurs to maintain a pH near
8,5 for the mixed stream.  If needed, the pE  of  the  mixed
process  waste  water  is  usually  adjusted  with  lime  or
caustic.

Solids removal  technology,  illustrated  in  Figure  7,  is
usually by means of settling and cooling towers  (Alternative
5), mixed process stream settling  (Alternative 4), and mixed
process stream settling and filtration (Alternative 3).  The
effectiveness   of  these  alternative  treatments  for  the
reduction of pollutant parameters is indicated in Table  37.
The  raw  waste  water from slag granulation was sampled and
characterized in Plant 9  (see Table 30).  No loadings  could
be calculated because the discharge concentrations were less
than  the  intake  concentrations.  The intake wacer used in
the quenching operation was recycled,  mixed  process  waste
water   contained   in  a  lagoon.   For  this  reason,  the
concentrations of the slag quenching waste water  are  given
to  enable  a  qualified  comparison  to be made.  In such a
situation, where large amounts of steam are evaporated, some
concentration of pollutants should occur; however, since the
                             123

-------
           TABLE 37,  EFFECTIVENESS CF TREAIttENT ALTERNATIVES
                      FOR WASTE VOTER FRCM SLAG QUENCH
                      GRANULATION

Loading
, kg/kkg (cone, mg/1) metal produced (or lb/
Treatment Alternative 1000
Pollutant
Parameter
Susp. solids
Cadmium
Copper
Lead
Mercury
Nickel
Zinc
Oil and grease
PH
Table
Referenced
1
Plant
9
3.51
(1284)
(a)
NIC
(0.067)
NLC
(0.071)
NLC
(0.192)
NLC
«0.003)
NLC
(0.03)
NLC
(0.622)
NLC
«D
8.3
V-22
4
Plant
39
0.0056
(64)
3 x 10"7
(0.004)
1.7 x 10"5
(0.20)
4.4 x 10"6
(0.05)
6 x 10~9
(0.0007)
NR
7 x 10'6
(0.080)
NR
8.9
V-18
523
Plant Plant Plant
12 17 10
0.126 Recycled, Recycled,
(12) no dis- seasonal
charge discharge
(b)
NR
0.0028
(0.27)
0.0042
(0.04)
NR
0.0021
(0.02)
0.0078
(0.74)
NR
8.3

(a)  NLC - rfo  loading calculable.
(b)  NR  = not  reported in  analytical data.
                           124

-------
waste water percolates through the slag pile, some reduction
of pollutants might occur on the surface and interstices  of
the  granulated  slag.   There  are  no  analytical  data to
substantiate this, but it would appear to be plausible.

In Alternative 4, in which a periodic discharge occurs  when
rain-water  accumulation  exceeds  evaporation, the apparent
loadings are very low because the daily discharge volume was
estimated from annual data.  For  comparison,  however,  the
concentrations   of   the   pollutant  parameters  are  also
presented  to  illustrate  the  values  in  the   discharge.
Alternative  5,  in  which the waste water undergoes primary
solids removal followed by a cooling tower that  requires  a
bleed stream discharge, is intermediate in its effectiveness
in removal of the pollutant parameters cited.

      Waste Water From Slag Milling and Classification

Copper-rich  slag that has been granulated or cast into slag
pots is processed by wet grinding and classification methods
to recover metal values.  Generally, the copper-rich slag is
crushed, ground in ball mills, and screened  and  classified
with   table  concentrators  to  produce  a  copper  product
containing 80 to 90 percent of the copper alloy and a gangue
containing about U to 5 percent of copper alloy.   The  slag
gangue  (tailings) is discarded and the copper concentrate is
remelted  in  reverberatory or rotary furnaces.  The milling
and concentrating are generally wet operations.

A large flow of water is used in the  concentrating  of  the
slags.   The water will contain suspended solids, because of
the fine product produced during milling, and a  portion  of
the  soluble constituents of the slag.  The  waste water goes
to a  settling  pond  and  is  recycled  by  most  companies
performing slag milling and classifying.

The  waste  water from the millixig of copper-rich slag has a
high pH due to hydrolysis of the basic metal oxides  derived
from  the  melting furnace flux contained in the slag  cover.
It also contains suspended solids and soluble  heavy   metals
that are present in the slag.

Only  six   (14  percent)  of  the 44 plants  surveyed process
copper-rich slags by wet milling and all are  copper   alloy-
ingot producers.  Of  the remaining 38 plants, 15 use furnace
processes for the recovery of copper alloy metal from  slags.
The  rest   (23)  sell  these slags to other  plants for their
recoverable metal content.  Refined copper producers usually
have the capability to treat such slags in a blast  furnace,
and  purchase  much of this material.  These plants use such
                           125

-------
slags as a source of black  copper  for  the  production  of
fire-refined  copper  or  anodes  for  electrolytic refining
operations.

The current control and  treatment  technology  alternatives
used  for  waste  water from slag milling and classification
are shown schematically  in  Figure  8.   Alternative  1  is
direct  discharge  of the effluent without any treatment and
is not practiced by any of  the  plants  surveyed.   Primary
solids removal before discharge  (Alternative 2}  is practiced
by one plant.  The remaining plants recycle the slag milling
waste   water  after  various  degrees  of  solids  removal.
Alternative 5 is in an entirely closed-loop with a  constant
reuse of the water and is practiced by Plant 11.

Identification of Control Alternatives

Recovery  of  the  metallic  content of copper-rich slags is
technically possible without the use of water.   This  could
be  done  by  dry milling.  It is being accomplished by melt
agglomeration in a blast or rotary furnace.  The waste water
discharge from wet milling  operations  can  be  reduced  or
eliminated   by  recirculation  of  the  waste  water  after
treatment.

Dry  Milling and Concentrating.  Slags can be milled dry and
concentrated by screening out the  coarser,  more  malleable
metal  fraction  from  the  finerr more friable slag oxides.
This approach is not being  used  by  the  secondary  copper
industry,  but  is  being  used  in  the  secondary aluminum
industry.  The operation would be expected to  be  extremely
dusty  and  would  require extensive dust control equipment.
Because of the composition of the slag, the dust could  pose
an added occupational hazard.  Dry milling and concentrating
is not a currently viable alternative to wet milling because
of   the   lack  of  technological  development  within  the
secondary copper industry.

Recovery of Metal by Melting.  An  approach  that  is  being
employed  to  recover  the metallic content from copper-rich
slags by the processors of large volumes of  such  materials
is  by  melting,  either  in blast or cupola  furnaces or in
specially designed rotary furnaces (specifically  Plant  9).
In  such operations, the large pieces of slag are reduced in
size by impacting with a heavy  weight   (crane  and  wrecker
ball).   The  fine  portion  of  the  slag  is pelletized by
grinding damp, fine slag and forming pellets in one  of  two
ways:

      (1)  Pellets are formed in a rotating disk
                              126

-------
o
                    iitia^..'
                      Discliar^e
                                                     Discharge
                                                                               Discharge
©
©
©
                        Finure  8.   Current; control airl tr--~triont  technology alternatives
                                    for waste vT^ter fron  sli"- i"Jllir>c and classification*

-------
           of cylinder pelletizers.  This system,
           developed by the iron ore concentrating
           plants, produces hard pellets about
           3/4 inch in diameter.  A small amount
           of clay or other binder is added if
           necessary.
      (2)  Pellets are also formed by grinding
           damp, fine slag, mixing the fine material
           with a small amount of organic resin,
           and roll briquetting the fines into
           pillow shaped briquettes about 2 inches
           square and 1 inch thick.

Direct  charging of the coarse slag and pelletized fine slag
into  a  blast,  cupola,  or   rotary   furnace   completely
eliminates    water   discharge   from   the   milling   and
concentrating process  and  improves  the  recovery  of  the
copper  from  the  slag.  Typically, the waste slag from wet
milling and concentrating contains  about  4  to  5  percent
copper  or  copper  alloy metal, while the waste or depleted
slag produced from a  melting  recovery  operation  contains
about  1  to  2  percent  copper or alloy.  In addition, the
reducing atmosphere in a blast or cupola furnace will reduce
copper or copper  alloy  values,  present  as  oxides,  into
metal.   Pelletizing  of  the  fine  slag  is  necessary  to
minimize the amount of dust blown out of  the  furnace.   An
extensive  baghouse  system  and  associated gas cooling are
necessary if the exhaust is to be cleaned dry.

The applicability of the melting approach for metallic value
recovery from copper-rich slags in order to eliminate  water
use  has  been  demonstrated.   It  is  part of the industry
practice but, to be efficient, it must operate continuously.
Therefore, it is nor a viable alternative for establishments
presently processing  small  amounts  of  slag  by  the  wet
milling operation.

Recirculation.  of Treatgd Waste Water.  The v/aste water from
slag milling and concentration  can  be  recycled  into  the
operation  if  the  suspended  solids  are removed either by
settling for primary  solids  removal  or  by  settling  and
filtering.   Both  methods  are used by the industry and are
illustrated in  Figure  8  as  Alternatives  3,  4,  and  5.
Alternatives   3   and  4  use  ponds  as  reservoirs  which
seasonally discharge rain runoff  water.  Water is also lost
from such ponds in varying amounts  because  of  percolation
through the soil.  Alternative 5 eliminates this possibility
by  using  settling and holding tanks for the recycle water.
The applicability of  total  recycle  of  process  water  is
demonstrated in current practice.  It is a viable method for
                           128

-------
the   elimination   or  reduction  of  process  waste  water
discharge from wet milling operations for small  amounts  of
copper-rich slags.

Identification of Treatment Alternatives

The  waste  water  discharged  from  wet  milling operations
contains suspended solids and dissolved  metals  contributed
by  the  slag,  as  well as oil and grease used to lubricate
milling equipment.  Before discharge or  reuse,  the  solids
must  be  removed  and  the  amount of heavy metals reduced.
This is done primarily  by  pH  adjustment  and  removal  of
suspended   solids  and  oil  and  grease  by  settling  and
filtration.  As was the  case  with  other  slag  processing
operations,  hydrolysis  of the basic metal oxides contained
in the slag produces a waste water with a  high  pH  and  is
well   suited   for   maintaining   a   low   heavy   metals
concentration.

The treatment  alternatives  illustrated  in  Figure  8  are
currently  being  used  by the industry.  None of the plants
discharge directly without at least primary  solids  removal
(Alternative  1).   Only  one  plant  of  the  six  surveyed
discharges after solids removal (Alternative 2).  All of the
remaining five plants recycle  the  waste  water  from  slag
milling    after   varying   degrees   of   solids   removal
(Alternatives 2, 3, Ur and  5).   Only  Alternative  5,  the
closed-loop  process,  employs  pH  adjustment  with acid to
maintain a pH of about 8.  In all of the  operations,  large
amounts  of  depleted  slag  must  be  disposed  of and this
material is usually kept at the plant site.

The effectiveness of Alternatives 2, 3, 4,  and  5  for  the
reduction  of  pollutant  parameter  loadings  for suspended
solids, cadmium, copper, lead, nickel,  zinc,  and  oil  and
grease,  compared  with raw waste water  (Alternative 1), are
indicated in Table 38.  The data for Plant 38 were  obtained
by  sampling  the  waste  water from slag milling before and
after two settling ponds of a closed-circuit, mixed  process
waste  water  treatment  facility  (Alternative 4) .  The data
for Plant 39, which operates a slag milling operation  at   a
site   removed  from  the  main  smelting  operations,  were
obtained from a  closed-circuit  operation.   However,  only
slag  milling  waste water was recirculated.  Data for Plant
11, Alternative 3, characterized the waste water  discharged
from a lagoon before the installation of a closed circuit in
1973  (Alternative  5).   Plant  10 normally does not have  a
waste water discharge in the closed circuit used  for  mixed
process  waste  water.   Waste  water,  derived  from excess
                           129

-------
                   TABU-  38.   LTT;:CTIVENi;SS Or CONTROL AND TREATMENT TECHNOLOGY ALTERNATIVES
                               FOR {JASTL ItfVTEP. FRCK SLAG MILLING AuT) CLASSIFICATION
OJ
o
Loadings ,
Pollutant
Parameters
Susp. solids
Cadmium
Copper
Lead
Mercury
Nickel
Zinc
Oi 1 & grease
pH
Table
Referenced

1
P Ian t
38(fl)
25.99
0.012
9.275
6.835
0.001
0.134
7.322
0.092
8.53
V-22



Plant
39(fl)
326
NR
0.11
0.0014
NR
NR
0.00014
NLC
9.55
V-22

kg/kkg metal produced (or lb/1000 lb itittal)
Treatment Alternative
2
Plant
11
3.182
0.006
0,10
0,116
NR
0.002
0.631
NR
9.8
V-19

3
Plant
43 (b)
1.247
NR
0.004
0.0053
NR
0.0002
0.022
NR
8.24
VII-6

4 5
Plant Plant Plant
3g(a,b) I0(a»k) 11 (c)39^ )
0.266 Recycle, Recycle,
seasonal no
discharge discharge
0.095
0.042
NLC
-------
rainfall, is discharged  only  after  filtration  through  a
filter bed.

The  use  of  settling  ponds  is  effective in reducing the
suspended  solids  loadings;  heavy   metal   loadings   are
correspondingly   reduced    (Alternative   1  compared  with
Alternative  2).   Further  reduction  in  the  loading   is
realized  if  part  or  all  of  the waste water is recycled
(Alternative 1 versus Alternatives 3 and 4).

There is a noticeable effect of pH of the waste  water  dis-
charge  on  metal  loadings,  especially  for  copper, lead,
nickel, and zinc, Ar a pH near 7  (Plant 38f Alternative  4) ,
the  levels  of  zinc,  nickel, lead, and copper are greater
than those at pH of about 8.2  (Plant  43,  Alternative  3),
even  though  solids  removal was greater for Alternative 4.
Therefore, it is necessary to maintain  a  high  pH  of  the
discharge.   Because  of the possibility of redissolving the
arnphoteric  hydroxides  of   lead   and   zinc    (Plant   11,
Alternative 2), the pH should not be maintained too high.  A
pH  between  8  and  9  appears  to  be suitable for maximum
reduction of heavy metal loadings.  No apparent reduction of
the oil and grease loading occurred for Plant  38;  however,
this  might be explained by  the fact that additional oil and
grease was contributed by cooling  water  that  entered  the
closed circuit beyond the point where the slag milling water
was sampled.

Total  elimination of the waste water discharge is practiced
by Plant 11 (Alternative 5).  After most of the  solids  had
been  removed  by  a  spiral classifier, a minus IG-mesh,  50
percent solids slurry discharged  from  a  settling  tank   is
dewatered  on  a disk filter.  The filtrate and rhe overflow
from the settling tank are  recirculated  from  four  holding
tanks back to the milling operation.  Sulfuric acid is added
to  maintain a pH near 8 for the  recirculated water.  In the
three months the system has  been  operational,  there  have
been no severe problems with its  operation.

         Waste Water from Furnace Exhaust  Scrubbing

The dusts, smoke, and fumes  formed in the  furnace operations
used  by  secondary  copper  or copper alloy smelters must  be
removed from the furnace exhaust  before being discharged   to
the atmosphere.  Cupola and  blast furnace  operations produce
large  quantities  of  particulate  matter  from dusty charge
materials, such as fine slags and from coke ash.   Emissions
are  also  produced  from the combustion of coke and organic
wastes in the  charge  materials.   Metal  oxide  fumes  are
                            131

-------
produced  from  zinc, lead, or other volatile metals present
in the charge materials.

Reverberatory  and  rotary  furnaces  produce  some   smoke,
especially if the charge contains organic waste materials or
when  green-wood  poles  are inserted to deoxidize the bath.
Particulate emissions are produced during  the  charging  of
fine  slags  or  fine flux materials.  Metal oxide fumes are
also produced from zinc,  lead,  or  other  volatile  metals
present in the charge materials.

Emissions from converters contain metal oxides of all of the
metals  present,  including some copper oxide and the oxides
of sulfur, phosphorus, or other  nonmetals  present  in  the
original  bath  of metal.  Emissions from furnace operations
are  usually  directed  to   individual   exhaust   cleaning
equipment,  although  more  than  one furnace exhaust may be
treated by a single emission control facility.

A considerable amount of zinc oxide and some lead oxide fume
is formed during pouring of  brass  or  bronze  alloys  that
contain  these  volatile  metals.   This  fume  is generally
collected  along  with  the  combustion  exhaust  gases  and
directed to the furnace exhaust cleaning equipment.

In  Table  5, the types of air pollution control used by the
industry were summarized.  Of the 41  plants  responding  to
the  survey,  52 percent use only dry air pollution control,
20 percent use  only  wet  air  pollution  control,  and  11
percent  use  both  types  to control emissions.  Another 11
percent presently do nor use emission control devices.

Identification of Control Alternatives

The amount of waste water generated during wet scrubbing  of
exhausts from furnace-related operations and the loadings of
pollutants  can  be  reduced  by recirculating treated waste
water.  Such an approach is currently being used  by  plants
employing  wet scrubber systems.  To eliminate the discharge
of  waste  water  from  furnace  exhaust  emission   control
devices, dry air pollution control devices such as oaghouses
or electrostatic precipitators are used.  Over 5C percent of
the industry employs such dry emission control methods.  The
solids  collected from exhaust cleaning consist primarily of
metal oxide fumes such as zinc oxide and lead oxide and  are
sold  or used for their metal content.  Therefore, efficient
recovery of particulates in the exhaust gases provides  some
return on investment in emission control devices.
                       132

-------
Dry  Air  Pollution  Control s.   The  most  common  dry  air
pollution control system  is  a  baghouse.   The  gases  are
cooled  either by dilution with air, by water cooling of the
hot gas ducts, or with water sprays  inside  of  the  ducts.
The  exhaust, before it is filtered, must be cooled to below
the ignition or fusion point  of  the  bags.   The  ignition
point  of  the  bags  varies with the type of fabric used to
make them.  Cotton or wool bags have  the  lowest  operating
temperature  and glass fiber bags have the highest operating
temperature.  Cooling water used on the outside of the ducts
is  generally recycled.  Water sprayed inside of  the  ducts
for  cooling  the  exhaust  must  be completely converted to
steam to prevent blinding of the bags.

