EPA-650/2-74-048
MAY  1974
                            Environmental  Protection  Technology Series
                                                  I ^W7 8

                                                   \ PR0^
                                           011
                                                            «> e lopm ent
                                                         of eci 10:0 Agency
                                                               20460

-------
                                                    ,*>

                                EPA-650/2-74-048
  DEVELOPMENT OF  AN APPROACH
  TO IDENTIFICATION OF  EMERGING
TECHNOLOGY AND  DEMONSTRATION
             OPPORTUNITIES
                     by

H. Nack. K. Murthy, E. Stambaugh, H. Carlton, and G.R. Smithson, Jr,

             Battelle-~Columbus Laboratories
                 505 King Avenue,
                Columbus, Ohio 43201
                Grant No. R-802291
                ROAP No. 21AFH-016
              Program Element No. 1AB015
           EPA Project Officer: W. Gene Tucker

              Control Systems Laboratory
          National Environmental Research Center
         Research Triangle Park, North Carolina 27711
                  Prepared for

         OFFICE OF RESEARCH AND DEVELOPMENT
         U.S. ENVIRONMENTAL PROTECTION AGENCY
              WASHINGTON, D.C. 20460

                    May 1974

-------
This report has been reviewed by the Environmental Protection Agency
and approved for publication.  Approval does not signify that the
contents necessarily reflect the views and policies of the Agency,
nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
                                11

-------
                           TABLE OF CONTENTS

                                                                  Page

CHAPTER I.     ABSTRACT	     1-1

CHAPTER II.    INTRODUCTION	 .  .  .  .    II-1

CHAPTER III.   DESCRIPTION OF THE APPROACH	   III-l

                    Steps in Preparation of Industrial
                    Profile	   III-l

                    Selection of Experts 	   III-2

                    Identification of Emerging Technology.  .  .   III-3

CHAPTER IV.    AIR POLLUTION PROBLEMS AND DEMONSTRATION
               OPPORTUNITIES 	    IV-1

                    Secondary Nonferrous Metals Industry .  .  .    IV-1

                         Burning of Insulation and Other
                         Organics from Copper Scrap in
                         Copper Segment  . 0	  .  .    IV-1

                         Removal of Organics such as Cutting
                         Oils, etc., in Brass and Bronze
                         Segment	    IV-1

                         Sulfur Oxide Emissions from Melting
                         of Battery Plate Scrap in the
                         Lead Segment	    IV-2

                         Collection and Utilization of Fumes
                         and Dust from Smelting and Refining
                         Operations and Disposal of Heavy
                         Metal Sludges from Wet Scrubbers.  .  .    IV-3

                         Development of New Processes  ....    IV-4

                         Modification of Current Processes  .  .    IV-5

                         Halide Evolution from Aluminum
                        . Segment	    IV-6

                         Pollution from Aluminum  Drosses ...    IV-6

                         Demonstration Opportunities  	    IV-6
                              111

-------
                          TABLE OF CONTENTS
                             (Continued)

                                                                  Page

                    Petroleum Refining Industry	    TV-7

                         Catalytic Cracker	    IV-7

                         Claus Plant	    IV-7

                         Disposal of High-Sulfur Resids.  .  .  .    IV-8

                         Combustion Sources	    IV-8

                         Discussion	    IV-8

CHAPTER V.    CONCLUSIONS AND RECOMMENDATIONS	    V-l

                    Methodology	    V-l

                    Demonstration Opportunities in Secondary
                      Nonferrous Metals Industry 	    V-2

                    Demonstration Opportunities in the
                      Petroleum Refining Industry	    V-3


                              APPENDIX A

NOMENCLATURE  (EPA-CSL)  	    A-l

LIST OF EXPERTS FOR PETROLEUM REFINING INDUSTRY	    A-3

LIST OF EXPERTS FOR THE SECONDARY NONFERROUS METALS  INDUSTRY  .    A-3
                              APPENDIX B
         (THE PETROLEUM REFINING INDUSTRIAL PROCESS PROFILE)


INDUSTRY DESCRIPTION  	     B-l

     Companies	     B-5
     Size	     B-5
     Location	     B-5
     Future Trends  	     B-7
                                 IV

-------
                            TABLE OF CONTENTS
                               (Continued)

                                                                  Page

ENVIRONMENTAL IMPACTS	    B-8

     Atmospheric Emissions 	 ....    B-8
     Liquid Effluents	    B-9
     Solid Wastes	    B-9

RAW MATERIALS	    B-9

PRODUCTS	    B-10

PROCESSES	    B-14

WASTE CONTROL METHODS	    B-49

     Flares	    B-49
     Wastewater Treatment	    B-50

REFERENCES	    B-51


                              APPENDIX C
      (THE SECONDARY NONFERROUS METALS INDUSTRIAL PROCESS PROFILE)


INDUSTRY DESCRIPTION 	      C-l

DISCUSSION OF SECONDARY NONFERROUS METALS INDUSTRIAL
  PROCESS PROFILE	      C-2

     Segments	      C-2
     Major Companies	      C-3
     Manufacturing Operations	      C-3
     Processes	      C-6
     Process Steps 	      C-6
     Future Trends 	      C-6

ENVIRONMENTAL IMPACTS	      C-7

     Atmospheric Emissions 	      C-7
     Emission of Aqueous Wastes	      C-8
     Solid Waste Emissions	      C-9

RAW MATERIALS	      C-10

PRODUCTS	      C-ll

-------
                            TABLE  OF  CONTENTS
                               (Continued)
PROCESS DESCRIPTION  OF ALUMINUM SEGMENT OF SECONDARY
  NONFERROUS METALS  INDUSTRY	       C-12

     Raw Materials	       C-12
     Products	       C-13
     Process Description  	       C-13
     Population of Secondary Aluminum Processors 	       C-27

PROCESS DESCRIPTION  OF THE ANTIMONY SEGMENT OF THE
  SECONDARY NONFERROUS METALS INDUSTRY 	   C-30

     Raw Materials	   C-30
     Products	   C-31
     Process Description  	   C-31
     Population of Secondary Antimony Processors ....'....   C-35

PROCESS DESCRIPTION  OF THE BERYLLIUM SEGMENT OF THE
  SECONDARY NONFERROUS METALS INDUSTRY	   C-37

     Raw Materials	   C-37
     Products	   C-37
     Process Description  	   C-37
     Population of Secondary  Beryllium Processors	   C-38


PROCESS DESCRIPTION  OF THE BRASS AND BRONZE SEGMENT OF THE
  SECONDARY NONFERROUS METALS INDUSTRY 	   C-39

     Introduction	   C-39
     Raw Materials	   C-39
     Products	   C-41
     Process Description  	   C-42
     Population of Secondary Brass and Bronze Processors ....   C-55

PROCESSING DESCRIPTION OF THE CADMIUM SEGMENT OF THE
  SECONDARY NONFERROUS METALS INDUSTRY 	   C-58

     Raw Materials	   C-58
     Products	   C-58
     Process Description  	   C-59
     Population of Secondary Cadmium Processors	   C-61

PROCESS DESCRIPTION  OF THE COBALT SEGMENT OF THE SECONDARY
  NONFERROUS METALS  INDUSTRY 	   C-63

     Raw Materials	   C-63
     Products	   C-63
     Process Description 	   C-64
     Population of Secondary Cobalt Processors 	   C-67

PROCESS DESCRIPTION  OF THE COPPER SEGMENT OF SECONDARY
  NONFERROUS METALS  INDUSTRY 	   C-69

     Raw Materials	   C-69
     Products	   C-70
     Process Description 	   C-70
     Population of Secondary Copper Processors 	   C-94
                                vi

-------
                               TABLE OF CONTENTS
                                  (Continued)
                                                                   Page
PROCESS DESCRIPTION OF THE GERMANIUM  SEGMENT  OF  THE
  SECONDARY NONFERROUS METALS  INDUSTRY  	    C-97

     Raw Materials	    C-97
     Products	    C-97
     Process Description  	    C-97
     Population of Secondary Germanium  Processors	    C-98

PROCESS DESCRIPTION OF THE HAFNIUM SEGMENT  OF THE
  SECONDARY NONFERROUS METALS  INDUSTRY  	    C-100

     Population of Secondary Hafnium  Processors	    C-100

PROCESS DESCRIPTION OF THE INDIUM SEGMENT OF  THE
  SECONDARY NONFERROUS METALS  INDUSTRY  	    C-101

     Population of Secondary Indium Processors  	    C-101

PROCESS DESCRIPTION OF THE LEAD SEGMENT OF  THE
  SECONDARY NONFERROUS METALS  INDUSTRY  	    C-102

     Introduction	    C-102
     Raw Materials	    C-102
     Products	    C-103
     Process Description  	    C-103
     Population of Secondary Lead Processors  	    C-114

PROCESS DESCRIPTION OF THE MAGNESIUM  SEGMENT  OF SECONDARY
  NONFERROUS METALS INDUSTRY 	    C-117

     Raw Materials .	    C-117
     Products	    C-117
     Process Description  	    C-118
     Population of Secondary Magnesium Processors	    C-120

PROCESS DESCRIPTION OF THE MERCURY SEGMENT OF THE SECONDARY
  NONFERROUS METALS INDUSTRY 	    C-122

     Raw Materials	    C-123
     Product	    C-123
     Process Description  	    C-124
     Population of Secondary Mercury Processors	    C-128

PROCESS DESCRIPTION OF THE NICKEL SEGMENT OF  THE SECONDARY
.  NONFERROUS METALS INDUSTRY 	    C-131

     Raw Materials	    C-131
     Products	    C-131
     Process Description  	    C-131
     Population of Secondary Nickel Processors 	    C-135

                                   vii

-------
                               TABLE OF CONTENTS
                                  (Continued)
PROCESS DESCRIPTION OF THE PRECIOUS METALS SEGMENT OF THE
  SECONDARY NONFERROUS METALS  INDUSTRY  	   C-138

     Raw Materials	   C-L38
     Products	   C-139
     Process Description  	   C-139
     Population of Secondary Precious Metals Industries	   C-142


PROCESS DESCRIPTION OF SELENIUM SEGMENT OF SECONDARY
  NONFERROUS METALS INDUSTRY  	   C-144

     Raw Materials	   C-144
     Products	   C-144
     Process Description  	   C-144
     Population of Secondary Selenium Processors  	   C-147

PROCESS DESCRIPTION OF THE TIN SEGMENT  OF THE SECONDARY
  NONFERROUS METALS INDUSTRY  	   C-150

     Raw Materials	   C-150
     Products	   C-151
     Process Description  	   C-151
     Population of Secondary Tin Processors	   C-157

PROCESS DESCRIPTION OF THE TITANIUM SEGMENT OF THE SECONDARY
  NONFERROUS METALS INDUSTRY 	   C-160

     Raw Materials	   C-160
     Products	   C-160
     Population of Companies 	   C-160
     Process Description  	 ...   C-161
     Population of Secondary Titanium Processors  	   C-163

PROCESS DESCRIPTION OF ZINC SEGMENT OF  THE SECONDARY
  NONFERROUS METALS INDUSTRY 	   C-165

     Introduction	   C-165
     Raw Materials	   C-165
     Products	   C-166
     Process Description  	   C-166
     Population of Secondary Zinc Processors 	   C-182

PROCESS DESCRIPTION OF THE ZIRCONIUM SEGMENT OF THE
  SECONDARY NONFERROUS METALS  INDUSTRY  	   C-185

     Population of Secondary Zirconium Processors	   C-185

                              viii

-------
                              1-1
                             I.   ABSTRACT
          Results of a study to develop methodology for characterizing
major industries from the standpoint of their present environmental impact
and assessing the probable effect of emerging process technology on
environmental considerations are discussed.  A systematic method for
separating the industries into process modules is described and illustrated.
Applicability of this approach is demonstrated, using the petroleum refining
and secondary nonferrous metals industries as examples.  These are two
industries with substantially different characteristics.  An approach
utilizing expert opinion for rapid identification of emerging technology
is also reported and a discussion of technology under development in the
two industries is presented.

-------
                          II.   INTRODUCTION
          The objectives of the study were to develop an approach to the
assessment of the environmental effects associated with industrial activities
and identification of new process technology which could be employed to
minimize adverse environmental effects.  The approaches developed were
intended to be suitable for rapid assessment of major industries so that
EPA could assess the future need for demonstration programs similar to
those used to promote the use of newly developed technology to the electric
utilities and by the iron and steel industry.
          The petroleum refining industry and secondary nonferrous metals
industry were selected for evaluation in a pilot program.  The differences
in the character of these two industries would help identify all pertinent
factors in a methodology which would be applicable, with little or no
modification, to any industry or interest.
          Phase I of the study was concerned with development of industrial
process profiles for each industry.  The profiles are included as Appendix B
(Refining) and Appendix C (Nonferrous Metals).  The companies of importance,
the raw materials used, processes employed, and the products and wastes
were identified.  Standard terminology under development by EPA's Control
Systems Laboratory for similar studies was employed, and is included as
Appendix A.  The industry profiles were developed from information obtained
from the literature available within Battelle and by telephone contacts
with industries.  After assembling readily available information, a list of
practicing industry experts was developed for Phase II.
          Phase II of the study consisted of consulting with the experts
from the two industries to verify the accuracy and completeness of the
profiles and to identify technological trends and developments germane
to the project.  The input by the experts to the profiles and to the
identification of environmental problem areas that have received recent
technological solutions was considerable.

-------
                                 II-2
          In Phase III information on emerging technology* was assessed
and candidate demonstration projects were identified.  Projects were
considered primarily from  the standpoint of their potential for achieving
a significant reduction in air pollution.  The feasibility of setting up
a jointly-sponsored government-industry project was also examined.
          In Phase IV experience gathered during the course of the study
was reviewed by participating staff as the basis for preparation of this
report.  Here the experience in applying the identification approach to
the petroleum refining and the secondary non-ferrous metals industries
were assessed.
          It is anticipated that the information developed in this study
coupled with EPA's broad knowledge of air pollution control needs can be
used to select candidate demonstration projects.  Pursuing selected can-
didate projects to obtain defined end results could be done by the EPA
either alone or in concert with a contractor mutually acceptable to both
the EPA and the candidate company.  It is also anticipated that the
techniques developed here will assist in similar assessment work of other
industries.
* The term "emerging technology" connotes technology in a developmental
  state that has a good potential for commercialization and significantly
  helps to abate existing environmental problems in the industry.  The
  technology may include a new process, a process modification, or an
  improved emission control technique or a combination of these.

-------
                                  III-l
                   III.   DESCRIPTION OF THE APPROACH
          The approach to identification of the emerging technology* was
comprised of the various tasks indicated in Figure III-l completed in four
phases and in four time frames.  As indicated in Figure III-l, some of the
tasks in each of the phases are accomplished concurrently.  The tasks in
each phase are defined as follows.
 Phase I.     (1)  Gather available in-house process data
             (2)  Obtain available process data from industry by
                  telephone contacts.   Also concurrently
                  establish industry contacts
             (3)  Incorporate the above data along with prior
                  in-house experience  into generation of industry
                  process profiles (See Appendix C)
 Phase II.    (4)  Concurrent with Tasks (1) and (2) of Phase I
                  conduct preliminary  selection of experts from
                  industry and private consultation firms
             (5)  Coincident with the  completion of Task (3) of
                  Phase I, select final list of experts
             (6)  Have the industry process profiles reviewed by
                  the experts of the industry
 Phase III.   (7)  Finalize the industry process profiles after
                  incorporating additions, changes and other
                  comments from the experts
             (8)  With expert opinion, complete the precise
                  definition of environmental problems
             (9)  List and elaborate on the identified emerging
                  technology*  in each industry
 Phase IV.   (10)  Prepare final report of  the results of the
                  approach.   Make appropriate recommendations.
 * See definition on Page II-2 (footnote).

-------
                           PHASE I
                                                                     PHASE II
                                                                                                 PHASE III
                                                                                                                       PHASE  IV
  TIME
FRAME  1
Gather Data
 In-House
(major Input)
 Gather Data
from Industry
(minor input)
 TIME
FRAME 2
Preliminary Selection
     of Experts
(from industry and
private consultants)
     Prepare Industrial Process
     Profiles.   Do Preliminary
     Identification of Environ-
     mental Problems & Solutions
  TIME
 FRAME  3
                                  Final
                                Selection
                                of Experts
                                                                      Review
                                                                        by
                                                                      Experts
                                                                                 Prepare Final
                                                                                     Process
                                                                                     Profiles
                                                                                                 Precise
                                                                                              Definition  of
                                                                                              Environmental
                                                                                                 Problems
                                                                                                  List
                                                                                               Identified
                                                                                               Emerging
                                                                                               Technology*
 TIME
FRAME
                                                                                                                                     H
                                                                                                                                     ro
                                                                                                       Prepare  Final
                                                                                                       Report with
                                                                                                         Recom-
                                                                                                       mendations
                               FIGURE III-l.  SCHEMATIC OF APPROACH TO IDENTIFICATION OF EMERGING TECHNOLOGY*

          * The term "emerging technology" connotea technology  in  a developmental  state  that has a good  potential  for
            commercialization and significantly helps  to abate  existing environmental problems  in the  industry.  The
            technology may include a new process, a process modification, or an  improved emission control  technique or
            a combination of these.

-------
                               III-3
          The approach described above while enabling an orderly perform-
ance of the tasks also permits planned contact with the most knowledgeable
persons in the area under study.

            Steps in Preparation of Industrial Process Profile

          The secondary nonferrous metals industry is highly fragmented
from the standpoint of processes employed, has a multiplicity of products,
utilizes numerous raw materials and produces a wide variety of potential
air pollutants.  In all, the industry encompasses some 20 different
segments, (comprising a total of 135 processes) each of which is unique in
regard to raw materials sources, products produced, processes employed and
pollution potential.  Therefore, each segment had to be treated separately.
The pe.troleum refining industry, more standardized from the standpoint
of technology employed, was reducable to 29 processes.
          In developing the industrial process profile for secondary non-
ferrous smelting, the first task entailed the development of industry
segment profiles.  This involved initially, the use of the literature and
Battelle personnel to develop flowsheets and process descriptions.   Each
flowsheet identified:
          (1)  The manufacturing operations
          (2)  The processes within each operation
          (3)  The processing steps within each process
          (4)  Raw materials, source of energy, etc., used
               in each process
          (5)  Types of potential pollutants—atmospheric
               emissions, aqueous waste, and solid waste
          (6)  Intermediate products and final products.
The flowsheets were then used as guides around which to build the process
descriptions.  A similar- approach was used for petroleum refining.
          In addition to discussing the above items, composition of
emissions, seriousness of the atmospheric pollution problems, and disposal
of the waste materials were taken into consideration and the pollution
potential of the present processes were defined.  For this task standard

-------
                                III-4
nomenclature  and  techniques  developed by  the Control Systems Laboratory for
industry analysis were  used.  The  nomenclature definitions are shown in
Appendix A. Having  completed  this  task, the next  task involved the
identification  of emerging  technology and obtaining expert opinion on
validity of the flowsheets and process descriptions.

                       Selection of Experts*

          Because of  the  complexity of the secondary nonferrous metals
industry, the selection of two or  three experts to cover the entire
industry was  not  possible.   Instead, it was necessary to select experts
in the specific segments  of  the industry.  Initial selection of experts
was made based  on recommendations  from management officials in the major
companies.-  The experts suggested  were then interviewed by telephone
and, if found technically qualified for the task, were enlisted to provide
assistance on this  project.
          The petroleum refining industry, being more systematized, re-
quired discussion with  fewer  experts.**  Those used were selected to pro-
vide a cross  section  of opinion; i.e., one was employed by a major petroleum
company, two were employed by a major engineering company, one was a private
consultant and  one  was a  Battelle  in-house expert.

              Identification of Emerging  Technology***

          First, a  preliminary initial identification of emerging tech-
nology was done by  the use of current literature and Battelle's in-house
expertise.  Next, experts in  the two industries of interest and government
agencies such as  the  U. S. Bureau  of Mines were contacted by telephone
and/or personal visits  to:
          (1)   Identify additional emerging technology
  * See Appendix A  (Page A-4) for list of experts contacted.
 ** See Appendix A  (Page A-3) for list of experts contacted.
*** See definition on Page II-2.

-------
                               III-5
          (2)  Obtain their opinion on the previously
               identified emerging technology
          (3)  Obtain comments on the accuracy and thoroughness
             .  of the process descriptions and flowsheets of
               the various segments and make corrections
               where necessary.
          In arranging visits, the normal procedure was to contact a
company by telephone at least 3 weeks prior to any visit to request
assistance on the subject.  If agreeable, as was the case in most instances,
a package including a process flowsheet, process description, and brief
write-ups on emerging technology was mailed at least one or two weeks
prior to the visit.  Many companies requested time to allow several
individuals to  review the data.
          During the visit (which was made generally by two BCL personnel),
the process descriptions and flowsheets were reviewed first, followed by
review of the emerging technology that BCL staff had identified.  Then
efforts were made to identify additional emerging technology in terms of
air pollution control approaches, future trends in processing, and also
obtain atmospheric emissions data.  Information on candidate companies
who would be interested in jointly funded demonstration studies was sought.
          Also, efforts were made to determine the attitude of the company
toward such matters as demonstrations with government support, type of
support most beneficial to the secondary industry, and technical capabilities
of the company.  The results of the efforts are described in appropriate
Sections on pages V-2, V-3, C-l and C-2.
          Simultaneously, the same packages were being reviewed by outside
consultants and the same questions were being posed to them.  Conferences
also were being held with consultants at BCL as well as in the field.

-------
                                 IV-1

      IV.  AIR POLLUTION PROBLEMS AND DEMONSTRATION OPPORTUNITIES

                 Secondary Nonferrous Metals Industry

          The secondary nonferrous metals industry presents a wide variety
of air pollution problems associated mostly with pyrometallurgical processes
used for smelting, refining, and burn-off of foreign materials.  Some of the
most important problems and specific solutions of interest are discussed
below.

Burning of Insulation .and Other Organics
from Copper Scrap in the Copper Segment

          Problems encountered are: (a) toxicity and corrosive nature of
the gases due to the halogen, sulfur, and heavy metals content, (b) high
concentration-of unburned organic materials, and (c) the loss of metal
values contained in the atmospheric emissions.  Efforts to control these
emissions have had limited success.  New or improved technology is needed.
          Specific solutions toward controlling atmospheric emissions being
tried are :
     (1)  The U. S. Metals Refining Company of Carteret, New Jersey, is
          using a reactant-coated baghouse to collect HC1 and other halides
          which are liberated when copper wire is burned to remove insu-
          lation.
      (2)  The Apex Smelting  Company of  Chicago,  Illinois, is  installing a
          chemically coated  baghouse at its aluminum smelter  in Cleveland,
          Ohio,  to collect  chlorides from the demagging operation.

Removal of Organics.  Such as Cutting Oils,
from Scrap Turnings,  Shavings, and Borings,
as in the Brass and Bronze Segment

          Problems encountered are: (a) high incidence of fires in the bag-
houses,  (b) heavy emissions  of zinc oxide and other metallic  fumes, and
(c) severe fire hazard during the charging of the scrap to the melting pot.

-------
                                    IV-2

           These problems are encountered in the Brass and Bronze Segment
 and the Copper and Aluminum Segments.
           One specific solution to the problem of fire in baghouses  in
 current use is described below.
           The ABC* Company of XYZ* City is injecting a fine  powder  into
 the off gases from the brass and bronze melting furnaces.  This  fine powder
 reduces the incidence of fires in the  baghouses,  apparently  by reaction
 with the fumes, dusts, and/or gases to form products which do not ignite as
 readily as the original material.   Other companies  are de-oiling the scrap
 before  melt-down by burning to reduce  chances  of  fire.   The  ABC  Company
 claims  that de-oiling is not necessary.

 Sulfur Oxide Emissions from Melting of
 Battery Plate Scrap in the Lead Segment

           Battery plate scrap is contaminated  with  residual  sulfuric acid.
 Failure to remove the acid prior to melting results in evolution of  sulfur
 oxides.   The SO  emissions vary, being high during  initial melt-down and
                A
 low at  the end of the processing stage.
           This is a major problem in the Lead  Segment; the Copper Segment
 faces  similar problems.
           Solutions being tried for the abatement of SO  emission from Lead
                                                        X
 Segment  are:
 (1)  Lime-sulfur dioxide scrubbing system at the  General  Battery Corporation,
     Reading,  Pennsylvania.   This  system uses  wet scrubbing  with hydrated
     lime.   The underflow sludge,  the  flyash resulting from  burning  pulverized
     coal  and  the crushed plastic  battery cases are being  tried  to produce  a
     composition that is  sanitary,  nonreverting,  nonleaching and dimensionally
     stable.
     The process  was  developed  by  G &  W.H.  Corson Inc., Plymouth Meeting,
     Pennsylvania.  The  Company is  not desirous of  EPA  assistance in  the
     project.
*
   Names and identity are deliberately withheld,  as requested.

-------
                                   IV-3

(2)   The U.  S.  Bureau of Mines  in College Park,  Maryland,  is developing a
     process for reducing  the sulfur oxide emissions from recovery of lead
     from scrap battery plates.   This process entails:
          (a)  Heating a mixture of the lead scrap and  calcium
               hydroxide in a calciner to convert the sulfur
               content to  calcium sulfate
          (b)  Adding solid reducing agent and flux and reducing
               the charge  at 650°C which is below the decomposition
               temperature of calcium sulfate
          (c)  Removing molten lead for further processing and the
               slag for disposal.  Consideration is being devoted
               to developing a process for  the regeneration of the
               calcium sulfate to  lime for  recycle and generation of
               elemental sulfur  for use  in  other processes.

Collection and Utilization of Fumes and
Dusts from Smelting and Refining Operations
and Disposal of Heavy Metal Sludges from Wet Scrubbers

          Problems encountered are: (a) collection of fine dust particles
(less than 0.5 micron in diameter), (b) loss of valuable metals, (c) high
level emissions to the atmosphere from current pyrometallurgical processes,
and (d) disposal of dusts  and fumes collected in baghouse in landfills
which could result in severe water pollution problems and possibly air
pollution problems.
          Wet scrubber sludges resulting from control of atmospheric emissions
contain metal values too dilute to render its recovery   economical.  Again,
these sludges are disposed off in landfills, thus making water pollution
problems a possibility.
          The melt-down of scrap fines together with coarse scrap in many
segments results in heavy evolution of metallic dusts and fumes.  To avoid
this problem, some companies dispose of the scrap fines in landfills rather
than recover the metal value in it.  The result could be a water pollution
problem from the leachates.

-------
                                    IV-4
          The above problems are being solved by the industry by multiple
approaches.  Examples are provided below.

             Development of New Processes.   (1)  Hydrometallurgical systems
 are being examined as a means  of reducing  atmospheric emissions  by
 eliminating the pyrometallurgical step in  the recovery process.   For example,
 Electrolytic Zinc Company of Australia,  Limited,  has developed a new hydro-
 metallurgical process for extracting lead  from  zinc plant residues using
 aqueous  solutions containing ammonia and ammonium sulfate to  dissolve lead
 compounds insoluble in  conventional  solvents.   The Bureau of  Mines,  Salt
 Lake  City Metallurgy  Research  Center,  Salt Lake City,  Utah, has  developed
 a  process for the recovery  of  copper for all  grades of scrap  copper  using
 an ammonium carbonate system.   Essentially, no  atmospheric emissions  are
 generated and  aqueous solutions  can  be regenerated and recycled.   The copper
 can be recovered  as  the powder,  oxide, or  as  cathodic  copper.
           (2)    U.  S. Metals Refining Company (Division of AMAX) at
 Carteret, New Jersey, is developing  a hydrometallurgical process for the
 recovery of metal values from  dust and fumes  collected as baghouse dusts  from
 the various segments  of the primary  and  secondary industries.  The process
 has been developed  through  the laboratory  stage and is now ready for pilot-
 plant development.
           Basically,  the process entails the  extraction of metal values
 from  the baghouse dusts with an aqueous  leachant  to produce a metal-laden
 liquor.   The metal  values,  such as zinc, are  then recovered from this liquor
 by an electrolytic  process.  In those  instances where  the dusts  contain
 high  concentrations of  iron values,  the  leach residue  after removal  of the
nonferrous  metal  values is  returned  to the steel  industry for processing
 in the blast furnaces.   Other  metals such  as  lead  and  tin are recovered at
various  stages  in the process.
          While this  process does not treat the air pollution problem from
the secondary nonferrous metals  industry per se,  it does  eliminate or
reduce a  potentially  serious water pollution problem which could arise upon
disposal  of  the dusts and sludges by landfilling.    Furthermore,  the process
recovers  valuable metals which would not otherwise be recovered.

-------
                                   IV-5

          (3)   Zinc dust manufacture is rapidly growing in the Zinc Segment.
One new process which has been introduced into this country is a Norwegian
process known as the Larvic process.  In this process, the zinc is vaporized
using graphite rod resistors above the melt contained in a reverberatory
furnace.  Consequently, emissions are minimized as there are no combustion
gases.  Currently, the process is being used by The American Smelting and
Refining Company, in New Jersey.  This process is in contrast to the pyro-
metallurgical processes for zinc powder manufacture used in the U. S.
Although theoretically hydrometallurgical processes can be used for making
zinc  powder, there is no evidence of its use in the U. S.
          (4)   Battelle's Columbus  Laboratories,  Columbus, Ohio,  is
developing a process for fluxless melting of magnesium.   The process is
designed to use small percentages of hexafluoride in air as a protective
atmosphere for molten magnesium in various molten metal handling operations.
Successful development of this process will: eliminate or minimize the use
of flux when melting magnesium; result in reduced air pollution problems
associated with the flux; reduce the solid wastes generated; and produce
cleaner castings.  Currently,  the process is in the laboratory stage of
development.

            Modification of Current  Processes.  Oxygen-enriched air or in
  some cases pure oxygen is being used in a number of industry segments,
  e.g., Copper, Lead, and Aluminum.   Advantages are reduced volume of
  off-gases, increased production capacity, and low emission of dusts and
  fumes per ton of metal produced.  Two companies currently using oxygen
  or enriched air are Franklin Smelting Company of Philadelphia, Pennsylvania,
  and Chemical Metals Corporation, East Alton, Illinois.  Franklin Smelting
  Company has developed a rotary converter for the production of black
  copper.  Emissions should be significantly reduced over conventional con-
  verters as surface lancing in place of tuyerers is used and pure oxygen
  is used in place of air.  Chemical Metals Corporation is using enriched
  air overhead converters.

-------
                                 IV-6
Hallde Evolution  from Aluminum Segment

          Demagging of aluminum with gaseous chlorine results in the
evolution of large quantities of chlorine, primarily as aluminum chloride.
The use of solid demagging agents such as aluminum fluoride or aluminum
chloride instead of chlorine reduces the degree of severity of the problem
and is being practiced by the industry.  A new approach involves the use of
a precoated baghouse (chromatographic baghouse) which removes both the
halides and particulate matter.  This technique is being tested on a
commercial in Canada, and several U. S. Companies are contemplating building
commercial-size units.

Pollution from Aluminum Drosses

          Drosses  from the Aluminum Segment consist of aluminum, sodium,
and potassium chlorides, fluxes, etc.  These react with atmospheric nitrogen
and water to form  ammonia, an atmospheric pollutant.  The quantity of drosses
is significant and solution to the problem is not attempted in the U. S. yet.
          It appears that the European industry has a process to recover
the aluminum from  the drosses and recycle the salts and fluxes.  The specific
details of this technology are not known  at  this  time.

Demonstration Opportunities

          Any of the solutions described above can be a potential candidate
for a demonstration project.  However, exact definition of the solution
being tried and the willingness of the developers to cooperate in a demon-
stration project with EPA needs detailed investigations.  As noted above,
many of the developers are unwilling to invite the EPA.
          Some of  the companies might welcome cooperation and support by
EPA through a mutually acceptable contractor or coordinator.  The secondary
nonferrous metals  industry is primarily production oriented and the suspicion
that EPA intervention might hinder their normal production activities appears
to .-have put the industry on guard.
          Further work in this direction to more clearly identify demon-
stration projects  and companies willing to cooperate is worthwhile.

-------
                                 IV-7
                      Petroleum Rafi.ni.ng Industry
          Petroleum refineries have four air pollution related problems:
(1) particulate and SO  emissions from the Cat-Cracker Catalyst Regenerator,
(2) emission of sulfur oxides in tail gases from Glaus plants, (3) emissions
from fuel combustion in the industry and (4) Disposal of high-sulfur residue
fuels.

Catalytic Cracker

          Catalytic cracker regenerator flue gases contain particulates and
at times significant quantities of sulfur oxides.  Electrostatic precipitators
are most commonly employed to remove particulates; sulfur oxides are not
normally controlled.  Exxon plans to install a full-scale (size) scrubber
that employs a soda ash solution for removal of both pollutants.  The unit
is expecfed to produce data needed for design of future units.  Evaluation
of the effectiveness of this unit may be useful if sulfur oxides from cat
cracking will require more effective control in the future.

Glaus Plf->f.
          A number of processes designed specifically for Glaus plants are
being introduced for inore effective control of sulfur emissions in the tail
gas.  These include Shell's Scot process, Union Oil's Beavon process, the
Cleanair process offered by J. F. Pritchard, the IFP process developed by
Institut Francais du Petrole, Lurgi's Sulfreen process and the Takahax
process licensed by Kellogg.  In addition, the Wellman-Lord process and
the citrate process are being offered for tail gas scrubbing.   A demonstra-
tion or evaluation of one or all of these processes would be appropriate
if EPA considers the development of data on the economics of control use-
ful.  Such information would be useful in defining the control alternatives
open to refineries as they replace dwindling supplies of sweet crude with
available high-sulfur crude.

-------
                                  IV-8
Disposal  of  High  Sulfur Resids

          Refining  capacity  in  the U. S. is being expanded and more high-
sulfur crudes  are being refined.  Therefore, supplies of high-sulfur resid
will  increase  and processes  for its utilization in economical environ-
mentally  sound ways will  be  increasingly useful.  A process that could be
used  to convert resid  into a nonpolluting fuel would be especially
attractive.  Two  possible processes for such service are the Chemically
Active Fluid Bed  and Exxon's Flexicoking.  Both gasify the coked resid.

Combustion Sources

          Major refineries contain furnaces in processes such as crude
distillation that are  as  large  as a furnace in a 100-MW power plant.
Demonstration  of  a  flue-gas cleaning system for such furnaces may be use-
ful in defining possibilities for control of such systems and may adapt the
furnaces  for use  of high-sulfur  fuel.  One of the by-product flue-gas
cleaning  processes  may  be especially appropriate since most refineries are
already in the sulfur  recovery business.

Discussion

          The  usefulness  of any of the demonstrations will depend in part
on EPA's  planned  approach to refinery control.   It is doubtful that any of
the processes  identified  present serious technical problems that most
refiners  could not  solve  for themselves.  Hence the situation is not
analogous to that in the  utilities industry where help is needed in the
solution  of the technical problems.   Justification for undertaking demon-
strations probably  is related to economic clarification or to support base
standards, rather than  to solution of technical problems.
          There is  some evidence to suggest that some companies (especially
the largest ones)  in the  industry will not readily welcome EPA cooperation
in what is considered the industry's area of responsibility.  However,

-------
                                 IV-9

probably not all refiners share this sentiment.  One consultant suggested
that the moderate-sized refiners would welcome assistance and suggested
contact with Petrofina, Ashland and Pasco.  The smaller refiners would
not have the economic or technical capability or physical facilities
necessary to cooperate in a demonstration program.

-------
                      V-l
       V.  CONCLUSIONS AND RECOMMENDATIONS

                   Methodology

The principal conclusions relating to methodology are as follows;
(1)  The methods developed for use in generating
     industry profiles and identification of the
     processes which comprise the industry appear,
     on the basis of their application to two
     dissimilar industries, to be generally applicable
     for systematic study of any industry.
(2)  Expert opinion can be used to develop the
     perspective needed to understand environmental
     effects of a given industry if a proper approach
     is used.  Consideration should be given to
     selection of experts who are affiliated directly
     with the industry and others who are knowledgable
     but not employed directly by companies in the
     industry.  This appears to help insure that problems
     are kept in proper perspective.
(3)  Also, it appears that at least three experts should
     be consulted.  Where fewer are used there seems to
     be a good chance that experience gaps can lead to
     development of an inaccurate concept of some
     controversial issues.
(4)  Also, it would appear that at least one paid consultant
     be used where review of industry profiles are concerned.
     Few of the experts employed by industry who cooperated
     without compensation found time for a detailed review of
     the draft version of the industry profiles that had been
     supplied for criticism.
(5)  Finally, it was evident that careful preparation prior
     to contact with experts was necessary to assure that
     maximum benefit was obtained.  Preparation of the best
     possible industry profile and complete list of potential

-------
                                  V-2
              new processes would help to bring in outside help
              and inputs.
         (6)  If future studies are undertaken, a document
              describing EPA's policies and procedures for
              demonstration' studies should be made available to
              industry representatives who are to be contacted.
              Such a document would have been helpful in elim-
              inating the suspicions and reservations relating
              to loss of proprietary rights and trade secrets,
              etc.
               Demonstration Opportunities in Secondary
                     Non-Ferrous Smelting Industry
          The principal conclusions relating to demonstration opportunities
in the secondary non-ferrous smelting industry are as follows:
     (1)  The secondary non-ferrous metals industry is in need of
          assistance in reducing or eliminating atmospheric emissions
          from the numerous processes involved throughout the entire
          industry.  However, the majority of the companies
          that make up the secondary non-ferrous metal industry are
          medium-sized privately-owned companies and are not generally
          equipped to deal with the development and application of new
          technology for control of pollution.  They lack the technical
          capability and financial resources which are needed.
     (2)  There is an indication that some work toward pollution abate-
          ment in the secondary nonferrous metals industry is underway and
          its application might be accelerated if demonstrations were
          given partial support.  Such support might also encourage
          the industry to undertake additional work.  From this stand-
          point, projects in this industry should enjoy high priority.
     (3)  The Environmental Protection Agency has developed an image
          in some instances as being a "police" force.  Consequently,
          companies are reluctant to enter into agreements with the

-------
                                 V-3
          Federal Government which would give the representatives
          of EPA access  to company data.  However, some companies
          would welcome  assistance in this area.
     (4)   Industry  is  concerned  that any venture with the Federal
          Government may result  in loss of patent rights to  the process.
          The  secondary  nonferrous industry  is very competitive and each
          company guards its secrets very closely.  If companies can
          be assured that rights will be guarded, they may be willing
          to enter  into  jointly-funded ventures.
     (5)   Although  companies in  the industry produce different pro-
          ducts, many  of the pollutants are  similar and in many cases,
          the  same.  Thus, pollution problems are common to  several
          segments  of  this ir.duptry.  For example, sulfur oxide
          emission  is  a  common pollutant to  the copper and lead
          segments  of  both the secondary and primary nonferrous metals
          industries while the manufacturing operations are  different.
          It was the opinion of  officials from several companies that
          emphasis  in  pollution  abatement should be directed wherever
          possible  toward the development of add-on pollution control
          equipment rather than  process modification.  Such  equipment
          could  then be  used by  several segments of industry and,  thus,
          many could benefit rather than a  few.  Also development  of
          add-on equipment could be conducted without disclosure of
          company secrets.
                  Demonstration  Opportunities  in the
                      Petroleum  Refining  Industry
          The principal  conclusions  relative  to  demonstration  opportunities
in the petroleum refining industry are  as  follows:
     (1)   In general  the industry understands its  problems  and has
          available  to them the  technology needed  to solve  their
          own problems.   Further they are  financially in a  better
          position to support  the work  necessary to bring their
          problems under control than many other industries.