Six of the 44 plants  surveyed  used  electrostatic  exhaust
cleaning systems to reduce emissions.  These are in addition
to  either  baghouse  or wet scrubber control systems.  They
claimed no waste water was generated in the operation or for
cleaning  of  electrostatic  precipitator  emission  control
devices.

Metal  oxides,  especially  zinc  oxide,  are  very small in
particle  size   (less  than  1  micron)  and  removal   from
baghouses  can  be  an  extremely dusty operation.  The dust
level during gathering and loading  for shipment  is  reduced
by  agglomeration  with  very  small  amounts of water.  For
plants surveyed,  the  use  of  dry  air  pollution  control
systems, despite the dust problem,  has been a very effective
way  to  reduce emissions without the need for a waste water
discharge.

The proposed performance standards  for  emissions  from  new
secondary  copper  alloy production plant furnaces have been
recommended<* *> to be as follows.

From reverberatory furnaces:
       (1)  No more than 5C mg/Nm3  (undiluted)
           or 0.022 gr/dscf,
       (2)  No more than 10 percent  opacity.
From electric or blast furnaces:
       (1)  The opacity of visible emissions
           shall be no more than 10 percent.

The  background  information  on  which  these   recommended
standards were based was developed  from data taken at plants
using   fabric   filter   baghouses.    Some  also  employed
electrostatic   precipitators.    Generally,   although   no
scrubber has yet been used to control emissions to the level
of  the  proposed  standard,  such  levels  are  within  the
capability of scrubbing  technology.   This  conclusion  was
                         133

-------
based  on  only  one  copper  alloy  producer who used a low
efficiency wet scrubber with  a  closed-loop  water  recycle
system.    High   efficiency   venturi-type  wet  scrubbers,
however, approach these new source air emission  performance
standards.
Wet  gas scrubbers selected by secondary copper smelters are
of the high-energy venturi type.   These  scrubbers  have  a
pressure  drop  of about 0.123 atm (50 inches of water), and
remove 90 to 99 percent of the entrained  solids.   Most  of
the solids are removed from the water with thickeners and/or
filters, and the water is discharged to storage.  The sludge
recovered  from brass and bronze operations contains over 50
percent zinc as zinc oxide and is  sold  to  zinc  smelters.
The  sludge  recovered from exhaust scrubbers used by copper
smelters contains about four percent copper and  is  usually
recharged  into  the  furnaces or stored for possible future
recovery of the values by  the  same  company  or  by  other
smelters.   Water discharged to a pond or settling tank from
a thickener will contain appreciable amounts of  solids  (of
about  the  same  composition  on  a dry basis as the sludge
removed)    and   soluble   constituents.     The    soluble
constituents  will  include most of the soluble salts in the
feed water plus the addition  of the soluble constituents in
the exhaust gases.  The soluble constituents contributed  by
the  process  when a cover flux is used are mostly oorax and
its metal-borate reaction product or soda  ash.   Hydrolysis
of  such  materials  increases  the pH of the scrubber waste
water.

Organic  residues,  soldering  fluxes,   various   plastics,
especially  polyvinyl  chloride, etc., in the scrap material
oxidize in the furnace to produce water soluble constituents
that lower the pH of the scrubber waste  water.   Therefore,
depending   on   the   specific   plant1s  method  of  scrap
preparation and smelting  (i.e., if  insufficient  alkalinity
is  not contributed by the flux constituents or by recycled,
mixed process waste water), the exhaust scrubber waste water
may require pH adjustment by the addition of caustic or lime
slurry.  Waste waters with pH values between 8  and  1C  are
recycled,  which  assures  removal  of soluble heavy (trace)
metals during solids removal steps in the treatment  of  the
recycle water.

The   large  volumes  of  water  necessary  to  operate  wet
scrubbers make it economically necessary to recirculate  the
water.   Treatment  for  solids removal provides a sludge of
primarily metal oxides (zinc oxide and lead oxide) that  has
seme  market  value  and  is  dust  free.  After most of the
                        134

-------
solids are  removed  by  a  thickener  and/or  a  filter  or
centrifuge,  some  form of settling is always used.  - Cooling
towers are used when the volumes of water  are  large.    The
amount of water added to the operation replaces that lost by
evaporation  and  in  the  dewatered sludge.   All of the six
plants visited that use  wet  scrubbers  recycle  the  waste
water from the scrubbers after treatment for  solids  removal.
The discharge from the treatment is either recycled  directly
to  the  scrubber  or  it  becomes part of the mixed process
waste water that is recirculated.

Alternative technologies currently being used for  treatment
and  control  of  scrubber  waste  water by the industry are
illustrated in Figure 9.  They range from solids removal and
discharge to  closed  loop  circuits  of  process  or  mixed
process   waste   water.   The  technologies   indicated  are
discussed  in  more  detail  in  the  section  on  treatment
alternatives.

Identification of Treatment Alternatives

The  waste  water discharged from wet scrubbing devices used
to control emissions contains  suspended  solids,  dissolved
heavy   (trace)  metals,  and  some  oil  and grease from the
exhaust of furnaces used for  smelting  operations.    Before
discharge  or reuse of the water, the solids must be removed
and the amount of heavy  metals  reduced,  primarily  by  pH
adjustment  and  the removal of suspended solids by settling
and filtration.  The pH of the waste water must  usually  be
adjusted  with  caustic  or lime to counteract the effect of
acid formation by the contaminants charged  with  the  metal
scrap.   In   some cases where pH adjustment is not used, the
waste water attains a high pH from the alkaline flux carried
from the furnace by the exhaust.

The treatment technologies that are currently being used  by
the industry  to remove solids and dissolved heavy metals are
illustrated   in  Figure  9,  Only one plant discharges waste
water from exhaust scrubbing after  adjusting  the  pH  with
ammonia  (Alternative  1) .   The  remaining  plants surveyed
recycle their water after one of the methods illustrated  as
Alternatives  2,3,4,5, and 6.

In  order  to  determine  the  effectiveness  of the various
alternative technologies  for  the  reduction  of  pollutant
parameters,   it was necessary to sample plants that employed
Alternative 6 at points in the process,  which  would  yield
information   on  successive  steps  in  solids removal and  a
characterization of raw waste water as it left the scrubber.
Plant 9, an unalloyed  copper  producer,  and  Plant  38,   a
                         135

-------
                                                                                       Water  Source
UJ
                                                                                                  r
                                            ~1
                            Discharge
                                           Recycle Water
                                                 or
                                             Discharge

                                                ©
Recycle WntkT
      or
  Discharge

     ©
Recycle Water
     or
  Discharge

    ©
Recyclo Wator
     ©
                                 Recycle Water
                                      or
                                   Discharge

-------
copper  alloy  producer, were chosen.  The concentrations of
selected pollutants at various sample points in the  process
are  given  in  Tables  39  and 40, respectively.  From this
information (and waste water flows and the daily  production
of  molten  metal)   average loadings for each sampling point
were determined.

In Plant 9, the raw waste water characteristics  had  to  be
taken  as  the  sum of loadings observed in a quench circuit
thickener discharge  and  a  scrubber  hydroclone  discharge
because  both  were  involved  in  removing  solids from the
emission.  The quench circuit operated as a  closed  circuit
with  no  discharge  of  waste water except for that removed
with the sludge.  In Plant  38,  the  raw  waste  water  was
sampled  at  a  thickener  discharge just after the scrubber
operation.

Effectiveness of  Alternatives  2,  4 ,  5,  and  6  for  the
reduction  of  suspended solids, copper, lead, zinc, and oil
and grease are indicated in Table 41.  A progressively lower
loading in suspended solids is  observed  as  the  level  of
technology  increases  in  sophistication.   There is also a
reduction  in  copper,  lead,  and  zinc  loadings  and   an
accompanying   reduction  in  loadings  for  cadmium,  lead,
mercury, and nickel.  The effectiveness of extended settling
periods in lagoons  {Alternative 6) is  obscured  because  of
the  mixing  of waste water from other processes.  For Plant
38 the effectiveness of one or three  lagoons  is  presented
under   Alternative   6   as  Plant  38-1  and  Plant  38-2,
respectively.

It should be pointed out that under Alternative 6, the pH of
the recycled water is about 7 for Plant 38-1, while that  of
Plant  9 is about 8.  This lower pH might explain the higher
loadings for copper, lead, and zinc  for  Plant  38-1,  even
though the suspended solids removal is less.

Plant  9  discharges  part of the mixed process waste water,
while Plant 38 recycles the  mixed  waste  water  to  a  wet
milling  operation.   Plants  17,  26,  and  9, which employ
Alternatives 4, 5, and 6, respectively, do not discharge the
treated scrubber water, but recycle  it  and  use  water  to
replace that lost by evaporation.

     Waste Water from Electrolytic Refining_Operatigns

Electrolytic  cells  in  tank houses electrolytically refine
anode  copper  into  high  purity   cathode   copper.    The
electrolyte solution consists of demlneralized makeup water,
copper   sulfate,   and   sulfuric   acid.    Normally,  the
                         137

-------
                                                                    TABLE  39. RESUlffS  OF SAMPLING WASTE WATER FPCM
                                                                                  FURNACE  EXHAUST  SCRUBBIBG,  COMPANY 9
00
Wasiewater Discharge
From Hydroclone,
. ma/1
Parameter

Susp. lolldi
Cadmium
Copper
Lead
Mercury
Nickel
Zinc
ml andOrcaw
PH
High

822
2.789
0. 165
0,742
0. 00022
0.028
7.4GO
<1
a. 04
Low

527
0.238
0.048
0.216
10,001
0.016
0.497
<\
• 7.B3
Avg

680
1.514
0.107
0.479
O.Q001I
0.022
3.979
<1
rt. 3-1
Wasiewater Discharge
Prom Thickener
Concent rat ion, ing /I
High

331
2.579
0.055
0.284
0.00108
U. 022
13.428
<1
7.63
LOW

223
1.731
0.023
0. 186
<0, 001
0.019
6.416
<1
7 .if)
Avg
(c)
277
2.158
0. 039
0.235
0. 000 &4
0.021
9.922
-.1
7 *2
Loading.
kfi/kkg

34.85
0.272
0.005
0.030
0.00007
0.003
1.248
0

Wasiewater Discharge
After Hydroclone
Con central Ion, mg/1
HiRh

3179
«. 102
0,067
0.49&
0.00046
0.013
O.U95
4.n
'J. 00
Low

3046
0.048
0.051
0.334
<0. 0001
0.006
0.497
 hv W pert-cm less or S. 700. coo 1'day.
        (cl Flow e Rim alt d 10 be ilic tamt ai Ilic dijcharRi; (hi -S. 700. dp" 1  day
        (d) Flow 175gpni ot 9M.OOU I .day.
        (e) Plow nsgpm or 95-1. ooc l/day.
        (f) Flow 222. 000 gpd  or 840,000 I/day.

-------
                                       TABLE 40.  RESULTS CF SAMPLING WASTE WATER  FROM FURNACE EXHAUST
                                                     SCRUBBING, AND MILLING AND CLASSIFYING SIAGS, COMPANY 38
Wasiewater Ilischarge After Waste water Discharge After Wastewater Discharge After
Thickener and Centrifuge, Thickener, Centrifuge, and Settling. Solids Removed and Two Settlings.
nig/l mg/1 mg/1
Parameter Hifih Low Av^ High I.ow Avg High
(I') (0
Susp. solids -I-16H 100 1RC1 97 -tS 7U 109
Cadmium 4 1 2.3 "2 o. 9 1. 6 o. 1
Coppct fil'C III 210 (i C 3.7 luO
Uad 1,'idO L'd 557 10 1 o 50
Mercury (>. GOG •.<>. U01 i>. o03 <('. 0(Jl <('. uOl  <5
7.7 7.9
Wastewatet Recycled After
Complete Treatment,
mg/1
High

65
0. I
30
7
<0.001
0.2
10
20
8.2
Low

2
<0.05
2
3
O.001
<0. 1
3
<5
7.4
Avg

34
0,07
12
5
<0. 001
0.1
6
11
7.7
Wastewater Discharge After
Milling and Classifying Slags,
rng/l
High

7505
3
2400
1500
0.020
30
2000
47
9.2
Low

1057
<0.05
450
350
0.003
9
450
<5
7.4
Avg

3502
2
1250
917
0.012
18
983
22
-•
(a) Production S»,7 KKg day <>f copper alloy.
(h) Wastewater flow 22, 000 I/day.
(c) Wastcwatet flow U. 4uu I/day.
(d) Wastewater flow 67.400 I/day.
(c) Wasiewater flow 72, 700 I/day.
(f) Wastcwater How 72.700 I/day.

-------
17J3LE 41.
                                                            OF TREAIMiMT ALTERNATIVES
           TOR WASTE';  WATER FROM '.
                                                                        SCRUBBING
h-1
*.
o
Loading, kg/kkg metal produced tor ID/lOUU lb metal)


PolluLaiiL
P_nrameters
Susp. solids
Cadmium
Copper
Lead
Mercury
Nickel
X i nc
Oil & grease
pll
Table
Referenced
(a) Plant 9



(b) Plant 38



Treatment Alternative
1 245 6


Plant Plant Plant Plant Plant Plant Plant Plant
9(a) 38 (b) 9(a) 38(b) 9 0.548 0.001 0.476 0.001 0.005 0.001 0
0.029(0 3.565 0.009 1.263 0.009 0.007 0.003 0
7xLO-5 IxHr6 6xiO-5 IxlO'7 2xlO~6 1.5xlO~6 2xlO"5 1
0.0028
-------
electrolyte  solution  is  continuously  circulated  through
thickeners  and  filters  to  remove the solids (slimes)  and
recycled back through the  electrolytic  cells.   The  cells
operate  hot so that makeup water is required to replace the
amount evaporated.  Most of the makeup  water  is  generally
added during the daily washdown of the tops of the cells.

Waste water from electrolytic refining operations originates
from  spills,  cell maintenance and repair/ and catastrophic
accidental losses.  Depending on the quality of  the  anodes
and  the  impurities  from  the scrap metal that are carried
through the  fire  refining,  soluble  metal  concentrations
build  up  in  the  electrolyte  which  cannot be removed as
slimes.  When this occurs, a bleed stream of the electrolyte
is required.  Such waste electrolyte normally is treated  to
remove  the  copper content first by high-voltage deposition
and finally by cementation with iron.   At  one  plant,  the
high  nickel concentrations permit the byproduct recovery of
NiSOit by means  of  barometric  condensers.   The  resulting
solution   may  then  be  neutralized  and  filtered  before
discharge.  some electrolytic refineries have a ready market
for the contaminated electrolyte.  Most of the  plants   sell
their  slimes (for the precious metal value they contain) to
primary copper refiners  or  others  equipped  for  precious
metal  recovery.  Plant 1 operates an on-site precious metal
recovery facility.

Makeup water, which must be low in total ion content,  comes
from  boiler  condensate  or  demineralizing  systems.   The
backwash from ion-exchange resins used to treat boiler water
feed or backwash from  demineralizers  could  in  effect  be
considered  part  of  the  waste  water load of electrolytic
refining.  However,  these  are  considered  to  be  boiler-
related   operations   and  not  process  waste  water   from
secondary copper manufacturing.
Identification of Control Alternatives

Except for Plant 1, unless a refinery has a market for waste
electrolyte, there is no viable  control  alternative  other
than  to  treat  the waste stream for copper recovery and to
neutralize the acid content.  At Plant 1,  the  waste  water
generated  from the electrolytic refining of anodes contains
a buildup of nickel which allows an economical  recovery  of
nickel  values  by  the  evaporation  techniques employed by
several primary copper refineries (i.e., recovery of  nickel
sulfate).   The  amount  of  arsenic  present  in  secondary
electrolyte solutions  is  negligible.   The  value  of  the
sulfuric  acid  alone  does  not  warrant evaporation of the
                            141

-------
spent electrolyte for acid value recovery after
has been removed.
the  copper
Copper   is  reduced  in  the  bleed  electrolyte  by  using
insoluble anodes and  depositing  the  copper  on  cathodes.
Such  recovered  copper  is  recharged  into anode furnaces.
Another method is to cement out the copper using scrap iron.
The copper is recharged into the  copper  smelting  circuit,
usually  at  the  converter or anode furnaces.  The depleted
electrolyte is then typically treated  before  discharge  or
reuse.   Electrowinning  and cementation can also be used in
series for copper content recovery.

At Plant 8, the depleted electrolyte is reacted with iron to
reduce the hydrogen ion concentration to give a pH of 7  for
the  combined  process  waste  water  discharge.   The mixed
process waste water is then discharged into a joint  primary
sewage  treatment  plant shared with other industries in the
area.   The  iron  sulfate  adds  coagulant  to  the   joint
treatment  plant.   At  Plant 12, the electrolyte is treated
only when breakdown occurs.  The depleted electrolyte is  pH
adjusted with caustic or lime, thickened, and passed through
a sand filter before discharge.  The unit is sized to handle
about   95   cu  m/day  (25,000  gpd)  and  the  tank  house
substructure is designed to hold all of the  electrolyte  in
the cells in case of catastrophic loss of electrolyte and to
prevent any discharge.

The  control and treatment technology alternatives currently
used by the industry for waste water from electrolytic cells
are illustrated in Figure 10.

Identification of Treatment Alternatives

The treatment alternatives  illustrated  in  Figure  10  are
currently  being  used  by the industry.  Plant 12, which is
the newest of  the  electrolytic  refiners,  is  capable  of
recycling electrolyte for extended periods of time without a
bleed  stream.   Plants  1,8,  and  9  use a bleed stream to
reduce impurities.  All remove slimes for eventual  recovery
of precious metals.