-------
                             V-4
(2)   The companies refining petroleum vary widely in size.
     The large companies neither need or would
     welcome government support for projects.   The small
     companies we«W generally lack financial  capability
     and technical support to participate in such studies.
     The medium size companies would appear to be the most
     likely to have the capability and motivation to par-
     ticipate in jointly funded work.

-------
                                 A-l
                            APPENDIX  A
                            NOMENCLATURE
         LIST OF EXPERTS FOR PETROLEUM REFINING INDUSTRY
         LIST OF EXPERTS FOR SECONDARY NONFERROUS METALS
         "                    INDUSTRY""
                                 NOMENCLATURE

 1.  RAW MATERIALS are feed materials for processes.   They- are of two types:
     primary raw materials that are used in. the chemical  form that they were
     taken from the land,  water or air and secondary  raw  materials that are
     industrial intermediate products.
2.    INDUSTRIES are made up of groups of companies that are considered
     competitors in production of 'che same products.   Industries have an
     identifiable population of companies and have a  high degree of commonality
     with respect to raw materials consumed, processes employed, products
     produced, environmental control problems experienced, pollutants produced
     .and control equipment used,
 3.  OPERATIONS are general industrial procedures  by  which materials are
     processed or products produced.  Operations  can  consist of a series of
     processes, or can be  accomplished by two or  more alternative processes.
 4.  PROCESSES are the basic units that collectively  describe industries.
     Processes comprise specific  arrangements of  equipment that accomplish, in
     a distinct way, chemical or  physical transformation  of input materials
     into end products, intermediate products, secondary  raw materials or
     Waste materials.   Other process outputs include  waste streams to the air,
     water, or land.  Input materials can include  primary or" secondary rav/
     materials, waste materials,  or intermediate  products.  Where two or more
     different combinations of process steps accomplish the same chemical or
     physical transformation but  have different environmental impacts (e.g.,
     different emission characteristics), each combination is a distinct process.

-------
                                      A-2
  5.  PROCESS STEPS are the basic components of a process that utilize process


      equipment or materials handling equipment (process equipment does not


      include control equipment).  In cases where a piece of process equipment


      has two. or more cycles or phases of operation with distinctly different


      emissions to the atmosphere, such cycles or phases can be considered


      sequential process steps.
                            ,.•'

  6.  SOURCES are process steps from which significant amounts of air,  water,


      or land pollution can be discharged.


  7.  CONTROL EQUIPMENT is equipment whose primary function  is to reduce emissions


      to the atmosphere.   Its presence is not  essential to the economic viability


      of the process.



  8.   COMPANIES include corporate sub-divisions  that have a  product  slate similar


      to other  companies  in an industry.


  9.   PLANTS are comprised of collections of processes  to produce  the products


      associated with  their industry.   Individual plants within an industry may


      employ different combinations  of processes but all plants will have


      some of the processes that  are  common to the industry.


10.   END PRODUCTS include only those  process outputs that are marketed for use or


      consumption in the  form  that they exit from the process.  After use,  an end


     product becomes  a waste  material.


11 •   INTERMEDIATE PRODUCTS are process output streams that go either to other


     processes  in the same industry in which they are produced, or to other


     industries where they become secondary raw materials..


12•  WASTE MATERIALS are  either process outputs that go to a scavenging industry,


     or are used end products that are disposed or processed to recover reusable


     constituents.'                    •

-------
                     A-3


LIST OF EXPERTS FOR PETROLEUM REFINING INDUSTRY
        Mr. W. L. Lewis
        Mr. H. H. Meredith
        The Exxon Company
        P. 0. Box 2180
        Houston, Texas

        Mr. E. Lewis Whittington
        Mr. A. G. Sliger
        Dr. W. F. Hoot
        M. W. Kellogg Company
        1300 Three Greenway Plaza East
        Houston, Texas  77046

        Mr. Lee H. Solomon
        Turner, Mason, and Solomon
        1950 Mercantile Dallas Building
        Dallas, Texas  75201

        Mr. David Moore
        Battelle-Columbus Laboratories
        505 King Avenue
        Columbus, Ohio  43201

        Mr. Paul W.  Spaite
        Consulting Engineer
        6315 Grand Vista Avenue
        Cincinnati,  Ohio  45213
        Telephone (513) 731-3991

-------
                                  A-4
                LIST OF EXPERTS FOR SECONDARY NONFERROUS
                            METALS INDUSTRY
         Name and Address                                 Area of Expertise

 1.  Albert L. Belcher,                                    Lead
    Bob Merritt
    National Lead Company
    Hightstown, New Jersey

 2.  John A. Bitler
    Manager, Manufacturing
    General Battery Corp.
    Reading, Pennsylvania

 3.  Dr. H. B. Bomberger                                   Titanium
    Director, Metallurgy Research Center
    RMI Company
    Niles, Ohio
    Telephone (216) 652-9951

4.  J. P. Brull, President,                               Titanium
    Earth Smelting & Refining Co.
    Newark, New Jersey

5.  H. S. Caldwell, Jr.                                   General
    U.S. Bureau of Mines
    College Park,  Maryland
    Telephone (301) 344-4027

6.  V. A. Cammarota                                       Mercury
    Mercury Specialist
    Division of Nonferrous Metals
    U.S. Bureau of Mines
    4015 Wilson Blvd.
    Arlington,  Virginia  22303

7.  Cobalt Information Center                             Cobalt
    Battelle Memorial  Institute
    Columbus,  Ohio  43201

8.  Mr. Denton
    Dept.  of Commerce
    Washington,  D.  C.

9.  Ray Familar                                           Cadmium
    Manager of  Engineering
    Cook County Air Pollution Dept.
    Chicago,  Illinois

-------
                                 A-5

       Name and Address                                   Area  of  Expertise

10,   Dr.  Ro Foos
     Brush Beryllium Company                             Beryllium
     Cleveland, Ohio

11.   E. Godsey                                           Aluminum
     American Smelting and Refining Company
     Salt Lake City, Utah

12.   Bruce G. Gonser                                     General
     Consultant
     Battelle Memorial Institute
     Columbus, Ohio  43201

13.   Keith Harris                                        Tin
     Division of Nonferrous Metals
     U.S. Bureau of Mines
     4015 Wilson Blvd.
     Arlington, Virginia  22303

14.   Crawford Hayes                                      Brass and Bronze
     Chief Project Engineer
     Bridgeport Brass Company
     Bridgeport, Connecticut  06602
     Telephone 366-6182

15.   Robert Henning, President                           Cadmium
     Belmont Smelting Company
     330 Belmont Avenue
     Brooklyn, New York   11207

16.   Dr. Kapplain                                        General
     U.S. Bureau of Mines
     Washington, D. C.

17.   B. Langston                                         Aluminum
     U.S. Reduction Company
     East Chicago, Illinois

18.   Dr. Thomas Leontis                                   Magnesium
     Magnesium Research Center
     Battelle Memorial Institute
     Columbus, Ohio  43201

19.   Dr. K. Libsch                                        Lead
     National Lead Company
     Hightstown, New Jersey

20.   Earl R. Marble, Jr.                                 Aluminum, Brass &
     Consulting Engineer                                    Bronze, Copper
     P.O. Box 816, Brainy Boro Station                      Lead,  Tin, Zinc
     Metuchen, New Jersey  08840
     Telephone  (201) 548-4990

-------
                                 A-6

       Name  and Addregg                                    Area of Expertise

 21.   Drew Meyer                                           Tin
      Vulcan Material  Company
      Box 720
      Sandusky, Ohio   44870
      Telephone  (419)  626-4610

 22.   R. L.  John Minnick
      Vice President,  R&D

      Plymouth Meeting, Pennsylvania

 23.   Stanton Moss                                         Aluminum, Brass, Bronze
      Manager, George  Sail Metal Company
      2255 East Butler Street
      Philadelphia, Pennsylvania  19137
      Telephone  (215)  743-3900

 24.   Howard Ness
      National Association of Secondary Metal Industries
      New York, New York
      Telephone  (212)  867-5000

 25.   H. R. Ogden                                          Magnesium
      Magnesium Research Center
      Battelle Memorial Institute
      Columbus, Ohio   43201

 26.   Dr. W. R. Opie,  Vice President                       General
     M. Houser, Plant Manager
     Amax Company
      Carteret, New Jersey

 27.  Allan Payne                                          Precious Metals
      United Refining  and Smelting Company
      3700 N. Runge Avenue
      Franklin Park,  Illinois
      Telephone (312)  455-8800

 28.  Milo Peterson
     Chairman of Committee,  SIC
     Office of Management and Budget
     Washington, D.  C.

29.  Dr. Carl Rampacek                                    General
     UcS.  Bureau of Mines
     Washington, D.  C.

30...  R. W.  Roe (and  J. Henderson,  Sup't of Research)      General
     Director of Research
     ASARCO
     South Plainfield, New Jersey

-------
                                 A-7

    Name and Address                                      Area of Expertise

31.  William Shirley                                      Aluminum
     Apex Smelting Company
     Des Plaines, Illinois

32.  Paul W. Spaite                                       General
     Consulting Engineer
     6315 Grand Vista Avenue
     Cincinnati, Ohio
     Telephone  (513) 731-3991

33.  Albert W. Spitz & Associates                         Lead, Tin, Precious
     Consultants                                            Metals, Cadmium
     Wyncote, Pennsylvania
     Telephone (215) 884-7182

34.  S. F.  Tauben
     Diversified Metals
     Hazelwood, Missouri

35.  Tin Research Institute                               Tin
     483 West 6th Street
     Columbus, Ohio  43201
     Telephone (614) 294-3341

36.  R. R.  Wells                                          Nickel
     Director, Abany Metallurgy Research Center
     Abany,  Oregon
     Telephone (503) 926-5811,  Extension 220

37.  Battelle-Columbus  Personnel
         Marty Forkas
         H.  Barr
         R.  Bengston
     Columbus,  Ohio  43201

-------
                                B-l
                             APPENDIX  B
           THE PETROLEUM REFINING INDUSTRIAL PROCESS  PROFILE
                         INDUSTRY DESCRIPTION

          The petroleum refining industry processes crude oil into a large
number of products including liquefied petroleum gas,  gasoline,  kerosine,
aviation fuel, diesel fuel,  a variety of fuel oils, and lubricating oils.
Some of the processes involved in the manufacture of these products are:
distillation, absorption, extraction, thermal and catalytic cracking,
isomerization, hydrogenation, dehydrogenation, polymerization, etc.
          Each refinery is more or less unique in that each operation is
carried out using equipment designed to meet needs peculiar to a particular
location.  It is possible, however, for purposes of analysis to consider all
refineries as consisting of some combination of the 29 process modules
shown in Table B-l.  Figure B-l is a flow diagram showing the interrelationships
between these processes.
          Only a few refineries employ all the processes shown in Figure B-l
because some of the processes are  (1) proprietary,  (2) representative of a
limited size range of refineries,  (3) typical of a  limited time period, and
(4) designed for a particular crude oil.  In addition to the processes  shown,
several hundred other process variations are used at a few refineries.  Most
of these processes are minor variations of the processes shown in Figure B-l.
Larger refineries generally use most of the processes shown.  American
refineries typically use more processes than foreign refineries because they
are designed  to produce a maximum  amount of motor  fuel.  European refineries
are designed  to produce a higher percentage of heating fuels.  The  complex
American refineries produce a minimum of residual  oil.   Less  complex
Caribbean refineries with minimum  cracking facilities  to supply local needs
for motor fuels are major suppliers  of  fuel oil  for the  U. S. East  Coast.

-------
                                                B-2
                         TABLE  B-l.  LIST OF PETROLEUM REFINERY PROCESSES
                                                                              (1)
Enrryy Required
Process
(1) Crude Storage
(2) Desalting

(3) Crude Distillation





(4)| Vacuum Distilla-
tion

(5) Chemical
Sweetening
(6) Hydrogen
Generation
(7) Naphtha Hydrogen
Treating

(8) Kerosene Hydrogen
Treating

(9) Gas Oil Hydrogen
Treating

(10) Lubricating Oil
Hydrogen Treating
(11) Residual Oil
Hydrogen Treating

(12) Catalytic
Hydrocracking


(13) Gas Processing




(14) Amlne Stripping

(15) Sulfur
Manufacture
US Capacity
Process fM bbl/SD
Type Jan. . 1972 Feed
Open A Crude
Closed a Crude

Closed 13.7 Crude





Closed 4.9 Topped Crude


Closed b Sour Distillate

Closed b Hydrocarbon
Closed 2.8 Gasoline


Closed 1.0 Sour Kerosene

Closed 4.9° Gas Oil


Closed 4.9C Sour Lube Oil

Closed 0 High-Sulfur
Residual

Closed 0.84 Gas Oil
Residuals


Closed 1.3 Mixed Cases




Closed a Hydrocarbon
H2S-Strcam
Open 1.2e HjS
Products
Crude
Dry Crude

.Refinery Gas
. Natural Gasoline
Kerosene
Distillate Fuel
Gas Oil
Topped Crude

Gas Oils
Vacuum Residual
Sweet
Distillate
Hydrogen
Gum- Free and
Sulfur-Free
Gasoline
Desu If urizcd
Kerosene
HjS
Desulfurlzed
Gas Oil
H2S
Desulfurized
Lube Oil
Low-Sulfur
Residual
H2S
Refinery Gas
Gasoline
Diesel Oil
Furnace Oil
Fuel Gas
PC
Butanes
Light Gasoline
Oleflnes
Sulfur-Free
Hydrocarbons
Sulfur
Elcctr irol-
Mechnnlcnl, Steam,
Effluents kwhr/bbl Ib/bbl
.Water b b
Salt 0.01 22
Water
Water 0.1-0.6 15


Oil


Water 0.1-0.3 8
Vent gas

Spent 0.01 b
Chemicals
Carbon b b
Dioxide
Spent 1.4 30-90
Catalyst

Spent 0.5-2 8
Catalyst

Spent 2 1-10
Catalyst

Spent 2.5-9 15-28
Catalyst
Spent 1-4 3-25
Catalyst

Spent Catalyst 1-6 (6)-18
Gas from .
Regeneration

2 0




d
Waste Amlne 0.5 (It

Tall-Cns 0.1 (4)d
Flred-
llcaters,
MBtu/bbl
b
0

100





50


b

0-300
0-50


0-70

5-70


35-140

60-100

100-250


0




0

0.4f
(1) Sec Hat of references at end of re
                             port.

-------
                                                          B-3
                                          TABLE B-l   (Continued)

(16)
(U)
(18)
(19)
(20)
(21)
(22)
(23)
(24)
(25)
(26)
(27)
(28)
(29)
Process
1 some rlzat Ion
Catalytic
Reforming
Fluid-Bed
Catalytic
Cracking
Moving-Bed
Catalytic
Cracking
Vlsbreaklng
Coking
Polymerization
Alkylation
Lube Oil
Processing
Asphalt
Processing
Storage and
Blending
Prime Movers
Electric
Steam
1C
Steam
Genera t ion
Process
Heaters
Process
Typt
Closed
Closed
Open
Open
Open
Closed
Closed
Open
Closed
Closed
Closed
Closed
Open
Closed
Closed
Closed
Open
Open
Open
US Capacity
MM bbl/SD
Jan. . 1972 Feed
0.2 N-Butanc
3.2 Naphtha
4.0 Gas Oil
0.59 Gas Oil
0.23 . Topped Crude,
Vacuum Residual
g Residual ,
0,12 Oleflns
0.6 Isobutane
Oleflns
0.22 Vacuum Gas Oil
Vacuum Residual
0.62 Vacuum Residual
a Process
• Streams
a
a Steam
a Fuel
Any Fuel
Gas-Liquid
Fuels
Products
lEobutane
Aromatlcs
Hydrogen
LPC
Isobutane
Refinery Gas
Gasoline
Heating Oil
Refinery Gas
Gasoline
Heating Oil
Refinery Gas
Fuel Oil
Gas Oil
Refinery Gas
Gasoline
Fuel Oil
Coke
Gasoline
Gasoline
LPC
Lube Oil
Wax
Asphalt
Products
Power
Pover
Power
Steam
Heat
Encrfiy Rc-qulred
Electrical. Fired
Mechanical Steam, Heaters,
Effluents kwhr/bbl Ib/bbl HBtu/bbl
Spent 1.2 20 30
Catalyst
Spent 3-6 0 200-400
Catalyst
Gas from
Regeneration
Flue Gas 0.4-3 (70)-40 0-70
Water
Spent
Catalyst
Flue Gas 0.1-1.5 (60)- 100 100-300
Water
Spent
Catalyst
1.8 (80) 260
Wash Water 15 (100) 350
Flue Gas
Spent 1.2 20 0
Catalysts
Spent Acid 5-10 100-300 0
2-10 100-400 0
Gas from 0.1-3 50-300 100-300
Air- 1 0 5-10
Blowing
Breathing b b 0
and Vent
Gases
None N.A. 0 0
None N.A. N.A. N.A.
Flue Gas N.A. 0 0
Used Oil
Flue Gas b
Ash
Water-
Treatment
Sludges
Flue Cas b - .
« - Not available,  large
b - Not available,  small
c - All hydrogen treating
d - Ib Bteam/lb  HS
c -  Million, ions/year
f -  M btu/lb sulfur
g -  41,000/tons/sd of coke
 ( )  - Production ratlicr thnn use
N.A.  - Not applicable

-------
                                                                                               03
FIGURE B-l.  PROCESS FLOW DIAGRAM OF PETROLEUM REFINING  INDUSTRY

-------
                                   B-5
                                Companies

          As of January 1, 1973, 121 companies operated 245 refineries
in the United States.  Table B-2 lists the 16 largest refiners and the
processing capacity of these companies along with the combined capability
                          (9)
of the other 105 refiners.
          The table indicates that refineries of the largest companies
average about 100,000 bbl/day capacity* while the refineries of the smaller
companies average about 20,000 bbl/day.  In addition, the smaller refineries
are less complex than the larger refineries.

                                 Size

          The largest refinery processes about 400,000 barrels of crude
oil per day and covers 1,100 acres.  Refineries with capacities greater
than 100,000 bbl/day process about 56 percent of the total crude oil and
more than 80 percent of the total is processed in refineries exceeding
50,000 bbl/day.  On the other hand, operating refineries process as little
as 1,000 bbl/day; however, only special circumstances—such as a remote
location (two new small refineries were built on Alaska's north slope) or
a specialty product, lubricating oil, asphalt, etc.--permit economic operation
of small refineries.

                               Location
          Refineries are located in 39 states.  However, 50 percent of the
total capacity is concentrated in Texas, California, and Louisiana, adjacent
to both major oil fields and deep water ports.  Other locations with many
large refineries, and perhaps 25 percent of U. S. crude oil capacity, are
* Capacity in the refinery industry is reported on a barrel per stream/day
  (BPSD) basis; i.e., the capacity of the unit when operating.  Because of
  maintenance shutdowns, this capacity is about 5 percent greater than the
  long-term capacity of the crude still and 10 percent greater than the
  long-term capacity of other process units.

-------
TABLE B-2.  LIST OF REFINERS

(1) Exxon
(2) Texaco
(3) Shell
(4) Amoco
(5) Standard (Calif.)
(6) Mobil
(7) Gulf
(8) ARCO
(9) Sun
(10) Union
(11) Sohio/BP
(12) Phillips
(13) Conoco
(14) Ashland
(15) Cities
(If-) Marathon
105 Smaller Companies
TOTAL
No.
Refineries
5
12
8
10
13
9
8
6
5
4
5
6
7
7
1
3
136
245
Crude
Capacity,
bb/sd
1,211,100
1,160,000
1,123,500
1,061,000
1,019,000
969,300
869,800
803,600
496,000
465,900
428,300
422,200
342,500
273,500
245,000
234,500
2,763,500
13,991,580
Cat Cracking
Feed
bb/sd
487,900
443,300
368,000
342,800
208,000
335,200
319,000
210,000
202,000
129,300
144,900
173,800
103,100
119,000
112,500
73,700
739 , 500
4,512,050
Cat
Reforming
273,600
232,600
278,900
243,800
246,000
241,900
227,800
247,000
143,800
122,000
114,500
111,600
79,200
58,000
39,000
57,000
557,200
3,273,918
Hydro-
. cracking
bb/sd
70,900
38,900
105,900
40,000
173,400
47,000
40,400
86,500
26,000
51,000
55,000
22,000
—
—
6,000
22,000
80,000
865,000
Other Hydro
Processing
bb/sd
614,268
329,300
693,500
278,200
234,200
407,600
409,400
390,000
148,300
245,800
170,800
140,200
. 121,900
164,000
51,500
57,500
772,000
5,228,488
Alkylation
81,500
56,200
72,100
47,150
38,700
63,uOO
70,000
28,700
37,200
28,500
22,900
43,100
18,000
14,000
26,000
11,750
153,2^5
812,045
                                                                           dd
                                                                           I

-------
                                   B-7

in New Jersey and Pennsylvania serving the East Coast population, and in
Illinois, Indiana, and Ohio near major consuming regions.
          Refineries frequently interchange products and raw materials with
neighboring plants of other industries.  Common neighbors are petrochemical
plants (which use some of the refinery products and often generate as
byproduct materials similar to some of the refinery intermediate products
which then are sold to the refinery), and electric generation plants (which
may buy fuel from the refinery and supply the refinery with steam and
electric power).

                             Future Trends

          The petroleum industry has been expanding at the rate of about
4 percent per year.  With the recent  (1972) modification of oil import
regulations and current gasoline shortage, the rate of expansion can be
expected to increase to 5 or 6 percent per year.  However, because of lead
times required, the increased rate of expansion is not expected for two or
three years, i.e., until 1976.
          Another major future trend  in petroleum refining is the increasing
dependence on imported crude oils.  The imported crudes contain more sulfur
than  the American crudes.  Therefore, increased quantities of sulfur will be
entering the refineries and  the sulfur will be removed from the oil in
various processes to meet both product quality standards and pollution
control  standards.  Some refineries cannot process high-sulfur crudes because
of corrosion problems, although these problems can be expected to be solved
by replacing mild steel components with corrosion resistent components  during
periodic maintenance shutdowns.  Other processing changes can be expected.
Most  of  the chemical sweetening processes  (Process 5)* change the form  of  the
sulfur in  the petroleum rather than  remove it.  With  the higher  levels  of
sulfur,  removal  is  required.   Therefore,  chemical sweetening processes  are
becoming obsolete,  and are being replaced with  sulfur removal processes
 (No.  7,  8,  9,  10, and  11).   The sulfur removal  processes  require hydrogen,
resulting  in use  of hydrogen generating processes  (No. 6  and 17).   Sulfur
plants will also  be  installed  to make sulfur  from  the hydrogen  sulfide
produced by  the  sulfur removal processes.
 * See Page 18.

-------
                                    B-8
           The petroleum industry is  already a  major  supplier  of  sulfur,
 supplying  over 1,000,000 tons (10 percent)  of  about  10,000,000 tons  used
 in  this  country.   In 1970,  only about 25  percent  of  the  sulfur in  the  crude
 oil was  recovered  as elemental  sulfur.  With increasing  desulfurization of
 products,  and increasing sulfur in the  crude,  the industry  could become the
 largest  supplier of sulfur  in the country.
           Another  trend is  toward manufacture  of  nonleaded  high-octane
 gasolines.  Alkylation (Process 23)* and  catalytic reforming  (Process  17)
 capacities  are being expanded to meet the demand  for higher octane fuels.
 Catalytic  reforming requires  a  sulfur-free  feed.   Naphtha desulfurization
 (Process 7) capacity is being expanded  to supply  this  fed.  Because  of the
 higher octane ratings needed,  less straight-run gasoline from the  still
 (Process 3) can be blended  into the  final product.  Catalytic cracking
 (Processes  18 and  19),  coking (Process  21),  and polymerization (Process 22),
 also make high-octane components that are blended into lead-free gasoline.
                          ENVIRONMENTAL  IMPACTS

                          Atmospheric Emissions

          The air contaminants emitted  from process equipment include
hydrocarbons, carbon monoxide, particulates, sulfur and nitrogen compounds,
and odoriferous materials such as mercaptans.  The various processes listed
in Table B-l are classified as open or  closed.  Open systems vent gases to
the atmosphere in normal  operation.  The vented gases may be contaminated
and cause pollution.  The major open process from an air emission standpoint
is the catalytic cracker  regenerator which vents gas from burning of coke
deposits on the catalyst.
          Closed systems do not vent process gas to the atmosphere and
emissions would be only from leaks or possibly from the vents of steam
ejector vacuum pumps.  Storage tanks are a special case where air in the
tank is contaminated with hydrocarbons and may vent to the atmosphere.
          Since the energy required for a 400,000 bbl/day refinery is about
the same as the energy required for a 1,000 megawatt steam electric generating
* See under "PROCESSES" starting on Page B-14.

-------
                                    B-9

 station, the potential air pollution from combustion sources in the
 refinery is very great.  Although particulates and sulfur oxides may be
 emitted in somewhat reduced amounts.

                            Liquid Effluents

           Liquid effluents are:  condensed steam from various processes,
 cooling water from many processes,  tank-cleaning wastes, spent chemicals,
 and some spilled oil.   All refineries have an oil-water separator on the
 sewage system to stop  oil from being discharged into nearby streams.  Process
 water is frequently sour (hydrogen  sulfide--H2S) so it is stripped of its
 acid (H2S)  before discharge.

                               Solid Wastes

           The major solid waste from refineries is  spent catalyst  which
 usually  is  landfilled.   Sludges from the  cleaning of equipment  storage  tank,
 oil-water  separator, etc.,  and  from lube  oil  manufacture also cause  a solid
 waste  problem.   The sludges may be  burned or  otherwise  disposed of.


                             RAW MATERIALS

          The major raw material processed  in a refinery is  crude  oil
 (11,210,000 bbl/day).*1 '  A group of materials  called natural-gas  liquids
 (1,699,000 bbl/day)  is the  other major raw material.  Various secondary
 raw materials are transferred between refineries  and  imported.  Many  materials
 are purchased and blended into  the products in  small quantities; for  example,
 alkyl  lead into gasoline and barium salts into  diesel fuel.
          Crude oil composition  varies widely depending  upon  its sources.
 Petroleum is a mixture of, paraffinic, naphthenic, and aromatic hydrocarbons
 containing small amounts of sulfur,  oxygen, and nitrogen compounds, plus
 trace quantities of various metals such as vanadium and nickel.
          Many different chemical compounds (probably over 3,000)^  are
present in crude petroleum and additional compounds  are made during refining
processes.   The hydrocarbons are generally grouped into series such as the

-------
                                    B-10
paraffins,  the  olefins,  the naphthenes,  the aromatics, and polycyclic
compounds.
           The sulfur  in  the crude  is  a major  source of sulfur dioxide
pollution  as most  of  the refinery  products ultimately are burned.   If the
sulfur  is  not removed in the  refining process,  it will be emitted as a
pollutant  when  the products are  used.  Sulfur may be present as  free sulfur,
hydrogen sulfide,  or  in  organic  compounds such  as thiophenes, mercaptans,
and alkyl  sulfides.   The mercaptans are  particularly obnoxious from an  odor
standpoint and  are sometimes  oxidized to disulfides to reduce the odor,  if
sulfur  removal  per se is not  required.
           Natural-gas liquids, which  are also called natural gasoline or
casinghead gasoline,  are hydrocarbons other than methane  in natural gas  as
it comes from gas  wells.  They are separated  from the methane by the natural
gas industry and  sold to refineries.  Natural gas liquids are similar in
composition to  various light  naphtha  streams  in the refinery and are blended
and/or  processed with them.
           Various  materials are  purchased for their fuel value at the refinery;
natural gas is  most common and frequently is  used in process heaters.   The
steam boiler usually  can be adapted to burn any fuel, so  the fuel used  here
is determined by  supply  and cost.
           Other miscellaneous materials  are purchased.  The n-butane  (feed
to the  isomerization  process  or  used  for gasoline blendings) is  both purchased
from the natural gas  industry and  supplied by other refinery processes.  Many
additives  for blending into the  various  products are purchased;  these include
alkyl lead for  motor  gasoline, barium compounds for diesel fuels, and additives
3Bor lubricating oils  such as  detergents  viscosity index improvers,  and
antioxidants.
                                 PRODUCTS

          Approximately 2,500  products  are  currently  produced wholly  or  in
 part  from petroleum.   A record 15,160,000 bbl/day  of  petroleum products
                                            (2)
 were  consumed in the  United  States  in 1971.      Table B-3 lists the major
 petroleum products  and their consumption  (1971).   Most petroleum products
 are blends  of several refinery streams  and  the  same material  often has a

-------
                          B-ll
     TABLE  B-3.   MA.10R PETROLEUM PRODUCTS, 1971
Product
Gasoline
Jet fuel
Kerosene
Distillate fuel
Residual fuel
LPG and LRG
Miscellaneous
Total
Consump tion
bbl/day
5,992,000
996,000
250,000
2,691,000
2,266,000
1,243,000
1,722,000
15,160,000
Net
Import
51,000
161,000
0
149,000
1,497,000'
25,000(a)
133,000
1,962,000
(a)
    Ne t export.
LPG - Liquefied Petroleum Gas



LRG - Liquefied Refinery Gas

-------
                                   B-12

different name when used for a different application.  In addition,
individual product specifications may be met by blends having different
compositions when produced at different times or by different refineries.
          Gasoline is almost one-half of the refinery output.^    Its value
is more than one-half of the value of all products sold by the refinery.
The gasoline product is invariably a blend of naphthas from several refinery
processes and includes several minor additives such as alkyl lead purchased
from other industries.  High octane rating, necessary for high compression
engine fuel, is  obtained from aromatic hydrocarbons which have octane ratings
of about  100, naphthenic compound with side chains, and paraffinic hydrocarbons
with several side chains.  Butane and  isopentane have good octaine ratings,
but the amount of these compounds in gasoline  is limited by their high
volatility.  Small additions of  alkyl  lead compounds  substantially increase
the octane rating of most  gasolines.
          Naphtha refers to hydrocarbon  fractions  boiling  in the 90-400  F
temperature  range.  Gasoline  is  a naphtha produced for use as motor  fuel
and designates both naphthas  for blending  into motor  fuels and the final
product.  A  single naphtha may be used both  as a motor fuel and  for  other
purposes  such  as a  solvent and on feed to  petrochemical  industry.
          Kerosene  is  a petroleum fraction boiling in the  350-550  F  range.
Historically,  it was  one  of  the  first  petroleum products  and was used  for
 lamps.   For  this use,  kerosene usually is  composed of paraffinic hydrocarbons
which  cause  less smoking when burned  in lamps. Various  processes  were
developed to remove  mercaptans  from kerosene to  reduce odor  problems.
Kerosene  is  used in small  scale  applications today such  as domestic  cooking.
           Jet aircraft fuels  are of two types, a  kerosene type  boiling in
 the 400-550  F range and a naphtha  type boiling in the 250-550  F range.   These
 fuels  may be treated to reduce freezing point by  removing wax  and  to reduce
 smoking by removing aromatic  hydrocarbons.
           Light diesel oil distills in 350-575 F range and can have a wide
 range  of specifications;  its performance is measured by a cetane rating that
 measures the ignition characteristics of the oil in a diesel motor.   Fuels
 which  naturally have a good cetane rating are used for diesel fuel while those
 with a poor rating are made into burner fuel.

-------
                                   B-13

          Distillate fuels have similar boiling ranges to diesel oil.  Any
oils that can be distilled either in the crude still or in the vacuum still
and oils of similar boiling ranges from various refinery processes are used
as fuel oil.  Generally, the oil is treated to remove sulfur.  Distillate
fuel is widely used for domestic heating.
          Residual fuels are hydrocarbons left in the still after the
volatile hydrocarbons have been distilled off.  Most residual oils from the
crude or vacuum still are diluted with kerosene or distillate oil, or
visbroken to reduce viscosity or sulfur content.  While residual oils are
not treated to remove sulfur now, processes are being installed in refineries
to remove sulfur from these oils.  Residual oils are usually burned  in large
boilers used for electric power generation and steam generation in large
industrial plants.
          Asphalt is a  hydrocarbon residue  from asphaltic base crude oils.
It is used with a rock  (aggregate) as a cement in road pavement, for manu-
facture of roofing materials, and for many other applications.  Petroleum
coke is a residual from the coking process.  It is used in the manufacture
of electrodes for electric furnaces and also as a fuel.
          Liquefied petroleum gas  (LPG) is a mixture of C™, C~, and  C^
hydrocarbons.  It is widely used for industrial heating and for domestic
heating and cooking where natural gas is not available or scarce.  Natural
gas companies frequently add LPG to natural gas at times  of peak demand.
LPG is an excellent motor fuel with a high octane rating  and minimum air
pollutant emissions.  It is occasionally used  for truck or bus fleets and
is quite widely used for fork lifts, payloaders, and other applications
inside buildings because of low emissions from motors using LPG.  Sometimes
the designation LPG is  restricted  to a product of the natural gas industry
and when that restriction is made, the same material made by the petroleum
industry will be called liquefied refinery gas (LRG).
          The petrochemical industry is based  on olefins, LPG's, and aromatic
hydrocarbons, which are secondary  raw materials supplied  in part by  the
natural gas industry.   In addition, naphtha is cracked in a  thermal  cracking
process to make ethylene.  The cracking process is performed in both refineries
and petrochemical plants.  The refineries have long  supplied aromatic

-------
                                   B-14

hydrocarbons to the petrochemical industry.  About 3 percent    of refinery
output is used to petrochemical feedstock.
                               PROCESSES

          Twenty-nine pertinent processes used in petroleum refineries are
shown in Figure B-l along with the flows of intermediate products among
processes.  Other refinery processes are not shown because (1) the process
is a minor variation of a process shown, and the raw materials, products,
and wastes are not significantly different from those in that process;
(2) the process is a specific application, perhaps obsolete, and is not
typical of the industry; or  (3) the process, while performed in some refineries,
is more typical of a different industry.  Two variations of catalytic cracking
are shown because their wastes are different.  Each variation has several
additional modifications, but they are not shown because the raw materials ,
products, and wastes are the same.  A third variation,  fixed-bed catalytic
cracking, is not shown because the process is no longer widely used.  Other
processes, such as cracking  naphtha to make ethylene, are considered part of
the petrochemical industry and are not described, even  though  the processes
are sometimes performed  in a refinery.
          Process heaters and process drives are treated as if they were
processes because their  emission  is characteristic of the heater or drive
and not of the particular process.  Thus, the emissions and wastes shown  for
each  process do not  include  those  from heaters or drives.  Emission from  the
heaters and drives are proportional to  the energy requirements for the  process.
          A brief description of  each of the 29  processes  follows  including
information on processing  techniques, equipment, raw materials,  products,
energy  requirements,  and wastes.

          Crude  Storage  (1). Crude oil  delivered  to  a  refinery  is stored
in tanks  until processed.   The  storage  tanks are sized  to  receive  the
largest  single  shipment  expected  and  to  assure  continuous  operation of  the
refinery.   The  amount  stored may  be anywhere between  a  2-week and  a 2-month
supply.   The  crude  is  stored in large  cone  or  floating  roof  tanks  of  up to

-------
                                   B-15

250,000-barrel capacity.   After storage,  the oil is sent to the desalter if
required and then to crude distillation.
          Only a small amount of electrical energy is required for pumping
of the stored crude.
          Gaseous hydrocarbon emissions from storage tanks relate to three
basic mechanisms:  breathing loss, working loss, and standing storage loss.
These are discussed later under storage and blending (Process No. 26).  Less
than 0.5 gal of water per bbl settles to the bottom of crude oil tanks and
is sewered.  This water effluent often contains salt.  Some crude oils form
sludges at the bottom of the storage tanks which are removed periodically and
burned (usually in the steam boiler).

          Desalting (2).   The function of desalting is to remove salt, water,
and water-soluble compounds from crude oil.  Water is added to the oil and
thoroughly mixed.  The wet oil is heated to break the emulsion.  The water is
separated by decantation and sewered.  In a variation of the process an
electrostatic coalescer is used to separate the oil and water.  The desalted
crude is then fed to the crude still.  Desalting is often performed in the
oil field by the oil producing industry.
          The thermal energy requirement for desalting is about 22,000
Btu/bbl assuming a 250 F desalting temperature and is usually obtained by
heat exchange with one of the hot streams from the crude still.  Alternatively,
the oil may be heated with steam or a fired heater.  About 0.01 kwh of
mechanical energy per barrel is required to pump the oil through the system
and to operate the electrostatic coalescer.
          No gaseous emissions or solid wastes are produced from the process.
About 2 gal of wastewater per barrel are drained from the desalter.  This
water contains any water-soluble material that had been in the crude and
frequently is high in salt content.  The wastewater volume is not very
large—about  140 gpm from a 100,000-bbl/day refinery.

          Crude Distillation  (3).  The function of crude distillation is  to
separate desalted crude oil into various products or intermediate products
with different boiling points by distillation and steam stripping.  The major
items of equipment  in crude distillation are the process heater  (pipe heater),

-------
                                   B-16
main distillation column, and stripping column.  The number of product streams
varies with the particular refinery.
          The intermediate products are light naphtha, heavy naphtha,
kerosene, distillate or diesel oil, gas oil, and topped crude.  In a very
simple refinery the intermediates are naphtha from the top of the still,
gas oil from a side stream, and topped crude from the still bottom.  In a
complex refinery three to five side streams may be withdrawn.
          In Figure B-l, the wet gas is shown as being processed further in
the gas plant.  However, in some refineries, this processing--the separation
of light gases from their naphtha component--is performed as part of crude
distillation.  The naphtha is blended into motor fuels or any of several of
the refinery products, or further processed to improve octane rating and/or
reduce sulfur content.  The kerosene may be chemically sweetened or hydrogen
treated and sold directly or sent to blending.  The distillate or diesel oil
may be sold for diesel or fuel oil, hydrogen treated, hydrocracked,
catalytically cracked, or blended.  The gas oil may be sold as fuel oil,
hydrogen treated, hydrocracked, catalytically cracked, or blended.  The
topped crude is usually the feed to the vacuum distillation process although
it may be sold for fuel, blended into fuels, hydrogen treated, or
catalytically cracked.
          The installed capacity for crude distillation in the U. S. was
13.7 million barrels per stream day in 1971.  The capacity of a crude still
varies from about 1,000 to 200,000 barrels per day.  The crude still is one
of the largest items of equipment in the refinery.
          Energy requirements include process heat from a heater, steam,
and mechanical drives.  About 100,000 Btu/bbl of crude are required from
the process heater.  The process heater associated with the crude still
consumes 15 to 30 percent of the fuel used in a refinery and  for the largest
unit--200,000 barrels per day—the heat release in the heater is similar to
the heat release in a boiler supplying a 100 MW electric generator.  About
15 pounds of steam per barrel of crude are required to pump the raw materials
and intermediate products.
          No atmospheric emissions or solid wastes are produced under
normal operating conditions.  The steam used is condensed with  the  light
naphtha  in  the condenser, separated from the oil by decanting,  treated  to

-------
                                   B-17
remove acids and odors,  and sewered.  Operating conditions have little or
no effect on wastewater.  The amount of hydrogen sulfide in the wastewater
is determined by the crude oil feed.