The  effectiveness  of  Alternative 3 can be only estimated.
The discharge from Plant 8, which is a mixed  process  waste
water,  was  \isei  as  representative of Alternative l.  The
discharge of treated waste water from Plant 12, even  though
it  is  not  continuous,  was  chosen  as  representative of
Alternative 3.  The results are  given  in  Table  U2.   The
apparent   effectiveness   of  the  treatment  for  reducing
loadings  is  influenced  by  the  small   flows   involved.
                          142

-------
                          Wat«r Sourc«
                                            Treatment For
                                          SpilU-Upsets-Bl««d«
     DUcbars*
Figure 10.   Current control and treatanent technology alternatives
             for waste water frcr. electrolytic refining.


                      143

-------
TABLE 42.  EFFECTIVENESS OF TREATMENT ALTERNATIVES FOR SflASTE
           WATER FROM ELECTROLYTIC REFINING

Loading, kg/kkg
metal produced
Treatment Alternative
Pollutant
Parameters
Suspended solids
Cadmium
Copper
Lead
Mercury
Nickel
Zinc
Oil & grease
PH
Table Referenced
1
Plant 8 (a)
3.334
NR(C)
0.092
0.035
NR
0.061
0.127
NR
7
V-7
2
Plant 12<.b;
0.0048
NLC(d>
3xlO'8
1.7xlO"7
NLC
1.7xlO~7
3xlO"7
NLC
8.0
V-23
 (a)   Mixed-process-was tewater discharge to joint
      treatment plant.

 (b)   Discharge would be outflow from treatment plant of
      excess wash-down water in event of breakdown and is
      not continuous .
 (c)   NR - not recorded in analytical data.

 (d)   NLC - no loadings calculable.

 Note:  Jjoadims also eru.ivalent to Ih/lOnnih retal
                      144

-------
However,  even  if  the  flows  were  an  order of magnitude
greater,  this   treatment   technology   reduces   loadings
significantly.   Alternative  4r  the  byproduct recovery of
NiSO4 by usage of barometric condensers, produces no process
waste  water  at  Plant  1.   Well  maintained  and   highly
efficient  deintrainment pads are employed in the condensers
to minimize carryover.  Except for Plant 1, slimes are sold.
Plant 1 produces a very small volume of process waste  water
during  precious  metal  recovery  (23 cu m/day  (6,000 gpd)).
Currently, part of this flow is impounded in lined ponds and
the remainder is discharged.
                Combined Waste Water Streams

Plant 32, which melts number 1 grade copper scrap into  wire
bar,  recently  (1973) made a considerable investment for the
reduction  of   pollutants   from   smelting   and   related
operations.    Extensive   pipe   segregation  preceded  the
installation of a treatment plant for  pH  adjustment   (lime
treatment)  and sludge removal.  The number of process waste
water discharge pipes was reduced from 10 to 4.  All of  the
sanitation   waste   water  is  directed  to  one  of  these
discharges and  eventually  will  be  sent  to  a  municipal
treatment  facility.   The processes discharging waste water
into the plant  treatment  facility  are  laboratory  water,
plant  wash  down,   furnace exhaust gas cooling before  (dry)
gas cleaning, and a  chemical recovery  system  for  precious
metals.

The  treatment  facility is shown schematically in Figure 11.
The industrial  process water  enters  a  polyvinyl  chloride
 (PVC)-lined,  concrete  surge tank.  This tank evens out the
fluctuating inflow,  allowing the level in the tank  to  rise
or  fail  while  allowing  the pumps to discharge a constant
flow to the mixing tanks.  Agitation  is  also  provided  in
this  tank  to  mix  acid  and alkaline incoming streams and
obtain some  natural neutralization.   The  three  transfer
pumps  provide  flexibility  to  handle  varying flows while
maintaining sufficient capacity  to  handle  excessive  flow
conditions.

The  waste  water,   of  about pH 1.5, is pumped to the  first
stage of three  PVC-lined, concrete mixing tanks.  A lime   (3
percent  calcium  hydroxide) slurry or, alternately, caustic
 (50 percent NaOH), depending on availability  and  cost,  is
added  to the first  stage where the pH is brought up to 4.5.
The water then  flows into the top of the third  stage  where
caustic  is  added   to bring the pH up to 8.2.  The water is
then "polished" in a rapid mix tank, a treatment  consisting
                           145

-------
      FROM
 PLANT
GENERAL WASTE
 SURGE  TANK
 (30,000 GAL.)
                                        NEUT. SYSTEM
NO.
        EFF. METER
           PIT
TO
                                                              ROTARY
                                                              VACUUM
                                                               FILTER
                                                                       SLUDGE TO
                                                                       SCAVENGER
                                 pipp viar>tc '-':ttcr
                                   (Plant 32)

-------
of complete mixing and a final caustic addition to raise the
pH  to  8.8  (considered  to  be  the  optimum precipitation
level).  A solution of ferric sulfate is  also  added  as  a
coagulant.   Facilities are also available for coagulant aid
(a polyelectrolyte solution) addition; however, this is  not
presently employed.  The rate of addition of lime or caustic
is  automatically regulated by continuous pH monitoring with
feedback to proportional controllers on the caustic or  lime
feed pumps for the various mixing tanks.

The  neutralized  water  is  then  pumped  to  a  centerflow
clarifier.  The clarified water is collected in a  circular,
90-degree  V-notch,  wired  trough, and then flows to a tank
where the  effluent  is  discharged.   Concurrent  with  the
settling   and  clarification  operations  is  an  automatic
semicontinuous  sludge  dewatering  process.   Here,   three
days/week  for  eight hours/day, the sludge is drawn off and
filtered on a rotary vacuum  filter.   The  filter  operates
with a three inch precoat of diatomaceous earth.  The sludge
is  "cut"  off  the  filter  and falls into a hopper located
above a truck.  The collected material, 35  percent  solids,
is  trucked  to  an  on-site landfill area.  The filtrate is
collected and recycled back to the rapid mix tank.

The entire plant is located in an area  approximately  60  x
120  feet,  with  all  the  equipment  except  the clarifier
located indoors.   An  elaborate  instrumentation  room  was
designed  into  the  facility;  from  the  control  room all
operations can be  monitored  and  most  can  be  controlled
manually.    The  effectiveness  of  the  new  facility  was
determined by comparing  the  combined  discharge  from  the
plant  before  the  treatment  facility  was installed  (RAPP
data) with the data after  the  new  facility  had  been  in
operation  for  two  months.   Weekly analysis reports for a
period of six to eight weeks of  operation  after  shakedown
were  used  to  determine  the  average  loadings.   For the
comparison, it should be noted that certain plant operations
had been eliminated from the plant site and  that  extensive
segregation  of  drainage pipes also was done.  By so doing,
the number of process waste water discharge  pipes   (to  the
treatment plant) was reduced from 7 to 3.  The effectiveness
of  the treatment plant in reducing loadings is indicated in
Table 43.

In another case, Plant 10 uses  continuous  recycle  of  its
mixed  process  waste  water  after settling and filtration.
The same system is employed  to  treat  discharge  from  the
plant  when  rainwater  exceeds  that lost by evaporation in
various processes, and for this reason, the  system  can  be
considered an end-of-pipe treatment.
                            147

-------
  r.ABT£ 43.  EFFECTIVE JES£ OF n-JD OF ^IPF,
                      ror- OYCT;JT> 7"rrrci
                          Plant  32
                   Loadings, kg/kkg  (Ib/ton) metal produced
   Pollutant
   Parameter
 Before Treatment
     Installed
 (Combination of 1
    Discharges)
 After Treatment
    Installed
(Combination of 3
    Discharges)
Susp. solids

Cadmium

Copper

Lead

Mercury

Nickel

Zinc

Oil and grease

pH
0.828 (1.656)

9xlO~6 (1.8xlO~5)

0.034 (0.068)

0.014 (0.028)

6.9xlO"6 (1.4xl(T5)

0.004 (0.008)

0.016 (0.032)

0.051 (0.051)

5.8
 0.036 (0.072)

       NT* (a)

 0.0007 (0.0014)

 0.0003 (0.0006)

       NR

 0.0003 (0.0006)

 0.0002 (0.0004)

       NR

 9.0
Source:  RAPP data and v?eekly  analysis  reports  to regional
         EPA office.

(a)  NR - not reported in  analytical  data.
                   148

-------
"Dirty"  process  water  from contact and noncontact cooling
operations and from slag quenching and milling is pumped  to
a holding pond for settling, then pumped through three sand-
and-coal  filters,  and then stored in a concrete reservoir.
Makeup well water is pumped  directly  into  the  reservoir.
The  filtered  water and makeup water are then pumped to the
various  water-using  process  steps.    The   filters   are
automatically  backwashed  when the flow is restricted (once
every day or two).  The backwash solids are sent to a  small
holding  pit  and  then  pumped  back  to the settling pond.
 (Backwash formerly  went  to  the  thickeners  in  the  slag
milling  and  classification  area  when  it was operating.)
Periodic cleaning of the pond (dredged once or twice a year)
removes these accumulated solids,  which  are  sent  to  the
depleted slag piles.

Plant  10  normally  does not discharge waste water, and for
this reason, no effluent characterization was available from
state or regional environmental agencies.
                            149

-------

-------
                        SECTION VIII

        COSTS, ENERGY, AND NONWATER QUALITY ASPECTS

                        Introduction
This, section  deals  with  the  costs  associated  with  the
various  treatment  strategies  available  to  the secondary
copper industry to reduce the pollutant load  in  the  water
effluents from contact water cooling, slag granulation, slag
milling   and   classifying,   exhaust  gas  scrubbing,  and
electrolytic cell operations.  In addition,  other  nonwater
quality aspects are discussed.

For  the  purpose  of  developing  cost  data on control and
treatment processes, a distinction was considered  to  exist
between  control  technology  and treatment technology.  The
former refers to any practice applied in order to reduce the
volume of  waste  water  discharged,  such  as  waste  water
recycle  and  conversion  from  wet   (water  using)  to  dry
(nonwater using) processes.  Treatment technology refers  to
any  practice  applied to a waste water stream to reduce the
concentration of pollutants in the stream before discharge.

This section is presented in the following format:

          (1)  Economics of present control
               practices,
          (2)  Economics of present treatment
               practices,
          (3)  Cost effectiveness of present
               practices,
          (4)  Economics of additional control
               and treatment processes,
          <5)  Nonwater quality aspects.
                 Basis for Cost Estimation
Data on  capital  investment  and  on  operating  costs  for
present  control  and treatment practices were obtained  from
selected secondary copper companies.  These data were  modi-
fied  as  needed  in the following way to put all costs  on a
common basis:

          (1)  The capital investment reported was
               changed to 1971 dollars by the use of
               the chemical Engineering Plant Cost
                           151

-------
               Index (quarterly values of this index
               appear in the publication Chemical
               Engineering, McGraw Hill).
          (2)   The operating cost was recalculated
               to reflect common capitalized charges.
               To do this, the annual operating cost
               was calculated as follows:

               Operating and maintenance - as
                 reported by the secondary copper
                 companies.
               Depreciation - 5 percent of the 1971
                 capital.
               Property tax and insurance - C.8
                 percent of the 1971 capital,
               Interest - 8 percent of the 1971
                 capital.
               Other - as reported by secondary
                 copper companies.

The majority of the  data  presented  in  this  section  was
estimated  from  equipment specifications only.  The present
control practices costs, and other control processes  costs,
were  estimated by the following procedure.  Equipment costs
were estimated from published data in  references<*2*.   The
total  capital  investment  was then calculated as this cost
plus:

          Installation     50 percent of equipment
          Piping           31 percent of equipment
          Engineering      32 percent of equipment
          Electrical
            Services       15 percent of equipment
          Contractor1s
            Fee             5 percent of equipment
          Contingency      10 percent of equipment

The operating cost was calculated by  estimating  labor  and
raw  material  requirements,  and  then adding the following
items:

          Maintenance      5 percent of investment:
          Depreciation     5 percent of investment
          Tax and
            Overhead       0.8 percent of investment
          Interest         8 percent of investment

In the following discussion, capital costs are expressed  in
$/kkg ($/ton)  of annual production capacity of copper metal.
                           152

-------
and operating costs are expressed in $/kkg ($/ton)  of copper
metal produced.

           Economics of Present control Practices

The  economic  data received from surveyed plants,  which are
discussed in this section, are summarized in Table 44.   The
table and accompanying Figures 12 through 16 present a total
picture  of  present control and treatment alternatives with
respect to the cost for control and treatment of waste water
in the secondary copper industry.  However, cost information
is absent for some categories.   The  following  words  have
been  used  to  denote  the  reasons for the absence of cost
information:

           (a)  Not used - no wet-type pollution
               control device is used,
           (b)  Untreated - the water is discharged
               untreated,
           (c)  Not done - the operation was not
               performed at this plant.

Those plants not included in Table UU are  those  for  which
insufficient  information  was  obtained  to  perform a cost
estimate.

Spray and Quench Cooling of Molten Metal

Essentially, there are two  basic  methods  to  control  the
waste  water  effluent  from  the  contact cooling of molten
metal:   (a) eliminate the use of contact water by conversion
to noncontact cooling, and  (b) collect the waste water  from
contact  cooling,  remove  the  undesired  contaminants, and
recycle.

Some estimates  of  the  total  capital  cost  of  equipment
installation  and  necessary  plant  facilities  to cool and
recycle noncontact cooling water were  obtained  during  the
survey  of  secondary  copper  producers.   In  this  survey,
eleven companies reported capital investments for noncontact
water cooling and recycle system in the range  of  $0.56  to
$6.23/ annual kkg  ($0.51 to $5.65/annual ton).

The  conversion  to  noncontact  cooling  would  necessarily
involve additional capital expenditure for new water  cooled
casting  molds  and  new  mechanical  systems  for ancillary
operations.  However, the  costs  for  the  water  treatment
system  would be lower than those for installing an entirely
new system since existing equipment  could  be  modified  to
provide at least part of the treatment.
                         153

-------
TABI£ 44.  SUMMARY OF OJRRZ2JT WASTE WA2ER CONTROL
           TREATMENT COSTS BY OPEPATICN AND BY COMPANY
Spray and Quench
Cooling of Molten Metal
Cost Treatment
Plant
No.
8
9
10
11
12
17
19
26
32
36
38
39
41
43
Capital Operating
$/annual kkg $/kkg
1.18 0.22
3.45 0.65
0.79 0.13

0.78 0.13
0.56 0.10
4,57 0.78
Untreated


0.47 0.09
2.81 0.56
0.69 0.13
0.05 0.01
Capital Operating Alter-
$/annual ton $/ton native <-a'
1.07 0.20 5-RD
3.13 0.59 5-R
0.72 0.12 6-R
Not
0.71 0.12 4-RD
0.51 0.09 2-R
4.14 0.71 2-D
Untreated 1-D
Not
Not
0.43 0.08 3-R
2.55 0.51 5-RD
0.63 0.12 2-D
0.05 0.01 2-D
Fraction
of Flow(")
1.0
0.28
0.20
done
0.50
0.40
0.70
0.50
done
done
0.04
0.60
0.25
1.0
                      154

-------
TABIE 44.   (contijuied)
Slag Granulation
Cost Treatment
Plant
No.
8
9
10
11
12
17
19
26
32
36
38
39
41
43
Capital Operating Capital Operating Alter-, .
$/annual kkg $/kkg ?/annual ton $/ton native^
Not
4.44 0.84 4.03 0.76 4-R
0.39 0.06 0.35 0.05 4-R
Not
0.78 0.13 9.71 0.12 5-R
0.28 0.05 0.25 0.05 2-R
Fraction
of Flow
-------
TABI£ 44.  (continued)
Slag Milling
and Classifying
Cost Treatment
Plant Capital Operating Capital Operating Alter- Fraction
No. $/annual kkg $/kkg $/annual ton $/ton native*-3-' of Flow
-------
TABLE 44.  (continued)
Melting and Refining
Furnace Exhaust Scrubbing
Cost Treatment
Plant Capital Operating Capital Operating Alter- Fraction
No. $/annual kkg $/kkg $/annual ton $/ton native^3' of Flow^b^
8 0.69 0.13 0.63
9 13.60 2.67 12.34
10
11
12
17 10.49 2.02 9.51
19
26 17.06 9.85 15.47
32 13.96 5.45 12.66
36
38 10.37 9.41
39 10.74 9.74
41
43 -
0.12 6-RD 1
2.42 6-RD 1
Not done
Not done
Not done
1.83 4-R 1
Not done
8.93 5-R 1
4.94 4-D 0
Not done
3.02 4-R 1
2.08 5-R 1
Not done
_ _
.0
.0



.0

.0
.38

.0
.0

_
      157

-------
                       TABLE 44.   (continued)
                                Equipment and/or Molten
                                Metal Noncontact Cooling
Plant
 No.


  8

  9

 10

 11

 12

 17

 19

 26

 32

 36

 38

 39

 41

 43
                            Cost
                                                     Treatment
  Capital    Operating    Capital     Operating  Alter-, ,  Fraction
$/annual kkg   $/kkg    $/annual ton   S/ton     native13-'  Of  Flow(b)
   2.03         0.39

   4.44         0.84

   0.79         0.13
   3.21

   0.56

   1.96
0.55

0.10

0.34
      Untreated

   6.23         1.19

   3.58         0.67

   1.07         0.20
           1.89

           4.03

           0.72
             0.35

             0.76

             0.12
2.91         0,50

0.51         0.09

1.78         0.31

   Untreated

5.65         1.08

3.25         0.61

0.97         0.18
4-R       1.0

5-R       0.36

5-R       0.20

   Not done

4-RD      1.0

          0.40

          0.30

          0.50

          1.0

          1.0

          0.09
2-R

2-0

1-D

4-RD

4-R

5-R

   Not done

   Not done
                           158

-------
                       TftBJJE 44.  (continued)
Electrolytic Cell
Operations
Cost Treatment
Plant
No.
8
9
10
11
12
17
19
26
32
36
38
39
41
43
Capital Operating Capital Operating Alter—
$/annual kkg $/kkg $/annual ton $/ton native'3'
1.31 0.32 1.19 0.29 3-D
0.0 0.0 0.0 0.0 2
Not
Not
2.08 0.40 1.89 0.36 3-D
Not
Not
Not
Not"
Not
Not
Not
Not
Not
Fraction
of Flow(b>
1.0
1.0
done
done
1.0
done
done
done
done
done
done
done
done
done
(a)   Control and treatment  alternatives  as illustrated in Figures  12
     through!6.        Note:   -D signifies  an alternative  which ultimately
     discharges, -R signifies  an alternative which employs complete
     recycle,  and -RD signifies an alternative which employs recycle  but
     has a bleed or blowdown discharge.
(b)
     fraction of the  total  flow to a combined treatment facility,
     generated by a specific operation,  times the  total combined
     treatment cost.
                               159

-------
                     Water Source
I
i . .1

1

SPRAT SJ'KAY
AND/OR AND/OR
fjL'F.SCH 0,1'KNCH
r.OOf.INC COO .IMC
of or
MOt.TCN MMI.'II.N
MJ.TAL METAL


























SfRAY
AND/OR
QULSCH
COOLING
OF
HOI.TEN
METAL
1

PRIMARY
SOL! OS
KIIWVAL
















1









!
PRIMARY
soi, ins
REMOVAL

i







i











SPRAY
AND/OR
QUENCH
COOLING
Of
MOLTEN
METAL
\

L












COOLING
TOWER






i











SPRAY
AND/OR
QUENCH
COOL I NG
OF
MlH.TI'N
METAL
1











l»J

~r ~i
+ \ T
s luugo 9 f
blowi oun
f Other

1
CLARiriCATION OtVicr





other
Proce»» — »•
Uitrr
I Water


MIXED
i'HOCIiSS
WATER
RKSKKVOIR



MIXf.U
HATF R
RKSERV01R









MIXED
1'KOCE.SS
WATEI!


EXTENDED
SETTI,iNi.i
AS'D










t












s 1 ml yet










*











SPRAY
AND/OR
QUENCH
com. ING
OF .
HOI.TEN
METAL




















MIXED
PROCESS
WATER


SETTLING
AND
COOL I NO






*_ Other Proc«*e
W.ter



J
sludges E*ckf«sh


f-

FILTRATION









Dlich«cg* Recycle Hci:ycle Recycle Recycle Recycle
Wjiifr WaiL'r Water Water Water
Or Or Or Or Or
Dli charge Discharge Discharge Disc large Dlicharg*
©
CD
CD
©
               cr.jntro
      v;aste  vati-'-r1  tnTm rontart  c-nolina  r^ rolfj£?n mot^I.

-------
                                       Water Source


SLAG
QUENCH
AND
CKANLTLATION












1













VIM charg*























SLAG
QUENCH
AND
GRANULATION


















PRIMARY
SOLIDS
REMOVAL







1





















Sludge








Recycle Water


Or

DU charge





1
SLAG
QUENCH
AND
GRANULATION

SLAG






QUENCH
AND


GKANULATION

MIXED
PHOCESS
WATER-
RE SRRVOIH

PRIMARY
SO- IDS
Rf.t.'0'JM

•
Proce«» l
Water f




MIXED
PROCESS
^Crther FTOC.M UATER.


"" SOI.
ns
,*J ' , — . REMOVAL
eludga Sludg*""^
Backwash
•« — 1 FILTRATION! 	 '

1
i
l_












— i


















•>


•



SLAC
QUEKCH
AND
GRANULATION





PRIMARY
SOLIDS
REMOVAL

T~
Sludge






COOLING

i
Recycle W«t«r Bleed Recycle W»t«r Slowdown R«c
Or
Discharge


Oc Wa
DLscharga 0
CD
DUchirg*


  ©
            rioure  13.   Qirr^r t rrsntrol  and tr^atmRnh technoloov alternatives
                         for v-.ste water  from slag Benching and granulation.

-------
I ©

-------
                                                                     Water Source
tT>
U)
                              gflBGE
                            •ludgd
Discharge
   CD
                                                 gasei
                       •ludg*
Recycle Water
     or
  Discharge

    ©
                                                                    gases
                                                           1 ENTRAINMENT 1
                                                           | SEPARATOR   |
                                                                                       g**ee
                                                        1 ENTRAINMENT 1
                                                        I SEPARATOR  1
                                                                                                                             g«i*i
Recycle Water
     ot
  Discharge

    ©
Recycle Water
    or
  Dtacharge

   ©
Recycle Water
     or
  Discharge

    ©
                                                                                                                     Recycle Water
                                                                                                                         or
                                                                                                                       Discharge
                                                                                                                        ©
                                    Figure  15.   Current control  and  treatment  technology alternatives
                                                   for waste water  frotr furnace exhaust scrubbing.

-------
                          W«t«t
     VUcharg*
       (D
                                            Tr«
                                           Spille-Up
                 	


• Cnent For        |->P.e'<5<"*
e-Upseta-Bleed*   _* .   om-«i"
Figure 16. . Current control and treatment technology alternatives
             for waste water from  electrolytic refining.
                               164

-------
Operating  costs  for  treatment of noncontact cooling water
with recycle obtained from the survey ranged from  $0.10  to
$1.19/kkg  ($0.05  to  $1.08/ton).   Contact  and noncontact
cooling water for both equipment and  molten  metal  cooling
are  often treated together.  Therefore, capital and operat-
ing costs for the individual operation were calculated as  a
fraction  (prorated  by  flow)  of the treatment cost of the
combined flows.

Cost information for the control and  treatment  of  contact
cooling  water with recycle was also obtained in the survey.
AS noted in Table U4, Plants 9,  10,  12,  17,  38,  and  39
employ some form of recycle system resulting in no discharge
or  a  partial  discharge  of a bleed stream.  Capital costs
ranged from $0.56 to $3.45/annual kkg ($0.51 to $3.13/annual
ton) with an average of $1.33/annual kkg  ($1.21/annual ton).
These costs include only the water control circuit;  namely,
primary  solids  removal  and  cooling in thickeners, ponds,
canals, or cooling  towers,  and  in  some  cases  secondary
solids  removal  such  as  additional  holding reservoirs or
filters, and associated pumps and piping.   Operating  costs
ranged  from $0.13 to $0.65/kkg  ($0.12 to $0.59/ton) with an
average of $0,25/kkg ($0.237 ton).  Disposal costs  for  the
collected   charcoal   (when  used)  were  included  in  the
operating costs,  since  it  is  considered  impractical  to
regenerate the charcoal.

Slag Granulation

Two  alternatives  exist for the control of waste water from
slag granulation and cooling:  (a) air cool and  mechanically
(dry)  crush the slag to a .more easily handled form, and  (b)
recover and recycle the slag granulation water.

Slag treatment must necessarily be  discussed  in  terms  of
metal-rich  slag and depleted slag.  The normal practice for
metal-rich slag treatment is the use of metal  cooling  pots
where  the  slag  is air cooled, followed by mechanical size
reduction,  and  then  by  the  metals   recovery   process.
Therefore,  discharges,  if  applicable, of slag granulation
water are normally associated with  processing  of  depleted
slag.

The cost for water treatment with the first alternative  (dry
processing)  would  be  nil  since  no  water  is  involved.
However an  "effective"  control  cost  for  this  dry  size
reduction alternative, defined as the difference in the cost
for  the  entire  dry processing system and the cost for the
wet slag granulation system with no water  treatment   (costs
based on new installation, no retrofit costs were included),
                        165

-------
can  be  estimated.  The effective cost, by definition, is a
calculated number assigned to a dry process alternative as a
waste water control cost so that it can be directly compared
with the waste  water  control  costs  associated  with  wet
process alternatives.  The capital cost for a new dry system
(installed),  including  cooling  potsf  crushers,  material
handling  equipment,  and  other  ancillary  equipment,  wa s
estimated   at  $U.69/annual  kkg  ($4.25/annual  ton),  and
operating costs were  estimated  at  $0.89/kkg   ($C.81/ton).
The   capital  and  operating  costs  for  a  new  wet  slag
granulation  facility,  including  only   the   quench   and
granulation   trough,   and  slag  pile  were  estimated  at
$0.59/annual kkg (SO.54/annual ton)   and  $0.11/kkg   (S0.10/
ton), respectively.  The effective water control capital and
operating  costs for the dry system would be, therefore, the
difference, or approximately SU.lO/annual kkg  ($3.72/annual
ton)   and  $0.77/kkg  ($0.7C/ton), respectively.  Capital and
operating costs for a slag granulation water control  circuit
are given in Table 4U.  As can be seen, only five of  the  13
companies  from  which cost data were ootained practice slag
granulation.   All  five,  however,  employ  some  form   of
recycle.  Capital costs for water treatment range from £0.23
to  $4.44/annual  kkg   (30.25  to  $U.03/annual ton).  These
costs include primary solids removal in  tanks,  thickeners,
and  ponds,  and  in one case, additional cooling in  coolina
towers, as well as associated pumps and piping.  The  capital
costs   average   $1.32/anriual   kkg    ($1.20/annual   ton).
Operating  costs  range  from  iO.05  to $C.84/kkg (SO.C5 to
$0.76/ton)  with an average of $C.25/kkg (iC.23/ ton).  Costs
for disposal of the depleted  slag  are  included  in -chose
cases  where  the  slag  is  landfilled,  but  not for those
companies that sell or reprocess their slag.

     Milling and_Classifying
Essentially, there are two alternatives for the  control  of
waste  water effluents from the metal-rich slag reprocessing
for metal value recovery:  (a)  remelt the processed slags  in
a  cupola, recover the metal values, and then cool and crush
the depleted slag  (as discussed under tne  slag  granulation
section) and (b) wet mill and classify the metal-rich slags,
thereby  recovering  the  metal  values, remove the depleted
slag and other  unacceptable  contaminants  from  the  waste
water and recycle the waste water.

The  cost  for  the  treatment  of  the waste water effluent
produced from the first alternative is nil  (except  for  the
slag  granulation  step  discussed  in  the  section on  slag
granulation).  Therefore, "effective"  waste  water  control
                        166

-------
costs  were  calculated for the purpose of comparing the wet
and dry waste water control costs.  The  effective  cost  is
defined  as  the  difference between the cost for the entire
dry processing system (with adequate air pollution controls)
and the cost for the wet processing  system  with  no  water
pollution  controls.  The capital cost for a new dry system,
including the cost of screening, pelletizing, and  materials
handling   equipment,   plus  a  complete  installed  cupola
facility equipped with air pollution controls and associated
equipment was estimated at $13.24/annual kkg  ($12.01/annual
ton);  and  operating  costs  were  estimated  at  $2.72/kkg
($2«47/ton).  These costs would therefore  be  the  cost  of
conversion  from  the  wet  to  the  dry  system  (excluding
retrofit costs).  The capital and operating costs for a  new
milling  and  classifying  facility including crushers, ball
mills, jigs, tables, etc., but minus the water control  cir-
cuit,  were estimated at $9.26/annual kkg ($8.40/annual ton)
and $1.76/kkg   ($1.60/ton),  respectively.   Therefore,  the
effective  water control capital and operating costs for the
dry treatment system would  be  the  difference,  or  $3.98/
annual  kkg   ($3.61/annual  ton)  and $Q,96/kkg  ($0.87/ton),
respectively.

Costs for the water control circuit  for  slag  milling  and
classifying facilities were obtained in the survey.  Capital
costs  ranged  from  $0.88  to  $16.91/annual  kkg  ($0.80 to
$15.39/ annual ton), with an average  cost  of  $6.UU/annual
kkg   (S5.84/  annual ton).  These costs include primary and,
in some cases, secondary solids removal in ponds  or  tanks,
and  associated  pumps  and  piping.  Operating costs ranged
from $0.32  to  $5.14/kkg   ($0.29  to  $U.66/ton),  with  an
average of $1.757 kkg ($1.58/ton).

Melting and Refining Furnace Exhaust Scrubbing


There  are  essentially  two  alternatives to the control of
waste water effluents  from  melting  and  refining  furnace
exhaust cleaning;  (a) employ dry air pollution controls such
as  baghouses  or  electrostatic  precipitators   and  (b) wet
scrub  the  gases,  collect  the  waste  water,   remove  the
unacceptable contaminants, and recycle the waste water.

The cost for the treatment of the waste water from the  first
alternative  is necessarily zero since no water is used.  In
a manner similar to that described previously, an  effective
cost  can  be estimated to compare the costs for  dry and wet
air pollution controls.  Capital and  operating   costs  were
estimated  from  published data at $3.72 to  $4.78/annual kkg
($3.37 to  $4.34/annual ton) and $0.44 to $0.72/kkg  ($O.UC to
                       167

-------
$0.65/ton), respectively, for new baghouse  facilities,  and
$7.78  to  $8.78/annual  kkg  ($7.06 to $7.96/annual ton) and
$0.67 to $0.89/kkg  ($0.61 to $0.81/ton),  respectively,  for
new electrostatic precipitator facilities.

Therefore, for example, the average cost to convert from the
wet to the dry collection system would be the average of the
above  costs, or $6.27/annual kkg ($5.69/annual ton) capital
cost, and $C.68/kkg  ($0.62/ton) operating cost  (based on the
average  of  the  range  of   baghouse   and   electrostatic
precipitator  costs).   The  capital  costs  for  a new high
energy venturi scrubber  (including installation) without the
water  control  circuit   were   estimated   at   $1.56   to
$2.17/annual  kkg   ($1.41  to  $1.97/annual  ton),  and  the
operating costs at $1.61 to $2.50/kkg  ($1.46 to $2.27/ton).

The "effective" waste water control  capital  and  operating
costs  for  the  dry  exhaust  gas cleaning alternative were
estimated as the difference in control costs for the dry and
wet systems, or $4.40/annual kkg  ($3.99/annual  ton)  and
$1.38/kg  (-$1.25/ton)  operating  costs, respectively.  The
effective cost by definition is a calculated number assigned
to a dry process alternative as a waste water  control  cost
so that it can be directly compared with waste water control
costs   associated   with  wet  process  alternatives.   Ine
negative effective  cost  means,  therefore,  that  the  dry
process  (a baghouse or an electrostatic precipitator) would
have a cost  advantage  over  the  wet  process  (a  venturi
scrubber)   even  before  the  waste  water control costs are
added to the wet process control costs.

The costs for the treatment  and  recycle  of  the  scrubber
effluent alternative were obtained from the industry survey.
Capital  costs ranged from $0.69 to $17.06/annual kkg  ($0.63
to $15.47 annual ton), with an average cost of $11.80/annual
kkg ($10.70/annual ton) .  These costs include  primary  and,
in  many cases, secondary solids removal, sludge dewatering,
and associated pumps and  piping.   Operating  costs  ranged
from  $0.13  to  $9.85/kkg  ($0.12  to  $8.93/ton),  with an
average of $3.31/kkg  ($3.00/ton).  These costs included  the
pH-adjusting medium, namely, lime, caustic, or ammonia.
Electrolytic Cell Operations
There  are  essentially  three  basic  alternatives  for ths
control of waste  water  effluents  from  electrolytic  cell
operations:   (a)  sell  the spent electrolyte, and  (b) treat:
spent  electrolyte  to  recover  or   remove   valuable   or
                         168

-------
undesirable  contaminants  and  reuse  the water for process
water  requirements,  such  as  for  slag  granulation,  wet
scrubbers,  etc., and (c)  evaporate the spent electrolyte to
recover nickel values as
As discussed in the section on control and  treatment  tech-
nology,  secondary  copper  electrolytic cell operations are
basically closed-loop systems.  The bleed solution is either
sold or treated to extract the valuable  components  of  the
contaminated electrolyte.  The costs for waste water control
and  treatment when the contaminated electrolyte is sold are
zero since no water treatment is involved.   The  costs  for
the  treatment  of  the  electrolyte  were  obtained  in the
industry survey from two plants.  Capital costs ranged  from
$1.31  to $2.08/annual kkg ($1.19 to $1. 89/annual ton), with
an average of $l,70/annual kkg   ($1. 54/annual  ton).   These
costs  include  cementation tanks for copper removal, and in
one  plant,  pH  adjustment   tanks   and   solids   removal
facilities.   After  the more extensive of the two treatment
processes, the water is of sufficient  quality  for  general
purpose   uses   and  could   (depending  on  the  operations
performed at the plant) be reused without further treatment.
Operating costs ranged from $0.32  to  $0.40/kkg   ($0.29  to
$0.36/ton), with an average of $0.36/kkg  ($0.33/ton).  These
costs  included  the cost of the iron for the cementation of
copper and the cost of pH-ad justment materials  (when  used) ,
without credit for recovered copper.

          Economics of Present Treatment Practices

In  the  following  paragraphs,  only the economics of those
treatment processes applied to waste water on a once-through
basis are discussed.  Process water recycle was considered  a
control rather than a treatment  technology, and was  covered
in  the  previous  paragraphs.   Only  the cooling of molten
metal involves  a  treatment  process  without  waste  water
recycle.

Costs  for  treatment of spray and quench cooling water were
obtained from two plants   (Plants  19  and  41,  Table  45) .
These  costs  include only the water treatment circuit, con-
sisting of primary solids removal and associated  pumps  and
piping.   Because the primary treatment is also employed for
other operations, the costs were apportioned on a flow basis
to obtain the  costs  of  spray  and  quench  cooling  water
treatment alone.