          Vacuum Distillation (4).  Vacuum distillation separates the
atmospheric residue from the crude still into a heavy residual oil and one
or more heavy gas oil streams.  The major items of equipment are the process
heater, the vacuum still, and the steam ejectors for producing the vacuum.
The installed capacity for vacuum distillation is 4.9 million barrels per
day (1971), which indicates that almost all of the topped crude is vacuum
distilled.
          Depending mainly upon the crude feedstock and partially upon the
individual refinery, the residual oil intermediate product may be sent to
the asphalt plant, thermally cracked in a coker to make gasoline, cracked
in a visbreaker to make distillate fuel oils, blended into a fuel oil, or
hydrogen treated to remove sulfur and then blended into a fuel oil.  With
suitable feedstocks the residual is sent to the lube oil process for
manufacture into lubricating oil.  The heavy distillate fraction from a
paraffinic crude charge is sent to the lube oil plant either directly or
thro'igh a hydrogen treating process.  Other distillates are treated
similarly to the gas oil stream from the crude still and catalytically
hydrocracked, catalytically cracked, or used as fuel oil.  The vacuum gas
oil may be processed to remove sulfur by hydrogen treatment before catalytic
cracking or use as a fuel oil.  Refinery-to-refinery variations are minor.
          About 50,000 Btu/bbl of thermal energy are required from a process
heater.  The product streams from vacuum distillation are usually cooled by
heat exchange with the feed to the crude still to conserve energy.  About
8 pounds of steam per barrel are required to operate the steam ejectors and
to strip the residual and side streams of their lighter fractions.  From 0.1
to 0.2 kwhr of mechanical energy per barrel are needed for pumping.
          The vent gas from the steam ejectors contains about 130 Ib of
hydrocarbon vapors per 1,000 barrels of feed.  The steam used in the injectors
is condensed in a barometric condenser.  The condensate may contain some oil.
The wastewater eventually passes through an API oil-water separator, where the
oil is removed before discharge of the water.  No solid wastes are generated.

-------
                                   B-18
          Chemical Sweetening  (5).  Chemical sweetening removes mercaptans
from petroleum products to improve odor.  At least 11 different processes
are used for this purpose including contacting the petroleum material with
various caustics, hypochlorites, solvents, or catalysts.  In most processes,
mercaptan sulfur is oxidized to an alkyl disulfide which is less obnoxious
than the mercaptan.  A few of  the solvent processes separate the mercaptan
which then becomes a product.  The amount of petroleum products chemically
sweetened is not known.  A chemical sweetening process is installed in most
of the older refineries while many newer refineries have replaced it with a
final hydrogen treatment before blending.
          The energy required by the process is minimal.  Steam is used to
strip mercaptans from solvents, but the solvent stream is much smaller than
the petroleum stream.  About 0.01 kwhr of mechanical energy per barrel is
required for pumping.
          Depending on the process, atmospheric emissions, liquid, and solid
wastes are produced in small quantities.  In some processes, the oxidizing
chemical is regenerated by air blowing.  In these processes air, slightly
depleted :a oxygen, is emitted.  The amount of air used is proportional to
the amount of mercaptan oxidizer.  In hypochlorite processes, water containing
sodium or calcium chloride is drained.  The amount of salt is small and
proportional to the amount of mercaptan sulfur oxidized.  In one of the
processes clay is used as a carrier for a copper chloride treating chemical
and when the clay is inactivated it is sent to a landfill.

          Hydrogen Plant (6).  The hydrogen plant supplies hydrogen for
hydrogenation reactions.  Frequently, all hydrogen is supplied by catalytic
reforming so that a hydrogen plant is not needed.  Hydrogen is made by
reacting naphtha or other hydrocarbons with steam at 1,400-1,600 F.  The
required temperature is obtained by external heating or by burning part of
the hydrocarbon with oxygen rather than air to prevent dilution of the product
hydrogen with nitrogen as illustrated in Figure B-2.  The gas from the reactor
contains hydrogen, steam, carbon monoxide, and carbon dioxide, and is passed
through a shift reactor where CO and H-0 are catalytically reacted to form
carbon dioxide and more hydrogen.  The carbon dioxide is removed by adsorption.
The small quantity of carbon monoxide remaining is catalytically oxidized

-------
                                  B-19
Hydrocarbon
                                           Steam
^
Steam
-*

Preheatei

                             Reformer
                                              T
Cooler
•^
^

Shift
Converter






>
co2
absorber
f
t

Second
Converter A
\
Absorbent
Regenerator
co2
bsorber
/

- Absorbent
2 Regenerator
                                                                          CO,
             FIGURE B-2.  HYDROGEN PLANT.

-------
                                    B-20
with  steam  to  carbon  dioxide  and hydrogen and  the  last  traces of carbon
dioxide are absorbed  with  caustic  or amine.  The hydrogen is dried before
use by condensation of water  at high pressure.  Single  units as large as
10,000 scfm have been installed.
          Thermal energy from steam is needed  to strip  the. carbon dioxide
from  the absorber solution.   Steam in about the same quantity is generated
by cooling  the gases  from  the partial oxidation of the  feed in a boiler.
With  external heating about 300,000 Btu/bbl of feed are required.  However,
a substantial  fraction can be recovered by heat exchange with the product.
A small amount of mechanical  energy is required for compression of the feed
and pumping of the fluids  through  the systems  if a liquid feedstock is used
or about 4 kwhr/bbl are required if a gasoline feedstock is used.
          The  only waste stream from the process is a carbon dioxide
atmospheric emission  from  regeneration of the  absorber  liquid.  From 0.25
to 0.5 cubic foot of  carbon dioxide is produced per cubic foot of hydrogen.

          Naphtha Hydrogen Treatment (7).  The function of the gasoline
hydrogen treatment is to remove sulfur from a naphtha stream, saturate
olefins '.o reduce gum formation, and/or remove aromatics from naphthas for
solvents, burning fuels, or jet fuels.  For gasoline treatment, the feed is
mixed with about 400  cu ft of hydrogen per barrel, heated in a fired heater
to 350-800 F and passed through a  catalyst bed.  The pressure is from 300 to
800 psi.  The  products are cooled, usually by heat exchange with the feed,
and the excess hydrogen is separated and recycled.  The gasoline product is
reheated and steam stripped or distilled to remove hydrogen sulfide.  A total
of 4.9 million barrels per day (1971) of petroleum products are hydrogen
treated, and 2.8 million barrels per day of catalytic reforming feedstock
(naphtha( are hydrogen treated.  The process product may be catalytically
reformed or blended directly  into  a refinery product.   The off-gas and
hydrogen sulfide go to gas processing for further treatment.
          Fired heaters require up to 50,000 Btu/bbl of gasoline treated.
Since the reaction is exothermic,  in some process variations all the necessary
heat  is supplied by the reaction.  From 30 to  90 Ib of  steam per barrel are
required to strip hydrogen sulfide from the gasoline.  About 1.5 kwhr of

-------
                                   B-21
mechanical energy per barrel are required to compress the hydrogen and to
pump the feed through the system.
          A gas stream containing carbon monoxide is emitted during
infrequent (months to years) regeneration of the catalyst.  The catalyst is
regenerated by blowing a steam-air mixture through the bed to burn off a
carbon deposit.  A liquid stream of sour water is drained from the stripper
in an amount equal to the steam used.  The spent catalyst comprises a solid
waste; however, catalyst life is usually more than 5 years.  The catalyst
is sold to a reclaimer of precious metals in some instances.

          Kerosene Hydrogen Treatment  (8).  The function of the kerosene
hydrogen treatment is to remove sulfur from kerosene, saturate olefins,
reduce gum formation, and remove aromatics.  The kerosene is mixed with about
400 cu ft of hydrogen per barrel and heated in a fired heater to 400-800 F
at 500-800 psi.  It is then passed through a catalyst bed where the reaction
occurs.  The products are cooled, usually by heat exchange with the feed,
and the excess hydrogen is separated and recycled.  The products are reheated
and steam stripped to remove hydrogen sulfide.  A total of 4.9 million barrels
per day (1971) of petroleum products are hydrogen treated.  Most kerosene—
1,000,000 bbl/day--is treated by a chemical sweetening process or by a
hydrogen treatment.  A total of 1,000,000 bbl/day of middle distillate stocks
(mainly kerosene) are hydrogen treated.  The treated kerosene is usually a
refinery product or blended into a product.  The hydrogen sulfide goes to gas
processing.
          Fired heaters require up to 70,000 Btu/bbl of kerosene treated.
Since the reaction is exothermic, in some process variations all the necessary
heat is supplied by the reaction.  About 8 Ib of steam per barrel are required
for the stripping of hydrogen sulfide from the product.  From 0.5 to 2 kwhr of
mechanical energy per barrel are required to compress the hydrogen and to pump
the feed through the system.
          The emissions for this process are about the same as those for the
Gasoline Hydrogen Treatment Process (7) except the internal between catalyst
regeneration is weeks to months.

-------
                                   B-22
          Gas-Oil Hydrogen Treatment  (9).  The function of the gas-oil
hydrogen treatment   is  to remove sulfur from oils.  The gas oil is mixed with
from 750 to 1,500 cu ft of hydrogen per barrel and heated in a fired heater.
The mixture then is passed through a  catalyst bed where the reaction occurs.
The pressures are from 500 to 800 psi.  The products are cooled, usually by
heat exchange with the  feed, and the  excess hydrogen is separated and recycled.
The products are reheated and steam stripped to remove hydrogen sulfide.  A
Total of 4.9 million bbl/day (1971) of all petroleum products are hydrogen
treated.  The fraction of gas oil that is hydrogen treated is not known.
However, at present, sulfur specifications in fuel oils are met by desul-
furizing gas oil to a very low sulfur content and blending with residual oils.
A total of 295,000 bbl/day (1973) of  cat cracking feedstock (a part of gas
                          (9\
oil) is hydrogen treated.     The treated gas oil may be catalytically cracked
or blended into a fuel oil product.   The hydrogen sulfide goes to gas processing.
          The fired heaters require from 5,000 to 70,000 Btu/bbl.  From 1 to
10 Ib of steam per barrel are required for the stripping of hydrogen sulfide
from the product.  From 2.5 to 9 kwhr of mechanical energy per barrel are
required to compress the hydrogen and to pump the feed through the system.
          Emissions from  this process are the same as those from the Kerosene
Hydrogen Treatment Process (7).

          Lubricating Oil Hydrogen Treatment (10).  The function of the
lubricating oil hydrogen  treatment is to remove sulfur, hydrogenate olefins,
remove gem forming compounds, improve color, and improve viscosity index of
lubricating oils.  The feed is mixed with 100 to 200 cu ft of hydrogen per
barrel, heated in a fired heater, and is passed through a catalyst bed where
the reaction occurs.  The products are cooled, usually by heat exchange with
the feed, and the excess hydrogen is  separated and recycled.  The oil is
reheated and steam stripped to remove hydrogen sulfide.  The fraction of
lubricating oil that is hydrogen treated is not known.  The hydrogen-treated
oil is sent to lube oil processing for further treatment and the hydrogen
sulfide stream is sent to gas processing.
          Fired heaters require from  35,000 to 140,000 Btu/bbl of oil treated.
From 15 to 30 Ib of steam per barrel  are required for the stripping of

-------
                                   B-23

hydrogen sulfide from the product.  About 2.5 kwhr of mechanical energy
per barrel are required to compress the hydrogen and to pump the feed
through the system.
          Emissions from this process are essentially the same as those
from the Gasoline Hydrogen Treatment Process (7).

          Residual Oil Hydrogen Treatment (11).  The function of the
residual oil hydrogen treatment is to remove sulfur from the oil usually
to about 0.3-0.5 percent concentration.  The feed  (3 to 5 hexant sulfur) is
mixed with recycled hydrogen and  from 400 to 700 cu ft of fresh hydrogen per
barrel and heated in a fired heater to 650 -850 F.  It then is passed through
a catalyst bed where the reaction occurs.  The pressure is about 1,000 psi.
The products are cooled, usually by heat exchange with the feed, and the
excess hydrogen is separated and  recycled.  The product is reheated and
steam stripped to remove hydrogen sulfide.  The first residual oil hydrogen
treatment units are now going on  stream and are fairly small.  The
desulfurized residual oil is blended into fuel oil.  The hydrogen sulfide  is
further treated in gas processing.
          Fired heaters require from 10,000 to 100,000 Btu/bbl.  From 3 to
25 Ib of steam per barrel are required to strip hydrogen sulfide from the
product.  From 1 to 4 kwhr of mechanical energy per barrel are required to
compress the hydrogen and pump the feed through the system.
          Emissions from this process are similar  to the Gasoline Hydrogen
Treatment Process  (7) emissions.

          Catalytic Hydrocracking  (12).  The function of the catalytic
hydrocracking process is to  convert a gas oil  in  the presence  of hydrogen
at 700-2,000 psi and 500-800 F into lighter, sulfur free, more valuable
petroleum fractions.  Catalytic hydrocracking  generally opens  the  ring
structure on polycyclic aromatics and naphthenes.   Paraffins,  single-ring
naphthenes, and single-ring  aromatics are resistant to hydrocracking.  About
                                                                    (9)
840,000 bbl/day  (1972) of petroleum intermediates  are hydrocracked.
Hydrocracking differs from hydrogen treatment  in  severity of  treatment
rather  than type of treatment.  The process  variations are  based  on  feed
and catalyst used  and include  single or  two-stage  processes.   The  feed  is

-------
                                    B-24

 usually a gas oil although occasionally residual oil or naphtha is fed.
 From 1,000 to 2,000 cu ft of hydrogen per barrel are consumed.   The product
 from the reactor is separated by distillation into a wide range of sulfur-
 free hydrocarbons lighter than the feedstock and some hydrogen sulfide.
 Intermediate products are furnished to a variety of processes  as indicated
 below.

           Intermediate Product          Process  to Which Furnished
           Hydrogen sulfide              Gas  processing
           Hydrocarbon gases             Gas  processing
           Light  naphtha                 Blending into gasoline
           Heavy  naphtha                 Catalytic  reforming
                                         Blending into gasoline
                                         Blending into solvents
           Kerosene                      Blending into jet fuel
           Gas  Oil                       Blending into fuel oil
                                         Blending into diesel oil
                                         Catalytic  cracker
                                         Recycle
           Residual                      Pitch  (product)
           The  oils produced by catalytic hydrocracking are sulfur-free
 saturated  hydrocarbons which make  then premium fuels  for burning in jet
 engines  and  diesel engines,  but  poor  fuels for automotive-type  engines.
           From 100,000 to 250,000  Btu  of process heat  per  barrel from a
 fired heater are  required to heat  the  reactor feed.  About 18 Ib of steam
 per barrel are required  for  stripping  and 24  Ib/bbl are  generated  in a
waste heat boiler which  cools  the  product.  From 1  to  6  kwhr of  mechanical
 energy per barrel are  required for  compression of  the  hydrogen  and  pumping
 of the feed  and products  through the process.
          Atmospheric  emissions--mainly  carbon monoxide — result  from
 regeneration of the catalyst.  Since regeneration  is  infrequent  (about 4
per year), the carbon  monoxide produced  should not be  a  problem.  A  liquid
stream, mainly condensed  steam with some H«S, is drained  from the  stripper.
The spent catalyst, a  solid waste,  is  not produced in  significant  amounts
becau'se the catalyst  life  is  several years.  The spent catalyst  is  sold to
a reclaimer of precious metals occasionally.

-------
                                  B-25
          Gas Processing (13).   The function of gas  processing  (frequently
called the gas plant) is to stabilize  light naphtha  by  removing gaseous
hydrocarbons from it, and separate the  various  fractions  of  hydrocarbon
gases.  Amine stripping, which  removes  hydrogen sulfide from the gases,  is
sometimes considered part of gas processing although it is  treated  as a
separate process in this study.   In some  refineries, gas-processing equip-
ment is associated with each gas-generating process  while in most new
refineries gas processing is performed  in a facility serving the entire
refinery.
          The separations are performed by a series  of  distillation and
absorption operations, the number of operations being one less  than the
number of products.  Gas processing can be a simple  scheme  producing fuel
gases composed of butane and more volatile hydrocarbons,  and a.light
naphtha; or a complex scheme producing  methane, ethane, ethylene, propane,
propylene, isobutane, butylene,  butadiene, n-butane, isopentane,  amylene,
n-pentane, and a light naphtha.
          The disposition of products  and intermediate  products is  shown
below.
                 Prod uc t              Use
               Methane             Refinery fuel
               Ethane              Refinery fuel
                                   Petrochemical feedstocks
               Ethylene            Petrochemical feedstock
                                   Refinery fuel
               Propane             LPG
                                   Petrochemical feedstock
               Propylene           LPG
                                   Petrochemical feedstock
                                   Polymerization
                                   Alkylation
               Isobutane           Alkylation
               Butylene            Alkylation
                                   Polymerization
               Butadiene           Petrochemical feedstock
               n-butane            Isomerization
                                   Fuel
                                   Blend  into gasoline

-------
                                  B-26
                 Product               Use
               Isopentane           Blend into  gasoline
               Amylene              Alkylation
                                    Blend into  gasoline
               n-pentane            Isomerization
                                    Blend into  gasoline
               Light naphtha        Blend into  gasoline
                                    Catalytically reform
                                    Blend into  solvents
                                    Isomerization
          Figure B-3 *s a flow diagram for a plant of intermediate complex-
ity which uses an absorption system.  The gases from the refinery initially
are compressed.  The high-boiling petroleum gases and gasoline are absorbed
in a heavy naphtha or kerosene.  In the flow diagram, methane, hydrogen
sulfide, and ethane pass from the top of the absorber de-enthanizer unit.
The ethane and methane are stripped of hydrogen sulfide with diethanola-
mine and used for fuel gas.  The propanes and less volatile components flow
from the bottom of the absorber to the debutanizer where propane and butanes
are separated from the gasoline by distillation.  The depropanizer is
another distillation column which separates butanes from propane.
          Thermal energy is required for the distillation column and strip-
ping the absorber solutions.  This energy may be supplied by hot process
streams from other processes rather than from a fired heater or steam.
Mechanical energy, about 2 kwhr/bbl, is required to compress the gases for
absorption as the distillation column normally operates under pressure.
          The process is performed in a closed system and no emissions are
generated.

          Amine Stripping (14).  The function of the amine stripper is to
strip hydrogen sulfide from hydrocarbon gases by absorption in an amine
solution.  Sour gas from gas processing is the feed and the intermediate
products are a sweet gas which is returned to gas processing and hydrogen
sulfide which goes to the sulfur plant.  The hydrocarbon gas containing
hydrogen sulfide is contacted with an absorbent solution, such as

-------
                                 B-27
DISTILLATE
DISTILLATE FROM
_CRUOE UNIT a CO
-------
                                   B-28

 diethanolamine, in an absorption column to absorb selectively the hydrogen
 sulfide.  Hydrogen sulfide is absorbed at a pressure of around 150 psi,
 and the absorbent solution is stripped at atmospheric pressure by boiling
 at the bottom of the stripper.
           Thermal energy, about 1 Ib of steam per Ib of H9S,  is required
 to strip the hydrogen sulfide from the absorber solution.   About 0.5 kwhr
 of mechanical energy per barrel is required to pump the liquids through
 the system.
           No atmospheric emissions are produced.   When diethanolamine is
 used as the  absorbent solution, about 1 gallon of spent solution is
 drained per  thousand barrels  processed.  However, since 10,000 to 20,000
 gallons may  be drained  at one time,  the impact on the  sewage  system  of
 changing solutions  may  be severe.   When monoethanolamine is used  for the
 absorbent solution,  about 1 Ib of  waste complex salts  (solid)  is  removed
 from the system for each 3,000 barrels processed.   No  other waste  is gen-
 erated.   The amount of  waste  is roughly proportional  to the amount of
 hydrogen sulfide  removed from refinery streams and,  therefore,  depends
 upon the amount of  sulfur in  the crude and  the extent  to which  the pro-
 ducts  are desulfurized.

           Sulfur  Manufacture  (15).   Sulfur  is  manufactured in  a  Glaus
 plant     as  a  method  of disposal of  hydrogen  sulfide.   About  1.2 million
 tons/year of sulfur  is  produced by  the  petroleum  industry and  this number
 is  growing.   The  feed is hydrogen  sulfide from the  amine stripper.   Where
 special  market  conditions exist, sulfur  dioxide or  sulfuric acid may  be
 made using processes  typical  of the  sulfur  industry.  As indicated by the
 flow diagram in Figure  B-4, the hydrogen sulfide  is burned with a  substoichio-
 metric quantity of  air  to make  sulfur  and water.  The off-gas  is cooled  and
 the sulfur condensed as  a liquid.  About 60 to  70 percent of the sulfur  is
 removed  in the  burner;  the remaining hydrogen  sulfide and sulfur dioxide
 gases are reheated  and  passed  through  a  catalytic converter.  The gases
 are cooled to condense  liquid  sulfur.   In most  systems, two to  four con-
verter stages  in  series  are built  into  the system.  Fifty to 60 percent
 of  the remaining  sulfur  is removed in each converter stage.  The total
sulfur recovery in Glaus  plants varies  from about 80 to 95 percent.

-------
                                             B-29
 I
 I
 I
r
 i
 i
 i
                                Burner Stage

                                     Steam
                   Converter Stage
Sulfur
H2S ^
Air



Reaction
Furnace
/


^

	 ^=^
Boiler
\
T
.so2
Desorber

-^


so2
Abso


"*^

Condenser


reatment Stage
Off-Gas

rber




Incinerator
- Air '
\


n





PoK

\
eat
/
Converter
\
/
Condenser

Sulfur

                                                                                         -I
                                                 Fuel
                                                              J	I
                                   FIGURE B-4.  GLAUS PLANT

-------
                                   B-30
           Frequently,  the  tail  gas  from the  Glaus  plant  is  treated  to
 remove  the  last  traces  of  sulfur-containing  gases.   The  tail gas  contains
 H2S,  S0_,  COS, and  CS  ,  compounds  that  have  a disagreeable  odor.  In old
 plants  they are  incinerated  to  reduce the  odor  problem,  although  S09 emis-
 sions result from burning.   Some new processes  essentially  add more con-
 verter  stages  to the Glaus unit, other  absorb the  sulfur-containing off-
 gases,  concentrate  them, and  recycle them  to the Glaus input, and still
 others  oxidize hydrogen  sulfide  to  sulfur  in a  wet process.  While  tail-
 gas  treatment  plants are being  installed,  long  operating experience and
 standard design  have not yet  evolved.   In  the flow diagram  (Figure  B-4)
 the  off-gas from the Glaus plant is incinerated to convert  all of the sul-
 fur  into S07 which  then  is absorbed.  In the Wellman-Lord process for S0_
 removal and recovery a  sodium sulfite solution  is used for  absorption while
 in other processes  an amine solution is used.   The clean off-gases are
 vented  to a stack.  The absorber solution  is regenerated and the  SO- is
 fed  back into  the Glaus plant.
          The Glaus plant requires  a fired heater, 400 Btu/lb of  sulfur,
 to reheat the off-gases in the catalytic states, and a small amount of
 mechanical  energy to move the gases through  the plant.   Steam, 4  Ib per
 Ib of sulfur,  is generated in a boiler  utilizing the heat content in the
 products of combustion  following the burner  stage.
          The emissions from  the Glaus  plant are primarily  unconverted
H S  and S0_.  Hydrocarbons in the feed  to  the Glaus  plant form carbonyl
 sulfide and  carbon disulfide which  are  also  emitted.  If the off-gas is
 incinerated, all sulfur compounds are converted to sulfur dioxide.  Negli-
gible liquid and solid wastes are generated.  In a refinery where most of
 the  sulfur  in the crude is removed  and  collected as H«S, the emissions
from the Glaus plant constitute the major  sulfur emissions.  As sulfur is
removed from products and high sulfur foreign feedstocks replace sweet
U.S. crudes, the emissions from the sulfur process will  increase.  A large
100,000-barrel-per-day refinery using a 1-percent sulfur feedstock removing
sulfur from its  fuel gases and desulfurizing many of its products and using
an efficient Glaus plant which converts 95 percent of the feed into sulfur,
emits 5 to  6 tons of sulfur per day from the Glaus plant.  About  127,000 tons
per year of  sulfur dioxide are emitted  from  sulfur manufacture in all
refineries.

-------
                                  B-31
          Isomerization (16).  The function of isomerization is to process
normal butane, pentane, or hexane into the corresponding isoparaffin.  Iso-
butane is used as a feedstock for alkylation.  Isopentane and isohexane
have a higher octane rating than normal pentane and normal hexane and are
blended into gasoline.  The process equipment consists of a heater, a
reactor, and a set of distillation columns.  The distillation columns
frequently are shared with the alkylation process which uses the isobutane,
or the distillation procedure may be included in gas processing.  The
reactor normally operates at 300 to 400 psi and at 400 to 500 F.
          About 1.2 kwhr of mechanical energy per barrel is needed to pump
the feed to the operating pressure.  A fired heater (30,000 Btu/bbl) is
used to heat the feed, and steam (20 Ib/bbl) heaters are used to drive the
distillation columns.
          The process is closed and should have no gas emissions or liquid
effluents in normal operation.  The solid catalyst is replaced after about
2 years of operation.  The spent catalyst is sold to reclaim its platinum
value.

          Catalytic Reforming (17).  Catalytic reforming is used to con-
vert low-octane naphtha into a high-octane gasoline, produce aromatics for
the petrochemical industry, and to manufacture hydrogen.  In 1971, about
3.2 million bbl/day of naphtha was reformed.  The feed naphtha is reformed
by passing it through a multiple-stage reactor with reheat between stages
to maintain the temperature at 900-1100 F.   Paraffins are dehydrogenated
to naphthenes, naphthenes are dehydrogenated to aromatics, olefins are par-
tially hydrogenated to paraffins, long and short chain hydrocarbons are
cracked to gaseous hydrocarbons, and short chain hydrocarbons are  isomer-
ized.  The process variations include methods of catalyst handling, differ-
ent catalysts, and different operating conditions.  One  factor affecting
process choice relates to product usage for  either petrochemicals  or
gasoline.  Another factor is the nature of the feedstock.
          Reforming process  throughput presently is 3.2  million barrels
per day which makes it one of the very large volume processes in refineries,
Additional facilities are being built rapidly because  the reformer yields
high-octane blending  stocks  used to minimize the need  for lead additives.

-------
                                  B-32
In addition, the hydrogen from reforming is needed for the hydrogenation
processes which remove sulfur from petroleum products.  The reformer is
a major user of energy in the refinery and the associated process heater
is one of the larger heaters in the refinery.
          The feed to the process is any desulfurized naphtha (sulfur
poisons the catalyst).  Heavy naphthas usually are fed when making gaso-
line, and light naphthas when making aromatics for the petrochemical
industry.  The products from the reformer are a high-octane gasoline or
an aromatic petrochemical feedstock, propane, butanes, ethane, and 800-
1500 cubic feet of hydrogen per barrel of feed.  The gasoline has a clear
(without lead addition) octane rating of 90-92 with existing units and 98-
102 with new units and is blended with lower octane gasolines for sale.
The propane is sold or used as fuel and the hydrogen is used for desulfur-
izing, hydrocracking, or for fuel.
          The energy required by the process is 200,000 to 400,000 Btu/bbl
and  is supplied from a fired heater to heat and reheat the feedstock.,  From 3
to 6 kwhr are required for compression and to pump the fluids through the
system.  Usually no steam is used although a few processes use up to 30 Ib
of steam per barrel to heat the reboiler in a product fractionator.
          The only atmospheric emissions are from regeneration of the cata-
lyst.  Usually the catalyst is regenerated by burning off carbon deposits
at infrequent intervals; however, in some variations, the catalyst is con-
tinuously withdrawn from the reactor and regenerated.  The major constituent
of the emission is carbon monoxide at 0.002 to 0.02 Ib/bbl (the amount of
CO formed is independent of batch or continuous regeneration) or about
30 Ib/hr in a large refinery that may typically reform 40,000 bbl/day.
This is a very small source and is about equal to the emissions from a
catalytic cracker with maximum controls and is less than the emissions
from the process heater.  Since the catalyst is mechanically stable and
the feed is sulfur-free, very little particulate or sulfur emission is
produced from catalyst regeneration.  Because of the low emission rate,
emission controls are not used.  No liquid wastes are generated.  The spent
catalyst is a solid waste and may be processed for recovery of precious
metal values or sent to a landfill.  The amount of solid waste generated
is small.

-------
                                  B-33
          Fluidlzed-Bed Catalytic Cracking  (18).  The  function of  the
catalytic cracking process is to convert distillate oils  into high-
octane gasoline, raw materials  for alkylate production, petrochemical
raw materials, heating and diesel oils, and liquefied  petroleum gases.
About 3.9 million bbl/day  (1971) of oil is  fed into fluid-bed catalytic
crackers not  including a 22 percent recycle.  Two major process varia-
tions are the fluidized bed and the moving bed.  Since the emissions
from the two  systems are different, they are discussed separately  in this
report.  The  fluidized-bed units are built  in sizes up to 75,000 bbl/day
with 40,000 bbl/day being typical.
          In  the fluidized-bed catalytic cracker, hot gas oil is fed into
a line at the bottom of the reactor where it mixes with the catalyst.
The gas oil is cracked as it passes up through the reactor.  The cracked
products leave the top of the reactor, are cooled, and fractionated in a
distillation column associated with the reactor into the product streams.
In a single pass, 50 to 80 percent of the feed is converted into lighter
hydrocarbons.  Some or all of the unconverted gas oil may be recycled.
The catalyst flows to the regenerator where the carbon is burned off with
air.  In about 50 percent of the units, the flue gas is burned in  a carbon
monoxide boiler, while in others the CO-rich flue gas is emitted to the
atmosphere.
          The major process variations involve catalyst handling and
reactor design.   In one variation, the reaction takes place in the riser
line which becomes the reactor.   In another variation, the recycle and
virgin feed  are reacted in different risers to obtain a more severe treat-
ment of the  recycle oil.
          The feed to the catalytic cracker may be any hydrocarbon stock
from kerosene to vacuum gas oil  or deasphalted residual oil.  The  feed is
usually the  distillate oils from the crude and vacuum stills, the heavy
oils from coking and hydrocracking, and a large recycle heavy oil  stream.
          A complete range of petroleum products is made in the catalytic
cracker and  a large distillation column is associated with the cracker to
separate these components.   The  amount of each product can be varied by
changing operating conditions.   The coke deposited on the catalyst is

-------
                                  B-34
burned during regeneration to supply some of the heat required by the
process.  The products and their special characteristics and uses are
listed below.

          Gases          Rich in isomers         Further processed in
                           and olefins             gas processing
          Naphtha        Rich in high-octane     Blend into gasoline
                           components
          Light oils            --               Fuel
                                                 Recycle
          Residual              --               Fuel
                                                 Recycle

Incidental to the process, the sulfur concentration in the light and
residual product oils is reduced to about 50 percent of the concentra-
tion of sulfur in the feed.  The partial desulfurization makes these oils
more desirable fuels.  In addition, the product oils are more easily desul-
furized than the feed oil.
          Thermal energy (up to 70,000 Btu/bbl) may be used to preheat the
feed.  Steam (about 40 Ib/bbl) is used to strip the spent catalyst and
fractionate the product.  Mechanical energy (0.3-4 kwhr/bbl) is used to
drive the air blowers and feed pumps.  The flue gases are usually cooled
by heat exchange in a boiler, and the carbon monoxide is burned in a
boiler.  The amount of steam generated (about 110 Ib/bbl) may be greater
than the steam used.
          The flue gas (about 2,000 cu ft/bbl) from the catalytic cracker
is a major atmospheric emission from a refinery.  The flue gas is a mix-
ture of carbon monoxide and nitrogen with traces of hydrocarbon and sulfur
compounds and, in the absence of a carbon monoxide boiler, contains most
of the carbon monoxide emitted by a refinery.  At present, almost all of
the 4.5 million tons per year of carbon monoxide emitted by catalytic
crackers comes from units without CO boilers.  The volume of stack gas
from a catalytic cracker is similar to that from a large industrial boiler
or a small electric-generating boiler.  In a fluidized-bed catalytic
cracker the catalyst is in the form of a coarse powder and the action of
the fluid-bed grinds the powder into a fine dust, some of which passes

-------
                                 B-35
through the dust-collection system.   This dust is a major source of partic-
                                                                        ( R ^
ulate emission (33,000 tons per year*) from refineries.  About 5 percent
of the sulfur in the feed deposits in the coke on the catalyst and the sul-
fur is oxidized in the regenerator and leaves in the flue gas.
          Analyses of the stack gas show that 15-60 percent (usually 30-50
percent) of the sulfur^12^ is emitted as S<>3 and the remainder as S02.  Thus,
the catalytic cracker is a major sulfur emitter (333,000 tons per year as
SO *) in refineries.  Hydrocarbons (165,000 tons per year*) and nitrogen
oxides (50,000 tons per year*) are emitted in significant amounts by cat-
alytic crackers.  A liquid waste stream from the fractionator is the
condensed steam from the process.  This water is sour and is combined and
treated with other sour waters before release.  About 0.1 Ib of catalyst
is used per barrel of feed, so that about 2 tons per day of solid waste
are generated by a 40,000-bbl/day unit.
          A variation in refinery operation which may reduce the atmos-
pheric emissions of SO  is desulfurization of the feed to the catalytic
cracker.  This change has been made in some refineries for economic
reasons, and it has been suggested as a general method of meeting antici-
pated sulfur dioxide limits on the regenerator stack gas.  Caustic scrub-
bing of the regenerator gases also has been suggested and Exxon plans to
install a sodium carbonate scrubber in a refinery where disposal of the
sodium sulfite solution generated will not be a problem.

          Moving-Bed Catalytic Cracking  (19).  The  function of  the moving-
bed catalytic cracking is  the same as fluidized-bed catalytic cracking.
510,000 bbl/day are fed into moving bed catalytic crackers not  including
a  20-percent recycle.  The feeds and  products are also similar.  The
moving-bed units are generally smaller than  the  fluidized-bed units.
Large units may process up to 35,000  bbl/day  and  15,000  bbl/day units
are  typical.  The  catalyst is  in  the  form of  beads,  1/8  to  1/4  inch in
diameter.  The catalyst is added continuously  to  the  top of  the reactor,
flows  through  the  reactor  and  regenerator by  gravity,  and  is  removed  from
the bottom of  the  regenerator.  An airlift  station  elevates  the catalyst
*  Calculated  from throughput  and  emission  factors.

-------
                                   B-36
 from the bottom of the regenerator to the top of the reactor.  The hydro-
 carbons flow down through the reactor and the combustion air can flow up
 cz  down thtougl. ti.Ł. regenerator depending upon the particular process
 variation.   CO boilers have not been used in moving-bed crackers.
           Thermal energy (100,000-300,000 Btu/bbl) is required to  heat
 the charge  to reaction temperature.  More heat is required than in the
    i
 fluidized-bed process because less heat from hot regenerated catalyst is
 available.   Steam (100 Ib/bbl) is required by the fractionator and to seal
 the gases  in the reactor from the gases in the regenerator.   Mechanical
 energy (0.1-1.5 kwhr/bbl) is required for blowing air into the regenerator
 and Lcr pumping oil.   Steam (160 Ib/bbl) can be generated by the hot  off-
 gas from the regenerator.
          The emissions from the moving-bed cracker  are less than  from
 fluidized-bed system,  primarily because of the smaller size  of the moving-
 bed units.   Tne catalyst perticles are  larger and less dust  is generated.
 Slightly less carbon  deposits on the  particles in the bed so that  less
 carbon monoxide and sulfur  dioxide are  emitted.   Hydrocarbon and nitrogen
 oxide  emissions are small.   The wastewater quantity  is about the same as
 the steam used.   The  water  is sour and  is treated before  release.   The
 spent  catalyst from the process is a  solid waste and  amounts to 0.1 to
 0.2 Ib/bbl.   In a large unit,  this amounts to more than a ton per  day.

          Visbreaking  (20).   The function of visbreaking  is  to thermally
 crack  residual oils into a  lighter oil  under mild conditions (850-890 F).
 The residual  oil  is passed  through a  heater  to crack  it and  then fraction-
 ated in  atmospheric and vacuum towers.   About 230,000 bbl/day (1971)  of
 residual oil  are visbroken  and  a  similar  amount  of gas-oil is  thermally
 cracked  in a  similar  process  (not  shown  in flow  diagram).  The  light  oil
 product  is used  to cut  (dilute)  the vacuum residue from the  visbreaker
which  is then  sold for  heavy  fuel  oil.   The  light product is  sometimes
 used as  a feed to a catalytic  cracker.   Visbreaking is  more  typical of
 foreign  refineries than American  refineries.

-------
                                  B-37

          The main energy requirement is 260,000 Btu/bbl from a fired
heater to crack the oil.  Mechanical energy (1.8 kwhr/bbl) is needed to
pump the oil.  Steam (100 Ib/bbl) is generated by cooling and condensing
the cracked oil and about 20 Ib/bbl are used in the fractionating tower.
          Since the process is closed, no atmospheric emissions are pro-
duced.  Water from fractionation is treated with other sour water.  No
solid waste is generated.

          Coking (21).  The function of coking is to crack heavy residuals
into a full range of hydrocarbon products and to produce petroleum coke.
About 20 percent of the feed is converted into coke (42,000 ton/day).  Most
coking processes are closed, although about 10 percent of coking is performed
in a fludized-bed process (an open process) where combustion of some of the
coke is used to supply the process heat.  The off-gas from the combustion
chamber in a fluidized-bed process is burned in a CO boiler and emitted to
the atmosphere.
          In a closed, drum-coking process, the oil is heated to 900-930 F
and then passed into a coking drum where it is cracked into lighter hydro-
carbons and coke.  Normally two coking drums are installed and one is used
while the other is emptied.  The volatile hydrocarbons are fractionated.
In the open, fludizing-coking process, hot oil is cracked in a reactor con-
taining a bed of coke at 930-950 F.  The heat for the process is supplied
by burning part of the coke in a second fluidized bed called the burner
where the coke is heated to about 1100 F.  The off-gas from the burner is
oxidized in a CO boiler to remove CO and conserve heat.
          The feed to the coker is usually a heavy residual oil from the
vacuum still or the catalytic cracker, or a deasphalted oil from asphalt
manufacture.  The products of the coker are a wide range of hydrocarbons
similar to the products of catalytic cracking and are used similarly.
About 20 percent of the feed is converted into coke which is burned as
fuel or sold to make carbon electrodes.
          In the drum coking process, from 300,000 to 400,000 Btu/bbl
are used to heat the feed in a fired heater.  In the fluid coker  this
heat is supplied by burning coke rather than using a fired heater.