Plant   19   reported  their  water  treatment  capital  and
operating costs at $4.57/annual  kkg  ($4. 14/annual  ton)  and
$0.78/kkg    <$0.71/ton),   respectively;   the  capital  and
                          169

-------
            TABLE 45.   COST EFFECTIVENESS FOR CONTROL AND TREATMENT
                       OF WATER FROM MOLTEN METAL COOLING
Capital Operating
Costs(b), Costs'-5''
Alternative. $/annual kkg $/kkg
Designation '($/ annual ton) ($/ton)
1

2

4

5
5

6

Noncontact
System
0.0
(0.0)
0.05
(0.05)
0.78
(0.71)
2.81
(2.55)
0.56
(0.51)
0.79
(0.72)
6.23
(5.65)
0.0
(0.0)
0.01
(0.01)
0.13
(0.12)
0.56
(0.51)
0.10
(0.09)
0.13
(0.12)
1.19
(1.08)
Loadings, k /kkg (Ib/ton)
Suspended
Solids Copper
1.69
(3=38)
0.171
(0.342)
0.126
(0.252)
0.0056
(0.0112)
0.0
(0.0)
0.0
(0.0)
0.052
(0.1041
0.010
(0,020)
0.004
(0.008)
0.0028
(0.0056)
1.7xlO"5
(3.4 x 10 ~5
0.0
(0.0)
0.0
(0.0)
9.7x10"^
Zinc
0.034
(0.068)
0.0053
(0.0106)
0.0047
(0.00941
4.4x!0"6_6
)(8o8 x 10
0.0
(0.0)
0.0
(O0o;
,NLcCd)
Oil
and
Grease
NR^C)

NR

NR

NR
)
0.0
(0.0)
0.0
(0.0)
NLC
(a)   Control-  and  treatment-alternative  designation defined  in Figure 12.
(b)   Ref:   Table  44     and  Table  36.
(c)   NR = not reported.
(d)   NLC = nc loadings calculable.
                              170

-------
operating costs for Plant 41 were reported  at  $l.Q2/annual
kkg    <$0.93/annual   ton)    and   $0»19/kkg   ($Q.17/ton),
respect!vely*

          Cost Effectiveness of Present Practices

Contact Cooling of Molten Metal

The cost data for spray and quench cooling of  molten  metal
presented  in  Table  45 were plotted against a single waste
water pollutant, suspended solids.  As noted in Figure 3 the
reduction in copper and zinc follows the same pattern as the
reduction in suspended solids concentration  (i.e., treatment
capable of removing one of these pollutants will also remove
the others).  Therefore, only suspended solids loadings were
employed in the cost  effectiveness  curves  in  Figures  17
through 21.

In  Figure   17,  it  is  clearly  shown  that  the  costs of
pollutant removal follow an exponential  relationship.   The
most  costly  treatment alternative is noncontact cooling to
achieve  no  discharge  of  pollutants.   The  capital   and
operating  costs  for  noncontact  cooling were estimated at
$6.23/annual kkg  (S5.65/annual ton)  and  $1.19/kkg   ($1.087
ton), respectively*

In comparison with a noncontact cooling alternative, the use
of  extended  settling in a mixed process water reservoir is
shown to be  equally effective in achieving no discharge   (as
demonstrated  by  Plant  9P  see  Table 44)  at comparatively
lower costs  (i.e., $2.81/annual kkg  ($2.32/  annual ton)  and
$0.56/kkg   ($0051/ton)  for  capital  and  operating  costs,
respectively).  These costs would be a function of the  size
and  the  construction  material of the settling  facilities.
Plant 10  (see Table 44) lias been able to  employ  a   smaller
pond  by  placing  sand  filters  in the recycle  circuit for
suspended solids removal.   These  costs  are  shown  to  be
considerably lower,  $0.79/annual kkg.($0.17/annual ton) and
$0.13/kkg   ($0.11/ton)  for  capital  and  operating  costs,
respectively.

Simple settling and recycle appear  to be even lower  in cost
while maintaining the same control  effectiveness  (no  dis-
charge.  Plant  17).   This option, however, applies  only to
those operations not employing a  charcoal   cover over  the
molten metal.

Thermal  discharge,  which  is  not plotted  on these  graphs,
would show a similar cost effectiveness curve when  loadings
are   calculated   in  kg-cal/kkg   (Btu/ton)  discharged  to
                         171

-------
- a
7


6

§ 5
4-1

r,
4-1
0 4
u -••
I— 1
(0
u
-H
a
ca
o 3






2

1


0
7



6 £
i|

5
00
^

- 4
U
cn
O
U
1— 1
ra
•H 3
a
crj
_ u





2

1
J-


0
1

















*

1
)


0
(0



t


v-ft/--5* Noncontact Cooling System —




I


,


1
©5



1
I
_l
A
\ ^ Average

^^-_
5 A3 t
O
1 1 | j 1




LEGEND


Numbers: Control and Treatment Alternative
Designation Defined in
Figure 12
O : Capital Cost Data Point
/\ : Operating Cost Data Point









Q4
~~~ " 	 	 	 	 	 ~A— 	 	

i i i i,l II i i 1
.0 0.05 0.10 0.
.0) (0.10) (0,20) (0.













1




—"~




• 	 — -_- 	 „.,
/TVi 3 . 1 ,
1 UJl i . /YA 	 -4

1.2


1.0

M
^ „ ^
0.8 3

„
4J
cn
O
a
•H
CO
$-i
QJ
a
n , o
0.4

n o
u. /


,0.0
.7


-1.0


.. o.e
o

•c/y
**
4J
U
C
4J
CD
M
11
- 0,4 ex
o

- .
-0.2



J3.0
30) (3.4)
            SUSPENDED SOLIDS LOADINGS, kg/kkg (lb/ ton)
Figure 17.  Cost effectiveness of control and t
            of water fror molten rretal conlina.

-------
5

-t
Capital Cost
ho U
1


0

5

4
00
* 3
1 !
Capital Cost
hO
1



0
(0
~4 ''- -Dry System
n
-\
^ — \^ 	 Average



1
.0 0.02 0.04
0) (0.04) (0.08) (

LEGEND
Numbers: Control- and Treatment -Alternative
Designation Defined in
Figure 13
O : Capital Cost Data Point
A : Operating Cost Data Point
A

i

l I \ \ /\
0.06 0.08 0.10 0.12 0.14 ^
0.12) 0.16) (0.20) (0.24) (0.28)
SUSPENDED SOLIDS LOADING, kg/kkg (lb/ ton)



—
~"

1
	 ,, .. I 	 f"\ •„ ,
r 304 3
(6.8) (7,
1.0

0.8
bO
0.6 £
o
4>
Operating Cost,
u.z
1

0.0 -
6
2)
                                                                                       -.1.0
                                                                                         0.8
                                                                                         0.6
                                                                                         0.4
                                                                                        0.2
                                                                                      _  0.0
Figure 18.  Cost effectiveness of control and treatment
            water from slag quenching and granulation.

-------
24
22
20
18
16
c
o
Z 14

J" 12
en
o
"10
to
-U
•i 8
ra
U
6
4
2
0
20
18
16
<* ^
^
^
£ 12
~ 4-)
01 i n
o 10
u
r-t
ro o
ij "
•H
a
ra
u 6
4
2
0
(0.
£
3

r;
>
i
r^ 4,
8
0)



^, Dry System
O4
A4
	 Average
^ 	
,
1
(2






.c
.(


LEGEND
Numbers: Control- and Treatment-Alternative
Designation Defined in
Figure 14
O : Capital Cost Data Point
A : Operating Cost Data Point

i i i 1 f i 1 	 1 	 1
2,0 3
)) . (4.0) ^ (6
—

—
—

2
— Q 1 1
^ A.-frf 	 A *rrt
V ' \/
.0 26.0 l 32.
.0) (52.0) (65.
5
~
4
A!
X
 4J
to
O
o
oc
c
•H
u -
9 ro
*- ^
Q)
a
o
1
0
6
2)
^
4

o
4J
3 <^
4J
(0
O
O
M
l-> 10
Operatin
0

                 SUSPENDED  SOLIDS  LOADINGS,  kg/kkg (Ib/ton)

Figure 19.  Cost effectiveness of control and treatment of
            v/atox from slao millino and classification.

-------
(.n

20
20
-
i
i ic

, A

O
4-)
co" 12
-U
co
O
U
I-H
ra
-1-1 B
>rf o
O.
CO
U
4




1
1U

-
j*?
^ 12
u
y)
o
" 8
ra
•H
ti.
\ 5 ' —
^5,6
O6



\xr— -- Averaefe
Ao5
>A
LEGEND


Numbers :


O
6

\
5 \ - Baghouse
\ -"/
\ /^'/ 4
t 6\ X / r^4
\ ADVr / C J
ra u\ (A A / ~
° CvtxT
4** ^
-------
-1. 
-------
navigable waters.  Again  those  alternatives  effective  in
removing  the other waste water pollutants would also reduce
thermal discharges.

The  following  conclusions  can  be  drawn  at  this   time
regarding the cost effectiveness of control and treatment of
waste water from spray and quench cooling of molten metal:

          (1)   The most cost effective means of
               control for new plants universally
               applicable is settling in a relatively
               small mixed process water reservoir
               combined with filtration and recycle.
          (2)   The most cost effective treatment
               alternative for existing plants
               would be (a) settling and
               recycle, or (b)  settling, filtra-
               tion, and recycle, depending on the
               particular aspects  (e.g., charcoal
               cover on ingots) of the casting
               operation.

Slag Granulation

Slag  granulation  waste  water control and treatment costs,
together with the waste water pollutant loadings, are  given
in  Table 46.  The capital costs and the operating costs, as
a function of these loadings, are presented in Figure 18.

Again, the cost effectiveness  curve  shows  an  exponential
relationship.   The most expensive alternative is conversion
to the dry processing system with approximately $4.69/annual
kkg ($4.25/annual ton) and $0.89/kkg  ($0.81/ton) capital and
operating costs, respectively.  Simple settling  for  solids
removal and recycle is also shown to be an effective control
alternative, but with much lower costs, namely, $0.28/annual
kkg   ($0.25/annual  ton)  and $0,05/kkg  ($0.057 ton) capital
and operating costs, respectively.

The following conclusions can be drawn concerning  the  cost
effectiveness  of  various  alternatives for control of slag
granulation waste water.

          (1)  The most cost effective means of
               control for new plants is primary
               settling and complete recycle for
               mixed process water.
          (2)  The most cost effective means of
               control for existing plants is the
               same system, namely, combined pri-
               mary settling and complete recycle.
                         177

-------
            TABLE 46.   COST EFFECTIVENESS  FOR CONTROL AND TREATMENT
                       OF WATER FROM SLAG  QUENCH AND GRANULATION
Capital
Costs (b)
Alternative $/annual kkg
De s igna t ion(a)( $ / annua 1 t on)
1
2
4(d)

4
5

Dry-System
Conversion
Dry-System
Effective
Cost
0.0
(0.0)
0.28
(0.25)
0.39
(0.35)
1.87
(1.70)
0.78
(0.71)
4.69
(4.25)
4.10
(3.72)

Operating
Costs (b)
$/kkg
($/ton)
0.0
(0.0)
0.05
(0.05)
0.06
(0.05)
0.37
(0.34)
0.13
(0.12)
0.89
(0.81)
0.77
(0.70)

Loadings , *•
Suspended
Solids Copper
3.51
(7.02)
0.0
(0.0)
= 0.0
(=0.0)
0.0056
(0.0112)
0.126
(0.252)
0.0
(0.0)
0.0
(000)

NLC(C)
0.0
(0.0)
= 0.0
(=0.0)
1.7xlO"55
3.4 x 10"
0.0028
(0.0056)
0.0
(0.0)
0.0
(0.0)

^ kg/kkeflb/torrt
Zinc
NLC
0.0
(0.0)
= 0.0
(=0.0-)
)(1. 4 x 10"
0.0078
(0.0156)
0.0
(0.0)
0.0
(0,0)

Oil
and
Grease
NLC
0.0
(0.0)
= 0.0
(=0.0)
(e)
NR
NR

0.0
(000)
0.0
(0.0)

(a)  Control- and treatment-alternative designation defined in Figure 13.

(b)  Ref:   Table 44     and Table 37.

(c)   NLC  = no loadings calculable.

(d)   Seasonal discharge only, with heavy rainfall.

(e)   NR = not reported.
                            178

-------
               mary settling and complete recycle. --

Slag Milling and Classifying

The cost effectiveness data pertinent to. waste  waters  from
slag  milling  and classifying;are given in Table 47.  These
data are plotted  in  Figure  19.   Again?  the  exponential
relationship  is  noted.  The m"b:st:costlyr alternative is the
conversion from conventional wet milling and classifying  to
pyrometallurgical  processing in a .cupola-  These conversion
costs are  approximately  $13.24/annual  kkg.   ($12aOd/annual
ton)  and $2.72/kkg ($2.47/ton). capital and .operating/costs „
respectively.  However, these., high capital  costs  would "be
incurred only when a plant converted from the wet to the dry
system.   The  effective  waste  water  control  capital and
operating costs for the dry system  {defined earlier  as  the
cost  of  the  complete dry system minus the cost of the wet
system without controls) have been estimated at $3.98/annual
kkg   ($3.61/annual  ton)   and   $0.'96/kkg    {S0.87/   ton) 9
respectively.   The  least  costly  alternative  is  primary
settling, filtration, and recycle; these capital and operat-
ing costs are $0.88/annual kkg  ($0.80/annual ton) and $C,96/
kkg  ($0.87/ton),  respectively.   The  average  capital  and
operating costs for the present practices by the industry in
waste water control technology are estimated at $6,44/annual
kkg    ($5.84/annual   ton)    and   $1.75/kkg   ($1,587  ton)f
respectively.

The following conclusions can be drawn at this time  regard-
ing  the cost effectiveness of waste water pollutant control
from slag milling and classifying water.

           (1)  The most cost  effective means of
               control  for new plants is the instal-
               lation of.a pyrometallurgical
               processing facility  (based on industry
               average  costs).
           (2)  The most cost  effective means of
               control  for existing wet processing
               plants is settling  in a. relatively
               small reservoir, followed by additional
               solids removal  by filtration and
               complete recycle.

Melting and Refining Furnace  Exhaust Scrubbing

Cost effectiveness data for furnace  exhaust   scrubbing  are
presented  in  Table 48.  These data are plotted  against the
suspended solids loadings in  Figure 20.;.
                            179

-------
           TABLE 47.  COST EFFECTIVENESS FOR CONTROL AND TREATMENT
                      OF WATER FROM SLAG MILLING AND CLASSIFYING
Capital Operating
Costs O^t Costs G>)»
Alternative $/ annual kkg $/kkg
Designation^a{$/annual ton) ($/ton)
1

1

2

3

3(e)

4

4

5

Dry- System
Conversion
Dry-System
Effective
Cost
0.
(0.
0.
(0.
2.
(1.
0.
(0.
16.
(15.
10.
(9.
1.
(1.
0.
(0.
13.
(12.
3.
(3.

0
0)
0
0)
06
87)
05
05)
97
39)
31
35)
97
79)
88
80)
24
01)
98
61)

0.
(0.
0.
(0.
0.
(0.
0.
(0.
5.
(4.
1.
(1.
0.
(0.
0.
(0.
2.
(2.
0.
(0.

0
0)
0
0)
38
34)
01
01)
14
66)
93
75)
32
29)
96
87)
72
47)
96
87)

Loadings , kg/kkg(lb/ton)
Suspended
Solids Copper
25.99
(51.98)
32.6
(65.2)
3.182
(6.364)
1.247
(2.494)
= 0.0
(=0.0)
0.266
(0.532)
= 0.0
(=0.0)
0.0
(0.0)
0.0
(0.0)
0.0
(0.0)

9
(18
0
(0
0
(0
0
(0
_
.275
Zinc
7
.550) (14
.11
.22)
.10
.20)
.044
.088)
0.0
(=0.0)
0
(0
~
.095
.190)
0.0
0
(0
0
(1
0
(0
^
.322
,644)
,00014
,00028)
.631
.262)
.22
.44)
0.0
(=0.0)
0
(0
=
.047
.094)
0.0
(=000^ (=0.0)







0.0
(0.0)
0.0
(0.0)
0.0
(0.0)








0.0
(0.0)
0.0
(0.0)
0.0
(0.0)

Oil
and
Grease
0.092
(0.184)
NLC

(c)

NR(d)

NR

= 0
(=0



.0
.0)
0.087
(0.174)
= 0
(=0
0
(0
0
(0
0
(0

.0
.0)
.0
.0)
.0
.0)
.0
.0)

(a)   Control-  and  treatment-alternative  designation  defined  in  Figure
(b)   Ref:   Table 44     and  Table  38.
(c)   NLC = no  loadings calculable.
(d)   NR = not  reported.
(e)   Seasonal discharge only, with heavy rainfall.
                             180

-------
              TABUS  48.  COST EFFECTIVENESS FOR CONTROL AND
                         TREATMENT OF WATER FROM WET SCRUBBING
Capital % Operating
Loadings (b)_, ka/kksClb/ton)
Costs (b) , Costs (b) ,
Alternative, N $/annual kkg $/kkg Suspended
Designation CS /annual ton) ($/ton) Solids Copper
1

1



3(c)
4

4

5

5

5

6

6

6

Dry-System
Conversion
Dry-System
Effective
Cost
0
(0
3
(3
6
(6

6
(6
10
(9
11
(10
17
(15
10
(9.
10
(9
16
(14
17
(15
4
(3
4
(3

.14
.13)
.44
.12)
.77
.14)
-
.93
.29)
.49
.51)
.10
.07)
.06
.47)
,74
74)
.37
.41)
.11
.61)
.46
.84)
,25
.85)
.40
.99)

0
(0
0
(0
1
(1

2
(2
2
01
2
(2
9
(8
2
(2
3
(3
3
(2
4
(4
1
CO
— 1
C-l

.03
.03)
.63
.57)
.35
.22)
-
.22
.01)
.02
.83)
.21
.00)
.85
.93)
.29
.08)
.33
.02)
.15
.86)
.72
.28)
.-8
.53)
.38
.25)

128.5
(257.0)
7.
C150
66
C133
-
4.
(8.
0.
CO.
0.
Cl.
0.
CO.
0.
CO.
0.
C00
0.
Cl.
0.
C00
0.
(0.
0.
fOt

521
042)
.6
.2)

22
44)
0
0)
779
558)
0
0)
0
0)
113
226")
568
136)
050
100)
0
Oi
0
0')

0.
(0.
0.
(1.
0.
(0.

0.
(0.
0.
(0.
0.
(0.
0.
(0.
0.
CO.
0.
C00
0.
(0.
0.
CO,
0.
C00
0.
ro.

006
012)
548
096)
001
002^
-
476
952)
0
0)
001
002)
0
0)
0
0)
005
010)
001
002)
018
036)
0
0)
0
0)

Zinc
1
(2
2
(5
0
(0

1
(3
0
CO
0
CO
0
(0
0
(0
0
(0
0
CO
0
(0
0
(0
0
CO

.024
.048)
.971
.942)
.016
.032)
-
.776
.552)
.0
.0)
.003
.006)
.0
.0)
.0
.0)
.181
0362)
.0142
00284)
.009
.018)
.0
.0)
.0
.0)

Oil
and
Grease
0.0
(0.0)
0.321
(Oe642)
0.053
(0.106)
-
0.133
(00266)
oeo
(000)
0.034
CO. 068)
0.0
(0.0)
0.0
(0.0)
0.007
(0.014)
0.002
CO. 004)
0.016
(00032)
0.0
C000)
0.0
(0.0)

(a)   Control- and  treatment-alternative designation defined in Figure 15.

(b)   Rcf:   Table 44     and Table 41.

(c)   Alternative not currently explored but amenable  to cooling and  solids
     separation requirements
                             181

-------
The most costly alternative is wet scrubbing with  extensive
water  treatment  rather than conversion to a dry system for
air pollution control.  The dry system baghouse  costs  were
$4,25/annual   kkg    ($3.85/annual   ton)   and  $0.587  kkg
($0.53/ton) for capital and operating  costs,  respectively.
The  capital  and  operating  costs  for  the entire dry air
pollution system were much  lower  than  the  wet  scrubbing
water  treatment circuit alone.  Comparison of the installed
cost for a complete dry system with that for a complete  wet
system/  excluding  the water treatment and recycle circuit,
shows that the effective capital and operating costs for the
dry system were  $2.38/annual  kkg  (32.16/annual  ton)  and
$l.U8/kkg  {S1.34/ton), respectively*

All  the control systems employed involve complete or nearly
complete recycle.   The  no  discharge  system  had  similar
control and treatment costs.  The most costly recycle option
was  primary  and  secondary settling, sludge dewatering, pH
adjustment, and complete recycle.  These capital and operat-
ing costs were $17.06/annual  kkg   ($15.47/annual  ton)  and
59.85/kkg  <$8.93/ton),  respectively.   The least costly no
discharge option was  primary settling, sludge dewatexing, pH
adjustment, and complete recycle.  The capital and operating
costs  were  $10.49/annual  kkg   ($9.51/annual   ton)   and
$2.02/kkg  <$l,83/ton),  respectively.   Therefore, even the
least costly no discharge  water  treatment  alternative  is
more costly than dry  collection methods.

The  following  conclusions  can  be  drawn  from  the  data
presented*

           (1)  The most cost effective means of
               control for new plants is the dry
               (baghouse) air pollution control
               for furnace exhaust fumes,
           (2)  The most cost effective means of
               control for existing wet scrubbing
               facilities is primary settling,
               sludge dewatering, pH adjustment,
               and complete recycle.
Electrolytic Cell_ Operations

Cost data  for  two  electrolytic  refining  operations   are
presented  in Table U9,  These cost, data are plotted  against
the suspended solids loadings in Figure 21.  The  data   show
that  current  treatment  technology  is  available to limit
significantly  the  quantity  of  waste   water   pollutants
discharged.
                           182

-------
            TAKE 49.   COST EFFECTIVENESS  FOR CONTROL AND TREATMENT
                        OF WATER FROM ELECTROLYTIC CELL OPERATIONS
                Capital       Operating 	Loadings    kg/Jckgdb/ton')
                Costs(b-> >    Costs(b) ,                              Oil
•Alternative    $/annual  kkg    $/kkg     Suspended                   and
 Designation^'($/annual  ton)  ($/ton)      Solids    Copper  Zinc    Grease
1

2(d)
3

1.31
(1.19)
-
2.08
(1.89)
0.32
(0.29)
-
0.40
(0.36)
3.38
(6.76)
-
0.0048
(000096)
0.092
(0.184)
-
3xlO'8f
6 x 10~£
0.127
(0.254)
-
. 3xlO~7
*X6 x 10"
NR(C)

-
7NLC(6)
7)
 (a)   Control- and treatment-alternative designation defined in Figure i6

 (b)   Ref:  Table 44     and Table 42.

 (c)   NR = not reported ,

 (d)   Plant sells electrolyte, no costs or loading available.

 (e)   NLC =  no loadings calculable
                                 183

-------
Plant 8 (see Table 44)  treats a continuous  bleed  of  spent
electrolyte  by cementation with scrap iron before discharge
to a municipal-industrial primary treatment plant.   Capital
costs   for  cementation  were  estimated  at  approximately
$1.31/annual kkg ($1.19/annual ton)  and operating  costs ,at
$0.32/kkg  ($0.29/ton).   At  Plant 12, waste electrolyte is
produced only during breakdown.  The  waste  electrolyte  is
cemented  with  iron,   pH adjusted,  and sand filtered before
discharge to a mixed process water reservoir (a  lake  which
continuously  discharges),  and  recycled to a central water
treatment plant serving the entire facility.  Capital  costs
were  estimated  at $2.OS/annual kkg {$1.89/annual ton), and
operating costs at $0.40/kkg ($0.36/ton).  A portion of  the
process waste water produced during precious metals recovery
at  Plant  1  is  currently  impounded  in lined ponds.  The
capital costs of these  ponds  with  areas  totalling  about
0.405 ha (1 acre) is approximately $40,000.

Because of the limited data available, control and treatment
effectiveness  and  costs  were  assumed to follow the usual
relationship.  It is expected  that  for  no  treatment  the
costs  will  be  less and the pollutant loading much higher,
and for additional  end-of-pipe  treatment,  such  as  total
evaporation  or  reverse osmosis, the cost would be at least
two to three times greater while improving the  waste  water
quality only slightly.

The  following  conclusions  can  be  drawn  from  the  data
presented.

          (1)  The most cost effective means of
               control for new plants is treatment
               (cementation, pH adjustment, and
               filtration) followed by recycle
               to processes with low quality water
               requirement.
          (2)  The most cost effective means of
               treatment for existing facilities
               is cementation, pH adjustment, and
               filtration.
            Economics of Additional Control and
                    Treatment Processes
An indepth cost study of those secondary  copper  facilities
currently  known  to  be  discharging process waste water to
navigable waters has been made.  Approximate costs as needed
to achieve compliance to the  recommended  no  discharge  of
                            184

-------
process  was-te  water  pollutant  guidelines  are  presented
below.

Plant 1

This   plant  is  a  secondary  copper  facility  practicing
electrolytic refining.  The  process  starts  at  the  blasr
furnace where scrap is charged.  Fluxes are added and copper
matte  and  slag  are tapped.  The slag is granulated at the
furnace site, and  the  matte,  along  with  blister  copper
received  from both domestic and foreign sources, is charged
into a reverberatory furnace.  The resultant copper is  casr
into  anodes  for  subsequent  electrolytic  refining.   The
product cathode copper is melted with high grade  scrap  and
cast  into billets, wire cars, cakes, and tubes.  Slimes are
collected from -cue rank house and are blended with purchased
slimes.  On-site recovery of precious metals  is  practiced.
Electrolyte is purged from the tank house circuit, and after
copper  removal  by  means of electrowinning calls, Ni3O4 is
produced as a byproduct.   Two  barometric  condensers  with
deintrainment   devices   are   used   for  this   byproduct
operation.   Copper  powder  is  also  produced  on-site  by
intentionally operating the electrolytic tanks incorrectly.

Recently,  numerous changes to existing plant water circuits
were  made.   Conversion  of  furnace  fume   scrubbers   to
baghouses  has eliminated this large source of process waste
water.  Part of the Bosh water is in complete closed circuit
with two cooling towers, while the remainder is operaced  on
a  noncontact  basis.   Spent  electrolyte is evaporated for
NiSO4 production and the barometric condensers are  operated
with  efficient  deintrainment: devices.  Slag milling is not
performed on-site.  A cooling tower  will  be  used  on  the
current  once-through  slag  granulation process waste water
source; the anticipated blowdown of this  3,000  1/min   (800
gpm)   source   is  unknown,  but  has  been  conservatively
estimated at 10 percent for the purposes of  this  analysis.
Three  process  waste  water sources are currently generated
during precious metals recovery from slimes.   Part  of  the
largest  source  from selenium recovery will be used to cool
the furnace gases prior to particulate removal  in  the  new
baghouses,  while  the remainder  (assumed to be a maximum of
23 cu m/day  (6,000 gpd}j will be discharged.  The other  rwo
sources,  much smaller in volume, are currently impounded in
four lined ponds.

Various recycle and reuse approaches for the small remaining
flow  (i.e.,  10 percent blowdown from  slag  granulation  and
small  precious metals recovery flow equal to maximum of 435
cu m/day  (80 gpd) plus 23 cu m/day  (6,000  gpd)  or  U58  cu
                          185

-------
in/day  (121,000  gpd) )   are  available  in  order to achieve
compliance to the recommended no discharge of process  waste
water pollutants to navigable waters guideline.  In order to
develop a cost estimate, the costs of artificial evaporation
are used, which should represent the maximum costs that this
facility should have.
    Capital Costs

    Recycle and reuse
    $/Annual kkg ($/Annual ton)

    Annual Costs

    Recycle and reuse
    $/kkg  ($/ton)
                                            1971 $

                                           $534,000
                                              2.78 (2.55)

                                             $/year
                                           $270,000
                                              1.40 (1.28)
Plant 7
Plant  7  is  a  secondary  brass and bronze facility.  Data
indicate that ingot quenching water is  used  to  indirectly
cool  an aluminum furnace door and is then discharged.  This
discharge is extremely small and has  been  estimated  at  a
maximum  of  2,500,000  gal/month,  since  a  large  unknown
portion is lost through volitilization.  Simple pumping  and
repiping  of  this  small volume back to the ingot quenching
pit should provide compliance.  Costs are negligible.

Plant 26

This  is  a  secondary  brass  and  bronze  facility,  which
currently  recirculates  all  of  its scrubber water with no
discharge.  Some ingot quenching water   (maximum  of  12  cu
m/day  (3,080  gpd))  is commingled with nearly 227 cu m/day
(60,000 gpd) of noncontact cooling water.   One  method  for
complying   to   the  recommended  limitation  would  be  to
segregate the contact portion of the discharge,  settle  out
suspended  solids  and  recycle  this  flow.  Costs for this
alternative are as follows:
                                                1971 $

                                               $4,000
                                                0.58 (0.53)
    Capital Costs

    Clarifier for contact water
    $/Annual kkg ($/Annual ton)

    Annual Costs

    Negligible

Plant 32
Plant 32 is a secondary copper electrolytic  refinery  which
                          186

-------
operates  its  wire bar casting cooling line in a noncontact
mode.  A treatment facility operating  on  an  electrostatic
precipitator   and  precious  metal  scrubber  effluents  is
currently discharging extremely low concentrations of metals
in about 380 cu m/day (100,000 gpd) of process waste  water.
Plant  personnel  indicate  that there would be no technical
difficulties in recirculating this flow.  Piping and pumping
costs are considered negligible.

Total Costs

The total estimated costs to Plants 1 and 26, on  the  basis
of   1971   dollars,   are  $538,000  capital  and  $270,000
operating, most  of  which  is  attributable  to  additional
treatment and control technology at Plant 1.
                  Nonwater Quality Aspects
Energy Requirements

Specific data on energy requirements were not available from
any  of  the plants surveyed.  Electrical energy is consumed
in the  waste  water  treatment  for  operation  of  process
equipment, such as pumps/ blowers, centrifuges, and filters.
The  vast  majority  of  operations  was located outdoors in
unheated  and  unlighted  areas,   and   little   fuel   and
electricity consumption was required.  Mechanical operations
totaling   50   HP   or   less  are  typical;  these  energy
requirements would amount only to 14.9 kwhr/annual kkg  (13.5
kwhr/annual ton)  (for 7200  hr/yr,  and  18,000  kkg  annual
secondary  copper  production)  or $0.15/kkg  ($0.14/ton)  (at
$0.01/kwhr), which is  negligible  when  compared  with  the
total energy consumption in the industry.

Thermal  energy  requirements  are nearly nonexistent in all
waste  water  treatment  processes,  except   for   the   dry
processing   of   the  metal-rich  slag.   This  alternative
involves remelting the metal-rich slag and  low-grade   scrap
metal  in  a  blast furnace, cupola, or rotary furnace.  The
thermal requirement for  fuel  for  the  slag  treatment  is
estimated  at  150,510  kg-cal/kkg (542,670 Btu/ton)  (10,000
tons/year of slag processed) or  $1.75/kkg   ($1.59/ton)   (at