-------
                                   B-38

 About 80 Lb of stem per barrel are used in the fractionator and 180 Ib of
 steam per barrel are generated by cooling the hot products of coking.
 Thus, the process generates 100 Ib of steam per barrel.  Mechanical energy
 (1.5 kwhr/bbl) is needed for high-pressure water jets to wash the coke
 from the drums, for compressing air,  and to pump fluids through the process.
           No atmospheric emissions are produced in the drum-coking process.
 In the fluidized coking process, the  thermal energy is supplied by burning
 the coke to carbon monoxide.  The carbon monoxide may be used in a boiler
 associated with the process or used for fuel at other places in the refin-
 ery.   About 5 percent of the carbon in the feed is burned and emissions
 are typical of this combustion.  Presumably the sulfur content of the feed
 would be distributed in a manner similar to a catalytic cracker where the
 sulfur concentration in the coke is slightly less than the sulfur concen-
 tration in the feed.  Therefore, 3-5  percent of the sulfur in the feed
 would be emitted  with the product of  combustion.   Both coking processes
 fractionate the product and the steam used for stripping is condensed and
 sent  to the sour-water stripper.  In  the drum-coking process,  high-pressure
 water jets  are used to break the coke from the drums and the water from
 these jets  goes into the plant sewers.   No solid  wastes other than coke
 dust  is generated.

           Polymerization (22).  The function of the polymerization process
 is  to produce  a high-octane gasoline  or  petrochemical feedstocks  from ole-
 fin gases.   It is  used in some refineries  in place  of isomerization and
 alkylation  (the generally preferred process).   The  olefins are passed over
 a catalyst  such as  phosphoric  acid  at 500  psi  and 275-375 F.   The  feed-
 stock is  an olefin  stream of ethylene,  propylene,  butylene,  and/or amylene
 from  gas  processing.   The products  are high-octane  gasolines or  petrochem-
 ical  feedstocks and  petroleum  gas which  is  used for fuel.
          Energy  from a fired  heater  is  required  only on startup  because
 the reaction  is exothermic  and the  feed  is  heated by  heat exchange with
 the product.   Steam (20 Ib/bbl)  is  used  for  fractionation of the  product.
Mechanical  energy  (1.2 kwhr/bbl)  is required  to pump  the feed  liquid.

-------
                                  B-39
          Since the process is closed, there are no atmospheric emissions.
Phosphoric acid is a liquid catalyst which may be washed from the reactor
during a maintenance operation.  Sometimes the phosphoric acid is absorbed
on a solid support and the support and acid is sent to a landfill when the
catalyst is replaced.  The quantities of liquid and solid waste are not
significant.

          Alleviation (23).  The function of alkylation is to synthesize
high-octane gasoline by reacting olefins, such as butylene, with isobutane.
812,000 bbl/day (1972) of alkylate is produced.  In other processes, per-
haps more typical of the petrochemical industry, benzene is alkylated with
ethylene or propylene to make petrochemical feedstocks.  Anhydrous hydro-
fluoric acid or sulfuric acid is the catalyst used.  The feedstock is an
olefin and isobutane from the isomerization process and/or gas processing.
Previously, only butylene was used, but now propylene and amylene are often
alkylated.  The product is high-octane gasoline.  Propane is an undesired
diluent in the feed and is a product of the fractionating tower associated
with alkylation.  Since the alkylation process is one of the few processes
capable of yielding high-octane unleaded fuel, it is being installed in
numerous refineries and present capacity is increasing.
          Two process variations are employed:  a sulfuric acid catalyst
(536,000 bbl/day); or an anhydrous hydrofluoric acid catalyst  (276,000
bbl/day) (1972)^  .  The major difference is in temperature of operation
(80 F for the hydrofluoric-acid process, and 45 F for the sulfuric-acid
process).  Hydrofluoric acid is regenerated in the process by  fractiona-
tion while sulfuric acid is regenerated outside of the process.
          Energy from fired heaters is not required.  Steam (100-300 Ib/bbl)
is needed to fractionate the intermediate product.  The quantity of steam
required is large because the recycle isobutane stream must be fractionated
from n-butane, a diluent.  Mechanical energy (0.5-5 kwhr per barrel) is
required to compress the feed and recycle gases, and in the sulfuric acid
process for refrigeration.

-------
                                   B-40
          No atmospheric  emissions are produced.  About 17 Lb of 90 percent
sulfuric acid  per barrel  are wasted from  the sulfuric-acid process.  The
sulfuric acid  is returned  to the sulfuric acid plant for regeneration.  The
feed acid strength  is about 98  percent.  The products, when using either
catalyst, are  given a caustic wash and 20 Ib of spent caus.tic solution per
barrel are disposed of.   No solid waste is produced.

          Lube Oil  Processing (24).  The  function of the lube oil process
is  to make a lube oil stock suitable for blending into lubricating oils
from selected  distillate  and residual feedstocks.  Widely differing pro-
cesses are used depending  upon  the feedstock, the ultimate use, and the
period of equipment installation.  In the traditional process, the feed
oil is contacted with sulfuric  aciu which reacts with unsaturates and
polyaromatics  and forms a  sludge.  The sludge is removed by filtration
with clay.
          Another process  (Duol-Sol) employs two solvents:  propane which
selectively extracts paraffinic hydrocarbons (lube oils) and rejects
asphaltic hydrocargons, and cresylic acid which preferentially dissolves
asphaltic and  naphthenic hydrocarbons.  The two solvents flow in a counter-
current manner through a  series of extraction stages.  The feedstock is
introduced near the middle of the unit.  The solvents are removed by dis-
tillation from the  lube oil and asphalt.
          After removal of asphalt, selective solvents and refrigeration
are used to separate waxes from lubricating oils.  In one dewaxing opera-
tion, propane  is added to  reduce the viscosity of the oil, the oil is
chilled to below its lowest anticipated operating temperature, and wax is
crystallized out and separated by filtration.
          The  preferred lubricating oils are a high-boiling paraffin with
several side chains.  Normal paraffins are unsatisfactory components for
low-temperature operation  because of their high melting point.  Naphthenic
compounds can  be used only within a narrow temperature range because their
viscosity changes rapidly with  temperature.  Polyaromatics and unsaturated
compounds form sludges and varnishes when present in lubricating oil and,
therefore, are unsatisfactory.  Therefore, the preferred feedstocks is an
oil rich in paraffins and  lean  in other hydrocarbons.

-------
                                   B-41
           The  products  of  lube  oil  processing  are  lubricating  oils  (which
 are  blended  into the  many  different lubricants), waxes,  fuel oil, and
 asphalt.
           Lube-oil  processing  is  a  large  source  of sludges  in  a  refinery.
 The  used  clays  from filtration  represent  a  major solid waste.  The  oils
 are  washed with  caustic solutions at various points  in the  process,  thus
 generating a liquid waste  stream.   The  lube-oil  process  is  a major  user of
 steam  and  mechanical  power  in  the refinery.
           Fired  heaters are not usually used in  processing  lube  oils.
 Depending  upon  the  process, 100 to  400  Ib of steam are required  per
 barrel, primarily for separation  of solvents.  Mechanical energy require-
 ments  are  large  (2  to 10 kwhr/bbl)  for refrigeration and pumping the oil
 through filters.
           Lube-oil  processing is  not a major source of air  emissions.  In
 some processes  the  oil  is blown with air, but  since  the  boiling  point is
 high,  no serious emission occurs.   In other processes a  decolorizing clay
 is regenerated by burning the sludge adsorbed  on it, producing small atmos-
 pheric emissions.
           The liquid waste from the process is condensed steam from  the
 solvent stripping which  is pure.  The sludge from  the acid-clay  process
 is frequently burned in  the refinery boiler.   The  clay is a solid waste.
 In at  least one  lub-oil  refinery  the sludge was lagooned and stored until
 the  lagoon accidentally  ruptured  creating water pollution.
           Replacement of the acid-clay process with a solvent process
 reduces the amounts of  sludge formed.

          Asphalt Production (25).  The function of the asphalt  process is
 to make asphalts from residual oils of asphalt-based crudes.  About 644,000
              (2)
 bbl/day (1972)    of asphalt is produced.  Asphalt is high molecular-weight
hydrocarbon containing  polycyclic aromatic rings.  Some residual oils have
 the desired properties and require no treatment.   In others, the asphalt
 stock is oxidized to increase the melting point by blowing air through the
 residual oil.  During air blowing,  the residual oil is heated to about
 500 F.   The reaction is exothermic and after initial heatup, additional

-------
                                 B-42
heat  is  not necessary.  Air blowing  is  stopped when  the asphalt reaches
the proper consistency.  Other asphalts are produced by mixing the feed-
stock with propane  followed by separation of a solid asphalt fraction
and a liquid nonasphalt fraction.  The  products are  sold to the various
asphalt-based  industries,  such as roadbuilding, roofing paper, and seal-
ant manufacture.
          Energy  from  fired heaters  (100,000 to 300,000 Btu/bbl) is re-
quired in the  solvent  process primarily for stripping the solvents from
the asphalt and  the deasphalted oil.  About 5,000 to 10,000 Btu/bbl are
needed in the  air-blowing  process to heat the feedstock to the reaction
temperature.   Fifty pounds of steam  per barrel are used to strip the
solvent  in the solvent process.  If most of the energy is derived from
fired heaters, little  is needed from steam and vice  versa.  Mechanical
energy (0.1 to 3  kwhr/bbl) is required  for the solvent process mainly
for agitation  of  the extractor stages.  About 1 kwhr/bbl is needed to
compress air for  the air-blowing reaction.
          The  solvent  process is closed and no atmospheric emissions are
formed.  While the air-blowing process emits gases to the atmosphere, the
quantity is small since the asphalt  previously has been distilled at a
high temperature.   Sometimes air-blowing produces an obnoxious odor and
the off-gas is used for combustion air in a nearby heater.  The condensed
steam from the solvent stripping operation is a wastewater stream.  No
solid waste is produced.

          Storage and Blending (26).  The function of storage and blend-
ing is to store intermediate products and to mix or blend the various
intermediate products  into final products.  The materials are stored in
large tanks, which are pressurized for liquefied gases, specially vented
for liquids with high vapor pressure, specially constructed for materials
of moderate vapor pressure, and vented for materials of low vapor pressure.
Liquids are blended in a blending tank by agitation.  Essentially all raw
materials, intermediate products, and products are stored in tanks.  Most
products are a blend of several intermediate products and perhaps purchased
raw materials.

-------
                                 B-43

          No fired heater is used with blending and storage.  A negligible
amount of steam is used to heat tanks containing heavy residual oils.  A
negligible amount of mechanical energy is required for pumping and agitation.
          Hydrocarbon emissions from storage vessels depend on three basic
mechanisms:  breathing loss, working loss, and standing storage loss.
Breathing and working losses are associated with cone-roof tanks and stand-
ing storage losses are associated with floating-roof tanks.     Breathing
losses are hydrocarbon vapors expelled from the vessel by expansion of
existing vapors due to increases in temperature or decreases in barometric
pressure.  Working losses are hydrocarbon vapors expelled from the vessel
during emptying or filling operations.  Emptying losses result from vapor
expansion caused by vaporization after product withdrawal.  Filling losses
are the amount of vapor (approximately equal to the volume of input liquid)
vented to the atmosphere by displacement.  Breathing and emptying losses
are usually restricted to fixed-roof tanks vented at atmospheric pressure.
Filling losses are experienced in fixed-roof tanks and low-pressure storage
tanks vented to the atmosphere.  Both working losses and breathing losses
can be significant.  Standing storage losses from floating-roof tanks are
caused by the escape of vapors through the seal between the floating roof
and the tank wall, the hatches, glands, valves, fittings, and other open-
ings.  The magnitude of hydrocarbon emissions from storage vessels depends
on many factors including the physical properties of the material being
stored, climatic and meteorological conditions, and the size, type, color,
and condition of the tank.
          The annual hydrocarbon emissions from crude oil, gasoline, and
distillate tanks are estimated at 1.3 million tons.  At present, 75 per-
cent of these tanks are equipped with floating roofs.  The annual estimated
emissions constitute about 3 percent of the total national hydrocarbon
emissions and about 7 percent of the 18.6 million tons/year emitted from
all stationary sources.  Minor liquid and solid waste quantities are gen-
erated by maintenance operations.

-------
                                  B-44

            Prime Movers  (27).  The function of the prime mover is to supply
 mechanical energy  to  pumps, blowers, compressors, etc.  About 7.5 kwhr of
 mechanical energy  are required per barrel of crude processed in a modern
 refinery.  Electrical drives are usually the most convenient, especially
 for smaller units.  For large units, steam turbines are typical; gas tur-
 bines or internal  combustion engines occasionally are used.  On some equip-
 ment more than one drive is installed to assure continuous operation.   For
 example, an electric motor and a steam turbine may drive the same pump,
 one unit being used normally and the other unit being on standby in case
 of failure of the  primary driver.  The steam turbine is especially appli-
 cable in a refinery since steam is normally distributed at about 400 psi
 and used at 175 or 30 psi.   A steam turbine is used both to supply mechan-
 ical energy and low-pressure steam to a  process.
           Electricity and steam are  secondary sources  of power  and the
 fuel is  burned at a place remote  from the process using the energy.  A
 gas tu bine would burn either refinery gas  or natural  gas  and a  diesel
 engine would  use  a  diesel oil.
           The  process  emissions  are  typical  of drives  and  not peculiar  to
 the refining  industry.  Since  most drives are steam or electric,  the
 emission relating to  the mechanical  energy  is at  the site  of steam or
 electric generation and  not  at  the process  site.

          jSteam Generation  (28).  The  function of  steam generation  is to
 supply steam  to the various  processes  for direct  use in  the  operation,  for
 heating,  and  to drive  steam  turbines.  Frequently,  steam is  used  for elec-
 tric power generation.   Overall about 30  to  100 pounds  of  steam are used
 per  barrel of  crude oil  processed at a refinery.   In a  refinery processing
 about  100,000  barrels  of oil per day, about 250,000 Ib/hr of  steam are
 used.  If the  refinery generates  its own  electricity (not usual practice),
 the  boiler is  typical  of one used in the  electric  power  industry and prob-
 ably operates  at a  steam pressure of 1000 psi or higher.  Steam for distri-
 bution at 500, 175, and  15 psi is supplied from bleeds off the turbine
driving  the electric generator.  If the refinery does not generate elec-
 tricity, steam is generated at about 500  psi  in a boiler typical of large
 industrial boilers.  Steam for distribution at 175 and 15 psi is obtained

-------
                                 B-45
by reducing the pressure of 500 psi steam and from steam turbines exhaust-
ing at the lower pressures.  In addition to generation in the main boiler,
steam is generated by boilers in several of the processes.  The largest
steam generator associated with a process is the carbon monoxide boiler
on the exhaust from the catalytic cracker.  Waste-heat boilers may be
placed in the flue gas streams for process heaters.  In some processes,
the process fluids are cooled by generating steam.  Most of these boilers
would generate steam at one of the lower distribution pressures.
          A steam generator is used as an incinerator for combustible
liquid and solid wastes.  Spilled oil, sludges, and residues from main-
tenance operations such as tank cleaning are usually incinerated in a
steam generator.
          Table B-4 lists the amounts of the different fuels used at
refineries.  Most of the nongaseous fuels and some of the gases would be
burned in the steam generators.  From 10 to 20 percent of the fuel used
in a refinery is burned in the steam generator.  Also while the industry
average energy demand is 700,000 Btu/bbl, many newer complex refineries
use only 500,000 Btu/bbl.
          The process emissions from the steam generator are typical of
conventional steam generators and the fuel used.  In the past, various
oily wastes, sour gases, and high sulfur oils have been burned in the
steam generator, but since pollution control regulations are becoming
more stringent, the use of such fuels is decreasing.  Liquid wastes are
generated by treating boiler feed water but present a minor problem.
Solid wastes include ash from the fuels such as acid sludge and coal, and
sludges from treatment of boiler feed water.

          Process Heaters (29).  The function of the process heaters is
to heat various process streams.  Most of the fuel used in a refinery is
burned in process heaters.  Steam heaters can be used at operating temper-
atures up to about 400 F and above that temperature fired heaters are
required.  In addition, superheated steam is required by a few processes
and the steam usually is superheated in the fired heater associated with
that process.  A pipe heater, as shown in Figure  B-5. is the standard fired

-------
                            B-46
    TABLE. B-4.  REFINERY FUEL AND  ENERGY  SOURCES  (1969)
Fuel
Fuel Oil, 1000 bbl
Acid Sludge, 1000 bbl
Coal, 1000 tons
Natural Gas, MMcf
Refining Gas, MMcf
Petroleum Coke, 1000 tons
Purchased Electricity, MMkwhr
LPG, 1000 bbl
Purchased Steam, MMlb
Total Energy Equivalent,
1012Btu
Crude Oil Run to Stills, MM bbl
Energy Consumption, Btu/bbl
Quantity/year
43,323
95 v
570
997,886
984,561
10,625
17,927
6,620
24,396
-
3,880
703,000
10 2Btu/year
263
0
14
998
1,000
320
61
25
27
2,728
-
—
of Crude Oil

-------
            B-47
           OIL INLETS
                                OIL
                              OUTLET
       OIL/CAS BURNERS
FIGURE B-5.   PIPE  HEATER
                            (4)

-------
                                  B-48

 heater in the petroleum industry.  In  this heater,  liquid petroleum passes
 through tubes exposed to a hot combustion zone.   The  oil enters at the top
 of the heater and is heated convectively and  countercurrently by the flue
 gases.  The oil is then passed into the tubes on the  side walls of the
 furnace where it is heated by radiation.   Steam  superheater  tubes,  if any,
 are  placed  at the top of the furnace just below  the oil  tubes.   The process
 heater on the crude still is larger than most industrial boilers and in the
 largest still is comparable in size to  the steam boiler  for  a 100 megawatt
 electric generator.  The heaters  for catalytic reforming,  catalytic crack-
 ing,  and coking compare in size with large industrial  boilers.   In processes
 wita  less throughput,  the units may be  fairly small and  compare in size to
 a  package steam boiler.
          Most  process  heaters are  equipped to burn gas  or oil  or both.
 The pipe heater usually cannot be adapted easily to solid  fuels.
          The emissions  from the  pipe heater  are those typical  of indus-
 trial  boilers.   Particulate emissions result  from ash  in the  fuel and
 unburned carbon that  pass  through the furnace.   Hydrocarbon emissions
 result  from incomplete  combustion.  Sulfur dioxide is  formed  from the
 sulfur  in the fuel.   Nitrogen  oxides are  formed  by reaction with  N?  in  air
 at the  high  combasLion  temperature.  Carbon monoxide is  formed  because  of
 incomplete  combustion of  the carbon in  the fuel.  Each of these  emissions
 is at  a  low  concentration  but  the total represents a major emission  because
of the  large  amounts  of  fuel burned.  Table B-5  lists estimated  emissions
from combustion  sources calculated  from emission factors^  '  and  fuel con-
sumed  in  the  petroleum refining industry.

   TABLE B-5.  ESTIMATES OF ATMOSPHERIC EMISSIONS FROM COMBUSTION
                SOURCES  IN  PETROLEUM REFINING  INDUSTRY  (1969)

                                                 Emissions,
     Emission Type	 1.000 short tons/year
     Particulate                                   60
     Sulfur dioxide                               270
     Carbon monoxide                                1.9
     Hydrocarbons                                  42
     N0v                                          500

-------
                                 B-49

                        WASTE CONTROL METHODS

          In addition to specific control devices associated with partic-
ular processes, the refinery employs emission control equipment that serv-
ices the entire refinery--for example, flares for control of atmospheric
emissions, and water treatment facilities for wastewater.  As indicated
previously, the steam generator usually is used to incinerate combustible
wastes.
                                Flares
          The function of the flare is to burn gases released in emergency
situations from any process in the refinery.  In the past, flares have
been used to burn unwanted gases, but at a modern refinery, combustible
gases are used for their fuel value.  Flares also had been used to vent
and incinerate sour and malodorous gases, but pollution control regula-
tions have reduced this practice.  At the present time, if an equipment
malfunction requires an emergency reduction in pressure in a large process
vessel, the gases are vented to a flare to eliminate fire hazards.  A flare
consists of a burner, pilot light, and air injection system.  Excess process
gases are sometimes vented to the flare at a very high rate and for short
times more gas may be burned in the open or a stack might be built around
the flare to reduce light and noise and to prevent hazards to nearby pro-
cess equipment.
          The flare requires a small pilot flame and steam to promote smoke-
less combustion.
          The atmospheric emissions caused by a flare depend upon the gas
vented; for example, sulfur in the gas will form S09.  A modern flare is
smokeless, and particulates, carbon monoxide, and hydrocarbons are not
emitted in quantity.  Since the flare is a flame device, NO  is undoubtedly
                                                           X
made and emitted.  The total quantity of materials flared over a period of
a year is small; therefore, the emissions from the flare should be small.
However, large quantities occasionally are flared which may cause a tempo-
rary air pollution problem.

-------
                                  B-50
                          Wastewater Treatment

           Wastewater  treatment  removes  impurities  from water effluents.
A refinery produces many  types  of wastewater streams such as used process
and cooling water, storm  drainage, and  sanitary sewage.  Much of the waste
process water  is  contaminated with hydrogen sulfide and other compounds
with obnoxious  odors.  This  sour water  is boiled and treated with acid to
remove hydrogen sulfide in a sour-water stripper.  The sour-water stripper
is usually a packed tower perhaps 10 feet in diameter and 30 feet or more
high.  About 10 gallons of sour water are treated  per barrel of oil pro-
cessed.  The products are sweet water and hydrogen sulfide gas (the latter
is sent to a Glaus plant).
           Storm drainage and process water are usually sent through an API
oil-water  separator which decants the oil from the water.  The API separ-
ator is a  large item of equipment.
           Sanitary sewage and any high BOD process water would be treated
in a biological treatment plant similar to a sewage plant for a small
city.
          The energy requirements for water treatment are small except
for steam used  by the sour-water stripper.  It uses about one pound of
steam per gallon of water treated.

-------
                                  B-51
                                REFERENCES


 (1)   Anon.,  "1972  Refining Processes Handbook",  Hydrocarbon Processing,
      51 (9),  pp  111-222  (September,  1972).

 (2)   Anon.,  Oil  and Gas  Journal,  .70, p 128 (March 27, 1972).

 (3)   Anon.,  Oil  and Gas  Journal,  70. p 92 (January 31, 1972).

 (4)   Bell,  H.  S.,  American Petroleum Refining, Fourth Edition,
      D. Van Nostrand,  Princeton (1959).

 (5)   Nelson,  W.  L., "Petroleum (Refinery Processes", Encyclopedia of
      Chemical Technology,  Volume 15, pp 1-77, Wiley and Sons, New York.

 (6)   Anon.,  "1973  Gas  Processes Handbook",  Hydrocarbon Processing,
      /:2 (4),  pp  91-128 (April, 1973).

 (7)   Anon.,  "Background  Information for Proposed New Source Performance
      Standards", APTD  352a, USEPA, Research Triangle Park, pp 31-36
      (June,  1973).

 (8)   Wollaston,  E. G., Forsythe,  W.  L., Vasalos, I. A., "Sulfur
      Distribution  in FCU Products",  API Division of Refining,
      Proceedings 1971, p 12-42.

 (9)   Anon., Oil  and  Gas Journal 71,  p.  96, April 2, 1973.

(10)   American  Petroleum Institute, "Petroleum Facts and Figures, 1971
      Edition,  Washington.

(11)   USEPA  "Compilation of  Air  Pollutant Emission Factors, Second Edition",
      AP-42,  Washington,  1973.

(12)   Baker,  Kenneth, USEPA,  Private  Communication to Herbert Carlton, BCL,
      February  11,  1974.

-------
                                  C-l
                              APPENDIX C

                    THE SECONDARY NONFERROUS METALS
                      INDUSTRIAL PROCESS PROFILE

                          INDUSTRY  DESCRIPTION

          The history of the metals recycling industry can be traced back
to antiquity.  Records of ancient peoples give evidence of crude melting
techniques that existed at the dawn of civilization.  Archaeologists believe
the rudimentary recovery of iron, lead, and copper occured in earliest times.
          But, recycling, as we know it today, is the development of the
past 100 years.  During this period, scientific and sophisticated technology
has been developed to transform waste material into valuable products.
More significantly, the volume of scrap expanded with the growth of
industrialization, particularly in the United States, which, today, has
the largest and most effective recycling industry in the world.
          More than 3 million tons of nonferrous scrap metals are recovered
annually by secondary smelters, refiners, ingot manufacturers, fabricators,
foundries, and other industrial consumers in the United States.  In its
total operation of metallics, the U. S. recycling industry is an $8 billion
industry,* occupying a major role in the economic life of the country.
And the growth potential of the secondary industry is substantial.
          In recent years the concept of recycling has come to the fore
impelled by increased concern for the environment, the awareness of
dwindling natural resources, and the realization that solid waste
accumulations could choke urban society.  Recycling does represent the
most affirmative environmental response and a highly constructive economic
response to the critical challenge of solid waste disposal.
          Furthermore, various studies have indicated that the world's
resources are fast being depleted.   Obviously, recycling must play a major
role in future conservation considerations.
* Fine, P., Rasher, H. W., and Wakesberg, S., Operations in the Nonferrous
  Scrap Metal Industry Today, published by NASMJ, New York, New York (1973).

-------
                                    C-2
           The companies  that make  up  the  secondary  nonferrous metals
 industry  are  generally  small and generally  are  not  well  equipped  to deal
 with  the  development  and application  of new technology for  the  control of
 pollution.  They  lack the needed technical  capabilities  and  financial
 resources.  However,  they are concerned about the environment and are
 making  efforts to reduce the pollution potential of the  industry.  These
 efforts could be  accelerated by partial support through  demonstration
 projects  from the government,  since such  support might encourage  industry
 to undertake  additional  work.

                    DISCUSSION OF SECONDARY NONFERROUS METALS
                          INDUSTRIAL PROCESS PROFILE

          The Secondary  Nonferrous Metals Industry  consists  of what may
 be considered for purposes of  this analysis to be industry "segments" that
 convert scrap metals  or  waste materials to  products  that are marketed for
 use or consumed in the form  they exit from  the process.  Each segment is
 comprised of  companies that  are considered  competitors in the production
 of the same products.  The secondary  industry and each segment of the
 industry have an  identifiable population  of companies and have a degree
 of commonality with respect  to raw materials consumed, process employed,
 products produced, environmental control problems, pollutants produced,
 and control equipment used.
          Detailed description of the processes for each segment follows.

                               Segments

          The  Secondary  Nonferrous Metals Industry consists of about 20
segments.   The major segments in regard to volume of metal recovered from
scrap are:
          (1)   Copper Segment
          (2)   Brass and Bronze Segment
          (3)   Lead Segment
          (4)   Aluminum Segment
          (5)   Zinc Segment

-------
                                  C-3
          The minor  segments  are:
          (1)   Tin
          (2)   Nickel
          (3)   Cobalt
          (4)   Magnesium
          (5)   Mercury
          (6)   Antimony
          (7)   Precious  Metals
          (8)   Titanium
          (9)   Selenium
         (10)   Cadmium
         (11)   Germanium
         (12)   Hafnium
         (13)   Zirconium
         (14)   Indium
         (15)   Beryllium

                            Major Companies

          The Secondary Nonferrous Metals Industry encompasses a host of
companies.  For example, in 1973, there were 125 companies producing
secondary aluminum, 130 companies producing secondary lead, and 44 companies
producing secondary copper and brass and bronze products.  The size of
these companies ranges from small family-owned facilities to  large
corporations.  The major companies are identified at the end  of each
segment description which follows.
          These companies are found throughout the United States.  However,
in most cases, as noted in Figures 1, 2, 3, and 4, which show the major
location of secondary aluminum, zinc, copper, and lead  segments,  they are
found in  the vicinity of populated areas where the  scrap generally  is  found.

                       Manufacturing Operations

          Manufacturing operations fall into 3 basic categories:  (1) scrap
pretreatment,  (2) smelting/refining, and (3) casting (product formation).

-------
                                             C-4
                                                                            r\
                    I.  New Englond
                    2.  Middle Allonlic
                    3.  Soulh Allonlic
4.  Eon North Cenlrol
5.  Cost Souih Ceniroi
6.  W«l North Cenlrol
                                                          9
  Weil South Cenlrol
  Mounloin
  Pacific  (includes Alaska
        and Hawaii)
FIGURE  C-l.   AVERAGE VOLUME  IN TONS  PER YEAR  OF  (1) ALUMINUM SCRAP.
                PROCESSORS,  AND (2)  ALUMINUM SCRAP  CONSUMERS,  BY  REGION,  1969
                Source:  Extensive  Survey
                                                                         IV16
                                                                                2343
                     NotCi Volume in nel tons
                     I. Mew England
                     2. MiODlr Allonlic
                     X. Souifi Allonlic
 4.  Cast Norm Cenlrol
 5.  Coil Soulh Control
 C.  Weil 1,'orlri Ctnlrol
7.  Weil Soulh Central
C.  Mountain
9.  Pacific (irtclutfci Aloslo
         and HowOii)
                  FIGURE C-2.   VOLUME OF COPPER HANDLED  BY
                                  TYPE  OF  RECYCLE  BY REGION

-------
                                           C-5
          (I)  Zinc Scrap
             Processor

         '(2)  Zinc Smeller
                  I.  New England
                  2.  Middle AiioMic
                  5.  South Atlantic
4.  Eosl North Cenlrol
5.  Cost South Centre I
6.  West North Ctnlrol
7.  Weil South Cenlrol
8.  Mountain
9.  Pacific (include! Alosko
         ond ilowoiil
  FIGURE C-3.  AVERAGE SIZE IN TONS  PER YEAR OF ZINC  OF  (1)  ZINC
                 SCRAP  PROCESSORS AND  (22)  ZINC SMELTERS, BY  REGION,  1969
                 Source:  Extensive  Survey
    : 1:1(1) Lead scrop processor
    KM
    ~](2) LcaJ smelter
                                            foil Horlh Ctolrol
                                            CO»I SOulh CtnlfOl
                                            \Vi\t tloilh Central
                            (y  Vftil South Cenlrcl
                            (i[l)  Mounlan
                            (V)  Pocldc (lncl«d««
                                     Alatlo on
-------
                                   C-6
In scrap pretreatment,  the scrap is treated by a number of processes to
densify it and/or to separate the nonferrous metal from gross impurities
to render the scrap more amenable to smelting.  Smelting is an operation
whereby the scrap is partially purified by heat.  From the smelting
operation, the scrap is given a final purification in the refining
operation and finally cast into the desired form.

                               Processes
          Processes comprise specific arrangements of equipment that
accomplish chemical or physical transformation of the scrap materials into
end products, intermediate products, and waste materials.  Other process
outputs include waste streams to the air, water, and land.  When two or
more different combinations of process steps accomplish the same chemical
or physical transformation but have different environmental impact, each
combination is a distinct process.  An example of a process is Fire/Refining
in the Copper Industry.  Black copper and/or blister copper are treated in
the molten state to remove residual metal values and produce a fire-refined
copper melt.  Other process outputs include atmospheric emissions, liquid
wastes, and solid wastes.

                             Process Steps

          Process steps are the basic components of a process that utilize
process equipment or materials handling equipment, not including control
equipment.  In each case where a piece of process equipment has two or
more cycles or phases with distinctly different emissions to the atmosphere,
such cycles can be considered sequential process steps.  An example of a
process step is blowing the melt with air in the fire-refining process.

                             Future Trends
          Modern technology, environmental effects, and the shift  in the
flow of raw materials are all having a direct impact on the secondary

-------
                                   C-7
nonferrous metals industry.  For example, the characterization of the
raw materials is changing.  Low-grade scrap which at one time was
disposed of by  landfill is now being recycled to the secondary industry.
Large volumes of metal-laden dust are no longer emitted to the atmosphere
but are collected in dust control equipment.  The collected dust becomes
a  source of raw material to the secondary industry.
                         ENVIRONMENTAL IMPACTS

                         Atmospheric Emissions

           The secondary nonferrous metals  industry  is one of the sources
 of environmental pollution.  The pollution may be in the form of atmospheric
 emissions, liquid wastes,  and solid wastes.  Atmospheric emissions
 generally  contain particulate and gaseous  materials, both of which are
 sources  of pollution and potential health  hazards.
           The composition of the atmospheric emissions  depends on the
 segment  of the  industry from which the emissions are derived.  However,
 it has been established that the industry  as a whole emits  such metallic
 materials  as lead,  zinc, mercury, arsenic, cadmium, antimony, precious
 metals,  magnesium,  nickel, copper, manganese, and aluminum.
           Emissions factors for atmospheric emissions for every segment
 of the industry are not available although it can be said that, in many
 cases, significant  quantities are emitted.  For example, the raw emissions
 factor for metallic zinc sweating process  with zinc chloride was reported
 to be 10.8 Ib of particulates/ton of scrap, whereas the raw emission factor
 for  sweating residual  scrap was reported at 24.5 Ib/ton of  scrap processed.
           Morphology of the particles is dependent  on the type of scrap,
 segment  from which  the particulates are generated,  and  many other factors.
 In most  cases,  the  particulates1 sizes range from less  than 0.1 micron  to
 several  microns.  Particle shape will vary from spherical to irregular  shapes,
           Gaseous emissions also depend on the segment  of the industry
•and  the  processing  step.  In general, atmospheric emissions may contain,

-------
                                    C-8
 in addition to the combustion products, harmful materials like sulfur
 oxides, halides, inorganic acids, hydrocarbons, and ammonia.
           A substantial portion of the pollution from the industry comes
 from the burning of fuels to provide energy for the processes.
 Quantitatively, data are not available on the energy demand for this
 energy.  However, the primary sources of energy for the secondary non-
 ferrous metals industry are:  (1) natural gas, (2)  fuel oil, (3)  coke,
 and (4) electricity.  Data on quantities of energy consumed by this
 industry are not readily available.

                       Emission of Liquid Wastes

           The  secondary  nonferrous  metals  industry  can be a  significant
source  of  liquid wastes  as water  is used for many applications  throughout
the  industry.   For example,  in  the  aluminum segment, aqueous wastes  are
generated  principally  in these  operations:  cooling molten aluminum  alloy,
wet  scrubbing  of  fumes during chemical  magnesium removal, and  the wet
milling  of aluminum  melt residues such  as  dross and slag.  Ingots and
shot are cooled with water by direct  contact with the mold and  metal.
Magnesium  content in aluminum alloys  is  adjusted by the chemical removal
of magnesium using either chlorine  or aluminum  fluoride.  Wastewaters
containing very large  levels of suspended  and dissolved solids  are produced
during  the welj; .rail.ling of^resjLdues  containing aTuminum.
           Another example is the  copper  segment, where wastewater is
generated  in 15 of 25 processes.
           Composition of these aqueous wastes depends on the segment of
the industry generating  the wastes.   Some  of the wastes are  simply cooling
water and  can be recycled with a minimum of treatment.  Other wastes contain
a wide variety of soluble and insoluble metallic and nonmetallic materials.
An example of the contaminants in the aqueous wastes for the secondary
aluminum industry is shown as follows.

-------
                                  C-9
                     Composition of Aqueous Waste
                     	From Aluminum Segment

                             Sulfate
                             Chloride
                             Fluoride
                             Aluminum
                             Calcium
                             Copper
                             Magnesium
                             Nickel
                             Sodium
                             Zinc
                             Cadmium
                             Lead
                             Manganese
                             Oil
                             Grease
                             Phenols


          Also, metal values such as arsenic, mercury, and barium are

found in the aqueous wastes.  While many of these heavy metal values may

be harmless, metals such as cadmium, mercury, and arsenic are known to

be toxic.
          In summary, the secondary nonferrous metals industry is a potential

source of aqueous wastes to the environment.  If these wastes are not

controlled by treatment before discharging or if they are not recycled,

serious pollution problems could arise.


                         Solid Waste Emissions


          Solid wastes are generated in this industry by the nature of

the numerous processes.  Slag from the smelting of copper and drosses

from the aluminum industry are examples.  Drosses from the treatment

of aqueous wastes generated in the production of electrolytic copper is

another example.  Another source of solid wastes common to this and other

industries is the dust collected in control equipment such as baghouses.

Solid wastes such as slurries (mixtures of solids and liquids) and fine

particulate materials are disposed of in lagoons, in landfills, or, in

many cases, become a source of raw material for the secondary industry.

-------
                                   C-10
          As with the other wastes from this industry, the composition of
this waste is dependent on the process and processing steps in each
segment.  These wastes are known to contain metallic and nonmetallic
materials found also in atmospheric emissions, aqueous wastes, and the
raw materials to this industry.  Many of them are toxic.
          In summary, this industry generates substantial quantities of
solid wastes.  In many cases, serious pollution problems can result if
these wastes are not disposed of in a safe and adequate manner.


                             RAW MATERIALS

          Raw materials for the industry are divided into three broad
categories as follows.
          (1)  Old Scrap.  This is the kind most commonly associated
               with the scrap business though not necessarily the
               largest in volume.  Old scrap is discarded, dismantled,
               worn out metallic elements.  Typical examples are:
               a radiator removed from a wrecked car; copper pipes
               taken from an old building; high strength, heat
               resistant rotor blades once used in a jet engine,
               applicances discarded by homeowners.
          (2)  New Scrap.  This is metal which has never been made
               into or used as an end product.   It comes from
               industrial sources and is the by-product of some
               part of the manufacturing process.  Common examples
               include:   a manufacturer of aluminum cans buys huge
               coils of sheet aluminum and when the can lids (tops)
               are made on stamping (blanking)  machines which punch
               the lids out of sheets of original material,  the
               remaining skeleton is  scrapped and usually described
               as  clippings;  or,  when household faucets are  produced
               in  foundries which make the body of the faucet in  a
               sand mold to produce a casting;  or, when pouring molten

-------
                                   C-ll
               metal  into  the  mold  some  will  spill over the mold
               opening or  into the  sand  rather than into the mold
               cavity and  these spillings  are scrapped because they
               pick up impurities  or become mixed with dirt and sand.
               These  are usually called  foundry spillings or residues.
                   This "new" scrap differs  from "old" scrap in that
               it is  generally available in larger and more uniform
               lots;  and its metallic constituents are more readily
               identifiable.
          (c)   Obsolete Scrap.  This category consists of generally new,
               unused but  technologically  obsolete parts, over-runs
               from the production process, inventory that is no longer
               required, repossessed merchandise or auctioned material.
               Some examples:   The U. S. Government sells for scrap,
               spare  parts for a radar network which is no longer
               needed for  national security;  or a railroad has in
               stock  a type of journal bearing but decides to standardize
               its entire  fleet of cars  with  foller bearings, making
               the solid bearings available as scrap.
          A detailed  description of the  source of raw materials for each
segment is included in the descriptions  which follow.
                               PRODUCTS

          Products from the Secondary Industry are generally ingots of
refined or partially refined metals which are shipped to the fabricator
for processing into a finished product or shipped to the Primary Industry
for further refining.  In some cases, the product is consumed as produced
from the process as described in discussions which follow on the products
from each industry segment.