$0.01/kwhr).
 Solid Waste Production
 Only
very   few  control  and  treatment  technologies
                           187

-------
identified  in  this  document  produce  solid  waste  as an
adjunct to their operation.  Solid wastes  are  produced  in
pH-adjustment   operations   employed  for  the  purpose  of
neutralization  (resulting  in  precipitation  of  insoluble
salts)   or to increase the insolubility of metal hydroxide^s.
The  only  instance  where  pH  adjustment  is   universally
employed is in wet scrubber operations.  The lime or caustic
addition  in  this case is not for the control and -treatment
of waste water effluents, but  for  the  protection  of  the
scrubber's metal surfaces against corrosion.

One  treatment  process  (Plant 32) involves extensive use of
pH adjustment, settling, and filtration for the treatment of
effluents from copper smelting operations.   A  sludge  pro-
duction  of 98 kg/kkg (196 Ib/ton), containing 35 percent by
weight of solids, was reported.

All other solid wastes noted result from the  collection  of
solids  involved  in  the production process (e.g., charcoal
employed for metal oxidation  prevention)   or  are  combined
with  production  solid  wastes   (e.g.,  a small quantity of
neutralization sludge at Plant 11  is  discharged  with  the
depleted slag after the milling and classifying operation).
                           188

-------
                         SECTION IX
       BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY
         AVAILABLE—EFFLUENT LIMITATIONS GUIDELINES
                        Introduction
The  effluent  limitations  that must be achieved by July 1,
1977, are  to  specify  the  degree  of  effluent  reduction
attainable  through  the application of the best practicable
control  technology  currently  available.    Such   control
technology  is  based on the average of the best performance
by plants of various sizes and ages, as  well  as  the  unit
processes  within  the industrial category.  This average is
not based upon a broad range of plants within the  secondary
copper industry, but upon the performance levels achieved by
the  exemplary  plants.   Additional  consideration was also
given to

          (1)  The total cost of application of
               technology in relation to the effluent
               reduction benefits to be achieved
               from such application.
          (2)  The size and age of the equipment and
               plant facilities involved.
          <3)  The process employed.
          (4)  The engineering aspects of the
               application of various types of
               control techniques.
          (5)  Process changes.
          (6)  Nonwater quality environmental
               impact  (including energy requirements).

The best practical control  technology  currently  available
emphasizes  effluent treatment at the end of a manufacturing
process.  It includes  the  control  technology  within  the
process  itself  when  the latter is considered to be normal
practice within the industry*

A further  consideration  is  the  degree  of  economic  and
engineering  reliability,  which must be established for the
technology to  be  currently  available.   As  a  result  of
demonstration projects, pilot plants, and general use, there
must  exist  a  high degree of confidence in the engineering
and economic practicability of the technology at the time of
commencement of construction or installation of the  control
or treatment facilities.
                        189

-------
         Industry CategQry_and Waste_Water .Streams
The  secondary  copper  industry  is  herein defined as that
portion of SIC 3341  {Secondary  Smelting  and  Refining  of
Nonferrous   Metals)  which  consists  of  plants  primarily
engaged in recovering copper metal and  copper  alloys  from
scrap and from residues from copper and copper alloy melting
operations.   The  definition  includes  plants  melting and
refining copper alloys from produced secondary brass  and/or
secondary  bronze  scrap  sources  to produce alloyed copper
ingots, as well as  those  melting  and  refining  purchased
copper-bearing  scrap  to  recover  pure  copper  (unalloyed
copper) .  Not included in this category are plants that were
designed primarily to process virgin copper  from  ores,  or
plants that remelt scrap produced in their own process.

Rather   than  attempt  to  recommend  effluent  limitations
guidelines  for  subcategories  of  the  industry  that  are
difficult  to  specify,  a  more practical approach for this
purpose is to deal with  the  various  waste  water  streams
themselves.  The streams identified are

           (1)   Waste water from direct contact cooling
               of metal (ingots, anodes, billets, or
               shot).
           (2)   Waste water from slag quenching and
               granulation.
           (3)   Waste water from slag milling and
               concentration.
           (4)   Waste water from wet air pollution
               control systems.
           (5)   Waste water from electrolytic refining.

Each stream has an associated loading of pollutants per unit
of   product   produced.    For   example,  the  recommended
guidelines would require a smelter generating  only  contact
cooling waste water to meet effluent limitations established
for  that  waste  stream.    A smelter generating waste water
from contact molten metal cooling, slag granulation, and wet
air pollution control would be required to meet the effluent
limitations established  for  each  respective  waste  water
stream.

On  the  basis  of  information:  contained  in  sections III
through VIII of this report, a determination has  been  made
as  tc  the degree of effluent reduction attainable for each
of the  process  waste  water  streams  listed  through  the
application  of  the  best  practicable  control  technology
currently available.
                           190

-------
               Waste Water From_.Metal Cooling


Effluent Limitations Based on the Application
of the Best Practicable Control Technology
Currently Available
The recommended effluent limitation based on the application
of  the  best  practicable  control   technology   currently
available  is no discharge of process waste water pollutants
to navigable waters.

The achievement of this limitation by  use  of  control  and
treatment  technologies identified in this document leads to
the complete recycle, reuse, or  consumption  of  all  water
within  the  combined  processes  of  the  industry  with an
associated result of no discharge of water.
Identification of_Eest Practicable Control
Technology Currently Available
The  best  practicable  control  and  treatment   technology
currently  available for waste water from the direcr contact
cooling of metal in the secondary  copper  industry  is  the
elimination of water discharge by recycling and reuse of all
waste  waters.  With reuse or recycle of water, the need for
solids and oil removal will be dictated by plant operational
procedures.  Removal of solids such as the charcoal used  to
cover  copper alloy ingots and the oxide scale and mold wash
from anode casting requires settling and  filtration  before
the  water  is  reused.  The pond used for settling provides
cooling.  Alternatively, a cooling tower circuit can provide
settling capacity.   For  smaller  tonnage  operations,  the
recycling  could  occur  on  a periodic basis when the metal
cooling pit required cleaning for  the  removal  of  sludge.
This  would require a tank to hold the water during cleaning
of the cooling tank pit.  To implement a recycle system  for
molten metal cooling, the requirements are

           (1)  The addition to existing facilities
               of cooling towers and holding tanks
               or a pond, pumps, and filters  (with
               capability for backwashing).
           (2)  Provisions for oil removal.
           (3)  Provisions for sludge removal,
               dewatering, and disposal.
                           191

-------
Rationale for Selecting the Best Practicable
Control Technology Currently Available

Of  the  44  plants  surveyed,  37 (84 percent)  cool ingots,"
anodes, billets, or shot with  water.    Twenty-five  percent
recycle  process  waste  water with no discharge,  22 percent
recycle with periodic discharge, and 12 percent recycle with
a continuous discharge.  The plants recycling with  periodic
or  continuous  discharge could adapt to a no discharge-type
recycle  at  minimum  cost.  Greater  expenditure   would  be
required  by  the remaining plants (41 percent)  which do not
recycle metal cooling waste water.
Age and Size of Equipment and Facilities
As  set  forth  in  this  report,  general  improvements  in
production  concepts  have encouraged modernization of plant
facilities throughout  the  industry.   This,   coupled  with
similarities  of  the  characteristics  of  waste water from
metal cooling for plants of varying size, substantiates  the
identification   of   total  recycle  of  cooling  water  as
practicable.  Slightly more sludge would  be  expected  from
smooth,  copper  alloy ingot production that uses a charcoal
cover on ingots than from plants producing  other  types  of
copper  alloy  or unalloyed copper.  Thus, more sludge would
have to be removed from ponds or settling  tanks  of  plants
practicing charcoal covering in production.
Engineering Aspects of Control Technique Application
This  level  of technology is practicable because 47 percent
of the plants in the industry  are  now  achieving  effluent
reductions  by  these methods.   The concepts are proven, are
available for implementation, and may be readily adapted  to
existing production units.

Process Change
This  technology  is  a  part  of the whole cost savings and
waste management programs now being implemented  within  the
industry.  While the application of such technology requires
process  changes,  it is practiced by existing plants in the
industry.
                           192

-------
Nonwater. Quality Environmental Impact
Solid waste disposal of dewatered  sludge,   especially  from
those  plants using charcoal covers, would have only a minor
impact because of its nontoxic character.  Sludges recovered
from unalloyed copper production, because  of  their  copper
value,  are recycled to the metal recovery process.  Oil and
grease in excess of that removed with the  sludge  would  be
collected during recycle water cooling operations and may be
disposed of through waste oil disposal contractors.
      Waste Water From Slag Quenching and Granulation
Effluent Limitations Based on the Application of
the Best Practicable Control Technology Currently
Available
The recommended effluent limitation based on the application
of   the   best  practicable  control  technology  currently
available is no discharge of process waste water  pollutants
to navigable waters.

The achievement of this limitation by use of the control and
treatment  technologies identified in this document leads to
the complete recycle, reuse, or  consumption  of  all  water
within  the  combined  processes  of  the  industry  with an
associated result of no discharge of water.
Identification of Best Practicable Control
Technology Currently Available
The best practicable control technology currently  available
for  waste  water from slag quenching and granulation in the
secondary  copper  industry  is  the  elimination  of  water
discharge by one of the following approaches:

          For copper-rich slags

           (1)  Recycle or reuse of waste water from
               slag quenching and granulation after
               treating the stream to reduce
               suspended solids by settling and
               filtration.
           (2)  Air cooling molten slag cast into
                            193

-------
               slag pots for subsequent solid metal
               recovery by dry processes.

          For depleted (waste)  slags

          (1)  Recycle or reuse of waste water from
               slag quenching and granulation after
               treatment to reduce suspended solids
               by settling and filtration.

To  implement  a  recycle  system  for  slag  quenching  and
granulation of both types of slag, the requirements are

          (a)  A lagoon or pond to provide
               settling and cooling or a cooling
               tower with some settling capacity.
          (b)  A filter system with a capability
               for backwash.

Implementation of air cooling  of  copper-rich  slags  would
require  the use of heavy metal pots with shapes that permit
easy discharge  of  the  solidified  slag.   Their  combined
capacity  would  have to be designed to meet smelting sched-
ules of various size furnaces and be related to  the  amount
of  slag generated by the smelting technique employed at the
plant.
Rationale for Selecting the Best Practicable
Control Technology Currently Available
Of the 37 copper-alloy  producers  surveyed,  the  four  {11
percent)   that use water to quench copper-rich slags recycle
their waste water after settling and report no discharge  of
process   waste  water  pollutants.   These  plants  process
copper-rich slags recovered from their own and other  copper
alloy  smelter  operations.   The remaining 33 use slag pots
and air cool their slags either for shipment  or  for  their
own use in subsequent metal recovery operations.

Of  the  seven unalloyed copper producers, four (57 percent)
quench depleted slag.   Three  of  these  four  recycle  the
quench  water  after settling.  The remaining three use high
grade scrap and produce only small amounts of a  copper-rich
slag that is recycled or sold for its copper content.  Waste
waters  originating  from both types of slag granulation are
reusable after settling to remove suspended solids.  Buildup
of dissolved salts is not a  problem  in  plants  practicing
total recycle.
                           194

-------
Age and Size of Equipment and Facilities
Plants  processing  copper-rich  slag  by melting inherently
produce  large  tonnages  of  depleted  slag,  which   makes
air-cooling  impractical and the resulting mass difficult to
handle.  Granulation produces a depleted slag  product  that
is easily handled and has a limited market.  Therefore, slag
granulation  by  quenching  with water in such operations is
necessary.  The waste water, regardless of  plant  size,  is
similar in character and makeup.
Engineering Aspects of Control Technique Applications
This  technology  of recycle and reuse of water is practiced
by six  (75 percent) of the eight plants surveyed that quench
depleted slag to reduce the  discharge  of  pollutants  from
such streams.  The concepts are proven and are available for
implementation.

The  process  employing  air  cooling  and  mechanical  size
reduction of copper-rich slag which eliminates water use  is
practiced by 84 percent of the industry.

Process Change
Only minor changes in waste water handling would be required
to  permit  plants using water for slag quenching and granu-
lation to effect solids removal and completely  recycle  the
waste  water  with  no discharge of process pollutants. Con-
version to a nonwater-using system employing air cooling and
mechanical size reduction of copper-rich slags would require
only minor process changes.
Nonwater Quality Environmental Impact
The copper-rich slags that have been quenched and granulated
with water are processed  further  to  recover  solid  metal
values  and are a commodity, not a solid waste.  Elimination
of the use of water by air cooling of copper rich slags  can
be  an  added  burden for air pollution control.  Similarly,
mechanical size reduction, a  very  dusty  operation,  would
require additional air pollution control.
                        195

-------
The granulated, depleted slags have been used as ballast and
as a source of roofing granules.  Amounts in excess of these
commercial  demands  are  dispersed  to  landfill.   They are
generally inert but may impart alkalinity  to  the   landfill
through  very  slow  hydrolysis  and  leaching.   The sludges
recovered from waste water treatment would be expected to be
of similar composition and be suitable for landfills.
      Waste Water From Slag_ Milling and Classification
Effluent Limitations Based on the Application
of the Best Practicable Control Technology
Currently Available
The recommended effluent limitation based on the application
of  the  best  practicable  control   technology   currently
available  is no discharge of process waste water pollutants
to navigable waters.

The achievement of this limitation by  use  of  control  and
treatment  technologies identified in this document leads to
the complete recycle,  reuse,  or  consumption  of  all  water
within combined processes of the industry with an associated
result of no discharge of water.

Identification of the Best Practicable
Control Technology Currently Available
The  best practicable control technology currently available
for copper-rich slag milling and classifying is the elimina-
tion of water discharge through the  use  of  the  following
approaches.

           (1)  Recycle and reuse of all waste waters
               after treatment to reduce solids
               content by pH adjustment to between
               8 and 9, if necessary, and settling,
               followed by filtration.
           (2)  Elimination of direct water use by
               melt-agglomerating the metal in a blast,
               cupola, or rotary furnace.

With  the  reuse  or recycle of all waste waters, solids re-
moval and pH adjustment is necessary.  Lagoons  or  settling
tanks  followed by filtration to "polish" the water are used
to remove solids.  The pH is maintained near a  value  of  8
with  acid  to control the extent of hydrolysis of the basic
metal oxides in the slag.
                          196

-------
Recovery  of  metals  from   copper-rich   slags   by   melt
agglomeration  is  done in either a blast,  cupola,  or rotary
furnace.  Such technology requires minor size  reduction  of
the slags, pelletizing of fines,  fuel in the form of coke or
oil, and extensive air pollution  control systems on exhausts
from the furnace.
Rationale for Selecting the Best Practicable
Control Technology Currently Available
Six  (29  percent)   of  the 21 plants processing copper-rich
slags use wet milling and classification.  Of the six, three
(50 percent) reported no discharge of process  water,   while
the other three discharged recycled water only periodically.

Fifteen  (71  percent)  of  the  21  plants use a furnace to
recover the metal content from copper-rich slag.
Age and Size of Equipment and Facilities
Regardless of size and age of the facility, the waste  water
generated  from  milling and classifying of copper-rich slag
is similar in character and makeup.

Operation of furnaces for the  recovery  of  metal  by  melt
agglomeration  is  most  economically  done  on a continuous
basis.  Therefore, such an alternative is better suited  for
large  tonnage  processors  of  slag.  Wet milling is better
suited for  processing  a  plant's  own  slags  with  enough
material purchased to keep the operation at full capacity 24
hours a day.
Engineering Aspects of Control
Technique Application
This  level  of technology is practicable because 50 percent
of the wet milling facilities  are  now  achieving  effluent
reductions  by  these  methods.   The  concepts  are proven,
available for implementation, and may be readily adapted  to
existing production units.

The  level  of technology associated with melt agglomeration
is also practicable because 71 percent of the processors  of
slags presently using furnaces for metal recovery from slags
                          197

-------
are  achieving effluent reductions by this method.   With the
use of furnaces, there will be an associated  use  of  water
for  noncontact  cooling  of the equipment and air pollution
control systems (dry).  In this area, also, the concepts are
proven and available for implementation.
Process Changes
Only minor process changes would be required to  permit  the
plants  to  settle  and recycle the waste water without dis-
charge.  A partial bleed from the system is realized through
the  removal  of  a  sludge  made  up  of   residual   slag.
Conversion  from wet milling for metal recovery to a furnace
process would require extensive process  changes.   However,
such a transition would not involve technology unfamiliar to
the industry.
Nonwater Quality Environmental Impact
The  wet  milling  of  slag generates large amounts of solid
waste.  Because of its relatively  high  copper  content  of
four  to  five  weight  percent, this solid waste is usually
stored at the  plant  site  in  heaps  or  landfills.   Slow
hydrolysis  of  the  basic metal oxide content could release
alkalinity to the soil.  The additional  amounts  of  solids
recovered  in  upgrading  the waste water for reuse would be
small compared with the amount of residual slag.

Metal  recovery  from  copper-rich  slags  with  a   furnace
produces  about  equal  amounts  of  depleted  slag per unit
weight  of  metal  as  does  wet  milling.   The  amount  of
hydrolyzable  basic  metal  oxide  content is reduced in the
melting operation.  This depleted slag is  usually  quenched
and  granulated  with water.  The amount not sold is usually
disposed of  in  a  landfill.   Except  for  some  potential
hydrolysis  that  could  increase  the pH of the surrounding
soil, it is considered suitable  material  for  a  landfill.
The  use  of furnaces will require fuel in the form of coke,
oil, or natural  gas,  depending  on  the  type  of  furnace
employed;  whereas,  wet  milling requires electrical energy
for comminution and classifying.

         Waste Water From Furnace Exhaust Scrubbers
Effluent Limitations Based on the Application
of the Best Practicable Control Technology
Currently Available
The recommended effluent limitation based on the application
                           198

-------
of  the  best  practicable  control   technology   currently
available  is no discharge of process waste water pollutants
to navigable waters.

The achievement of this limitation by use of the control and
treatment technologies identified in this document leads  to
the  complete  recycle,  reuse,  or consumption of all water
within the  combined  processes  of  the  industry  with  an
associated result of no discharge.
Identification of the Best Practicable
Control Technology Currently Available


The  best practicable control technology currently available
for waste water from furnace exhaust gas  scrubbing  is  the
elimination  of  water  discharge  by  one  of the following
approaches.

           (1)  Recycling all of the waste water from
               furnace exhaust scrubbing after pH
               adjustment to between 8 and 9, and
               removal of solids by settling and
               filtration or centrifugation.
               Cooling towers may or may not be
               necessary depending upon the waste
               water storage capacity available,
               the size of the emission control
               system, and the period of time it is
               operated each day.
           (2)  The use of dry air pollution control
               equipment  (baghouse air filters).

For implementation of a total recycle  system   for  scrubber
waste  water,  the  requirements  are  that existing plants,
using wet  scrubber recycle systems, improve  solids  removal
operations   by  pH  adjustment  to  between  8  and  9  and
filtration  or  centrifugation.   Some  additional  settling
capacity   and/or  cooling  towers would be necessary in some
plants.  The discharge from the treatment  may  be  recycled
directly   to  the  scrubber or it can be combined with other
process waste water and reused in other operations.
Rationale for Selecting the Best Practicable
Control Technology Currently Available

Wet air pollution control of furnace exhausts  is  practiced
by  13  (30  percent)  of the 44 plants surveyed.  Of the 13
                          199

-------
plants  using  furnace exhaust scrubbing, eight (62 percent)
recycle all their water.  Of the plants surveyed,  77 percent