-------
                                  C-12
               PROCESS DESCRIPTION OF ALUMINUM SEGMENT OF
                 SECONDARY NONFERROUS METALS INDUSTRY
          Tonnage-wise, the aluminum segment constitutes the second
largest segment of the secondary nonferrous metals industry.  Based on
1969 data, U. S. production rate was 1,056,000 tons.  Emissions from
this segment include fine particulate matter and gaseous materials which
may become atmospheric pollutants, and aqueous and solid wastes which,
if not properly disposed of, will pollute the water system and the land.

                             Raw Materials

          Sources of raw materials to this segment include both new and
old scrap.  The new scrap, that which comes from a fabricator who does
not choose or is not equipped to recycle the scrap, accounts for about
75 percent of the scrap.  Old scrap, a product of obsolescence, becomes
available to this segment when consumer products have reached the end of
their economic life and have been discarded, and accounts for approxi-
mately 25 percent of the domestic scrap consumed in the U. S.  Basically,
the scrap can be divided into 6 categories:  (1) sheet and castings,
(2) new clippings, (3) borings and turnings, (4) high aluminum-iron alloy scrap,
(5) drosses or skimmings with fluxing salts, and (6) drosses or skimmings
without fluxing salts.
          The choice of scrap which a secondary smelter purchases for
use in its furnaces is determined by the equipment or flowsheet of the
individual smelter.  Obviously, a smelter with no burning or drying
equipment for processing oily borings and turnings cannot use this
material.   Likewise, smelters without crushing or residue processing
equipment are similarly restricted in the types of scrap they can
process.  Air pollution codes in many cities also have limited the processing
of heavily painted material such as painted siding or Venetian blinds.
Hence, smelters having limited processing equipment must be selective
in scrap purchasing, while more sophisticated smelters have greater latitude
in scrap purchasing.

-------
                                   C-13
                                Products

           The  products  from the secondary aluminum segment are:
 (1)  aluminum alloy  castings,  (2)  aluminum shot,  (3)  hot metal,
 (4)  aluminum fines,  and (4) hardeners.   The aluminum a.lloy castings
 may  be  in the  form  of ingots (15  to 30  Ib), billets  (approximately
 1000 Ib),  notched bar (2  to 5  Ib),  and hardeners of  different weights.
 "Hot metal"  is molten aluminum alloy which is tapped directly from the
 furnaces  into  preheated crucibles with  capacities up to 15,000 Ib and
 transported  directly up to distances of  300-400  miles to the consumer
 (foundries).   Aluminum shot is small beads of quenched aluminum metal.
 Aluminum  fines are  the undersize  (-20 microns) material from screening
 of the  aluminum scrap treated  by  the burning/drying  process.
                          Process Description

          The recovery of aluminum from scrap normally involves two
manufacturing operations:   (1) scrap pretreatment, and (2) smelting-
refining.  The two manufacturing operations and the individual processes
under each operation are shown in the attached industry segment flowsheet
entitled "Aluminum Segment of the Secondary Nonferrous Metals Industry".

Scrap Pretreatment

          Aluminum scrap is pretreated prior to smelting to remove
contaminants and physically prepare the material for further processing.
Three types of pretreating  (mechanical, pyrometallurgical, and hydro-
metallurgical) are used.  The pretreatment process employed depends on
the type of scrap.  The individual pretreatment processes are indicated
in the flowsheet by numbers 1 through 6.

-------
                                   014

           Shredding/Classifying  Process  (1).   The  iron  core  and
 neoprene  or  plastic  insulation is  removed  from electrical  conductor
 scrap  containing superpure  aluminum  by  the Shredding/Classifying
 Process  (1).   This  treated  aluminum  scrap  is  used  to  produce,  among  other things,
 hardeners.   The  processing  steps are:   (a)  shredding  of the  scrap  into
 small  pieces  to  separate  the  iron  core  and plastic coating from the
 aluminum  alloy,  (b)  magnetically treating  to  remove the ferrous portion
 of  the scrap,  and (c)  separating the neoprene or plastic  insulation
 from the  high-purity aluminum by an  air  classification  system.
           Energy demand  for this process is that necessary to  drive  the
 equipment.
           The  Shredding/Classifying  Process  (1)  is a  minor source  of
 atmospheric  emissions.  However, significant  quantities of solid wastes--
 ferrous scrap  and neoprene  or plastic waste—are generated.  The scrap is
 recycled  and  plastic waste  is disposed  of  in  a landfill.
           This process has  no serious potential  pollution  problems of
any kind.

           Baling Process  (2).  Densification  or  compaction of  sheet,
 castings,  and  clippings is  achieved  by baling in specially designed
 baling machines.  Baling  is normally conducted by  the scrap  dealer or
 at  the source  of scrap generation.   Occasionally,  the baled  scrap  is further
 processed by  crushing and screening  prior  to  smelting.
           Energy demand is  limited to that needed  to  drive the equipment.
          Atmospheric emissions  from this  process  are composed of  suspended
 particulate matter containing primarily  dirt  from  the scrap  and alumina
 resulting  from the oxidation  of  the  aluminum  dust.  Solid  wastes
 generated  arc  scrap  iron, magnesium, and other scrap  found mixed with
 the scrap  aluminum.
           The  quantity of pollutants generated by  baling is  low;
 therefore, the process has  a  low pollution potential.

          Crushing/Screening  Process (3).  Borings  and  turnings which
 result from machining and drilling are  treated by  the crushing/screening

-------
                                   C-15
process to density the aluminum values and  remove  contaminants.   This
process entails three process  steps:   (a) crushing in  a hammermill  to
densify the scrap, (b) deoil,  (c) dry,  (d)  screening to remove  aluminum
fines, and then (e) passing over a magnetic  separator  to  remove  the
tramp iron.
          Energy demand for this process  is  that needed to  drive the
equipment and oil/gas for  the  dryer.
          The process produces essentially no atmospheric emissions and
no aqueous wastes.  The quantity of solid wastes such as  tramp iron
generated is expected to be low as the majority of  the iron is removed
prior to crushing.
          The process has no potential for serious  pollution problems.

          Burning/Drying Process (4).  Borings, turnings,  and other organic-
contaminated scrap are,  in some cases, smelted without removal of the
organic contaminants and water.  However, the scrap is generally treated
to remove the water and organic matter such as machining  oils by  the
burning/drying process.   This  process involves several processing steps:
(a) clashing in a hammermill to densify the scrap,  (b) heating the
crushed material in a gas-oil  fired rotary dryer to remove organic
contaminants and water,  (c) screening the dryed material  to remove
the aluminum fines which are sold for explosive or  pyrotechnic purposes,
and (d) icagne tic ally treating  the remainder to remove the tramp  iron.
          Łnergy demands for this process are;  (a) gas or oil to
supply the heat to burn the organic compounds and evaporate water from
the scrap, and (b) that required to drive the equipment.
          The burning/drying process is a source of atmospheric  emissions
and solid wastes.   The atmospheric emissions consist of gaseous  products
primarily carbon dioxide from  combustion of the fuels and the organic
contaminants,  and particulate matter entrained in the gases.  The gases
may also contain some chlorides, possibly fluorides and sulfur oxides,
depending on the composition of the organic contaminants.   The particulate
matter is parimarily alumina resulting from oxidation of  the small
particulates of aluminum swept from the kiln by the combustion gases.
The solid waste is primarily tramp iron removed in  the magnetic  treatment
of the crushed scrap.

-------
                                  C-16
          Thus, the burning/drying process presents serious potential
pollution problems if the emissions are not controlled properly, especially
in those cases where the organic contaminants contain significant
quantities of halides, where significant quantities of alumina are
emitted, and where oil is used in place of gas as the fuel.  Normally,
the atmospheric effluent from the Burning/Drying Process is treated
with an afterburner located in the stack.  However, wet scrubbers are
beginning to replace the afterburner, in which case the air pollution •
problem can become a water  pollution  problem.  The  solid wastes  generated
are not a serious pollution problem.

          SweatinjL_Pr_Qc_e_sJL _L5_1.  The  contaminant-iron is removed from
high iron scrap by the sweating process, employing a sloping hearth or
grate-type furnace.  The processing steps employed are:  (a) heating
the scrap to melt the aluminum and other low melting constituents which
flow by gravity into a collecting pot or ingot mold, and (b) casting
the melt into pigs (30 Ib ingots) or  sows (up to 1000 Ib ingots) in air-
cooled molds.  The furnace  is heated  to approximately 1400 F to separate
the low melting aluminum along with other low melting materials from
the scrap.
          Energy demand for this process is natural gas and that needed
to drive the equipment.
          Emissions from this process are:  (a) atmospheric emissions
composed of the combustion  products and particulate matter, primarily
aluminum trioxide, and (b)  solid wastes containing  iron contaminated with
aluminum and other nonferrous elements such as zinc, magnesium, and
lead.  Gaseous emissions from the furnace are generally passed through
an afterburner before being emitted to the atmosphere.  The solid
wastes are discarded.
          The process can cause serious atmospheric pollution problems,
if not properly controlled.  According to a survey   , raw  (uncontrolled)
(1) Duprey, R. L., "Compilation of Air Pollution Emission Factors",
    U. S. Dept. HEW, NAPCA, Raleigh, North Carolina, pp 28-29  (1968).

-------
                                 C-17
particulate emission factor from the sweating process is reported to
be 14.5 Ib/ton (7.25 Kg/MT) of metal processed.  This factor does not
include gaseous emissions.  Composition of the emissions, both gases and
particulate matter, will need to be determined by source testing.  A
baghouse is usually used to control dust emissions.
          The solid wastes should cause no pollution problems.

          Leaching Process (6).  Leaching removes the contaminants such
as fluxing salts and other water soluble components from drosses,
skimmings, and slags to produce an aluminum scrap suitable for the
smelter.  The processing steps are:  (a) wet milling of the scrap in an
attrition mill or a ball mill to densify the scrap,  (b) screening to
remove  the fines and dissolved salts,  (c) drying to remove the water,
and finally  (d) treating with a magnetic separator to remove the
ferrous portion.
          Energy required  is that needed to operate  the equipment and
to dry  the crushed  scrap.
          The process produces no atmospheric  emissions except possibly
in the  drying step.  However, significant quantities of water and solid
wastes  are produced.  The  water wastes  containing dissolved and  suspended
solids  are disposed of via a series of  settling  ponds.  The solid wastes
result  from  the settling  pond and  the  undersize  material  from the screening
operation.
          The process does not present  an atmospheric pollution  problem;
however,  there  is  a water pollution problem as well  as  a  problem relating
 to disposal  of  the  solid  wastes.   From a recent  survey  of the secondary
aluminum  industry  by  Battelle,  the water pollution  problem essentially
 can  be handled  by  disposing  of  the water wastes  in  settling ponds.   The
 solid wastes can be placed in  a  landfill.

 Smelting/Refining  Operation
           Reverberatory (Chlorine) Smelting-Refining Process (7).  Alloy
 ingots, shot,  and  hot metal are  produced from treated aluminum scrap,
 sweated pigs,  and,  in some cases,  untreated scrap by this process.

-------
                                  C-18
          The process steps are:   (a) charging of the scrap to the
furnace;  (b) melting of the scrap;  (c) fluxing to remove certain
contaminants; (d) alloying, i.e.,  the addition of certain metals to
produce a melt of the desired composition;  (e) mixing of the melt to
produce a homogeneous material; (f) demagging with gaseous chlorine;
(g) degassing with an inert gas such as nitrogen or nitrogen-chlorine
mixture to remove entrapped hydrogen and other gases; and (h)  skimming
to remove the slag or dross containing the impurities.  After slag
removal, the melt is (1) poured into molds and cast into alloy ingots,
billets, and notched bars; or (2) poured onto a vibrating feeder and
quenched in water to produce shot; or (3) poured into heated crucibles
and transported to the consumer as "hot metal", i.e., molten metal.   Any
given smelter may not incorporate all of these steps into the process,
but may use a combination of the steps.
          The reverberatory furnace, a rectangular box usually ranging
in capacity from 15 to 90 tons is used in this process to smelt and
refine the aluminum.  The furnace  is direct fired; furnace fuel may be
either natural gas or fuel oil.  Heat input ranges from 2,000 to 2,500 Btu
per pound of alloy.  Additional energy is required to operate the
auxiliary equipment.
          Emissions from this process are atmospheric emissions (gases
and particulate matter), aqueous wastes, and  solid wastes.  In addition
to the combustion products, the gases may contain chlorine, hydrogen
chloride, zinc chloride, magnesium chloride, aluminum chloride, and
aluminum oxide, along with minute  quantities of a wide variety of
other metals contained in the scrap and added during the smelting-
refining.  Likewise, the aqueous and solid wastes contain a wide variety
of metal values depending on the scrap.
          All processing steps are sources of atmospheric emissions.
The addition of scrap to the furnace and melting of the scrap is a
major source of atmospheric emissions depending on the quality of the
scrap.  Quantitative data are not  available for the secondary aluminum
                                                     (2)
segment.  However, for the brass and bronze segment,    raw emission
 (2) "Air Pollution Aspects  of  Brass and Bronze Smelting and Refining
    Industry", U. S.  Dept.  HEW, NAPCA, Raleigh, North Carolina  (1969).

-------
                                   C-19

factors for the charging step are reported to range from 11.7 to 59.0 Ib
of particulate matter per ton of feed.  Comparable emission factors may
be expected for the charging step for the secondary aluminum segment,
especially at those smelters charging untreated scrap and scrap containing
                                                             •
significant quantity of volatile impurities such as zinc.
          Fluxing is practiced to some extent at most secondary aluminum
smelters.  Some of the components volatize during the smelting-refining
while others, along with impurities or contaminants in the scrap
aluminum, are entrained in the furnace exit gases.  Composition of the
atmospheric emissions will vary depending on the scrap and the flux.
However, these emissions have been found to contain such elements as
sodium, aluminum, magnesium, calcium, iron, lead, manganese, potassium,
chromium, zinc, and nickel, in addition to the combustion gases and
hydrogen halides.
          Alloying produces minor amounts of fumes and dust which are
carried from the furnace by entrainment in the combustion gases and
other gases formed during this processing step.
          Mixing of the melt to insure uniform composition and to mix
the fluxes into  the melt is generally accomplished by injecting nitrogen
gas below the surface of the melt.  As a result, mixing  becomes a
significant source of atmospheric emissions.  The gaseous portion of the
emissions is composed of nitrogen, hydrogen halides, and other volatile
components.  Composition of the particulate matter is similar  to the
emissions from the fluxing processing step.
          Removal of magnesium  (demagging) is accomplished by  chlori-
nation.  This entails lancing the molten aluminum with chlorine gas
which reacts with the aluminum  to form aluminum  chloride.  The aluminum
chloride then reacts with  the magnesium to form  magnesium chloride which
is carried along with other metallic  and nonmetallic impurir-ies and
gaseous contaminants to  the surface  of the melt.  Some of these are
trapped  in the flux on  the surface of the melt,  while the remainder  is
volatized and becomes part of the atmospheric emissions.

-------
                                    C-20
          The demagging step is a major source of atmospheric emissions
in the secondary aluminum segment.  Raw emission factor for this
                            (2)
processing step is reported^ ' to be 1000 Ib of particulate matter per
ton of chlorine used  (500 Kg/t).*  Through the use of a baghouse as the
control device  (which does not remove the gases), the particulate emissions
factor is reduced to 50 Ib of particulate matter per ton of chlorine used
(25 Kg/t).
          In order to remove the gases and the particulate matter, a
wet scrubber using a 10 percent caustic solution as the scrubbing
                                                                   (4)
medium in series with a baghouse is employed.  In one installation,
two of the scrubbers were arranged in parallel.  After scrubbing, the
fumes were sent to a five-compartment baghouse for particulate removal.
In this installation, the scrubber removed virtually all of the hydrogen
chloride gas and greater than 90 percent of the chlorine gas.  Wet
scrubbing also hydrolyzes and removes the majority of the chlorides such
as aluminum chloride as the corresponding oxides or hydroxides.
          Composition of the atmospheric emissions from the demagging
step depends somewhat on the composition of melt and fluxes employed
in the fluxing step.  However, in addition to the combustion gases, the
gaseous portion of the atmospheric emissions is composed of chlorine,
hydrogen halides such as hydrogen chloride, along with chlorides of the
volatile metals.  The particulate emissions are composed of such metal
values as calcium, copper, magnesium, nickel, zinc, cadmium, and aluminum.
          Degassing of the molten aluminum prior to casting is necessary
to remove hydrogen absorbed from the atmosphere or other sources of
moisture or water vapor.  The metal is degasified by lancing with dry
nitrogen, chlorine, or mixtures of the two gases.  If a smelter does not
have adequate ventilation and air pollution abatement equipment, nitrogen
is used for degassing, because degassing with chlorine or mixtures of
chlorine and nitrogen results in severe fuming.  Composition of these
(3) Duprey, F. L., "Compilation of Air Pollution Emission Factors",
    U. S. Dept. HEW, NAPCA, Raleigh, North Carolina, pp 28-29 (1968).
(4)  Danielson, John A., ed., Air Pollution Engineering Manual, U. S.
     Dept. HEW, Cincinnati, Ohio, pp 284-292  (1967).
 * Kg/t  = kilograms per  ton  (1000 Kg).

-------
                                   C-21

fumes may vary from smelter to smelter,  but,  in general,  is similar to
those emissions from the demagging processing step.
          Skimming to remove the dross or slag collected  on the surface
of the melt and casting of the ingots are minor sources of atmospheric
emissions.
          Another potential source of atmospheric emissions results
from cooling and from storage of the slag (drosses and skimmings)  while
enroute to the processor.  If allowed to come in contact with water, the
nitrides and carbides of aluminum react with the water to form hydrocarbons
and ammonia which are liberted to the atmosphere.
          Aqueous wastes are generated during ingot and shot cooling or
quenching, and from scrubbing of the emissions from the reverberatory
furnace.  Also, if the drosses and skimmings are stored in the open,
runoff water may become a source of aqueous wastes.  The waste cooling
water is disposed of by vaporization, discharging directly to a municipal
sanitary sewer or stream, or a pond.  In a survey of 50 secondary aluminum
plants, 24 discharged to sewers or streams, 4 discharged to a pond,
13 recycled continuously, 7 discharged after recycle, and 2 vaporized the
water.  This wastewater contains significant quantities of heavy metals,
phenol, and other contaminants and is, therefore, a potential source of
water pollution.
          The other source of wastewater from the Reverberatory (Chlorine)
Smelting-Refining Process  (7) is that from the wet scrubbers.  This waste
which may or may not be neutralized  is discharged to ponds.  That which
has not been neutralized has a pH of about 1.5 and contains hydrolyzed
metal chlorides of aluminum, magnesium,  zinc, manganese, cadmium, copper,
nickel, and lead.  The neutralized scrubbing  liquor with a pH of 9  to  11
contains  sodium, potassium, and calcium  and  lesser quantities of the
heavy metals, aluminum and magnesium.
          Solid wastes generated by  this process  include:   (1) drosses
and  skimmings from the process  itself, and  (2) wastes  from  the air
pollution control equipment.  The drosses and skimmings  are recycled,
while the others are probably disposed of by  routine methods  such as
landfill.   If not properly prepared,  the leachate  from the  landfill can
enter the ground water and cause pollution problems.

-------
                                  C-22
          Thus, the Reverberatory (Chlorine) Smelting-Refining
Process  (7) is a major source of atmospheric emissions from the
aluminum segment of the secondary metals industry.  These emissions
containing gaseous and fine particulate matter present serious pollution
problems if emitted to the atmosphere.  Raw emission factors exclusive
of the demagging processing step for this process have been reported to
be 4.3 Ib of particulate matter per ton  (2.15 Kg/t of metal processed.
Using a baghouse or an electrostatic precipitator as the pollution
control device reduced the emission factor to 1.3 Ib of particulate
matter per ton (0.65 Kg/t of metal processed.  Raw emission factor
for the demagging processing is reported at 1000 Ib of particulate
matter per ton of chlorine (500 Kg/t) used.  The emission factor is
reduced  to 50 Ib of particulate matter per ton of chlorine (25 Kg/MT)
used    by employing a baghouse as the control device.
          Currently, most of the secondary smelters using chlorine in
the demagging processing step employ wet scrubbers alone or in combination
with baghouses to reduce the atmospheric emissions.  Although emission
factor data are not available, it is expected that this combination of
pollution abatement equipment will remove the gaseous emissions such as
chlorine and hydrogen chloride as well as the particular matter more
efficiently than either the baghouse or electrostatic precipitator.  In
one installation, the scrubber removed virtually all of the hydrogen
chloride gas, greater than 90 percent of the chlorine, and greater than
80 percent of the aluminum chloride.
          Particle morphology of the particulate emissions, i.e.,
particle size and shape, is somewhat dependent upon the composition of
the scrap and the processing parameters.  However, in general, the
particulate matter is composed of particles ranging in size from a few
hundredths of a micron (approximately 0.05 micron) to several microns
(approximately 2 to 5 microns).  In one case, the fume from salt-
cryolite mixtures was found to be composed of particles ranging in size
from less than 2 microns to less than 0.1 micron.  In another case the
fume from a demagging operation was found to be composed of a mixture of
particles with 90 to 95 percent less than 1 micron in diameter.  This

-------
                                  C-23

small particle size makes it difficult to collect the emissions in
baghouses and electrostatic precipitators.
          The emissions are generally composed of particles exhibiting
both regular and irregular particle morphology.  The morphology will
range from acicular shapes (long needle shape particles) to spherical
particles.
          Solid wastes and aqueous wastes,  if not disposed of properly,
can present pollution problems.

          Reverberatory  (Fluoride) Smelting-Refining Process (8).  This
process is essentially the same (i.e., the same processing steps are
employed as in Reverberatory (Chlorine) Smelting-Refining) except that
aluminum fluoride  (A1F-) is used in place of gaseous chlorine in the
demagging processing step.  In Process 8, the magnesium is removed by
mixing solid A1F,  into the molten metal.  The A1F3 reacts with the
magnesium to give  aluminum metal and magnesium fluoride which floats or
is carried by  the  mixing gas to the surface of the molten metal and is
removed as part of the dross or skimmings.
          Conducting the demagging with A1F.J results in a significant
reduction in the quantity of atmospheric emissions.  Consequently,  the
problems associated with atmospheric pollution are significantly
reduced, yet not completely eliminated as significant quantities of
atmospheric pollutants are discharged.   Instead  of large quantities of
chlorine gas,  the  emissions contain fluorides  as gaseous fluorides  or
fluoride dusts.  If not  properly  controlled,  the fluorides as well  as
the  other particulate matter and  gases in the  effluent  can cause serious
pollution problems.  The atmospheric emissions may be controlled by  the
same dry  or wet methods  used in Process  7.
          Aqueous  waste  generated  in  this process consists of waste
cooling water  generated  during ingot and shot  formation.   This waste
water is  disposed  of either by discharging  to  sewers, streams,  or ponds;
recycled  continuously;  recycled partially;  or  evaporated  (see  discussion
of waste  cooling water  under Process  7 as same treatment  and disposal

-------
                                   C-24
methods are employed).  The wastewater  from the fume scrubber  (which is
recycled)  is  first  treated with caustic to remove the fluoride.  The
solids formed during neutralization are separated in settling  tanks and
the effluent  is recycled  to the scrubber system.
           Solid wastes generated by this process are:   (1) drosses and
skimmings  from the  process itself, and  (2) solids from  the air pollution
control equipment.  The dross and skimmings are recycled.  Solid waste
(sludge) from the wet scrubber is dewatered and placed  in a landfill.
If not properly prepared, the leachate  from the landfill can enter the
underground water system  and cause pollution problems.  Those  smelters
using the  dry collection  system also dispose of the fume dust  and bag
coating substances  in landfills.  Although the fluorides are considered
to be insoluble, the solubility may be great enough to  contaminate
ground water.
          Because of the  toxic and hazardous nature of  the pollutants
generated by  this process, the process presents serious pollution
problems if these pollutants are not collected and disposed of in a
proper manner.


           Crucible  Smelting-Refining  Process  (9).   For  producing  small
quantities of aluminum alloy castings,  i.e., up  to  approximately  1000  Ib,
the Crucible  Smelting-Refining Process  (9) is used.  The processing
steps are:   (a) charging  of the melt  to the furnace,  (b) melting  of
the charge,  (c) fluxing to remove the contaminants  if necessary,
(d) alloying  to produce a melt of the desired composition,  (e) mixing
to homogenize the molten  metal,  (f) demagging,  (g)  degassing,  and
(h) skimming.  Afterwards, the melt is  poured and cast  into the desired
shapes.  Any  given  smelter may not incorporate all  of these steps into
the process,  but may use  a combination  of the steps depending  on  the
source of  scrap.
          Energy demand is limited to that required to  operate the
equipment and to heat the furnace.  The furnace is heated indirectly
with,gas or fuel oil as the source of fuel.  However, electricity may
also be used as the source of energy.

-------
                                   C-25
           Potential  environmental  pollutants  from  this  process  are:
 atmospheric  emissions which  are  composed  of gases  and particulate matter,
 aqueous wastes  containing dissolved and suspended  solids  and  solid wastes.
 Since  this process is quite  similar to reverberatory smelting-refining
 except for the  size  of  operation,  see discussions  in the  previous sections
 on  Processes  7  and 8 for data  on composition  of pollutants, processing
 steps  generating  the wastes, and disposal of  the pollutants.
           This  process  has the potential  for  generating significant
 pollution  problems.

          Induction Smelting-Refining  (10).   This  process  produces
hardeners,  alloys of known composition,  which are  used   to introduce
precise amounts of particular metals into a melt to meet predetermined
specifications.  The most common hardening agents  are titanium, boron,
and chromium.  The hardeners  are produced by melting and blending
electrical conductor scrap (superpure  aluminum) with the hardening agent
in an  induction furnace.  The processing steps are:  (a) charging of the
scrap  to the furnace, (b) melting of the scrap, (c) blending the molten
metal with the alloying agent, (d)  skimming of the melt to remove the
oxides on the surface,   (e) pouring of the melt, and (f) casting into
notched bars.
          Energy demand is limited to that needed  to run  the equipment
and the electricity  to melt  the  scrap.
           The process produces small quantities of atmospheric  emissions
 and aqueous  and solid wastes.  The atmospheric emissions  contain, in
 addition to  aluminum, small  amounts of the alloying agent and  other
metals found  in the  scrap.   These  emissions are generated in  all of the
 processing steps.  The  aqueous wastes are generated during  the  casting
 of  the notched  bars, whereas the solid wastes  are  drosses (skimmings
 from  the surface  of  the melt).   These wastes  can be collected  and
 disposed of  by  the methods employed in Process 7.
           This  process  has a low potential for the production
 pollutants.

-------
                                   C-26
          Rotary Furnace Smeltinp-Refining  (II).  This process is employed to
recover the aluminum values from such raw materials as drosses to produce
high aluminum ingots which are refined in the reverberatory furnace.
The processing steps are:  (a) charging of  the scrap and flux, (b) melting
of the charge, (c) pouring, and (d) casting of the ingots.
          The energy demand for this process is that needed to drive the
equipment and natural gas or fuel oil to heat and melt the charge.
          The process produces atmospheric  emissions composed of gases
such as the combustion products, entrained  air, and volatile metal values
and particulate matter such as the flux and particles of the charge.
Solid wastes are the slag containing impurities extracted from the
aluminum and the sludge from the wet scrubber.  Aqueous waste consists
of primarily the cooling water used in casting the ingots.  These wastes
may be disposed of by methods used for disposal of similar wastes from
other processes.
          The process can cause serious pollution problems, if not
properly controlled.

-------
                                   C-27
                Population of Secondary Aluminum Processors
 (1)  Alloys and Chemicals Corporation
      4365 Bradley Road SW
      Cleveland, Ohio  44109
      Telephone:  (216) 661-8600

 (2)  Aluminum Billets, Inc.
      3786 Oakwood Avenue
      Youngs town, Ohio
      Telephone:  792-6511

 (3)  Aluminum & Magnesium
        Tncorporated
      Huron and W. Monroe Streets
      Sandusky, Ohio

 (4)  Aluminum Smelters Incorporated
      322 Legion Avenue
      New Allen, Connecticut

 (5)  Aluminum Smelting and Refining
        Company, Inc.
      5463 Dunham Road
      Maple Heights, Ohio  44137
      Telephone:  662-3100

 (6)  Apex Smelting Company
      Division of Amax Aluminum Company
      2515 West Taylor Street
      Chicago, Illinois
      Telephone:  (312) 332-2214

 (7)  Aurora Refining Company
      Box 88
      Aurora,  Illinois

 (8)  Barnum Smelting Company
      Barnum Avenue
      Bridgeport, Connecticut  06608
       (11)  Joseph Behr and Sons, Inc.
            1100 Seminary Street
            Rockford, Illinois
            Telephone:  (815) 962-7721

       (12)  Belmont Smelting & Refining
              Works, Inc.
            320 Belmont Avenue
            Brooklyn, New York  11207
            Telephone:  DI2-4900

       (13)  W. J. Bullock, Inc.
            Post Office Box 539
            Fairfield, Alabama  35064
      (14)
      (15)
      (16)
      (17)
 (9)   Batchelder-Blasius,  Inc.
      Post Office Box 5503
      Spartanburg,  South Carolina

(10)   Bay Billets Inc.
      1364 Olds  Street
      Sandusky,  Ohio
      (18)
                                         (19)
29301
      (20)
 Colonial  Metals .Company
 Columbia,  Pennsylvania
 Telephone:   (717)  684-2311
J. R. Elkins,  Inc.
518 Gardner Avenue
Brooklyn, New  York
                                11222
Excel  Smelting Corporation
1300 North  Seventh  Street
Memphis, Tennessee  38107

Federated Metals
Division of American Smelting
  and  Refining Company
12 Pine Street
New York, New York

Firth  Sterling, Inc.
3113 Forbes Avenue
Pittsburgh, Pennsylvania
  15230

General Smelting Company
Division of Wabash  Smelting
  Incorporated
2901 EW Moreland Street
Philadelphia, Pennsylvania
Telephone:  GA3-3200

Gettysburg Foundries
Post Office Box 421
Gettysburg, Pennsylvania
  17325
Telephone:  334-5616

-------
                                  C-28
 (21)  Hall Aluminum Company
      1751 State Street
      Chicago Heights, Illinois

 (22)  Harco Aluminum, Inc.
      4528 West
      Chicago, Illinois  60651

 (23)  Henning Brothers & Smith, Inc.
      91-115 Scott Avenue
      Brooklyn, New York

 (24)  Holtzman Metal Company
      5223 McKissock Avenue
      St. Louis, Missouri  63147

 (25)  North American Smelting Company
      Post Office Box 1952
      Marine Terminal
      Wilmington, Delaware
      Telephone:  OL4-9901

 (26)  Northwestern Metal Company
      North 27th Street
      Lincoln, Nebraska

 (27)  Paragon Smelting Corporation
      36-08 Review Avenue
      Long Island City, New York  11101
      Telephone:  (212) RA9-3641

 (28)  Pioneer Aluminum, Incorporated
      3800 East 26th Street
      Los Angeles,  California

(29)  George Sail Metals Company,  Inc.
      2255 East Butler Street
      Philadelphia,  Pennsylvania  19137
      Telephone:   (215) PI3-3900

(30)  Silberline Manufacturing Company,
        Inc.
      Lansford,  Pennsylvania
      Telephone:   (717) 645-3161

(31)  Sonken-Galamba Corporation
      Second  and Riverview Streets
      Kansas  City, Kansas 66118
      Telephone:   (913) MA1-4100
(32)  Superior Industries,  Inc.
      3790 Oakwood  Avenue
      Youngstown, Ohio   44509

(33)  U.  S. Aluminum Corporation
        of Pennsylvania
      Railroad and  Biddle  Streets
      Marietta,  Pennsylvania
      Telephone:  426-7811

(34)  U.  S. Reduction Company
      Box 30
      East Chicago,  Indiana
      Telephone:  RE1-1000

(35)  Wabash  Smelting, Inc.
      Post Office Box 453
      Wabash,  Indiana 46992

-------
                    SCRAP  PRETREATMENT
                                                                                                               BELTING/REFINING
                    MECHANICAL
 SHtn.
 CASTINGS, CLIPPINGS
 ELECTRICAL cowouCTofls -
_  UNTREATED I
 .  SCRAP   '
                       S »CATED
                       PIC/SOW
                    HTQROMETALLURGICAL
DROSSES.SKIMMINGS.
SLACS
r AUOTIN6 AGCNF
 • -NITROGEN
 I  —CHLORINE
1 ,   —ruEi
Hii —fu.
                                                                                         LEGEND

                                                                                O ATMOSPHERIC EMISSICMS

                                                                                A LIOUIO WASTES

                                                                                O SCH.ID WASTES
                                                                                                                                                 SCCONDMT WW
                                                                                                                                       MATERIALS fW USE •» OTHCB
                                                                                                                                       nousrnict
                                                                                                                                      INTCRMCOUIC maoucT
                                                                                                                 SIGNATURE DIV DATE
                                                                                                                                                                         it.5 7AUG73
                                                                                                                                          BATTCLLC MEMORIAL INSTiniTe
                                                                                                                                             COUJMBUI uvio
-------
                                   C-30
             PROCESS DESCRIPTION OF THE ANTIMONY SEGMENT OF
                THE SECONDARY NONFERROUS METALS  INDUSTRY
           The secondary antimony segment recovers  antimony  as  an alloy
with  lead  rather than as pure metal because of the far  greater demand
for the  alloy.   Also,  primary lead  refineries  recover  the metal as
antimonial lead.   The bulk of the antimonial lead  is used in storage
battery  grids and contains about 3  percent  antimony.
           Statistics  for the secondary  antimony industry for 1971 are
presented  below.
Kind of Scrap
New scrap
Old scrap
Total scrap
Production,
Short Tons
3,342
17,575
20,917
Form of Recovery
An antimonial lead
In other lead alloys
Total recovery
Production,
Short Tons
15,839 .
5,078*
20,917
     * Includes  11  short  tons  in  tin-base alloys.

Further, in  1971, by-product antimonial  lead produced at primary lead
refineries amounted  to  19,686  tons containing  1,191 tons of antimony
(6 percent).

                             Raw  Materials

          New scrap  consisting of residues and drosses resulting from
manufacturing and casting amounted to 16 percent of the total scrap
processed in 1971.   Old scrap, obtained mostly from used lead-acid type
battery grids, amounted to the remaining 84 percent.  Greater than 99 percent
of both old and new  scrap was  in  the form of lead-base alloys while less
than 1 percent was comprised in tin-base alloys.
          Although the  increased  useful  life of batteries tended to reduce
the quantity of available battery scrap, the trend was soon counter-
balanced by the increase  in the automobile population, thus insuring a

-------
                                  C-31

continued supply of used battery grids as scrap.  The raw materials to
this industry, therefore, include:
          (1)  Old battery grids
          (2)  Residue and drosses from manufacturing and casting
          (3)  Scrap from the machining and manufacturing industry.

                               Products

          Products from the antimony segment include:
          (1)  Antimonial lead alloys used in storage battery
               grids containing about 3 to A percent antimony  (grid metal)
          (2)  Body solder used in automobile bodies
          (3)  Type metal used in printing.  This alloy has
               4-23 percent antimony, 17-30 percent  tin, and the
               remaining is lead
          (4)  Master alloys containing large amounts of antimony
               (15 percent or more) and used in blending to
               manufacture other alloys
          (5)  Pure lead as a by-product.

                          Process Description

          The recovery of antimony as alloy from scrap  involves three
manufacturing operations:   (1) scrap pretreatment,  (2)  smelting, and
 (3) refining/casting.  These operations and the major individual processes
under each operation are shown on the flowsheet of  this  segment of  the
secondary nonferrous metals industry.

Scrap Pretreatment Operation

          New scrap generated in machine  shops  is not pretreated.   Old
scrap from type and babbit metals is not  only  insignificant  in quantity,
but is generally not pretreated before  smelting.  However, since  70 percent
of  the old scrap is used battery  scrap, pretreatment of these  used  batteries

-------
                                   C-32
will be described.   The flowsheet indicates  a single  scrap pretreatment
process which is discussed below.

           Battery Breaking, Crushing,  and  Hydroseparation Process  (1).
This process which  separates the metallic  parts  of  the  old. battery from
the  plastic and rubber portions  is conducted in  one of  two ways.  The more
common method,  adopted by about  75 percent of the industry, consists of
the  following steps:  (a)  mechanical sawing of the top of the battery,
(b)  manually separating the bottom case  from the acid and grids by
dumping,  (c) cleaning grids by water spray,  (d)  crushing the battery tops
and  separating  the  metals on a vibratory table,  (e) crushing the bottom
case in a hammer mill for disposal in  landfills, and  (f) neutralizing
the  acid  effluent from dump tanks with lime  in a settling pond.
           The second  method,  used in about 25 percent of the industry,
consists  of the following process steps: (a)  crush  the whole battery (as
received)  in a  hammer mill, (b)  drain  and  treat  the acid, and  (c) conduct
heavy media separation to separate plastics  from the  lead oxide and lead
metal.  This process  produces a  richer feed  to smelters.
           Energy requirements for this process are  electrical  energy
for  the vibratory feeder,  the hammer mill, and the  heavy media separation
column.
           The wastes  generated are about the same in  both processes and
consist of:  (J)  acidified (sulfuric) wastewater, (2)  shredded  plastic and
rubber, and  (3)  fine  particles of metal  and  plastics  as ambient air
emissions  from  the  hammer  mill and vibrating table.
           The potential for pollution  from these wastes is greatly reduced
by the  following waste treatment  processes in current use:  (1) neutralization
of acid wastewater  with dolomitic lime (CaO)  in  a settling pond and
(2)  landfilling  or  utilization of shredded plastics in road surfacing
and  to  produce nonleaching landfill  material.     As  a result  of these
waste treatment  steps, this process does not have much pollution potential.
If the  treatment  steps are not adopted, the pollution can be serious.
(1)  John A. Bitler and L. John Minnick, "Lime-Sulfur Dioxide Scrubbing
     System and Technology for Utilization of Underflow Sludge",
     Industrial Wastes, March/April 1973.

-------
                                  C-33

Smelting Operation

          This operation consists of two processes which are described
below.

          Reverberatory Smelting Process (2).  This process melts,
purifies, and separates the metallic portions of the feed scrap generated
in the pretreatment steps.  The process steps are:  (a) charging the
furnace, (b) melting the charge, (c) pouring out the lead metal, and
(d) removing the slag.
          Energy required is from the fuel oil to operate the furnace and
from electricity to operate the auxiliary equipment.
          Wastes from the process are atmospheric emissions containing
flue dust and sulfur oxides and liquid wastes.
          These wastes are treated effectively.  The flue dust has
sufficient lead metal value to warrant almost complete recovery for which
purpose a baghouse is used.' The collected dust is recycled to the furnace.
The sulfur oxides are scrubbed with dolomitic lime and the resulting
sludge  (calcium-magnesium sulfates) is used  in road surfacing or in
preparing nonleachable landfill material.
          The pollution potential of this process can be serious  if the
pollution control systems are not properly maintained.

          Blast Furnace Smelting Process (3).  The blast furnace  produces
lead metal with a high antimony content and  also reduces the oxides of
lead and antimony to  their respective metals.  The feed to this furnace
includes slag from the reverberatory furnace.
          The process steps are:   (a) continuous charging of coke, slag,
and treated battery scrap;  (b) heating with  blasts of air, and  (c) with-
drawing  the metal and slag.
          Heat energy in  the form  of coke is the main requirement of  the
process.
          The wastes  produced are:  atmospheric emissions containing  flue
dust  and flue gas rich in sulfur oxides, solid waste as blast  furnace slag,
and liquid waste as waste cooling  water.

-------
                                   C-34
           The atmospheric  emissions  are  treated by  the  same method used
for emissions from  the  reverberator/ smelting process.  The slag is
probably disposed of  in a  landfill.
           The process has  the potential  for producing serious pollution
problems if  the  emissions  are not controlled and  if collected wastes are
not disposed of  in  a nonpolluting manner.

Refining and Casting Operation

           Pot Molding and  Casting Process  (4).  In  this process, the metal
products from the reverberatory and  blast  furnaces are molded after
adjusting  to required alloy compositions.  Air blowing  is done  if removal
of all antimony  is  desired.
           The process steps are:  (a) charging the furnace, (b) melting
the charge,  (c)  blowing if necessary, (d)  pouring the molten metal into
the molds, and (e)  casting the metal  into  ingots.
           Heat energy is the main requirement.
           The wastes are mainly atmospheric emissions containing gases and
metal oxides, dust, and fume.  An afterburner burns incinerable fumes and
a baghouse collects the dust and the metal oxides.  Finally, the scrubber
takes out  acidic oxides  before the off gases are vented to the atmosphere.
           Due to current flue gas treatment employed, the process has
little pollution potential.  However, if not controlled, the process could
be a source of pollution problems.

-------
                                   C-35


                Population of Secondary Antimony Processors
 (1)  Allie Smelting Corporation
      5116 W. Lincoln Avenue
      Milwaukee, Wisconsin 53219
      Telephone: (414) 541-7830

 (2)  Dixie Lead Company, Inc.
      Post Office Box 8625
      Dallas, Texas 75216
      Telephone: WA6-2132

 (3)  Electric Storage and Battery Company
      2 Penn Central Plaza
      Phildelphia,  Pennsylvania

 (4)  Florida Smelting Company
      2640 Capitola Street
      Jacksonville, Florida
      Telephone: (904) 353-4317

 (5)  Frankel Company, Inc.
      19300 Filer Avenue
      Detroit, Michigan
      Telephone: S06-5300

 (6)  General Battery Corporation
      Post Office Box 1262
      Reading, Pennsylvania

 (7)  Inland Metals and Refining Company
      651 E. 119th  Street
      Chicago, Illinois 60628
      Telephone: (312) 928-6767

 (8)  Seitzinger's, Inc.
      900 Ashby Street NW
      Atlanta, Georgia 30301
      Telephone: (404) 876-3787

 (9)  U.S.S. Lead Refinery, Inc.
      5300 Kennedy  Avenue
      East Chicago, Indiana
      Telephone: (219) 397-1012

(10)  Hyman Veiner  & Sons
      Post Office Box 573
      Richmond,  Virginia 23205
      Telephone: (703) 648-6563

-------
                                                                                                                                                              BEVI1IONS
          SCRAP PRETREATMENT
                                                                                  SMELTING
                                                                                                                                     REFINING/CASTING
OLD SIOBACE
e»TTEBJCS  ~
WATER 	
LIME 	
                                                                                                                      LEGEND
d
                                                                                                                           QR SEGOOAttY RAW
                                                                                                                     MATERIALS FOR USE UuOTtCR
                                                                                                                     INDUSTRIES
IMTTCLLC MCMOAIAL INfTITUTC
   CCT.i»«»m uwofMTonci
 KING AVC.. COLUMBUS. OHIO 41301
                                                                                                                                                        1~HE SECCfJCARY NONFERROUS
                                                                                                                                                        VtETALS  INDUSTRY
                                                                                                                                                           79986
                                                                                                                                                                                          n
                                                                                                                                                                                          I
                                                                                                                                                                                          u>

-------
                                  C-37
             PROCESS DESCRIPTION OF THE BERYLLIUM SEGMENT
             OF THE SECONDARY NONFERROUS METALS INDUSTRY

          Beryllium, like indium, is a very expensive metal with a
current market value of about $6 per ounce.  Total U. S. production of
beryllium can be estimated at less than 500 tons per year.  Exact
production figures are a trade secret and no data on secondary production
are available.  In fact, there is no distinct secondary segment because
most of the scrap is generated in-house.

                             Raw Materials
          Details of raw materials to this industry are not available.
Tonnagewise, the raw material availability is estimated at less than
100 tons per year.

                               Products

          Pure beryllium metal and alloys of beryllium with copper are
some of the products.

                          Process Description

          There are only two beryllium processors in the U. S.  They are
not willing to reveal the process steps because of the competitive nature
of the industry and the need to protect the proprietary nature of their
process.
          Also, a discussion of the process will not be of much avail
because both the processors feel that it would not be in their best interest
to obtain R&D assistance from external agencies, either public or private.
The companies conduct their research in-house.
          The following information provided by one of the companies is
reported for record.

-------
                           C-38
(1)  Scrap beryllium is treated by pyrometallurgical methods
     to produce pure metal.  Typically, vacuum casting

     followed by hot pressing and grinding are used.
(2)  Excellent hooding and bag fillers where necessary are

     used to prevent escape of beryllium.
(3)  Beryllium inhalation produces effects akin to

     silicosis and, therefore, extreme care is taken to
     minimize the indoor and ambient concentration of
     this metal.

(4)  The company has no problems that they cannot solve by
     their own efforts.


   Population of Secondary Beryllium Processors
(1)   Brush Wellman Engineered Materials
     17876 St.  Clair Avenue
     Cleveland, Ohio  44110
     Telephone:  (216)  486-4200

(2)   Kawecki Berylco Industries,  Inc.
     220 East 42nd Street
     New York,  New York  10017
     Telephone:  (212)  682-7143

-------
                                   C-39
              PROCESS DESCRIPTION OF THE BRASS AND BRONZE
          SEGMENT OF THE SECONDARY NONFERROUS METALS INDUSTRY
                              Introduction

          The brass and bronze segment constitutes a large portion of
the secondary nonferrous metals industry.. Since World War II, the
production of brass and bronze ingots in  the United States has been
fairly constant, averaging slightly over  300,000 tons annually.  In
1969, the production rate was 326,000 tons.  Potential environmental
pollutants from this industry are atmospheric emissions, both gases and
particulate matter, liquid wastes, and solid wastes, which if not
controlled and properly disposed of can result in serious pollution
problems. .Emission potential of particulates alone has been estimated
at 10,000 tons annually, based on an annual production of 300,000 tons
of ingots.

                             Raw Materials

          Obsolete domestic and industrial copper-bearing scrap is the
basic raw material of the brass and bronze segment.   About two-thirds
of the scrap is in the form of brasses and bronzes;  the other one-third
is received in the form of copper scrap.   Of the many hundreds of
copper-base alloys that become available  for reuse through scrap recovery
channels, 54 primary types of copper-bearing scrap are now included in
the standards published by the National Association of Secondary Materials
Industries.      These are listed in Table 1.
          Scrap as received is frequently not clean and may contain any
number of undesirable metallic and nonmetallic impurities that contribute
nothing to the composition of the ingot but increase the problems in
producing high quality products.   Among these undesirable constituents
are oil,  grease, paint, insulation, rubber, and antifreeze.
(1) Bulletin NF-66, National Association of Secondary Materials Industry,
    330 Madison Avenue,  New York,  New York.

-------
                                C-40
 TABLE C-l.    TYPES  OF COPPER-BEARING  SCRAP
No.
                      Designation
 1.
 2.
 3.
 4.
 5.
 6.
 7.
 8.
 9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22-
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
38.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
No. 1 copper wire
No. 2 copper wire
No. 1 heavy copper
Mixed heavy copper
Light copper
Composition or red brass
Red  brass composition turnings
Genuine babbitt-lined brass bushings   •            »*-.
High-grade, low-lead bronze solids
Bronze paperraill wire cloth
High-lead bronze solids and borings
Machinery or hard red brass solids
Unlined standard red car boxes (clean journals)
Lined standard red car boxes (lined journals)
Cocks and  faucets
Mixed brass screens
Yellow brass scrap
Yellow brass castings
Old rolled brass
New brass  clippings
Brass shell cases  without primers
Brass shell cases  with primers
Brass small arms and rifle shells, clean fired
Brass small arms and rifle shells, clean muffled (popped)
Yellow brass primer
Brass pipe
Yellow brass rod turnings
Yellow brass rod ends
Yellow brass turnings
Mixed unsweated auto radiators
Admiralty brass condenser tubes
Aluminum brass condenser tubes
Muntz metal tubes
Plated rolled brass
Manganese bronze  solids
New cupro-nickel clippings and solids
Old cupro-mckel solids
Soldered  cupro-nickel solids
Cupro-nickel turnings and borings
Miscellaneous nickel copper and nickel-copper-iron scrap
New monel clippings and solids
Monel rods and forgings
Old monel sheet and  solids
Soldered  monel sheet and solids
Soldered  monel wire, screen, and cloth
New monel wire, screen, and cloth
Monel castings
Monel turnings and borings
Mixed nickel silver clippings
New nickel silver clippings and solids
New segregated nickel silver clippings
Old nickel  silver
Nickel silver castings
Nickel silver turnings

-------
                                  C-A1
                               Products

          The products from the brass and bronze segment of the secondary
nonferrous metals industry are hardeners and brass and bronze alloy ingots.
Brass and bronze are copper-base alloys with zinc and tin, respectively, as
the  largest secondary component.  Other alloy agents may  include  such elements
as lead, iron, aluminum, nickel, silicon, or manganese.  Members of the
Brass and Bronze Ingot Institute produce 31 standard copper-base alloys
as shown in Table 2.
             TABLE C-2.  NOMINAL CHEMICAL SPECIFICATIONS
                         FOR BBII STANDARD ALLOYS
Alloy
No. Classification
1A Tin bronze
IB Tin bronze
2A Leaded tin bronze
2B Leaded tin bronze
2C Leaded tin bronze
3A High-lead tin bronze
3B High-lead tin bronze
3C High-lead tin bronze
3D High-lead tin bronze
3E High-lead tin bronze
4A Leaded red brass
4B Leaded red brass
5A Leaded semi-red brass
SB Leaded semi-red brass
6A Leaded yellow brass
SB Leaded yellow brass
6C Leaded yellow brass -
7A Manganese bronze
8A Hi-strength mang. bronze
SB Hi-strength mang. bronze
8C Hi-strength nang. bronze
9A Aluminum bronze
98 Aluminum bronze
9C Aluminum bronze
9D Aluminum bro:ize
IDA Leaded nickel brass
10B Leaded nickel brass
HA Leaded nickel bronze
11 B Leaded nickel bronze
ISA Silicon bronze
12B Silicon brass
Cu, %
86.0
88.0
88.0
87.0
87.0
80-0
83-0
85.0
78.0
71.0
85.0
83.0
81.0
76.0
72.0
67.0
61.0
59.0
57.5
64.0
64.0
88.0
89.0
85.0
81.0
57.0
60-0
64.0
66.5
88.0
82.0
Sn.%
10-0
8.0
8.0
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







2.0
3-0
4.0
5.0


Pb,%


1.5
1.0
1.0
10.0
7.0
9.0
15.0
24.0
5.0
6.0
7.0
6.5
3.0
3.0
1.0
1.0







9.0
5.0
4.0
1.5


Zn.%
2.0
4.0
4.0
4.0
2.0

3.0
1.0


5.0
7.0
9.0
15.0
24.0
29.0
37.0
37.0
39.0
24.0
24-0




20.0
16.0
8.0
2.0
6.0
14.0
Fe.%

















1.0
1.0
3.0
3-0
3.0
1.0
4.0
4.0




1.5

Al.%

















0.6
1.0
5-0
5.0
9.0
10.0
11.0
11.0






Ni.-H,























2.0
4.0
12.0
16.0
20.0
25.0


Si.%





























4.0
4.0
Mn.%

















0.5
1.5
3.6
3.5


0.5
3.0




1-5


-------
                                   C-42

                          Process Description

          The production of brass and bronze products using scrap as
the basic source of raw material entails two manufacturing operations:
(1) scrap pretreatment and  (2) smelting-refining.  The two manufacturing
operations and the individual processes under each operation are shown
in the attached flowsheet entitled "Brass and Bronze Segment of the
Secondary Nonferrous Metals Industry".

Scrap-Pretreatment Operation

          Before the scrap is blended in a furnace to produce the alloy
of a desired composition, removal of some of the metallic and nonmetallic
impurities or contaminants and densification of the scrap are conducted
to produce a material more suitable for subsequent smelting-refining.
The pretreatment process employed depends upon the type of scrap as
noted in the flowsheet by Numbers 1 through 9.

          Stripping Process (1).  Insulation is removed from electrical
conductors such as cables by specially designed stripping machines or
by hand.
          Energy demand is that needed to drive the equipment.
          Essentially no atmospheric emissions or liquid wastes are
generated by this process.  However, significant quantities of solid
wastes are produced.  These wastes consist of primarily organic materials
such as plastics and other materials used as protective coverings on
copper scrap .
          The pollutants generated are expected to cause no atmospheric
pollution problems, unless the solid wastes are disposed of by burning.
Disposal of the solid wastes in landfills may possibly cause water
pollution if the landfill is not properly prepared.

-------
                                  C-43
           Briquetting Process  (2).  Compressing  the bulky scrap  such
as borings,  turnings, and wire  into small bales  densities the  scrap,
permits more compact storage, and makes for easier handling and  faster
melting.   Briquetting is carried out by compacting the scrap with
hydraulic  presses.
           Energy required is that to drive the equipment.
           Essentially no atmospheric emissions and no liquid or  solid
wastes are generated.
          The process has little or no potential for the production of
pollution problems.

          Shredding Process  (3).  The  shredding process  also
achieves  separation of  the  insulation  from the copper-bearing scrap.
The process steps are:   (a)  introducing the insulated copper scrap
such as copper wire into a  hammermill  where the scrap is cut into small
pieces and the insulation is broken loose from the metal, and  (b) removing
the insulation by air classification.   This process is used in larger
plants because of high  capital costs.
          Energy demand is  that required to drive the equipment.
          Potential environmental pollutants from this process are
atmospheric emissions (gases and particulate matter)  and solid wastes.
The atmospheric emissions are the fine particulate matter composed of
the insu1   ":ion and fine metal particles and the gas,  generally air, used
in the clarification.   The air is not a pollutant; however, the par-
ticulate matter is a potential pollutant if not collected and  disposed
of properly.  Cyclones  are  used as the pollution abatement device.  Solid
wastes are the insulation and metal particles removed from the scrap
by the air classification.
          The process has the potential for creating environmental
pollution problems.  The fine particulates may cause atmospheric
pollution problems; the solid wastes may cause water pollution problems
if not disposed of in an approved landfill.

-------
                                   C-44

          Magnetizing  Process  (4).   The  scrap may  be  a mixture  of
 ferrous  as well  as  nonferrous  components.   The  ferrous component of
 the  scrap is  removed by  the  magnetizing  process which entails passing
 the  scrap over magnetized  pulleys.   Scrap  treated  in  this manner is
 brass borings and small  items.
          Energy required  is limited to  that to drive the equipment.
          The only  wastes  generated  by this process are  solid wastes--
 scrap iron which may be  contaminated with  other metals and organic
 compounds such as the  machining  oils.  These are disposed of by either
 landfill or selling to a ferrous  scrap dealer.
          The process  has  essentially no potential for the production
 of a pollution problem.

          Sweating  Process  (5).   Much of the scrap such  as radiators
 contains low  melting components  such as  lead, solder, and babbitt metal.
 These are removed from the scrap  by  the  sweating process which entails
heating  the scrap in a furnace.   The process steps are:   (a) charging
 the  furnace,  (b) melting the low-melting components,  (c) collecting
 the melt, and (d) removing the treated scrap from  the furnace for
 further processing.  The collected metal may be made  into white alloys,
 used for lead and tin  addition to the  copper base alloys, or sold as
 produced to a refinery.
          Energy required  includes the fuel to fire the  furnace and
 electricity to drive the equipment.   Several types of furnaces — rotary
kiln, tunnel  furnace,  pot  furnace, or  reverberatory furnace--may be
used.  Both gas and oil  are  potential  sources of fuel, depending on
 the availability and type of furnace.
          Environmental  pollutants generated by this  process are:
atmospheric emissions, solid wastes,  and possibly aqueous wastes.
Atmospheric emissions  contain primarily  fumes and combustion products
of antifreeze residues,  soldering salts, hose connections, and fuel.
Metal content of the emissions is expected  to be low  because of the low

-------
                                   C-45
sweating  temperature.  Solid wastes are  those from  the pollution
abatement equipment.  If wet scrubbers are used  to  reduce atmosphere
                                       (2)
pollution,  liquid wastes are generated.
          The process is a potential source of serious atmospheric
pollution and presents potential pollution problems resulting from
disposal of the solid wastes and liquid wastes,  if  generated.

          Burning Process (6^.  Much of  the scrap is covered with
insulation  such as polyethylene, polypropylene,  or  polyvinyl chloride.
These contaminants are removed from the  scrap by the burning process
using such  furnaces as muffles and rotary kilns.  The process steps
are:  (a) charging the furnace, and (b) burning  off the organic con-
taminants.  Whereupon, the pretreated scrap is removed from the furnace
for further processing.
          Energy required is the fuel--gas or oil--to heat the furnaces
and electricity to drive the equipment.
          The burning process is a potential source of serious
pollution problems.   Burning of the organic contaminants in the scrap
results  in atmospheric pollution problems.  In addition to the combustion
products such as carbon dioxide and water, the emissions may contain
such gases as ..-ithalic anhydride and hydrogen chloride from the burning
of, for  example, polyvinyl chloride.  Fluorocarbon  insulation releases
hydrogen fli ..ride when burned.   Many of these gases are highly toxic
and corrosive.
          Little information is available on these  emissions.  Source
tests in Los Angeles indicate that uncontrolled  emissions can be dense
black smoke containing particulate matter in concentrations as large as
29 grains/scf at 12 percent carbon dioxide.  These  particulates must
have been primarily carbon, because burning the  emissions at 2000 F
(2) Schwartz, H. E., Kramer, H., and Company, Controlling Atmospheric
    Contaminants in the Smelting and Refining of Copper-Base Alloys,
    J. APCA, V5 Ml, May, 1955.

-------
                                    C-46

 (probably in an afterburner) reduced the particulate matter level to
 0.16 grains/scf at 12 percent carbon dioxide.  '
           Solid and liquid wastes are not generated by the process;
 however, both may be generated by the pollution control devices.
 Disposal of these materials is probably by landfill and settling ponds,
 respectively.
           Drying Process  (7).  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 the contaminants.
           Energy required is the fuel to heat the furnace and drive the
 equipment.  Fuel used in  this case may be oil or gas.
           Drying results  in  the evolution of considerable quantities
 of hydrocarbons depending on the amount present in the scrap.  In
 addition, the oils, greases, and cutting fluids contain sulfonated
 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 possible 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 to oxidize the hydrocarbons to carbon
 dioxide and water.   However,  this technique does not remove the sulfur
 oxides and chloride emissions.   Wet scrubbing is required.
           This  process can present atmospheric pollution  problems,  if
 the emissions are  not controlled.

           Cupolaing Process  (8).   This  process densities  bulky scrap
 and recovers  metal  values  from  slags,  skimmings,  and other  low copper
 scrap  to  produce cupola  melt  (black copper)  which is refined  to produce
 the finished  alloy.   The process  steps  are:   (a)  charging  of  the
<3>  Air Pollution Engineering Manual. Air Pollution Control District,
    County of Los Angeles, Public Health Service Publication
    No. 999-AP-40, pp 270-284, 1967.

-------
                                  C-47
cupola, (b) melting the charge, and (c) removing the slag.  Afterwards,
the cupola melt is poured and cast.  The charge is made up of coke, flux,
and the copper-containing scrap.  Air is introduced through tuyeres
around the bottom of the shaft.  Coke is used both as a fuel and as a
reducing agent.  Limestone or other materials is used for fluxing.  Slag
and concentrated alloy (cupola melt) are tapped near the bottom of the
furnace.
          Energy required for this process is coke which is used both
as a fuel and as a reducing agent.
          The process  produces:   (a) atmospheric emissions containing
both gases and particulate matter (fume and dust),  (b)  liquid wastes,
and (c) solid wastes.   The composition of the particulate matter and
gases from the cupola  are variable because of the wide  variety of scrap,
slag, and skimmings added as the source of alloy and the various fluxes
used.  However, it is  expected that the particulate matter will contain
such metal values as zinc, lead, tin,  copper, silicon,  manganese, and
some unburned coke, with the majority of the emissions  being zinc because
of its high vapor pressure at the cupolaing temperatures.  The gases are
expected to contain, in addition to the combustion products, such materials
as sulfur oxides and halides.
          Emission rates also vary because of the wide  variation in
the charge composition.  For example,  raw emission factors (furnace
emission factors) were reported to range from 16.7 to 73.2 Ib of
particulate matter per ton of feed.  Using a baghouse with a collection
efficiency of 96.4 percent as the pollution control device, emission
                                                                     (4)
factors were reduced to within 0.9 to 4.1 Ib of dust per ton of feed.
          Since zinc oxide is normally the major component in the fume,
particle shape is generally acicular,  i.e., long needles with a large
length to width ratio  (~5 to 1).  This shape is characteristic of
zinc oxide.  In some cases, the particle resembles a wheel with the
rim removed.  Particle size ranges from 0.03 to 0.3 micron which makes
(4)  Air Pollution Aspects of Brass and Bronze Smelting Refining
     Industry, U. S. Dept. HEW, NAPCA, Publication No. AP-58,
     Raleigh, North Carolina (1969).

-------
                                  C-48
 collection very difficult.   The dust particles  have  an irregular  shape
 and are expected to be much larger,  possibly in the  5  to  10  micron
 range.^ '
           Liquid wastes are generated primarily as cooling wastewater
 from water-quenching of the slag and from cooling of the  cupola.   Solid
 wastes  generated by this process are slags,  fumes and  dusts  collected
 in the  baghouse, spills, and sweepings.   The wastewater is disposed  of
 in settling ponds,  recycled, or sent to  sewers  or nearby  streams.  Some
 of the  solid wastes are recycled;  others are discarded.
           Atmospheric emissions and  liquid and  solid wastes  generated
 by the  cupola can result in serious  pollution problems.

           Gravity Concentration Process  (9).  Metallic values  are
 recovered  from slags,  drosses,  skimmings,  spills, and  sweepings by the
 gravity concentration process,  whereby the heavy  (more dense)  particles
 settle  faster than  the lighter  particles in  a water  medium.  The
 process steps are:   (a) grinding,  (b)  screening,  and (c)  gravity
 separation in a  water medium.
           Energy required is that  necessary  to  drive the  equipment.
           Only minor  quantities of atmospheric  emissions  are expected
 from  the gravity separation process.   These  are generated in the crushing
 and  screening steps.   However,  large quantities  of liquid wastes containing
 both  suspended and  dissolved solids  are  generated in the  gravity
 separation step.The liquid  wastes  are  probably  treated in settling ponds
 and  the water recycled or discharged  to  sewers or streams.
           This process does  not pose  an  atmospheric  pollution  problem;
however, if not  controlled,  liquid and solid  wastes  could cause water
pollution  problems.
(5)   Air Pollution Engineering Manual. Air Pollution Control District,
     County of.Los Angeles, Public Health Service Publication
     No. 999-AP-40, pp 185-186, 1967.

-------
                                  C-49
 Smelting-Refining Operation

           Pretreatment  of  the  scrap  removes  a portion of the metallic
 and  nonmetallic  impurities  found  in  scrap  and physically prepares  the
 material  for further  processing by the  smelting-refining manufacturing
 operation.   In this operation, additional  metallic  and nonmetallic
 impurities  are removed  and  the composition of the alloys adjusted  to
 produce alloy ingots  of the desired  specifications.   The processes
 employed  to produce the alloy  ingots  are discussed  in the sections  below
 and  shown on the  flowsheet  by Numbers 10 through 13.

           Reverberatory Smelting-Refining  Process  (10).   Brass  and
 bronze alloys of  desired specifications are  produced  by  the  reverberatory
 smelting-refining process.   This  is achieved by the removal  of  metallic
 and  nonmetallic  impurities  from pretreated scrap and  by  the  addition of
 alloying  agents.   The process  steps  are:   (a) charging of the rever-
 veratory  furnace,  (b) melting of  the  charge,  (c) fluxing to  remove  the
 impurities,  (d) alloying to adjust the composition  of the melt,  (e) pouring
 of thr molten alloy,  and (f) casting  of the  molten  alloy into ingots.
          This process  produces large quantities of atmospheric emissions
 and  liquid  and solid wastes.  The atmospheric  emissions  are  composed of
 gases and particulate matter.  The particulate matter  includes  such
materials as carbon particles,  entrained dust, unburned  fuel, and metallic
 fumes.  The gases in the atmospheric  emissions include carbon dioxide and
 carbon monoxide from combustion of the fuel,  sulfur oxides, halogens,
 and nitrogen oxides.   Each  processing step  is a source of atmospheric
 emissions.
          Charging is  a major source  of atmospheric  emissions from the
 reverberatory smelting-refining process.   The type  and condition of the
 scrap are factors that affect the  quantity  and composition of the emissions.
If the scrap is oily,  the emissions will contain,  in addition to the
combustion products,  unburned hydrocarbons  and dust  particles.  When the
scrap contains large  quantities of highly volatile  constituents such as
zinc, heavy evolution  of fumes  will occur.

-------
                                   C-50
           Emissions are also dependent upon factors  such  as  location
 of the charging doors and method of charging.   Overhead charging  results
 in heavy evolution of emissions  containing both gases  and particulate
 matter.   End and side charging results in lower emissions.   Batch
 charging produces large bursts of emissions that are almost  impossible
 to control.
           Melting of the charge  is another major source of atmospheric
 emissions from this process.   These emissions  contain  larger proportions
 of metallic  fumes than those from the  charging step.
           Emissions data are not available for each  individual  step.
 However,  data collected in an earlier  survey of industry^ '  revealed
 that  particulate emission factors for  charging-melting ranges from  11.7
 to 59.0  Ib/ton of feed charged to the  furnace.   These  particulate
 emissions contained,  in some cases,  60 to 90 percent zinc, probably as
 zinc  oxide;  in other cases,  the  particulate emissions  contained 33.7 to
 73.6  percent nonmetallic materials,  16.7  to 52.8 percent  zinc, probably
 as zinc  oxide,  and 0.38 to 4.62  percent copper.   No  doubt, the particulate
 emissions also contained trace quantities of other metallic  materials
 such  as  lead and cadmium.
           Emission factors are not available for the gaseous emissions.
 However,  large volumes of gases  are  evolved from combustion  of the
 fuel  and  other sources.
           Reported particle  size also  varied over a  wide  range, possibly
 because  the  extremely  fine particles may  have  passed through the  filter
medium used  to collect the samples.  In any event, particle  sizes were
 reported  to  be less  than 20 microns  in some cases and  in  others,  less
 than  1 micron.
           The  fluxing  process  step is  a purification or smelting-
 refining  step,  whereby impurities  are  removed  from the melt.  These
materials  are  removed  by the  addition  of  gaseous, liquid, or solid fluxes.
Consequently,  fluxing  can be  a major source  of  atmospheric emissions,
especially in  those  cases  where  gaseous fluxes  are used.  These emissions
may contain  a  wide variety of  metallic constituents  such  as  iron,
(6)  Survey conducted by Battelle's Columbus Laboratories.

-------
                                   C-51
manganese,  silicon, aluminum, copper, zinc, and  lead, along with those
materials from  the flux.  These emissions may be volatilized from  the
melt as  fume or carried from  the melt by entrainment in the gaseous
emissions.  Emission factors  for this step are not available.
          In the alloying step, virgin metal or  specialized scrap  is
added  to adjust the composition of the melt.  Normally, this step  is
not a  major source of atmospheric emissions, unless high zinc alloys
are being produced.  In this  case, large quantities of zinc fumes may
be emitted.
          Metal oxide fumes are produced as the hot metal is poured
through the air into the molds.  Other emissions are also produced,
depending on the type of linings or coverings associated with the mold
as it  is filled with hot metal.  Thus, the pouring step can be a
significant source of atmospheric emissions and will vary depending on
such factors as composition of the alloy, pouring temperature, pouring
rate,  and type of molds.  Raw particulate emission factors collected in
an earlier survey were noted  to range from 0.4 to 10.9 Ib of dust per ton
of product.  These emissions  contained a high zinc content; in one case,
60 to  90 percent.
          Casting is a minor  source of atmospheric emissions.
          Thus, the reverberatory smelting-refining process for the
production of brass and bronze ingots is a major source of atmospheric
emissions   Raw particulate emissions factors (including both fumes and
dusts)  range from 125 to 140  Ib per ton of feed.  Composition will vary
but,  in general, the emissions will contain both metallic and nonmetallic
constituents.   The metallic emissions are composed of,  in addition to
a high concentration of zinc,  varying concentrations of lead, tin,
copper, silicon, and other metal values.   In one case,     the dust
collected in a brass and bronze smelter baghouse contained 45.0 to 77.0
percent zinc,  1.0  to 12.0 percent lead,  0.3 to 2.0 percent tin,  0.05 to
1.0 percent copper,  0.5 to 1.5 percent chlorine, and 0.1 to 0.7 percent
sulfur.  Gaseous emissions contain,  in addition to the  combustion
products,  volatilized organic  materials such as oil and grease,  sulfur
oxides, nitrogen oxides, and hydrogen halides such as hydrogen chloride.
The baghouse is the most widely used pollution abatement device.

-------
                                   C-52
          Liquid wastes generated by this process are primarily
cooling wastewater.  One source is cooling of the ingots by a water spray.
          Significant quantities of solid wastes--slags, flue dusts, and
baghouse dusts--are generated by this process.  In one case,    10,000 Ib
of slag and 4,000 Ib of flue dust were generated in the production of
178,000 Ib of brass ingot product.  Losses designated as gases, dusts,
and others were estimated at 1,600 Ib.
          Thus, the reverberatory smelting-refining process produces
large quantities of potential environmental pollutants.  Therefore,
this process has the potential for the production of serious pollution
problems.

          Rotary Smelting-Refining Process (11).  This process, like
the reverberatory smelting-refining process,  produces brass and bronze
ingots from the various types of scrap.  Capacity of the rotary furnace
used in this process ranges from several tons to approximately 50 tons
of nonferrous metals.  The process steps are:   (a) charging of the scrap
through ports on the side of the cylinder, (b) melting of the charge,
(c) fluxing to remove impurities, and  (d) alloying to adjust composition
of the melt.  Afterwards, the melt is poured and cast into ingots.
          Energy required is the fuel used in the various process steps
and electricity to drive the equipment.  The rotary furnace is direct-
fired using oil or gas as the fuel.
          The process produces significant quantities of atmospheric
emissions, liquid wastes, and solid wastes.  The atmospheric emissions
are generated in each of the process steps.  Since the rotary smelting-
refining process is similar to the reverberatory smelting-refining
process in that both are direct-fired and the same process steps are
employed,  the quantity, composition, and particle morphology of emissions
are comparable.  For example, the raw emissions factor for the rotary
smelting-refining process was reported to be 147 Ib of particulate matter
per ton of feed, whereas the factor for the reverberatory smelting-refining
process was reported to be 156.9 Ib of particulate matter per ton of  feed.
(7)  Spendlove, Max J. , Methods for Producing Secondary Copper, U. S.
     Dept. of Interior, Bureau of Mines, Bureau of Mines IC8002 (1961).

-------
                                  C-53
          Liquid wastes generated by this process are the wastewater
from cooling of the ingots during casting.   Solid wastes include wastes
such as slag and baghouse dusts.
          Thus, the process has a high potential for the production of
serious pollution problems if emissions are not controlled.

          Crucible Smelting-Refining (12).   The crucible smelting-
refining process is employed for producing brass and bronze  alloys from
clean,  well segregated scrap and for refining specialized alloys.  The
process steps are the same for this process as for the other smelting-
refining processes.
          Energy required is the fuel necessary to fire the furnace and
the electricity to drive the equipment.  The furnace is indirect fired
using gas or oil as the source of fuel; thus, the charge never comes  in
contact with the flame.
          The process produces a modest quantity of potential environ-
mental pollutants.  Atmospheric emissions are generated in each
processing step but at a rate significantly less than for the rever-
beratory smelting-refining process.  For example, furnace emissions
factor for crucible-smelting-refining was reported to range from 6.5
to 12.3* Ib of fume per ton of feed^   , whereas furnace emissions  factor
for reverberatory  smelting-refining was reported to range from 125  to
                               (Q\
140 Ib of dust per ton of feedv  .  Using baghouses with collection
efficiencies of 93.7 percent and 96.2 percent,  respectively, the
atmospheric emissions were  lowered  to 0.24  Ib per ton of feed for  the
low zinc alloy and 0.80 Ib per ton  of  feed  for  the high zinc alloy.
Liquid wastes are  generated in the  casting  of the ingots.  Solid
wastes generated by this process include slags  and baghouse dusts.
Composition and particle morphology of atmospheric emissions and
 (8)  Air Pollution Engineering Manual, Air Pollution Control District,
     County of Los Angeles, Public Health Service Publication
     No. 999-AP-40-, p 274, 1967.
 (9)  Industry survey.
 * Higher emissions factor resulted from high zinc content  in the melt
   (24.8 percent vs. 3.8 percent).

-------
                                   C-54
 composition of the Liquid and solid wastes  should  be  comparable  to  those
 from the other smelting-refining processes.
           Although this process  produces  significantly  less  potential
 environmental  pollutants than the above smelting-refining processes,
 improper disposal  of  the pollutants and/or  emitting them to  the
 environment can result  in atmospheric  and water pollution problems.

           Electric Crucible Smelting-Refining  Process  (13).  This
 process  is  used to produce special  high-grade  brass and bronze alloys
 from treated scrap.   The process  involves the  same process steps as
 employed in the other smelting-refining processes.
          Energy required is  the  electricity to drive the equipment and
 process  the alloy.
           Electric crucible smelting-refining  produces  significant
 quantities  of  atmospheric emissions, solid wastes, and  liquid wastes.
 These  emissions and wastes are generated  in the same processing  steps
 as  in  the other processes.   Also,  the  composition will  be similar.
 The  primary difference  is the atmospheric emissions do not contain
 combustion  products since the source of heat for the electric smelting-
 refining process is electricity  rather than fossil fuels.  Thus, the
 quantity of atmospheric emissions,  including both gases and  particulate
 matter,  are significantly reduced.  Data  are not available for the
 gaseous  emissions.  However,  furnace particulate emission factor was
 reported to be  approximately  2.6  Ib per ton of feed.^ '  The baghouse
 removed  96.0 percent of the particulates.*  Other wastes generated by
 the  electric crucible smelting-refining process include liquid wastes
 from cooling of the ingots  during casting and solid wastes such as
 slags and baghouse dusts.
          Although  this  process emits  significantly less particulate
matter than other  smelting-refining processes, there is the potential
 for pollution of air and  water if atmospheric emissions and  liquid
and solid wastes are not  disposed of properly.
* Alloy  contained  3.5  percent  zinc which  accounts  in part  for  the
  low  furnace  emissions  factor.