use either total recycle of the scrubber waste water or bag-
houses to eliminate the discharge of waste water.
Age and Size of Equipment and Facilities
All plants regardless of size or age have installed or  have
made  plans  to  install  air pollution control equipment to
meet air pollution control standards.   As a result, most  of
the air pollution equipment is relatively new,  regardless of
the  size  or  age  of  the  plants.   Of the 13 plants that
operate  wet  air  pollution  control   equipment,   complete
recycling with no discharge is practiced by old, new,  small,
and  large plants.  Among those plants that discharge  all or
part of the  scrubber  waste  water,  the  size  or  age  of
facilities has no bearing on this practice.
Engineering Aspects of Control Technique Application
This  level  of technology is practicable because 62 percent
of the plants surveyed that use wet scrubber systems are now
achieving effluent reductions by this  method.    Buildup  of
dissolved  solids  is  limited  by  the  constant removal of
dewatered sludge and has not been shown to be a problem  for
plants  practicing  closed-cycle  operations.   The level of
technology implied by the use of  baghouses  is  practicable
because 64 percent of the plants surveyed are now using them
to achieve effluent reductions.  In both cases, the concepts
are  proven,  are  available  for implementation, and may be
adapted to existing production units.
Process Changes
Only minor changes would be  required  in  the  handling  of
waste water from scrubbers to permit recycle of this stream.
No changes would be required in the process itself.  The use
of  baghouses  would  not  require  extensive changes in the
furnace operations, but would require  extensive  additional
gas cooling capability.
Nonwater Quality Environmental Impact
In  both  alternatives,   the  solids  recovered from furnace
exhaust gases are either sold or recycled  for  their  metal

-------
content.   Recovery  of  the  solids  from  baghouses   is  an
inherently  dusty  operation  and  emission  control  during
recovery  is necessary.  The energy requirements of both the
recycled  wet  scrubber  system  and  the  baghouse control
alternative are estimated to be equivalent.
     Waste Water From Electrolytic Refining Operations
Effluent Limitations Based on the Application
of the Best Practicable Control Technology
Currently Available


The recommended effluent limitation based on the application
of   the   bast  practicable  control  technology  currently
available is no discharge of process waste water  pollutants
to navigable waters.

The achievement of this limitation by use of the control and
treatment  technologies identified in this document leads to
the complete recycle, reuse, or  consumption  of  all  water
within  the  combined  processes  of  the  industry, with an
associated result of no discharge of water.
Identification of Best Practicable Control
Technology Currently Available
The best practicable control technology currently  available
for  waste  water from electrolytic refining is the elimina-
tion of water discharge by treating the bleed  or  breakdown
stream  from  electrolytic  cell  operations  so  that it is
suitable for reuse in other plant processes or suitable  for
sales or production of copper or nickel sulfate.  For reuse,
the  treatment  consists of removal of copper by cementation
with iron metal and/or electrowinning,  lime  neutralization
to  a  pH  of  between 8 and 9, and sand filtering the waste
stream to remove solids before  discharge  into  a  combined
process water reservoir serving other plant water needs.

Implementation of such a treatment requires that a treatment
facility have

          (1)  Storage capacity for waste electro-
               lyte equivalent to the total capacity
               of the electrolytic cells.
          (2)  Cementation tanks, lime treatment
                         201

-------
               facilities,  and sand filters with
               associated pumps and plumbing sized
               to process total electrolyte volume
               in 1 to 2 days of operation.

The  best practicable control technology currently available
for the relatively  small  volume  of  process  waste  water
generated  during  precious metals recovery is to reuse this
flow for baghouse hot offgas cooling,  or  for  other  plant
uses, after, as needed, neutralization and precipitation.
Rationale for Selecting the Best Practicable
Control Technology Currently Available
Of  the  four  producers  of secondary unalloyed copper,  one
plant (25 percent)   employs  such  an  operation  for  spent
electrolyte.   Of  the remaining three, one has a market for
the electrolyte, one treats the electrolyte  by  cementation
and the resultant iron sulfate solution is discharged into a
joint  treatment  plant,  and  one  evaporates  the solution
during metal sulfate recovery.  Only the  first  case  deals
with  treatment  of  the waste water to a level suitable for
reuse in other processes within the plant.

Only one of the four plants is  known  to  recover  precious
metals  on-site,  and  the small production of process waste
water can easily be reused elsewhere.
Age and Size of Equipment and Facilities
The  characteristics  of  waste  water   from   electrolytic
refining  operations  will vary with the nature of the scrap
and slags used to make anodes.   If  high  concentrations  of
metals  such  as  nickel  develop  in the electrolyte during
electrolysis, then recovery of nickel sulfate by evaporation
is warranted.  However, where the buildup of valuable  metal
sulfates  is  small  or  nonexistent,  the  variation in the
characteristics of the waste water would be  independent  of
the  age  and size of the facility.  Therefore, waste waters
can be treated, in the manner described, to a level suitable
for reuse in other processes in the plant.
Engineering Aspects of Control
and Treatment Applications
This level of technology is practicable because  25  percent
of  the  plants  that electrolytically refine copper are now
                        202

-------
achieving  effluent  reductions  by  these   methods.     The
concepts  are  proven, are available for implementation,  and
may be readily adapted to existing units.
Process Changes
This technology is part of the waste management programs now
being  implemented  within   the   industry   and   requires
essentially no process changes.
Nonwater Quality Environmental Impact
The  solid  waste, primarily hydrated iron oxide and calcium
sulfate, recovered from the filters, would have only a minor
impact in the landfills used for their disposal.
                Combined Process Waste Water
In all of the secondary copper  industry  plants,  water  is
consumed through evaporation and sludge removal.  Therefore,
with judicious water management, including that collected in
rain  water  runoff,  only  makeup water need be added.  The
buildup of dissolved salts does not impair  the  closed-loop
operations  since  sludge  removal  provides the means for a
bleed of salts from the system.  In effect, the discharge of
water from secondary plants could be reduced to  the  amount
of rainwater in excess of the amount evaporated during plant
operations.   The  treatments  for  individual  waste  water
process streams described in the preceding sections are also
applied to combined process waste  waters.   Treatment  just
before  transfer into storage for recycle with the option to
discharge the treated water during extended periods of heavy
rainfall is being used in one plant (Plant 10).  Considering
the levels of pollutants in a waste water discharge after an
end-of-pipe treatment used by Plant  32,  this  waste  water
would appear to be suitable for reuse or recycle water.  For
purposes  of  reducing  loadings,  part or all of this water
could be recycled to existing  plant  operations  to  assure
complete consumption.
                     Storm Water Runoff
Special  provisions  to  this  no discharge of process waste
water pollutants to  navigable  waters  proposed  limitation
follow:
                         203

-------
A process waste water  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 waste water 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.

During any calendar month there may be discharged from a
process  waste  water  impoundment  either  a  volume of
process waste water equal to the difference between  the
precipitation  for  that  month  that  falls  within the
impoundment and the evaporation within  the  impoundment
for  that  month,  or,  if  greater, a volume of process
waste water equal to the  difference  between  the  mean
precipitation  for  that  month  that  falls  within the
impoundment and the mean evaporation for that  month  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).

Any process waste water discharged pursuant to the above
paragraph  shall  comply  with  each  of  the  following
requirements:

                            Effluent limitations
   Effluent                              Average of daily
characteristic          Maximum for       values for 30
                         any 1 day       consecutive days
                                         shall not exceed
                             Metric units (mg/1)
TSS                        50                   25
Cu                          0.5                  0.25
Zn                         10                    5
Oil and Grease             20                   10
pH                      Within the range 7.0 to 10.0
                       204

-------
                                 English units  (ppm)
TSS
Cu
Zn
Oil and Grease
PH
50
0.5
10
20
Within the range
25
0.
5
10
7.0 to 10

25


.0
                        Total Costs
On the basis of information contained  in  Section  VIII  of
this  document,  it  is  concluded that those two plants not
currently  achieving  the   recommended   best   practicable
limitations would require an estimated total maximum capital
investment of about $538,000 and an increased operating cost
of about $270,000/year to achieve these limitations.
                           205

-------

-------
                         SECTION X

                 BEST AVAILABLE TECHNOLOGY
             ECONOMICALLY ACHIEVABLE—EFFLUENT
                   LIMITATIONS GUIDELINES
The  best  available  technology  economically achievable is
identical  to  the  best  practicable   control   technology
currently  available.  The corresponding effluent limitation
is no discharge of process waste water pollutants  to  navi-
gable waters.
                             207

-------

-------
                         SECTION XI

              NEW SOURCE PERFORMANCE STANDARDS
The   best   available   demonstrated   control  technology,
processes, operating  methods,  or  other  alternatives  are
identical   to   the  best  practicable  control  technology
currently available.  The  corresponding  standard  of  per-
formance  is  no discharge of process waste water pollutants
to navigable waters.
                            209

-------

-------
                        SECTION XII

                      ACKNOWLEDGMENTS
This development document was prepared by the  Environmental
Protection  Agency  on the basis of a comprehensive study of
this industry  performed  by  Battelle  Memorial  Institute,
Columbus,  Ohio,  under contract no. 68-01-1518.  Mr. Eugene
Mezey,  under  the  direction  of  Mr.  John  B.  Hallowell,
prepared the original (contractor's) report.

This  study was conducted under the supervision and guidance
of  Mr.  George   S.   Thompson,   Jr.,   Project   Officer.
Preparation,  organizing,  editing,  and  final rewriting of
this report was accomplished by Mr. Thompson.

The following members  of  the  EPA  working  group/steering
committee provided detailed review, advice, and assistance:
W.J. Hunt, Chairman
G.S. Thompson, Jr.,
  Project Officer
S. Davis
D. Fink
J. Ciancia

T. Powers
Effluent Guidelines Division
Effluent Guidelines Division

Office of Planning and Evaluation
Office of Planning and Evaluation
National Environmental Research
  Center, Edison
National Field Investigation Center,
  Cincinnati
Excellent  guidance  and  assistance  were  provided  to the
Project Officer by his associates in the Effluent Guidelines
Division,  particularly  Messrs.  Allen   Cywin,   Director,
Effluent   Guidelines   Division,   Ernst  P.  Hall,  Deputy
Director, and Walter J. Hunt, Branch chief.

The cooperation of individual  secondary  copper  companies,
who   offered   their  plants  for  survey  and  contributed
pertinent data, is gratefully appreciated.  These include:

    Cerro corporation
    Chemetro
    Southwire company
    American Smelting and Refining Company
    Franklin Smelting and Refining Company
    Interstate Smelting and Refining Company
    Libberman-Gittlen Metal Company
    Nassau Smelting and Refining
    North Chicago Refiners and Smelters, Inc.
    Reading Metals Company

                            211

-------
    River Smelting and Refining Company
    Roessing Bronze Company
    I, Schuman and company

Acknowledgment and appreciation are also given  to  Ms.  Kay
Starr,  Ms.  Nancy  Zrubek,  and  Ms.  Brenda Holmone of the
Effluent Guidelines Division secretarial staff.
                              212

-------
                       SECTION XIII

                        REFERENCES
 (1)  Spendlove, Max J- , Retired,  Bureau  of Mines,  Private
     Communication-

 (2)  "Copper  Industry  in  December,  1972", Mineral  Industry
     Surveys,  U.  S. Dept.  of  Interior, Bureau of Mines,
     Washington,  D. C.,  (February 28,  1973).

 (3)  "Copper  Industry  in  July,  1973",  Mineral Industry
     Surveys,  U.  S. Dept.  of  Interior, Bureau of Mines,
     Washington,  D. C.  (September 28,  1973).

 (4)  Rombert,  B.,  Operations in  the Nonferrous Scrap Metal
     Industry  Today, Fine,  P., Rasher,  H. W.,  and Wakesberg,
     Si  (Eds.)  published by the  National  Association of
     Secondary Material Industries (1973).

 (5)  Spendlove, Max J. , "Methods for Producing Secondary
     Copper",  U.  S. Dept.  of  Interior, Eureau of Mines
     Information  Circular 8002  (1961).

 (6)  Anon,, "AMAX:  in Perspective;  Carteret-copper,
     Specialty Alloys  and Precious Metals",  Engineering
     and Mining Journal  (September,  1972).

 (7)  National Air Pollution Control Administration, "Air
     Pollution Aspects of Brass and Bronze  Smelting and
     Refining Industry",  U. S.  Dept. of  Health, Education,
     and Welfare  (November, 1969).

 (8)  Branner,  George C.,  "Secondary Nonferrous Metals
     Industry in  California", U, S.  Dept.  of  Interior,
     Bureau of Mines Information Circular 8143 (1962).

 (9)  Dorrielson,  J. A.  (Ed.)  Air Pollution  Engineering,
     2nd Edition, Office  of Air and Water Programs,
     Environmental Protection Agency (1973).

(10)  "A Study to  Identify Opportunities  for  Increased
     Solid Waste  Utilization",  National  Association of
     Secondary Materials  Industries, Inc.,  Vols. II through
     VII (1972),  PB-212  730.

(11)  Anon., "Technical Report No. 11 - Secondary Brass
     or Bronze Ingot Production Plants"  in  Background
     Information  for Proposed New Source Performance
                           213

-------
      Standards,  Vol I,  U.  S.  Environmental Protection
      Agency/  Office of  Air and Water Programs,  Office of
      Air Quality Planning  and Standards,  APTD-1352a, Research
      Triangle Park, North  Carolina (June, 1973).

(12)   Peters,  M., and Timmerhaus,  K.,  Plant .Design and
      Economics for Chemical Engineers,  McGraw-Hill,  New York
      (1968).
                             214

-------
                        SECTION XIV

                          GLOSSARY

Act

The Federal Water Pollution Control Act Amendments of 1972.


Alloying

The process of altering the  ratio  of  components  in  base
metal,  such  as  copper, by the addition or removal of such
components.  Brass and bronze are alloys of copper.
Anode

A casting of fire-refined copper of a  suitable  shape  that
fits  into  an  electrolytic cell for further refining.  The
positive terminal of an electrolytic cell.
Baghouse

An air cleaning system consisting of multiple bag filters.


Best Available Technology Economically Achievable

Level of technology applicable to effluent limitations  that
is to be achieved by July 1, 1983, for industrial discharges
to  surface waters as defined by Section 301(b)(2)(A) of the
Act.
Best Practicable Control Technology
Currently Available

Level of technology applicable to effluent limitations  that
is to be achieved by July lr 1977, for industrial discharges
to  surface waters as defined by Section 301(b) (1) (A) of the
Act.

Copper Eillet

A large copper casting suitable for fabrication into piping,
wire, or similar products.
                           215

-------
Blinding of Bags in Baghouses

A restriction of the flow of air through the bag due to  any
fine dust, moisture, oilr or other material that fills up in
the pores of the filter bag.
Capital Costs

Financial  charges  which  are  computed  as cost of capital
times the capital expenditures for pollution control.   cost
of  capital  is based upon the average of the separate costs
of debt and equity.
Casting wheel

A disc-shaped array of  molds  used  to  prepare  ingots  or
anodes from molten metal.
Category and Subcategory

Divisions  of  a particular industry which possess different
traits that affect  waste  water  treatability  and  require
different effluent limitations.
Cathode

The negatively charged electrode of an electrolytic refining
cell on which copper is deposited during refining.


Cathode Copper

Finished product from the electrolytic refining of copper.
Cement Copper

Copper  that  has  been  precipitated  out  of a solution by
metallic iron scrap.

Copper-Rich Slag

Slag recovered from melting furnaces with  recoverable  free
copper or copper-alloy value.
                            216

-------
Depleted Slag

A  slag  recovered from furnaces with very little or no free
metal content.
Demineralized Water

Water treated to remove most of the cations (metal ions) and
anions*
Effluent

The waste water discharged from a point source.


Effluent Limitation

A maximum amount per unit of production  (or: other  unit)  of
each specific constituent of the effluent that is subject to
limitations in the discharge from a point source.
Electrolyte

A  solution  that is an electric conductor in which electric
current is carried by the movement of ions.
Electrolytic Cell        .

Device for the purification of copper.  Copper  from  impure
copper  anodes  is  electrically  plated  onto  pure  copper
cathodes through the electrolyte.
Electrostatic Precipitator

An  air  cleaning  system  in  which  dust   particles   are
electrically  charged  and  then  collected on plates of the
opposite electrical charge.

Fire-Refined Copper

Copper metal prepared  by  a  smelting  procedure  employing
oxidation  to  remove  impurities   (converting), followed by
reduction with carbon or green poles  (poling).
                         217

-------
Flux

A component added to a slag cover on a bath of molten copper
or copper alloy to alter the slag fluidity.
Ganque

A waste rock or slag material remaining after  most  of  the
metal values have been removed.
Lime, Slaked Lime, Hvdrated Lime

Calcined limestone, CaO, or hydrated lime, ca(OH)2.


Matte

A  crude  mixture  of  sulfides  of copper and other metals,
which  is  formed  when  sulfur-containing  copper  ores  or
residues are melted.
One  cubic  meter  at  standard  conditions  of pressure and
temperature.
Pigging Machine

An endless conveyerized mold system that is used to  prepare
ingots  (pigs) that weigh about 25 pounds.
Point Source

A  single  source  of  water  discharged  from an individual
plant.
Pollutant Parameter

Constituents of waste water determined to be detrimental and
requiring control.
Rasorite
A flux used in copper refining which is  primarily  composed
of borax (Na2B407»10 H20).
                             218

-------
Residues
Slags,  drosses,  or skimmings that are recovered from metal
operations for metal content.
Rough Brass or Bronze Ingots

Commercial 25-pound ingots cast with  no  protective  cover.
These ingots leave a rough surface caused by gas evolution.
Skimmings

Wastes  from  melting  operations  that are removed from the
surface molten metal; the wastes consist of  metal  that  is
contained in oxidized metal.
Sla<
A  molten  mixture  of oxides that protects the surface of a
molten bath of copper or copper alloy.  After use, the  slag
may  contain  metal ,  metal  oxides , and impurities from the
molten metal.
Smooth Brass and Bronze Ingots

Commercial 25-pound ingots cast with charcoal cover.   These
ingots have a smooth surface.
Soda Ash

Sodium carbonate, Na2C03_.


Solids

Copper or copper alloy scrap metal.


Standard of Performance

A  maximum weight discharged per unit of production for each
constituent that is subject to limitations.  The  weight   is
applicable  to  new  sources as opposed to existing sources,
which .are subject to effluent limitations.
                       219

-------
Table Classifier

A vibrating, ribbed table designed to separate dense ore  or
metals   from   the   lighter  constituents.   Normally  the
classifier is used with a flow of water.
Tank House

A building containing a series of electrolytic cells.
Tuyere

A nozzle through which an air blast is delivered to a cupola
or a blast furnace.
Venturi Air Scrubbers

An air cleaning system  consisting  of  intense  water-spray
cleaning  of the air at a point where the air goes through a
restriction (venturi) in the duct.
Waste Water Constituents

Materials which are carried  by  or  dissolved  in  a  water
stream for disposal.
                            220

-------
MULTIPLY (ENGLISH UNITS)
              TABLE  50

             METRIC TABLE

           CONVERSION TABLE

                     by
                       TO OBTAIN (METRIC UNITS)
    ENGLISH UNIT

acre
acre - feet
British Thermal
  Unit
British Thermal
  Unit/pound
cubic feet/minute
cubic feet/second
cubic feet
cubic feet
cubic inches
degree Fahrenheit
feet
gallon
gallon/minute
horsepower
inches
inches of mercury
pounds
million gallons/day
mile
pound/square
  inch (gauge)
square feet
square inches
ton (short)
yard
ABBREVIATION

  ac
  ac ft

 •BTU

  BTU/lb
  cfm
  cfs
  cu ft
  cu ft
  cu in
  °F
  ft
  gal
  gpn
  hp
  in
  in Hg
  Ib
  mgd
  mi

  psig
  sq ft
  sq in
  ton
  yd
CONVERSION   ABBREVIATION   METRIC UNIT
                            hectares
                            cubic meters
0.405
1233.5
0.252
0.555
0.028
1.7
0.028
28.32
16.39
0.555(°F-32)*
0.3048
3.785
0.0631
0.7457
2.54
0.03342
0.454
3,785
1.609
(0.06805 psig +1)*
0.0929
6.452
0.907
0.9144
ha
cu m
kg cal
kg cal/kg
cu m/min
cu m/min
cu m
1
cu cm
°C
m
1
I/sec
kw
cm
atm
kg
cu m/day
km
atm
sq.m
sq cm
kkg
m
* Actual conversion, not a multiplier
                            kilogram - calories

                            kilogram calories/kilogram
                            cubic meters/minute
                            cubic meters/minute
                            cubic meters
                            liters
                            cubic centimeters
                            degree Centigrade
                            meters
                            liters
                            liters/second
                            killowatts
                            centimeters
                            atmospheres
                            kilograms
                            cubic meters/day
                            kilometer

                            atmospheres  (absolute)
                            square meters
                            square centimeters
                            metric ton  (1000 kilograms)
                            meter
                                       221
                                                                                            J

-------


-------
*
 «

-------
U.S. ENVIRONMENTAL PROTECTION AGENCY (A-107)
WASHINGTON, D.C. 20460
           POSTAGE AND FEES PAID
ENVIRONMENTAL PROTECTION AGENCY
                        EPA-335

-------