-------
                                  C-55
             Population of Secondary Brass and Bronze Processors
(1)   Earth  Smelting  Corporation
     99-129 Chapel  Street
     Newark,  New Jersey
     Telephone:   (201) MA2-4908

(2)   Bridgeport  Brass  Company
     Division of National  Distillers
       and  Chemicals Corporation
     30 Grand Street
     Bridgeport, Connecticut   06602

(3)   Bristol Brass  Corporation
     999 Broad Street
     Bristol, Connecticut
     Telephone:   582-3161

(4)   W. J.  Bullock,  Inc.
     Post Office Box 539
     Fairfield,  Alabama

(5)   The Bunting Brass and Bronze Co.
     715 Spencer Street
     Toledo,  Ohio  43601
     Telephone:   (419) EV2-3451

(6)   Cerro  Corporate Brass Company
     Division of Cerro Corporation
     16600  St. Clair Avenue
     Cleveland,  Ohio  44110
     Telephone:   (216) 481-3000

(7)   Colonial Metals Company
     Columbia, Pennsylvania
     Telephone:   (717) 684-2311

(8)   Federated Metals
     Division of American  Smelting
       and  Refining Company
     12 Pine Street
     New York, New York

(9)   Franklin Smelting and Refining
       Company
     Castor Avenue
     East of Richmond
     Philadelphia,  Pennsylvania   19140
     Telephone:   (215) NE4-2231
(10)   Freedman Metal  Company
      310 McGinnis  Boulevard
      Brooklyn, New York  11222
      Telephone: EV9-4131

(11)   General Copper  and Brass
        Company
      Post Office Box 5353-D
      Philadelphia, Pennsylvania
      Telephone:  SA6-7111 (215)

(12)   Benjamin Harris & Company
      Eleventh and  State Streets
      Chicago Heights, Illinois

(13)   Henning Brothers & Smith,
        Inc.
      91-115 Scott  Avenue
      Brooklyn, New York

(14)   K. Hettleman  & Sons
      Division of Minerals &
        Chemicals
      Phillip Corporation
      Ninth Street  and Patapsco Ave.
      Baltimore, Maryland  21225
      Telephone:   (301) 355-0770

(15)   Holtzman Metal Company
      5223 McKissock Avenue
      St. Louis, Missouri 63147
      Telephone:   (314) CH1-3820

(16)   H. Kramer & Company
      1339-15 West  21st Street
      Chicago, Illinois  60608
      Telephone:  CA6-6600

(17)   Lewistown Smelting and
        Refining Inc.
      Post Office Box 708
      Lewistown, Pennsylvania
      Telephone:   (713) 543-5631

(18)  Magnolia Metal Company,  Inc.
      Magnolia Park
      Auburn,  Nebraska
      Telephone:   (412) 274-3152

-------
                                   C-56
 (19)   Metal  Bank  of  America,  Inc.         (29)  U.  S. Metal Products
       6801  State  Road                            Company
       Philadelphia,  Pennsylvania   19135        Post Office Box 1067
       Telephone:   (215)  332-6600               Erie, Pennsylvania  16512
                                               Telephone:  (814) 838-2051
 (20)   North  American Smelting Company
       Post Office Box  1952
       Wilmington,  Delaware
       Telephone:   OL4-9901

 (21)   Northwestern Metal  Company
       North  27th  Street
       Lincoln, Nebraska
       Telephone:   434-6341

 (22)   Phelps Dodge Refining Corporation
       300 Park Avenue
       New York, New  York
       Telephone:   751-3200

 (23)   Riverside Alloy Metal Division
       H. J.  Porter Company, Inc.
       309 Porter Building
       Pittsburgh,  Pennsylvania  15219
       Telephone:   (412) 391-1800

 (24)  Rochester Smelting and Refining
        Company,  Inc.
       Post Office Box 547
      Rochester, New York

 (25)  Roessing Bronze Company
      320 Barbour
      Pittsburgh, Pennsylvania

(26)  The George Sail Metals Company,
        Inc.
      2255 E. Butler Street
      Philadelphia, Pennsylvania  19137
      Telephone:    (215) PI3-3900

(27)  SIPI Metals Corporation
      1722 N. Elston Avenue
      Chicago,  Illinois

(28)  Solken-Galamba Corporation
      Second and  Riverview Streets
      Kansas City, Kansas  66118
      Telephone:   (913) MA1-4100

-------
SCRAP PRETREATMENT
MECHANICAL
E.ECtHlCAL CONDUCTORS 	
STRIPPING

AMD OTHER BULKT 	 -\ BPIOUETTING
SC««P


1 -JUKI
TURNINGS. BORINGS
C 'N'M ITEVS
LEAD, SO^OEH , BABBIT T -
FUEL 	
GONTAull.NATCD SCRAP *
rua — •
CHIPS
AJR.FLU'.GOKE.V/ATER 	
SLACS.WIMMIK6S C
»ES'OUES
WATTS 	 -
SM.MNG^SW.LS C
9
SHREDDING

»«„««
O ... . 	 ^_
p


'YROMEIALLUBGlCAL
O
SWEAtlNG
/LEAD, \
1 SOLDE", 1
\6ABar T /
6
BURNING

7
DR1ING

B
CUPOLAING
HYOTOMEWLLU
9

o
b
p
o

X /CUPOLA \


•H V'-l OICCHt-TIBH ( 0*11 1 »«««fO
SMELTING/REFINING
1
r ALLQTIHG AGENT
1 ' r- FUJ*
1 > — FUEL Q
Q
1 RŁVE«BŁOAIORY O
Swutc-flEFnriG
! 	
• FLU« (-1
1 i.<-Futi PA
1 i , , -. Rf>T»!T« ^ .

| ^ 	 AiLOTINC AGENT / m0, \
i ;j— FUEL P^ V INGOTS J
€i rjiiirjBif $>
\ ' I svu.TriG-«tri«i6 	 »

j . r— ALLOTIN6 AGENT !
l?m»rra«:,r b k
1 SMainG-ncrMiG f
1 .
1
i • :
1 • ;
1
| LEGEND . i
1 . ;
1 r> ATMOSPHERIC
1 ° EMISSIONS
| A. LIOUIO UVASTES
1 O SOLIO vwsrss
1 ' X* \ PRODUCTS OS SECONOARr
/ \ RAW MATERIAL TOR USE SIGNATURE 3iv DATE Slf\ BATTCLI.C MEMORIAL INSTITUTE

\ / STAMIAUGH •• •• ""-DOnCC r QDnM7C CLT^MrMT

f ^\ METALS IMDUSTRY
\ J 	 — D 79986
a 7 6|S^4 3 2 1
O
 I

-------
                                   C-58

               PROCESSING DESCRIPTION OF THE CADMIUM SEGMENT
                OF THE SECONDARY NONFERROUS METALS INDUSTRY

           Cadmium Is a byproduct of the primary zinc system.   During 1971,
 total U.S. cadmium production was 7.9 million pounds of which the,secondary
 cadmium segment production was 400,000 pounds or about 5 percent of the total.*
           Cadmium is a poisonous metal.  Ingestion as fumes or in other
 forms is known to cause the painful "itai-itai" disease.  Hence,  it is
 generally considered both necessary and safe to use a replacement metal
 that provides all the excellent properties of cadmium without its
 toxicity.   Zinc is a possible replacement metal.

                               Raw Materials

           Raw material is available both as old and new scrap.   Examples
 of  old  scrap  are:  cadmium plated parts from junked automobiles,  nickel-
 cadmium batteries,  cadmium coated electrical contact points,  and  used
 cadmium alloys.   New scrap,  which constitutes only a small  percentage  of
 the total,  consists  of factory rejects from manufacturing of  bearings
 etc., Ni-Cd battery  rejects,  and scrap from plating (electrodeposition)
 cells,  and  scrap  solder  used to solder aluminum.
           In  the United  States,  cadmium is  not  recovered from junked
 automobile parts because  of  economics.  Also, used  nuclear  reactor
 control  rods  (containing  80  percent  cadmium  and 20  percent  silver and
 indium)  are not processed  by  the  secondary  cadmium  industry.  Instead
 these rods are  sent  to fuel  processors  (e.g.,  Mallinckrodt  Chemical  Works,
 St. Louis, Missouri).

                                Products

          Products of  the  cadmium  segment are as follows:
           (1)   Recast  cadmium metal  (sticks  and balls)
           (2)   Recast  cadmium alloys.
* U. S. Bureau of Mines

-------
                                 C-59
                            Process  Description

           The  three manufacturing operations  employed  in scrap processing
 are scrap pretreatment,  smelting/refining,  and casting—as  described  below
 and as  shown on the flowsheet  of  this  segment.   Of  these, the major
 operation—smelting/refining—involves pyrometallurgy.

 Scrap Pretreatment  Operation

           The  only  process  in  this  operation  is  the vapor degreasing  of  alloy
 scrap as  noted by Process 1.

           Vapor Degreasing  Process  (1).  This  process  removes  oil  and
 grease .adhering to  the scrap alloys.
           The  process steps are:  (1) heating  solvent to  generate vapors
 (perchloroethylene), (2) circulating solvent vapors through the scrap in a
 pot, and  (3) condensing  solvent for reuse.
           Heat  energy is the main requirement of this  process.
           The major waste generated is  the  liquid waste—grease/oil residue
 from the  solvent regeneration  pot.  The quantities of  this waste are  very
 small and  are usually either incinerated at the municipal incinerator or
 dumped into sewer lines.  Other waste  generated is atmospheric emission
 composed  of organic vapors.
           The potential  for pollution  from  this process  is not  significant,
 and is regulated in many states.

 Smelting/Refining Operation

           Two processes—melting or  retorting—are used  to recover cadmium
 from scrap.

          Alloy Smelting/Refining Process (2).  This process purifies the
pretreated alloy scrap.
          The process steps  involved are:  (1)  heating the alloy scrap,
 (2) adding the  flux, (3)  skimming the slag,  and (4)  pouring  the molten

-------
                                  060
metal Into molds for casting.
          Heat energy Is utilized in the process.
          Wastes generated are atmospheric emissions containing metal fumes
and solid wastes consisting of slag.  The fumes are not significant to
cause any pollution.  The slag is recycled and ultimately disposed of in
a landfill.  Thus, the process has a low pollution potential.

          Retort Smelting/Refining Process (3).  This process recovers pure
cadmium by distilling cadmium alloys.
          The process steps are: (1) charging the retort, (2) melting the
charge, (3) vaporizing the cadmium, (4) condensing the cadmium, (5) pouring
the molten metal,  (6) casting the ingots, and (7) discharging retort
residue for shipping to residue processors.
          Heat energy is utilized in the process.  The potential pollutant
generated by this process is atmospheric emissions containing cadmium fumes.
          If properly controlled, this process has little potential for
producing serious pollution problems.

          Melting Process (4).  This process purifies the scrap cadmium
metal collected from electrodeposition cells as sticks and rods.  These
rods and sticks are usually contaminated with acid salts or mixed with
zinc occasionally.
          The process steps are: (1) charging scrap to pot, (2) melting
the charge, (3) adding the flux, (4) chlorinating when required for zinc
removal, (5) skimming the slag, (6) pouring into molds, and (7) casting
the ingots.
          The process utilizes heat energy.
          Wastes generated in the process are: (1) atmospheric emissions
containing cadmium fume, zinc chloride dust when dezincing operation is
done,  (2)  solid waste consisting of slag, and (3) liquid waste composed
of cooling water which may be recycled.  The zinc chloride dust is
collected with a baghouse.  Slag generated is about 2000 pounds per year
in a plant producing 200,000 pounds of cadmium per year.  The slag which
contains some cadmium is disposed of in a landfill.

-------
                                  C-61
          Thus, this process has the potential for the production of
pollution problems.


Casting Operation


          This is a simple operation and consists of one process step.


          Casting Process (5).  The molten alloy and the molten metal
from the retorting and melting processes are cast into required shapes
by this process.  The processing steps consist of pouring the molten
material into molds and casting with water cooling.
          Electrical energy is used to circulate cooling water and
auxiliary equipment.
          No wastes are generated in the process.  The process has no
pollution potential.


              Population of Secondary Cadmium Processors
          (1)  Belmont Smelting & Refining Works
               320 Belmont Avenue
               Brooklyn,  New York

          (2)  Joseph Behr & Sons,  Inc.
               1100 Seminary Street
               Rockford,  Illinois

          (3)  United Refining and  Smelting Company
               3700-20 N.  Runge Avenue
               Franklin Park,  Illinois  60131

          (4)  Wolverine  Metal Company
               6500 E.  Robinwood Street
               Detroit, Michigan

-------
8-7 6 5 4 3
SCRAP PRETREATMENT SMELTING / REFINING CASTING
	 , ^A ,,-^ TA- P
ivnn^R 	 «™ ^ r 	 -C'REJ^TED\ • ? -1.1-0. 6
COOLING ««7EH i 	 • DECREASING 1 SCPW 1 ^J^. 	
j— MEAT JO j— COOLINC
5 . 5
x^ — >.
L; 	 J RETWT \
\ HESIOUt 1
E-MLORINE V /
au« « N^ ^X
-HE" /-*
4 X
SCB«I> xEUL W
(USEO WU.S, STICKS) • '• • • ""-TING 	 •

LEC5ENO
O 'TUOSPHOIC EMISSIONS
A LIQUID WASTES
O SOLID WASTES
O'ROOuCTS OR SŁa
MATERIALS FOR a
INDUSTRIES
j J IHTEBUEIMTE PR
i

fHJjyr tcCJrA
VB*LCS ANoy


***(*y RAW «IGNATUHB JIV OATt /W\ •ATTO.Le urunaiAt iMTrm.rrT
>E W OTHER 57?^ «Ł«, c rrr7i \wt ooujmu* L»O*ATO*«>
^,iHr - - «~cADMiUM °r™TNTTir~

— • 1 ML oLUUMUAl (Y NCJNr tH
ROl K MFTAI R iwpi IQTRY

OOuCT — =-™»« .. « _« „
Sg— ~ • D 79986 565 - -
D
C
n
— i
N3
e
A

-------
                                   C-63
              PROCESS DESCRIPTION OF THE COBALT SEGMENT OF
                THE SECONDARY NONFERROUS METALS INDUSTRY

          The volume of scrap available to the cobalt segment of the
secondary nonferrous metals industry is estimated at two million pounds
annually.  The majority of this is recovered as cobalt-base or nickel-
base alloy in the United States.  Some of the refined high grade cobalt
scrap is exported to Japan for recovery of pure metal.  Approximately
5 to 10 percent of the scrap cobalt is used in the production of chemicals.
          Emissions from the cobalt segment include (1) water wastes from
vapor degreasing, pickling and vacuum melting, and (2) minor quantities of
wastes to the ambient air and land from other process steps.  Generally,
these wastes are effectively controlled and therefore their potential
for pollution is minimized.  However, if the control methods are rendered
ineffective, a moderate potential for pollution of mainly the waterways
exists.

                              Raw Materials

          Raw materials consist of cobalt bearing superalloy grindings
and turnings and scrap superalloys (stellite, etc.) from jet engine
components.   The total scrap available can be classified into cobalt-
base supe -Hoy scrap containing 50 to 60 percent cobalt and nickel-
base scrap consisting of 10 to 20 percent cobalt.   A quantitative breakdown
of the scrap into these categories is not available because of the lack
of information,  published or otherwise.

                                Products

          Products from the secondary cobalt  industry are as follows:
          (1)   Pig alloys (stellites,  etc.)
          (2)   Refinery grade cobalt scrap.

-------
                                   C-64
                            Process Description

           Processing of scrap cobalt alloys involves three major operations-
 scrap pretreatment, smelting, and casting/refining.   These operations are
 shown in the attached flowsheet for this segment.

 Scrap Pretreatment Operation

           A complex series of processes are involved in this operation.
 Some companies specialize in these processes and produce a clean scrap as
 their product for sale to smelting facilities.
           The four processes (Process 1 through Process 4) employed  under
 this operation are described below.

           Hand Sorting Process (1).   This  process identifies the scrap
 components and separates them into cobalt-base,  nickel-base and  nonpro-
 cessable  components.   The hand sorting operation is  also aided by
 identifying the source of scrap and  storing them in  different lots to
 avoid mixing.
           The  processing steps are:  (1)  spreading the dirty scrap on
 the  floor,  and  (2)  visually  identifying and segregating the scrap.
           Human labor  is the only  requirement of this process.
           Waste produced is  a minor  amount  of dust which is  collected  as
 sweepings  and  disposed  of  in trash cans  and ultimately  in  a  landfill.
           The  process has  no  potential  for  pollution.   The cobalt free
 scrap  collected in  the  process  is sent  to other  processing facilities.

          Vapor Degreasing Process (2).  This process removes the oil and
 grease from the scrap by using hot vapors of perchloroethylene.
          The processing steps are:  (1) charging dirty  scrap  to degreasing
unit,  (2) heating to generate and circulate hot solvent vapor, and (3)
discharging the  degreased  scrap to the blasting box.
          Heat  energy is the main energy requirement of  the process.

-------
                                   C-65
           Waste emissions include minor amounts  of solvent vapor to the
 atmosphere and grease and oil wastes  to be incinerated or disposed of in
 severs.
           Since the process is a closed loop  operation,  the only signifi-
 cant waste with a potential for pollution is  the grease  and oil from the
 solvent  recovery unit.

           Blasting Process (3).   This  process cleans  the surface of the
 scrap material of all extraneous dirt,  oxides, and rust.
           The  process steps are:  (1) blast the scrap  either batchwise or
 continuously with grit,  and (2)  discharge the clean scrap.
           The  process requires  electrical energy to obtain compressed
 air  used  in the blasting equipment.
           Since the process is  a closed loop  operation,  no significant
 wastes are generated.  Hence the process  has  no  potential  for pollution.

           Pickling  and Chemical  Treatment  Process  (4).  Because the alloy
 produced  as the final product of  this segment  has  to be  free of all
 impurities, the pickling process  is utilized  to  clean  the  scrap of
 all  residual oxide  coatings.  The chemical  treatment operation  is a trade
 secret and  is  known  to remove lead from the scrap.
           The  process steps  are:  (1) treating  the  scrap with a  mixture
 of acids  to remove rust  and  oxides, (2)  treating with  a chemical to
 remove lead, and  (3) washing the scrap with water.
          The  process requires electrical energy to drive pumps and
 other auxiliary  equipment.
          Waste discharges include (1) small amount of acid fumes and
 (2) acidic wastewater containing metallic Impurities.
          The  acidic wastewater is neutralized before discharge to  the
waterways or sewer and hence has a reduced pollution potential.   The
acid fumes are usually not substantial to create serious ambient air
pollution problems.

-------
                                  C-66
SmeIting/Refining Operation

          The treated scrap  Is virtually free of all impurities except for
some dissolved gases which are removed by smelting/refining.  Usually this
operation is carried out in  an electric arc vacuum furnace or a vacuum
induction furnace.

          Vacuum Melting Process  (5).  This process refines the scrap by
removing volatile impurities under the influence of both heat and vacuum.
          The process steps  include:  (1) charge scrap to the vacuum
furnace, (2) evacuate the system, (3) melt the scrap by electric arc or
induction, and (4) discharge the molten alloy into molds.
          Large amounts of electrical energy are used both to create
vacuum and heat the charge.
          No significant wastes are produced.  The vacuum pump discharge
is contaminated with traces of gaseous wastes too insignificant to
constitute any pollution.  Vaporized heavy metals and other potential
pollutants are trapped by the vacuum pump.

Casting Operation

          This is the final operation of the secondary cobalt industry.
The castings produced by this operation are used as pig alloys or if the
quality of the alloys produced is refinery grade cobalt alloy, it may
be shipped to a cobalt metal recovery facility.

          Casting Process C6J.  This process produces castings of pig
alloy from the molten charge obtained in vacuum melting.
          The process steps are: (1) pouring the molten metal into molds
and (2) casting the ingots.
          Energy requirements of this process are not significant.
          No wastes are produced in the process.

-------
                         C-67
       Population of  Secondary  Cobalt Processors
Alloy Metal Products,  Inc.
626 Schmidt Road
Davenport, Iowa 52808
Telephone: (319)  324-3511

Max Zuckerman and Sons
Music Fair Road
Owings Mills, Maryland 21117
Telephone: (301) 484-0400

Pfizer Metals and Composite Products
235 E. 42nd Street
New York, New York 10017
(Processing only inhouse scrap)

Union Carbide Stellite Division
Kokomo,  Indiana
Telephone: (317) 457-8411

-------
            8  .
              SCRAP  PRETREATMENT
D
C:
SMELTING/REFINING
CASTING
           8
                                                                                                                      LEGEND


                                                                                                                   
-------
                                   C-69
               PROCESS DESCRIPTION OF THE COPPER SEGMENT
                OF SECONDARY NONFERROUS METALS INDUSTRY
          Tonnage-wise, the copper segment (which produces refined
copper) constitutes one of the major segments of the secondary
nonferrous metals industry.  Based on 1972 data   ,  1,210,070 tons of
copper were recovered from scrap.  Of this production, 280,730 tons were
recovered by this segment and 571,095 tons were recovered by the brass
and bronze segment.  An additional 381,790 tons were recovered by the
primary nonferrous metals industry.  Emissions from the copper segment
of the secondary industry include:  gases and particulate materials
which are emitted to the atmosphere, liquid wastes emitted to the water
system, and solid wastes emitted to the land.
                             Raw Materials

          Sources of raw materials to this industry include both new
and old scrap.  New scrap, which accounted for approximately 21 percent
of the copper recovered from the scrap in 1972, refers to scrap produced
in the manufacturing process by a fabricator of a finished product.
Old scrap, comprising obsolete, worn out, or damaged articles, accounts
for approximately 69 percent of the copper recovered by the copper
segment in the U. S.
          Segregating scrap according to classification standards is
one of the most important steps in the recovery of secondary metals.
                                                           (2)
Currently, copper-bearing scrap is classified into 54 types    as shown
in Table III.
          Copper scrap as received generally contains metallic and
nonmetallic impurities.  Included among these are:  lead, zinc, tin,
antimony,  iron, manganese, nickel, chromium, precious metals, and
organic compounds such as plastics, oils, and greases.  These impurities,
which are removed during the recovery of copper, constitute major sources
(1) "Copper industry in January 1973", Mineral Industry Surveys, U. S.
    Dept. of the Interior, Bureau of Mines, Washington, D. C.
(2) Circular NF-58, National Association of Waste Materials Dealers, Inc,

-------
                                   C-70
of emissions  to  the  environment,  if not collected and disposed of by
an acceptable method or  recovered  as by-products.

                               Products

           Products from  the  copper segment of the secondary nonferrous
metals  industry  include:
           (1)  Babbit, lead,  and  solder recovered from the
               sweating  process.   This mixture of materials may
               be made into  white-metal alloys, used for  lead
               and tin additions  to copper base alloys, or sold
               as produced to a refiner.
           (2)  Copper powder
           (3)  Copper shot
           (4)  Fire-refined  copper
           (5)  Electrolytic-refined copper
           (6)  Oxygen-free high conductivity copper  (O.F.H.C.)*

                          Process  Description

           The recovery of copper  from scrap involves three manufacturing
operations:  scrap pretreatment,  smelting, and refining/casting.  These
operations and the individual processes under each operation are shown
on the  flowsheet entitled "Copper  Segment of the Secondary Nonferrous
Metals  Industry".

Scrap Pretreatment Operation

          Copper scrap is pretreated prior to smelting to remove some
of the metallic and  nonmetallic impurities or contaminants and to
physically prepare the material for further processing.  Three types of
processing--mechanical, pyrometallurgical, and hydrometallurgical--are
used.  The pretreatment process varies according to the type of scrap.
The individual pretreatment processes are numbers 1 through 14 on the
segment flowsheet.
* O.F.H.C. is a  trade name of  the U. S. Metals Refining Company.

-------
                                   071

          Stripping Process (1).  Insulation and lead sheathing are
removed from electrical conductors by special stripping machines or
by hand.
          Energy demand is that needed to drive the equipment.
          The process produces quantities of solid wastes.  These
wastes include lead and insulation.  The lead is probably sold to a
secondary lead smelter, whereas the insulation may be sent  to a  landfill
or incinerator.
          The process has little potential for production of serious
pollution.

          Briquetting Process (2).  Wire, thin plate, wire  screen, and
other bulky scrap are pressed into briquettes, bales, or bundles by
hydraulic presses.  In this form, the scrap is easier to handle, store,
and load into the furnace.
          Energy required is that necessary to drive the presses.
          The process produces essentially no wastes or emissions.
          The process has no potential for production of pollution
problems.

          Shredding Process (3).  Large  items are reduced in size by
pneumatic cutters, electric shearing machines, or manual sledging.
The smaller pieces are easier to handle.
          Energy demand is limited to  that needed to drive  the equipment,
          The process may produce a small quantity of atmospheric
emissions consisting of dusts with  an approximate composition of the
scrap.  Collection of  these dusts may be via a baghouse.  Most likely,
the emissions are not  controlled.
          The process has essentially no potential for production of
pollution problems.

          Crushing Process (4).  Brittle spongy turnings, borings, and
long chips are densified by the crushing process.  The process steps
are:   (a) crushing in hammer-mills or  ballmills to reduce bulk, and
(b) running over a magnetic separator  to remove tramp iron.

-------
                                   C-72
        Energy demand  is  that  required  to  drive  the equipment.
        The  process  produces small  quantities of  atmospheric emissions
consisting  of dust  particles  composed  of  dirt, organic compounds from
the  scrap,  heavy metals,  and  solid wastes.  Most  likely,  the area may be
hooded  to carry the dust  away from the vicinity  of the crushing.
        The  process  has little or no  potential for causing serious
pollution problems.

        Grinding Process  (5).   Prills or metallics are seperated from
the  gangue  in slags,  drosses,  skimmings,  foundry  ashes, spills, and
sweepings by  the grinding process.   The process  steps are:  (a) grinding,
(b)  screening, and  (c) gravity separation.
        Energy required is that to  drive the equipment.
        The  process  produces atmospheric emissions, liquid wastes, and
solid wastes.  The  atmospheric emissions  are dusts from the grinding
and  screening steps.  These dusts  may  contain, in addition to fluxing
materials and  dirt, small quantities of heavy metals.
        The  liquid wastes  containing both  dissolved and suspended solids
are  generated  in the  gravity  separation step.  The solid wastes are
generated during the  screening step.
        As significant quantities of atmospheric emissions, liquid wastes,
and  solid wastes are  generated by  the  grinding process, the process has
a potential for the production of  pollution problems.

        Muffle/Kiln  Burning/Drying  Process (6).  Much of the scrap contains
oil, grease,  cutting  fluids,  insulation,  and moisture.  These components
may be  removed prior  to smelting by the muffle/kiln/burning/drying
process.  The process steps are:   (a)  charging of the scrap to the
muffle  or kiln, and (b) heating to remove the organic contaminants and
moisture, afterwhich  the  treated scrap is removed for further processing.
        Energy required for this process is from gas or fuel oil to heat
the furnace and electricity to drive the  equipment.

-------
                                  C-73
          The process produces significant quantities of atmospheric
emissions.  These emissions consist of both gases and particulate
matter.  The gaseous emissions are composed of the gases from combustion
of the fuel and the organic contaminants.  Depending on the organic
contaminants, the gases may contain such materials as the chlorides,
sulfur oxides, fluorides, and hydrocarbons.  The particulate matter
(fume and dust) is composed of a variety of'heavy metals depending on
the composition of scrap.  Examples of heavy metals which may be found
in the particulate matter are copper, zinc, tin, and lead.
          Emissions data are not available for the burning/drying of
all types of scrap.  However, from burning of insulated wire,
particulate emissions are estimated at 275 Ib per ton of wire processed
or an annual emissions total of 41,000 tons based on treating 300,000
tons of insulated wire.
          A variety of methods may be employed to control the atmospheric
emissions.  Included in the list are afterburners to destroy the
hydrocarbons and other organic materials, wet scrubbers to remove the
particulate matter and toxic gases, and baghouses to remove the
particulates.
          In view of the toxic and hazardous nature o'f the atmospheric
emissions, this process could be a source of serious pollution problems
if the emissions are not controlled.

          Sloping Hearth Sweating Process (7).  Scrap such as journal
bearings, radiators, and lead-sheathed cable contains lead, solder, or
babbitt which would contaminate the melt.  These contaminants are removed
by the sloping hearth sweating process.  The process steps are:
(a) charging the preheated furnace with scrap, (b) melting the low-
melting constituents,  (c) raking the sweated scrap over the hearth  to
remove all of the low-melting alloys,  (d) collecting the solder, lead,
or babbitt in a collecting pit, and (e) removing the sweated scrap for
further processing.
          Energy for this process is from gas to fire the furnace.
(3)  Vandegrift, A. E.,  et al., Particulate Pollutant System Study,
     Handbook of Emissions Properties, Midwest Research Institute,
     Kansas City, Missouri, Volume III, p 406 (May 1, 1971).

-------
                                   C-74
           In addition to the lead, solder,  or babbitt which are
 recovered for subsequent use or sale, the process produces atmospheric
 emissions.  These emissions are composed of gases and fumes.   The gases
 contain the products from combustion of the fuel and any organic  matter
 present in the scrap.  Particulate matter is composed of such heavy
 metals as lead,  tin, antimony,  and copper,  and organic materials  such
 as soot.
           Emissions data are not available  for the sweating of the
 various types of scrap.   However,  the sweating of radiators results
 in the evolution of 15 Ib of particulate matter per ton of scrap.
           Emissions may  be controlled by baghouses,  wet scrubbers,
 and  electrostatic precipitators.
           Due to the hazardous  nature of some of the pollutants and
 the  quantity  emitted, this process has a potential for the production
 of serious pollution problems.

           Reverberatory  Sweating Process (8).   For removal of solder
 from  scrap which is difficult to sweat,  i.e.,  the solder  remains  in
 seams  and  folds  when melted,  the reverberatory sweating process may be
 employed.   For this process  a reverberatory  furnace  with  a shaking
 grate  is  used.   The molten solder  removed from the items  by a shaking
 motion falls  to  the floor and flows to the  collecting sump.   The
 process steps are:   (a)  charging the furnace, (b) heating the scrap
 to melt the low-melting  components,  (c)  shaking  to remove  the low-melting
 components, and  (d)  collecting  the  low-melting material.   The sweated
 scrap  is  subsequently removed for  further processing.
           Energy demand  is from the fuel oil  or gas  to heat  the direct-fired
 reverberatory  and electricity to drive  the equipment.
           Waste  materials  produced  by  this process are  atmospheric
emissions  consisting  of  gases and particulate  matter.   Composition  of
 these  emissions  is  similar to those  from the  sloping hearth smelting
process.   In  fact,  if  the  same  type  of  scrap were  sweated  by  both
processes, the emission would be essentially  identical with the possible
exception  that the  emissions from  the  reverberatory  sweating  process may

-------
                                  C-75
contain some dust resulting from shaking action.  This dust is carried
from the furnace by entrainment in the combustion gases.
          Particulate emission factor for reverberatory sweating
process is estimated at 15 Ib/ton of radiators.  The factor may be
lower or higher for other types of scrap.
          Emissions are controlled with the same equipment as is used
for other sweating processes.
          Atmospheric emissions produced by this process could cause
pollution problems.

          Pot Sweating Process (9).  Removal of low-melting constituents
from copper scrap is achieved by the pot sweating process.  The process
steps are:  (a) dipping the scrap into a pot of molten alloy,
(b) melting the low-melting constituents, and  (c) removing the sweated
scrap from the pot.
          Energy required is fuel--gas or oil--necessary to keep the
pot of alloy molten.
          Potential pollutants generated by this process are atmospheric
emissions containing fumes and possibly some gases if the scrap to be
sweated contains any organic matter.  Composition of emissions and
emission factors should be comparable to those from other sweating
processes.
          The process has the potential for producing pollution problems,
as well as hazards to the operators of the equipment.

          Tunnel Sweating Process (10).  This process is used by some
smelters to sweat copper scrap.  The process steps are:  (a) load
scrap placed in trays or on racks onto a continuous conveyor passing
through the tunnel furnace, (b) remove the major portion of the low-
melting constituents by passing the scrap through a heated tunnel furnace,
and (c) dump hot partially sweated scrap onto tilted screen to remove
remaining low-melting constituents.  The molten low-melting constituents
are collected in a floor sump.
          Energy required is from oil or gas to heat the scrap and
electricity to drive the equipment.

-------
                                  C-76
          This process produces atmospheric emissions composed of
gases (combustion gases from the fuel and gases from burning or
volatilization of organic contaminants in the scrap), and particulate
matter (fumes and possibly some dust from dropping of the partially
sweated scrap onto the screen).  The individual components in the
emissions will be the same as those in emissions from other similar
processes.
          Particulate emission factor may be somewhat higher for this
process (>15 Ib/ton of scrap sweated) as the partially sweated scrap is
exposed to the atmosphere while hot.  This results in rapid oxidation
of molten metal and subsequent volatilization of the oxides as fumes.
          The process produces atmospheric emissions which can cause
pollution problems.

          Ammonium Carbonate Leaching Process (11).  The copper values are
                                                                     (45)
leached from copper scrap by the ammonium carbonate leaching process.  *
The process steps are:  (a) heating copper scrap in an ammonium carbonate
solution while sparging the solution with air,  (b) separating the crude
copper ammonium carbonate solution from the leach residue, and (c) puri-
fying the clarified copper solution.  Copper values are then recovered
from this intermediate product by the steam distillation process (12)
or by the hydrothermal hydrogen reduction process  (13).
          The energy required for this process  is that necessary to
heat the solution and to drive the equipment.
          The potential environmental pollutants generated by this
process are atmospheric emissions, liquid wastes, and solid wastes.
The atmospheric emissions are gases emitted from the leaching of the
copper scrap with ammonium carbonate in the preparation of the crude
copper ammonium carbonate solution.  These emissions contain ammonia,
(4) Kunda, W., et al.,  "Production of Copper from the Amine System",
    presented at Extractive Metallurgy Division Symposium on Copper
    Metallurgy, Denver, Colorado, February 15-19  (1970).
(5)  Ryan, V. H., et al., Production of Copper Powder:  AICE,
     National Meetings, Washington, D. C., March 9,  1954.

-------
                                  C-77

water vapor, carbon dioxide, nitrogen, and excess air.  Before being
emitted to the atmosphere, the gases are cleaned via a wet scrubber
which removes the ammonia and carbon dioxide.
          Solid wastes generated by the process are the leach residues
and residues from the various stages of solution purification.
          Essentially the only liquid wastes generated are those
adsorbed on the surface of the discarded residues.  Other liquid
effluents generated are recycled to the process.
          Thus, this process has essentially no potential for the
production of atmospheric pollution problems.  The only atmospheric
emission generated is nitrogen enriched air  from the  leaching operation.
However, there is a potential for water pollution resulting  from disposal
of the  leach residues from the ammonium carbonate leaching of the copper
scrap and the disposal of purification residues.  Pollution  problems
resulting from disposal of liquid wastes are negligible as essentially
all of  the  liquid effluents are recycled.

          Steam Distillation Process  (12).   Copper oxide  is  precipitated
from  the copper solution  prepared from the  ammonium carbonate leaching
process by  the steam distillation process.   The process steps are:
 (a) heating  the copper solution to  precipitate  the copper,  (b)  separating
copper  values from slurry,  (c) drying  the precipitated copper oxide,
and  (d) recycling  the aqueous effluent to the ammonium carbonate
leaching process to prepare  fresh copper.   The  copper oxide  is  an
intermediate product for  the production of  copper by  such processes
as  (15) and  (24).  Step  (a)  is conducted  at atmospheric pressure  (boiling)
or under pressure.
          The energy requirement  is that  to produce  the steam to heat
 the  calciner.
          The process produces some atmospheric emissions from  the  copper
ammonium carbonate decomposition  step  (Step a),  and  during  drying  of the
 copper oxide,  and  possibly some  liquid wastes.   The gaseous emissions
 from Step  (a)  are  composed  of essentially water vapor,  ammonia, and
 carbon dioxide.  These gases may  contain  a  trace of  copper  carried
 from the  system  by entrainment  in the gaseous  emissions.   Those emissions

-------
                                  C-78
from drying of the copper oxide contain gaseous emissions composed of
water vapor, carbon dioxide, and possibly some ammonia, and particulate
emissions consisting of essentially copper along with trace quantities
of other metals found in the copper oxide as impurities.
          Control of the atmospheric emissions should be possible by
using a wet scrubber for controlling those from Step (a), and by using
a wet scrubber or baghouse  to control those from the calciner.
          The liquid wastes are dilute ammonium carbonate solutions from
washing the precipitated copper oxide.  These contain, in addition to
ammonium carbonate, copper  compounds along with trace quantities of
impurities associated with  the copper.  In most cases, these wastes
can be recycled.
          Because of the small amount of wastes produced by this process,
it is expected that pollution problems associated with the wastes are minor.

          Hydrothermal Hydrogen Reduction Process (13).  The copper value
is precipitated as metallic copper from the ammonium carbonate leaching
process by the hydrothermal hydrogen reduction process.  The process
includes fhe following process steps:   (a) heating the copper solution
in an autoclave v.'ith hydrogen at an elevated temperature and pressure to
precipitate the copper,  (b) removing the stripped liquor from the
metallic copper,  (c) washing the copper free of adsorbed liquor,  (d) drying
and sintering the copper powder under a hydrogen atmosphere,  (e) pulver-
izing the sinter, and  (f) screening the powder.^ '  The  reduction of
the copper solution is conducted at approximately 325  F  and 500 psig of
hydrogen.  The stripped  liquor is recycled to produce more copper
solution by the ammonium carbonate leaching process.
          The energy requirement is that needed to heat  the copper
solution in the reduction step, to dry and sinter the  copper product,
and to drive the  pulverizing and screening equipment.
          Atmospheric  emissions and possibly liquid emissions are
generated by this process.  Sources of atmospheric emissions are
 (1) drying and sintering of the copper powder,  (2) pulverizing and
 (6) Kunda, W.,  et  al.,  "Production of  Copper  From Amine  Carbonate
    System",  1970  Extractive  Metallurgy  Division Symposium  on Copper
    Metallurgy,  Denver,  Colorado,  pp 40-43  (1970).

-------
                                  C-79

screening of the copper sinter, and (3) reduction of the copper solution.
The emissions from drying and sintering of copper powder contain water
vapor, hydrogen, ammonia, and carbon dioxide as gases, and possibly
particulates of copper powder or copper oxide.  Those from the
pulverizing and screening of the copper sinter contain particulates
of copper.  The gas in these emissions is entrained air.  Hydrogen and
water vapor are emitted from reduction of the copper solution.
          Liquid wastes are ammonium carbonate solutions containing such
metal value as copper, nickel, lead, and zinc.  Normally, these are
regenerated and recycled.  If the ammonia and ammonium carbonate contents
are low, the solutions may be discarded.  No solid wastes are produced
by this process.
          Thus, the process produces emissions and wastes which could
cause pollution problems.  However, the quantity of emissions is expected
to be low; therefore, pollution problems associated with this process
are expected to be minor.

          Sulfuric Acid Leaching Process (14).  Copper values are
extracted from scrap copper as copper sulfate by this process.  The
process steps are as follows:  (a) digesting copper scrap in hot aerated
sulfuric acid solution to convert the copper values to copper sulfate,
(b) separating the soluble copper sulfate from the undissolved portion
of the scrap by filtration, and (c) purification of the copper sulfate
solution.  This intermediate product — aqueous copper sulfate solution--
is a source of copper for the electrowinning process.
          The energy requirement is that to heat the digester solution
and to operate the auxiliary equipment.
          The wastes produced by this process are atmospheric emissions
and solid waste.  The source of atmospheric emissions is the digester.
These consist of air containing fine droplets of the pregnant leach
liquor.  Most are equipped with demisters to reduce the emissions to
the environment.
          The undissolved portion of the scrap and residues formed during
the purification step are the sources of solid wastes.  These are, most
likely, disposed of via landfill.   However, care must be taken to prevent
contamination of the water by leachate from the landfill.  A portion of
the wastes may be reclaimed.

-------
                                  C-80

          This process produces essentially no atmospheric emissions
and, thus, does not pose an atmospheric pollution problem.  However,
solid wastes disposal may result in a water pollution problem.

Smelting Operation

          The scrap pretreatment operation achieves a partial purification
or denslfication of copper-bearing scrap.  Further purification is
achieved by the smelting operation as outlined in the segment flowsheet
by Processes 15 through 17.  Via this operation, additional metallic
and nonmetallic impurities are removed from the copper scrap to produce
copper intermediate products (black copper and blister copper) containing
(75 to 88) and (90 to 99) percent copper, respectively.

          Blast Furnace  (Cupola)/Reverberatory Smelting Process  (15).
Low-grade scrap (irony copper and brasses, motor armatures,  foundry
sweepings, slags, drosses, and skimmings)  is  treated by the  blast furnace
(cupola)/reverberatory smelting process  to recover the copper as an
intermediate product—black copper—for  further processing.   In  this
process, two major pieces of equipment are used—the blast furnace and
the reverberatory furnace.  The blast furnace is used  to purify  the scrap,
whereas the reverberatory  furnace is used  to  separate  the slag from the
molten metal.  The process steps for this  process are:  (a)  charging of
the blast furnace (cupola), (b) melting  the charge,  (c) mixing of molten
mass, (d) tapping of slag and metal into the  reverberatory furnace,
(e) allowing slag and metal to separate  into  layers, and (f)  tapping of
slag and black copper melt.  Afterwards, the molten melt of  black copper
is either cast into ingots or transferred  in  the molten state to the
converter for further processing.
          Energy required for this process is from coke which serves both as
a reducing agent and a source of fuel.
          Potential environmental pollutants produced by this process are
atmospheric emissions, solid wastes, and liquid wastes.  The atmospheric

-------
                                   C-81
emissions are composed of gases and particulate matter.  The gases are
generated by the combustion of coke and burning of any organic
constituents contained in the charge.  Chemical composition will vary
depending on the type of scrap but generally the gases will contain
carbon dioxide, carbon monoxide, nitrogen, sulfur oxides, .and possibly
nitrogen oxides.  The gases may also contain halogens and hydrocarbons,
if present in the charge.
           The  particulate  emissions  are composed  of  a  mixture of  fumes,
metal  particles  formed by  the volatilization and  condensation of  metal
values,  and  dusts removed  from  the  furnace  by  entrainment  in the  gaseous
emissions.   These emissions normally contain such materials as  zinc,
lead,  tin, copper, antimony, chlorine, and  unburned  carbon.  Zinc is
normally  the major component.
           Data  are limited on the composition  of  particulate emissions
from  the  blast  furnace.  However, baghouse  dusts  from  one  installation
 had  the  following  composition:
                              .(7)
At this installation,
Zinc
Lead
Tin
Copper
Antimony
Chlorine
the cupola melt
Copper
Tin
Lead
Antimony
Iron
Zinc
Sulfur
Percent
58-61
2-8
5-15
0.5
0.1
0.1-0.5
contained the following:
Percent
75-88
1.5
1.5
0.1-0.7
0.5-1.5
4-10
0.5-1.25
(7) Spendlove, M. J., Information Circular 8002, U. S. Dept. of
    Interior, Bureau of Mines (1961).

-------
                                   C-82

           Emission factors vary depending on the composition of the
 charge.  However, for treating scrap and residues, the emission factor
 is estimated at 50 Ib per ton of charge.^
           Solid wastes generated are slags and baghouse dusts (discussed
 above).  Composition of the slag is variable depending on such factors
 as type of scrap and fluxing agent.  However,  the slag will normally
 have a composition approximating the following:
                                           Percent
                      Iron Oxide (FeO)       29
                      Calcium Oxide          19
                      Silica                 39
                      Zinc                   10
                      Copper                <1.5
                      Tin                    0.7
 It will represent approximately 5  percent  of the charge.
           Liquid wastes  are generated as wastewater  from  cooling  the
 blast  furnace,  in casting of the ingots, and quenching of the slag.
           Thus,  the  blast furnace/reverberatory  smelting  process  has
 a  high potential for  the production of serious pollution  problems.   These
 problems  could  result from pollution of the  atmosphere and  the water
 systems,  if  the  wastes and emissions are not collected and  disposed  of
 in a nonpolluting manner.

           Converter Smelting  Process (16).   Black  copper  is purified,
 i.e.,  the  heavy  metals concentration is  lowered  to produce  an inter-
mediate product  containing 90  to 99  percent  copper, by the  converter
 smelting proces-s.  The process  steps are:   (a) charging of  the converter
with molten black  copper,  (b)  blowing  of the molten charge  (blow  1),
 (c) deslagging,  (d) blowing of molten  charge (blow 2), and  (e) removing
 the slag,  if any  is formed.  Afterwards, the copper — blister  copper—is
poured and cast  into  ingots for  refining or  transferred in  the molten
state directly to  the refining  furnaces.  Some produce the copper shot
product by quenching  the blister copper  to form small  pellets.
(8) Vandegrift, A. E., et al., Particulate Pollutant System Study,
    Volume 1-Mass Emissions, Midwest Research Institute, Kansas City,
    Missouri (May 1, 1971).

-------
                                  C-83
          Essentially no energy is required for this process.  In fact,
care must be taken to prevent overheating of the converter.
          The process produces atmospheric emissions, solid wastes, and
liquid wastes.  The atmospheric emissions contain both particulate
matter and gas.  The particulate matter is composed of fumes  (metal
particles resulting from volatization and condensation of metal values)
and dusts entrained in the gaseous emissions.
          The major sources of particulate emissions are the charging-
melting and blowing steps.  Emission (furnace) factors for these steps
are estimated at 30 and 39 Ib of particulate matter per ton of charge
processed, respectively.  Emission factor for pouring is estimated at
only 0.6 Ib of particulates per ton of charge processed.  Emission
factor for casting is comparable to that for the pouring step.  The
high emission factors for the charging-melting and blowing steps result
from the heavy evolution of fumes when the charge is loaded into the
furnace and melted down and when the melt is fluxed with a gaseous
fluxing agent (air).
          Quantitative analytical data are not available on the com-
position of these emissions.   However,  qualitatively, the particulate
emissions contain such metal values as tin, lead, antimony, iron, zinc,
sulfur, copper, silicon, and calcium.
          These emissions are in the form of dust and fumes.   The dust
is carried from the converter by entrainment in the "blowing" air,
whereas the fumes result from volatization and condensation of the
volatile metals.  The fumes have a particle size in the sub-micron
range.   The dust particles are much larger, probably in the 5 to 20
micron range or larger.   The particles have no definite shape, i.e.,
an irregular shape.
          The atmospheric emissions can be controlled with baghouses,
electrostatic precipitators,  and scrubbers.  Probably the most widely
used device is the baghouse with control efficiency of approximately
95 percent.
          Other wastes include solid waste and liquid wastes.  The solid
wastes  generated are baghouse dusts and converter slags.  Much of the

-------
                                   C-84
 solid wastes are recycled or treated for recovery of metal values.   For
 example, the converter slags may be returned to reverberatory smelting
 (Process 15) for copper recovery.  Liquid wastes are generated as
 wastewater from casting of the ingots,  from wet scrubbers, if used,  and
 from quenching of the slags.
           Thus, this process can be a source of serious pollution
 problems,  if the pollutants are not collected and disposed of in a
 nonpolluting manner.

           Electric Smelting Process (17).   This process is very similar
 to Processes 15 and 16 in that blister  copper and black copper,  inter-
 mediate products for refining by the electric smelting process operation,
 can be produced by both processes.   The advantage of Process  17  over the
 combination of Processes 15 and 16  is that the quantity of atmospheric
 emissions,  both gases and particulates, is significantly reduced.  Using
 electricity in place of coke as the fuel and pure oxygen in place of air
 to oxidize  the melt result in lower atmospheric emissions. Consequently,
 since much  of the particulate emissions is carried from the smelting
 furnaces by entrainment in the gases,  the  reduced volume of gases
 results  in  a reduced amount of particulate matter.   Thus,  with  the
 strong emphasis being placed on pollution  abatement,  this  process is
 being viewed strongly as the preferred  process for smelting of copper scrap.
          The process steps for the electric smelting process, which
 are  essentially the same as those for Processes  15  and 16,  are:
 (a)  charging of the electric  furnace,  (b)  melting of  the charge,
 (c)  removing the  slag,  (d)  adding high  iron scrap and virgin  copper,
 (e)  blowing the melt (blow 1),  (f)  skimming to remove the  slag  formed
 by blow  1,  (g)  adding more flux,  (h)  blowing the  melt (blow 2),  (i)  skim-
 ming to remove the slag formed by blow  2,  and (j) transferring the melt
 to the holding  furnace  for fire-refining or casting as  blister copper.
 In some  cases,  the  copper  is  given  a  third  blow  termed  the  "finish blow".
          The  energy required  for this  process  is the electricity
necessary to melt  the charge  and  drive  the  equipment.   The  heat  evolved
during  the  blowing  is sufficient  to keep the melt molten.   In  fact,  in
many  cases,  care must be  taken  to prevent  overheating of the  furnace.

-------
                                  C-85
          Atmospheric emissions, liquid wastes, and solid wastes are
generated by this process.  The atmospheric emissions consisting of
gases, fumes, and dusts are generated throughout the process.  The
process steps which are the major contributors are (1) charging of
the furnace, (2) melting of the charge, and (3) blowing of the
melt.
          The composition of the emissions will vary depending on the
composition of the charge.  Normally, the gases contain sulfur oxides,
nitrogen, carbon dioxide, and carbon monoxide.  The particulate matter
includes fumes and dusts composed of such metal values as zinc, lead,
tin, copper, antimony, chlorine, unburned carbon,  precious metals
(gold  and silver),  and constituents making up  the  fluxes.
          Particle size of the fumes and dusts ranges from 0.05 micron
to approximately 1 micron for the fumes to approximately 5 microns or
greater for the dusts.  The dusts are readily collected using such
devices as baghouses or electrostatic precipitators.  Cyclones may be
used in conjunction with these.  However, because of the small particle
size of the fumes,  collection is difficult and much of the fumes pass
on through the control devices into the atmosphere.
          Emissions data are lacking and it is difficult to even estimate
emission factors for this smelting process.  However, it is estimated that
the furnace emissions factors may range from about 80 to about 450 Ib
of particulates per ton of scrap processed.  These estimates are based on
the fact that the emission factor for smelting/refining in the brass and
bronze segment was estimated at approximately 80 Ib of particulates per
ton of alloy produced,(9) and emissions factor for similar processing in
the primary copper industry was estimated at approximately 450 Ib of
particulates per ton of copper produced.
          Solid wastes and liquid wastes generated by this process are
the same wastes as generated by Processes 15 and 16.  Data are lacking
(9)  Spendlove,  M.  J.,  Methods for Producing Secondary Copper, U. S.
     Dept.  of Interior, Bureau of Mines, Information Circular 8002,
     p 21 (1961).
(10) Vandegrift, A.  E., et al.,  Particulate Pollutant System Study,
     Volume III, Handbook of Emission Properties (pp 203,522), p 262
     May 1,  1971).

-------
                                  C-86

from which to calculate quantities.  However, the slags contain such
metal values as zinc, tin,  lead, copper, iron, alumina, silica, antimony,
and other nonvolatile metals present in the. scrap and the fluxes.  Many
of the slags are recycled for copper recovery and the recovery of other
metal values before being discarded.  Liquid wastes from cooling of the
equipment, quenching of the slags, and cooling of the ingots contain
both soluble and suspended  solids.  These wastes are recycled, disposed
of in settling ponds, or dumped  into streams or sewers.
          Thus, this process produces waste products which can cause
serious pollution problems  if the wastes are not collected and disposed
of in a nonpolluting manner.

Refining/Casting Operation

          Blister copper, black  copper, and high grade copper scrap are
purified by the refining/casting operation.  The products from this
operation containing approximately 99.9 percent copper are:   (1) fire-
refined copper cast as ingots, billets, slabs, cakes, and bars for
manufacturing plates, sheets, rods, and copper base alloys;  (2)
electrolytically refined copper  cast as billets, wire bars,  ingots, or
cakes; (3) O.F.H.C. copper  (oxygen-free high conductivity copper); and
(4) copper powder.  These are produced by Processes 18 through 25 as
shown in the copper segment flowsheet.

          Fire-Refining Process  (18).  The final purification of scrap
copper may be achieved by the fire-refining process.  The process steps
are:  (a) charging the furnace which may be either a reverberatory or
cylindrical tilting type; (b) melting the charge in an oxidizing atmos-
phere until the melt begins to "work", i.e., begins to bubble and
liberate sulfur oxides; (c) skimming the melt;  (d) blowing the melt with
air; (e) covering the melt with  a reducing agent such as coke, charcoal,
or coal  (anthracite); (f) poling with green wooden poles; (g) skimming,
if necessary; (h) pouring;  and (i) casting into ingots, slabs, wire bars,
and-billets.  In some cases, molten metal from the smelting  operation is
charged directly to the reverberatory furnace.  In regard to  (f) above,

-------
                                  C-87

the green poles used are largely maple and birch.  They are approximately
10 inches in diameter at the base, at least 20 feet long,  and weigh
approximately 200 Ib.  Maple is preferred because it burns more slowly than
other woods.  The quantity of green poles consumed varies  depending on the
degree of reduction necessary.  In the manufacture of wire bars from scrap
copper, approximately 100 Ib of poles per ton of copper are required.
As an alternative natural gas is being developed and in some cases may
be used in place of green poles.
          Energy required for this process is that necessary to keep the
melt molten.
          Atmospheric emissions, solid wastes, and liquid  wastes are
produced by this process.  Essentially each process step is a source of
atmospheric emissions which are composed of gases and particulate matter
made up of fumes and dusts.
          Emissions data are lacking for the fire-refining process.
However, based on the chemistry involved and  the composition of  the
melt,  the gases are known  to contain sulfur oxides, carbon dioxide,
nitrogen, carbon monoxide, and most  likely, hydrocarbons if green  poles
are used, or ir-ethane if  natural gas  is used in  the  reduction phase of
the refining.  The particulate emissions volatilized as fume or  carried
from the furnace by entrainment in the gases  contain such metal  values
as zinc, tin, copper, lead, and others contained in the melt.  In
addition, the emissions  may also  contain unburned carbon and materials
from the fluxing agents.
          The atmospheric  emissions are controlled with baghouses,
electrostatic precipitators, or wet scrubbers.  A cyclone may be used
in conjunction with these  devices.
          Other wastes generated  by  the process are solid wastes and
liquid wastes.  The solid wastes  are slags containing  the fluxing
materials and metal impurities from  the black,  blister, and scrap  copper
and the impurities from  the green poles.  The liquid wastes are  cooling
wastewater  from cooling  or quenching of the castings and cooling of  the
furnace.  The water contains soluble phosphate  used to condition the
molds  and  the  inhibitor from the  cooling  water.
 (11) Schench, W. A., et al., Trans. AIME, Institute of Metals Division,
     p 299  (1930).

-------
                                  C-88
          Although emission factor data are not available, this process
does generate large quantities of materials which can cause serious
atmospheric and water pollution problems.

          Fire (Partial) Refining Process  (19).  When the copper is to
be cast into anodes, an intermediate product for electrolytic refining,
the melt is not completely fire-refined by oxidizing and poling.  Instead,
the copper is partially fire-refined and cast into anodes.  The anodes
contain about 99 percent copper and small amounts of silver, gold,  lead,
selenium, tellurium, and other metals.
          The process steps, energy required, pollutants generated,
emission factors, and control of pollutants are essentially the same
for this process as for the full fire-refining process,  Process 18.
          This process does generate significant quantities of potential
environmental pollutants and is, therefore, a source of potential
pollution problems.

          Electrolytic Refining Process  (20).  Partial fire refined
copper--anodes--is converted to high purity copper cathodes by the
electrolytic refining process.  The impurities in the anode copper
either dissolve in the electrolyte or fall to the bottom of the cells
as slime.  The slimes may contain such impurities as sulfur, arsenic,
antimony, lead, nickel, selenium, tellurium, gold, and silver, if present
in the anode copper.  The cathode copper assaying about 99.9+ percent
copper contains trace quantities of the above impurities and is the
intermediate product for Processes 21, 22, and 23 for the production of
electrolytic refined copper product and for the production of copper powder.
          The process steps for the electrolytic refining process are:
(a) making up the electrolyte containing water, sulfuric acid, copper
sulfate, and addition agent; (b) placing the copper anode in the
electrolyte bath as one of the electrodes — the anode; (c) dissolving
the anode; (d) depositing the copper on the starting sheets — the cathode;
(e) removing the cathode for melting and casting; (f) regenerating the
spent electrolyte; and (g) removing slimes for recovery of metal values.

-------
                                  C-89
          Energy required for this process is electricity to produce
the cathodes and to drive the equipment.
          This process produces essentially no atmospheric emissions
if the anode copper does not contain arsenic.  If arsenic is present,
arsine (AsH_) is formed and evolved during electrolytic refining of
copper.  This has not presented a serious problem for the operators as
the tank houses are generally well ventilated and the arsine is ejected
outside the house.  However, arsine formation can be a problem in
electrolyte regeneration.
          The major wastes produced are solid wastes (aqueous slurries
composed of the slime) and liquid wastes  (spent electrolyte).  The
slimes are sent to precious metal recovery where such metal values as
gold, silver, nickel, and lead are recovered.  A "black liquor", liquid
waste, is formed during electrolyte purification.  This material is
either discarded, generally after neutralization, or used in leaching
operations in associated plants.  Additional liquid wastes are generated
during recovery of nickel, iron, zinc, and other metal values from the
spent electrolyte.
          Thus, the electrolytic refining process can present serious
pollution problems.  Arsine, an atmospheric pollutant which is volatile
and poisonous, is generated, if arsenic is present in the cathodes.
Furthermore, large quantities of liquid wastes and solid wastes are
generated which can cause water pollution problems.

          Electric Melting Process (21).   Cathode copper is melted and
cast into the desired shape by the electric melting process.  Normally,
the process steps are:   (a) feeding the cathodes into the furnace through
a charge slot to maintain a molten bath;  (b) removing molten copper from
the tap hole; and  (c) casting the molten copper as billets, wire bars,
ingots, or cakes.  Periodically, flux is added to the melt to refine
the copper and slag is removed as the waste product.
          Energy required is the electricity to melt the copper and
drive the auxiliary equipment.

-------
                                    C-90
           Wastes generated by this  process  are  small amounts of
 atmospheric emissions,  liquid wastes,  and  solid wastes.   The atmospheric
 emissions  result primarily from the evolution of  gases  from  the melting
 operation  and from pouring and casting of  the pure  copper.   The solid
 wastes  are the slags  or skimmings from the  melting  furnace,  whereas
 liquid  wastes are formed during ingot  casting and cooling of the
 equipment.
           Emissions data are  not available  for this  process.   It  is
 expected that this process would constitute a minor  source of  pollution
 problems in this segment of the secondary nonferrous metals  industry.

           Reverberatory Melting Process (22).  This process  is an
 alternative process for converting  cathode copper intermediate product
 to the  desired shapes of electrolytic  refined copper.   The process steps
 are:   (a)  charging the reverberatory furnace, (b) melting the cathodes,
 (c)  blowing (flapping)  of melt, (d) skimming  of melt,  (e) poling  of
 melt,  (f)  skimming of melt, (g) pouring,  and  (h)  casting.
           Energy required is  the fuel  to melt and keep  the charge molten
 and  that required to  drive the auxiliary equipment.
           Atmospheric emissions, liquid wastes, and solid wastes  are
 produced by this process.   The atmospheric  emissions—gases,  fumes,
 and dusts--are formed during  each processing  step with  the majority of
 the emissions being evolved during  blowing  (flapping) and poling  of the
 melt.   Emissions data are  not available on  the quantity  and  composition
 of these emissions; however,  it is  expected that  the emissions contain
 gases such  as  carbon  dioxide,  carbon monoxide, sulfur oxides,  and
 hydrocarbons.   The fumes and  dusts  are composed of,  primarily, copper,
 and small quantities  of such  metal  values as  lead, nickel, selenium,
 and tellurium.
          Liquid wastes  result  from casting of the melt  into  the desired
 shapes and  from  cooling  of the  equipment.   These  liquid wastes, primarily
wastewater, contain soluble inhibitors  and  insoluble solids  such as the
bone ash to condition the  molds.  In some cases,  phosphates may be used.

-------
                                   C-91
          Solid wastes are the slags or skimmings formed and removed
from the melt during the melting (refining) of the cathodes.  These
wastes contain the impurities from the cathode copper and the fluxes,
if added.
          In view of the waste products and emissions generated by this
process, pollution problems can result if these pollutants are not
collected and disposed of in a nonpolluting manner.  However, it is
expected that this process is a minor source of pollution problems
when compared to some of the other processes.

          Induction Melting Process (23).  Oxygen-free-high-conductivity
(O.F.H.C.) copper is produced by the induction melting process using
cathodes as the source of copper.  The O.F.H.C. copper is oxygen-free
with a reported purity of 99.99 percent.  The process steps are:
(a) clean the cathodes, (b) preheat the cathodes in an atmosphere of
reducing gas which is low in hydrogen,  (c) melt the clean, preheated
cathodes in a low-frequency induction heater, (d) cover the melt with
graphite granules, (e) discharge molten copper to a low-frequency
induction-heated "pour hearth" which distributes the copper to the
casting machine, and (f) cast the O.F.H.C.* copper.  A nonoxidizing
atmosphere is maintained throughout melting and casting.
          Energy required is the electricity to melt the cathodes and
keep the melt molten and to operate the auxiliary equipment.-
          Waste products produced by this process are atmospheric
emissions, solid wastes, and liquid wastes.  The atmospheric emissions
are produced during preheating of the cleaned cathodes, melting of the
cathodes, and casting of the copper melt into ingots and other shapes.
Emissions data are not available; however, the emissions no doubt consist
of reducing gases and carbon monoxide from melting of the cathodes.  The
gases contain a small quantity of particulate matter which is composed
of copper along with other metals found in the melt and graphite particles,
The solid waste is basically graphite used to cover the melt.  The liquid
wastes are wastewater used in the casting of the melt and cooling of the
equipment.
* O.F.H.C. is a trade name of the U. S. Metals Refining Company and
  also means oxygen free high purity copper.

-------
                                   C-92
          This process produces minor quantities of potential
environmental pollutants.  Therefore, the process has little or no
potential for producing serious pollution problems.

          .Electrolytic Winning Process  (24).  Copper in the form of
impure copper cathode, an intermediate product to electrolytic refining
process, is recovered from copper sulfate solutions by the electrolytic
winning process.  The deposit is not as pure as the cathodes from the
electrolytic refining process and, therefore, must be purified.  The
process steps are:   (a) prepare electrolyte, (b) electrolytically
deposit the copper on thin copper starter sheets, (c) remove the copper
cathodes from the electrolytic cells, (d) clean cathodes by soaking in
water, (e) replace copper starter strips, (f) regenerate electrolyte,
and (g) repeat series of above steps.  Spent electrolyte is is con-
tinuously bled from  the system, regenerated, and returned.
          Energy  required is  the electricity to operate the process.
          The waste  products  generated  by the process are primarily
liquid waste consisting of spent electrolyte and solid wastes consisting
of slimes formed  during the electrolysis and resulting from regeneration
of the electrolyte.  If the electrolyte contains arsenic, gaseous arsine
(AsH-j) is liberated.  This material  is generally vented to outside of
the building.
          Emissions  data are  lacking.  However, from data which are
available on electrolytic refining, most likely, the waste products
produced by the electrolytic  refining process can cause water pollution
problems.

          Electrolytic Powder Production Process (25).  Copper powder
is prepared from  copper sulfate solutions by the electrolytic powder
production process using pure copper cathodes from the electrolytic
refining process  as  the source of copper.  The process steps are:
(a) prepare electrolytic cell for powder production using cathode
copper as the anode, (b) electrolytically deposit copper powder,

-------
                                   C-93
(c) remove copper powder from cell, (d) return electrolyte to cell,
(e) wash electrolyte from copper powder, (f) heat powder in hydrogen-
carbon monoxide atmosphere to remove water, (g) classify dried powder,
(h) blend powders of different particle size to obtain correct particle
size distribution, and (i) package product.
          Energy required is the electricity to produce the copper
powder and drive the equipment and the fuel to heat the dryer.
          Waste products produced by this process are atmospheric
emissions and liquid wastes.  The atmospheric emissions contain gases
composed of water vapor, carbon monoxide, hydrogen, possibly arsine,
and unburned fuel.  The particulate portion of the atmospheric emissions
is copper powder from the dryer, blender, and classifier.
          The liquid waste is the spent electrolyte from the electrolytic
cell and wash liquor from washing the copper powder.  The spent liquor
is normally regenerated and recycled to the electrolytic cell.  The
wash liquor containing sulfuric acid,  water, and some soluble copper
is probably neutralized and disposed of in a holding pond.
          Thus, waste products produced by this process can cause
pollution problems if not properly controlled.

-------
                                   C-94
                  Population of  Secondary Copper Processors
  (1)  Earth  Smelting Corporation
      99-129 Chapel Street
      Newark, New Jersey
      Telephone:  (201) MA2-4908

  (2)  Batchelder-Blasius, Inc.
      Post Office Box 5503
      Spartanburg, South Carolina
        29301
      Telephone:  (803) 439-6321

  (3)  Bay State Refining, Inc.
      Chicopee Falls, Massachusetts

  (4)  Joseph Behr and Sons, Inc.
      1100 Seminary Street
      Rockford, Illinois
      Telephone:  (815) 962-7721

  (5)  Belmont Smelting and Refining
        Works, Inc.
      320 Belmont Avenue
      Brooklyn, New York
      Telephone:  DI2-4900

  (6)  W. J. Bullock, Inc.
      Post Office Box 539
      Fairfield, Alabama

  (7)  Cerro Corporate Brass Company
      Division of Cerro Corporation
      16600 St.  Clair Avenue
      Cleveland, Ohio  44110
      Telephone:  (216) 481-3000

 (8)  Circuit Foil Corporation
      23 Amboy Road
      Bordentv)v;, New Jersey
      Telephone:  (609) 298-4800

 (9)  Colonial Metals  Company
      Columbia,  Pennsylvania
      Telephone:  (717) 684-2311

(10)  General Copper and Brass Company
      Post Office Box 5353-D
    •  Philadelphia,  Pennsylvania
      Telephone:  SA6-7111
(11)  Samuel Greenfield Company,
        Inc.
      Stone and Ingot Streets
      Brooklyn, New York

(12)  Holstead Metal Parts, Inc.
      West Newcastle Street
      Zelienople, Pennsylvania
        16063
      Telephone:  (412) 452-6500

(13)  Benjamin Harris & Company
      Eleventh and State Streets
      Chicago Heights, Illinois
      Telephone:  SK5-0573

(14)  Henning Brothers & Smith,
        Inc.
      91-115 Scott Avenue
      Brooklyn, New York

(15)  K. Hettleman & Sons,
      Division of Minerals and
        Chemicals
      Phillip Corporation
      Ninth Street and Patapsco
        Avenue
      Baltimore, Maryland  21225
      Telephone:  (301) 355-0770

(16)  Holtzman Metal Company
      5223 McKissock Avenue
      St.  Louis, Missouri  63147

(17)  H. Kramer & Company
      1339-59 West 21st Street
      Chicago,  Illinois  60608
      Telephone:  CA6-6600

(18)  Metal Bank of  America,  Inc.
      6801 State Road
      Philadelphia,  Pennsylvania
        19135
      Telephone:  (215)  332-6600

-------
                                  C-95
(19)   Nassau Smelting and  Refining Co.,
        Inc.
      5  Nassau Place
      Tottenville,  New York
      Telephone:   (212) YU4-1970

(20)   Phelps Dodge  Refining
        Corporation
      300 Park Avenue
      New York, New York
      Telephone:   751-3200

(21)   Riverside Alloy Metal Division
      H. K. Porter  Company, Inc.
      309 Porter Building
      Pittsburgh, Pennsylvania  15219
      Telephone:   (412) 391-1800

(22)   Roessing Bronze Company
      320 Barbour
      Pittsburgh, Pennsylvania

(23)   I. Schumann & Company
      4391 Bradley  Road
      Post Office Box 2219
      Cleveland,  Ohio

(24)   M. Seligman & Company
      3401 S. Lawndale Avenue
      Chicago, Illinois

(25)   SIPI Metals Corporation
      1722 N. Elston Avenue
      Chicago, Illinois

(26)   U. S. Metals  Refining Company
      1217 Avenue of Americas
      New York, New York  10020
      Telephone:   (212) PL7-9700

-------
SCRAP  PRE TREATMENT


    MECHANICAL
                                                                              SMELTING
REFINING/CASTING
  K •i«ic,wr«{ t

3


J


1


ipmaxt
P


^>


>o


p
^ rmi-j O
• PmniiNt | 	










\
SCUM
    , COUHMINATCD
                                                                                         poaoucrs CR stgoxoMn uw
                                                                                I       I MATcnui.9 tons « ono
                                                                                         Nouanuci
                                                                                                                                                  COPPER SEGMENT OF THE
                                                                                                                                               SECONDARY NONFERROUS

                                                                                                                                               METALS  INDUSTRY

-------
                                   C-97
             PROCESS DESCRIPTION OF THE GERMANIUM SEGMENT OF
                THE SECONDARY NONFERROUS METALS INDUSTRY

          Annual production volume of secondary germanium is about 8000
pounds.  Because of the high cost of germanium (~$50/lb), process losses
through air, solid waste, and water emissions are reduced to a minimum.
Also, the emphasis placed on the highest possible purity of the final
product insures that all processing operations are conducted in closed
systems to prevent atmospheric contamination of the product.

                              Raw Materials

          Germanium scrap sources are as follows:
          (1)  Solid scrap (100 percent solid metal) obtained as
               scrap ends from zone refining
          (2)  Slicing compounds from single crystals obtained
               as sludge containing 50 to 80 percent germanium
          (3)  Acid etching scrap
          (4)  Grindings and polishing wastes from the infrared
               industry
          (5)  Scrap from the electronic industry.

                                Products

          High purity germanium is the only product of this segment.

                           Process Description

          One manufacturing operation—hydroraetallurgical refining—is
involved in the processing of germanium scrap.  This operation and the
processes involved in it are shown in the process flowsheet of this
segment.

-------
                                    C-98
Hydrometallurgical  Refining Manufacturing  Operation

           This  operation  Involves  three processes—chlorination, hydrolysis,
and hydrogen  reduction.   These  are discussed  in detail below.

           Chlorination Process  (1).   In this  process, germanium is converted
to germanium  tetrachloride.  The process steps are (1) charge scrap  to
vessel,  (2) heat and  add  sodium chloride.
           The volatilized tetrachloride with  any impurities is distilled
to get germanium tetrachloride.
           The process requires  minor  amounts  of heat energy.
           Small quantities  of gaseous wastes  are generated.
           The emissions are  water  scrubbed and the solids recycled.
Scrubber water  is also recycled.
           The process has no significant pollution potential.

           Hydrolysis Process (2).  This process converts the tetrachloride
to germanium  dioxide by ice  water hydrolysis.
           Details of the  process steps are not known.
           Minor amounts of water waste (with  insignificant pollution
potential) are generated.

          Hydrogen Reduction Process  (3).   This process converts the
germanium dioxide to the pure metal.
          The process steps  are (1) pass hydrogen,  (2)  heat to 650 C.
          Heat energy is utilized in this process.
          The process produces no pollutants.

              Population of  Secondary Germanium Processors

(1)   Belmont Smelting and Refining Works      (2)   Kawecki Berylco  Industries
     320  Belmont Avenue                             (KBI)
     Brooklyn, New York                           220 East 42nd  Street
                                                  New York,  New  York 10017
                                                  (212)  682-7143.

-------
8 7 | 6 | 5 4 3
SCRAP PREATMENT PROCESS/REFINING
SODIUM
r~CHLORlDE r\
1 f— HEAT x^A
.- » C.Ht ORlNATlON
SCRAP 	 •
( TETRA-)
\O-LDB IDE/
rCE WATER 1 — HYOPOGEN
A x-^\ ! rr^L
/CCRMANIUM\ HYDROGEN
HYDROLYSIS "I UIUXIUL, I ' REDUCTION

LEGEND
- OA™O5PHEWC EMISSIONS
^LIQUID \MHSTE
OSOUD WASTE
S \ PRODUCTS OR SEO>
/ \RAW MATERIALS FO
I JlN OTHER INDUSTR
[ JINTERMEDIATE PROC
8 1 7 6 5 4 3
2 I

"t METAL 1

i'-^'Bu SIGNATURE DIV DATE .^RS BATTELLC MEMORIAL INSTITUTE
ES ^^^t< 56? 23J22 'S' SB KINGAVC.. COLUMBUS. OHIO 4E01
piSrHY -. - 	 ""GERMANIUM CEGMEN
5TAUBALCH • - nr~fi_fr QprfSKinARY NOtvi-
FERROUS METALS INDU5TPY
XJCTS — — — «— "'— —"" ~"
StVLT " • " ^ /S)aut)
cu ^ i~n
D
C
8
A



_] 	 i____ 1
o
 I
vo

-------
                                 C-100
               PROCESS DESCRIPTION OF THE HAFNIUN SEGMENT
              OF THE SECONDARY NONFERROUS METALS INDUSTRY
          Since hafnium occurs in nature with zirconium, both hafnium
and zirconium are processed and isolated in the same facility.  The quantity
of hafnium marketed in the U. S. is very small  (less than a million ounces).

          Hafnium is not a toxic metal.  Due to the high unit price of the
metal, recovery is maximized by excellent waste control.

          These considerations indicate the environmental pollution problems
from the secondary hafnium industry are insignificant.

          Details of the process are difficult to obtain because of the
desire of the U. S. hafnium processors to protect the proprietary nature
of their process.


              Population of Secondary Hafnium Processors
          (1)  Amax Speciality Metals Division
               American Metal Climan, Inc.
               6000 Hake Road
               Akron, New York  14001
               Telephone:  (716) 542-5454

          (2)  Teledyne Wah Chang
               P. 0. Box 460-T
               Albany, Oregon

-------
                                 C-101
               PROCESS DESCRIPTION OF THE INDIUM SEGMENT
              OF THE SECONDARY NONFERROUS METALS INDUSTRY
          Efforts to obtain information on this segment have not been
as successful as in other areas.  The Indium Corporation of America is
the only producer of secondary indium and information obtained from this
company is summarized below.
          (1)  The total annual U. S. production (1972) of both
               primary and secondary indium is less than 2 million
               ounces (<62 tons).  The market value of indium is
               about $4.50 per ounce.  This high cost of indium makes
               the recovery process very profitable and necessary.
          (2)  The process of recovery of indium consists of using
               a small blast furnace followed by a series of typical
               chemical and electrical recovery processes, details
               of which are proprietary.
          (3)  Indium is not toxic.  There are no environmental
               problems or emissions.
          (4)  The industry is not interested in any external
               assistance in research and development work.  The
               entire process is proprietary.  The industry is
               very careful to protect that status.

               Population of Secondary Indium Processors
                   The Indium Corporation of America
                   1676-1680 Lincoln Avenue
                   Utica, New York  13502
                   Telephone:  (315) 797-1630

-------
                                  C-102
              PROCESS DESCRIPTION OF THE LEAD SEGMENT OF
               THE SECONDARY NONFERROUS METALS INDUSTRY
                              Introduction
          This segment of the secondary nonferrous metals industry
ranks second in consumption of scrap materials.  In 1971,    784,700
tons of lead scrap were consumed.  In the recovery of the lead value
from scrap, waste products are generated in the form of atmospheric
emissions, liquid wastes, and solid wastes.  These materials can cause
pollution problems.
                             Raw Materials

                                                   (2)
          The principal sources of lead scrap are:
                         Soft lead
                         Hard lead
                         Cable lead
                         Battery-lead plates
                         Mixed common babbits
                         Solder and tinny lead
                         Type metals
                         Drosses and residues.
New scrap in the form of purchased drosses and residues make up  18 percent
(143,400 tons) of the total.  The remainder, old scrap, is predominantly
battery scrap with small amounts of the other scrap.  The scrap  is
essentially all from domestic sources.  In addition  to containing metallic
lead or compounds and alloys of lead, the scrap contains a variety of
organic materials such insulation, grease, and oil.  Common alloying
(1) Ryan, J. P., Minerals Yearbook, U. S. Dept. of Interior,  Bureau of
    Mines, Vol. I, p 671  (1973).
(2) ibid, p 683 (1973).

-------
                                  C-103
agents found in the scrap are tin, antimony, arsenic, cadmium, copper,
indium, silver, zinc, tellurium, and bismuth.

                               Products

          Products from the lead segment of the secondary nonferrous
metals industry are:  (1) lead ingots  (pure/soft),  (2) lead  ingots
(hard/semisoft),  (3) lead ingots (alloys),  (4)  lead oxide  (battery
lead oxide), and  (5) lead pigments (Pb3<>4 and PbO).

                         Process Description

          Lead is recovered from lead  scrap by  three manufacturing
operations:  (1)  scrap pretreatment, (2) smelting,  and (3) refining/
casting.  These operations and the processes associated with each
operation are shown in the flowsheet entitled "Lead Segment  of the
Secondary Nonferrous Metals -Industry".

Scrap Pretreatment Operation

          In this operation, the lead  scrap is  treated to make it more
amenable to further processing.  This  treatment involves densification
and/or partial removal of metallic and nonmetallic  contaminants.

          Battery Breaker Process  (1).  The major source of  lead is
obsolete automobile batteries.  By this process,  the  lead is separated
from the nonmetallic portion of the battery.  The process steps are:
(a) draining the  battery if not received dry, (b) breaking  (crushing)
the battery to break the lead portion  from the  nonlead portion, and
(c) separating the lead from the battery case.  This  lead scrap in this
form can be fed into the reverberatory or blast furnace for  further
processing and recovery of the lead.
          Energy  required for this process is that  to drive  the
equipment.

-------
                                  C-104
          Waste products  generated are primarily  liquid wastes and
solid wastes.  A  small  quantity  of dusts may be generated if the
batteries are  treated dry.   These dusts are composed of dirt, plastic,
or battery case materials and  lead compounds such as lead oxide and
lead sulfate.
          The  liquid wastes  are  composed of sulfur acid, water, lead
compounds, and the alloying  agents from the lead plates.
          The  solid wastes,  which make up the bulk of the waste products
from this process are composed of the organic materials used in battery
case fabrication.  In addition,  these solid wastes contain some sulfuric
acid and lead  compounds.
          In view of the waste products generated by this process,
serious pollution problems can arise if the wastes are not disposed of
in a nonpolluting manner.

          Crushing Process  (2).  Much of the drosses, residues, and
possibly slags are received  in large pieces, i.e., larger than desired
for further processing.   These scrap materials are crushed with jaw
crushers to a  suitable  size.  The process steps are:  (a) load the
crusher and (b) crush the scrap.  Afterwards, the scrap is removed and
further processed to recover the lead content.
          Energy required is limited to that necessary to drive the
equipment.
          Waste products  from this process are dusts resulting from
the handling and crushing of the scrap.
          Emissions data are not available.  However, significant
quantity of emissions could  be generated.  Therefore, the process can
present pollution problems,  if the dusts are not collected.

          Rotary/Tube Sweating Process (3).  Lead sheathed cable and
wire,  aircraft tooling  dies, type metal drosses, and lead dross and
skimmings are treated by  the rotary/tube sweating process to recover
the lead value.  The process steps are:  (a) charge the furnace with
the scrap,  (b) melt the lead value,  (c) collect the molten lead,

-------
                                 C-105
 (d) cast the molten lead, and  (e) remove the residue from the
 furnace.
          Energy required for  this process is the fuel to heat the
 rotary furnace or sweating tube and electricity to drive the equipment.
          Atmospheric emissions and solid wastes are generated by this
 process.  The emissions contain gases composed of sulfur oxides,
 entrained air, nitrogen oxides, and the fuel combustion products.
 The particulate portion of the atmospheric emissions is composed of
 fumes, dusts, unburned fuel, soot, and fly ash.  Furnace atmospheric
 emissions data are not available.  However, based on data from similar
 processes, emissions factors are estimated to range from 70 Ib of
 particulates per ton of metal processed (raw emissions factor for rotary
 reverberatory furnace smelting of lead)    to 32 Ib of particulates
 per ton of scrap processed^ '  (raw emissions factor for sweating of
 residual zinc).
          Particle size of the emissions varies.  The larger particles
 (dusts) are probably in the 5 to 20 micron or larger range, whereas
 the unagglomerated lead fumes vary in diameter from 0.07 to 0.4 micron
with a mean particle size of 0.3 micron.
          Solid wastes are the metallic and nonmetallic portion of the
 scrap after removal of the lead.
          As significant quantities of atmospheric emissions and solid
wastes are generated by this process and since lead and lead compounds
are toxic or hazardous materials, the waste products from this process
can cause serious pollution problems if the waste products are not
controlled.  Failure to control the atmospheric emissions can result
 in pollution of the atmosphere, whereas disposal of the solid wastes in
an unapproved manner can result in water pollution.
(3) Vandegrift, et al., Particulate Pollutant System Study, Vol. Ill,
    Handbook of Emission Properties, Midwest Research Institute,
    Kansas City, Missouri, p 406 (May 1, 1971).
(4) Herring, W. 0., Secondary Zinc Industry, Emission Control Problem
    Definition Study, APCO, EPA, Durham, North Carolina, p Vl-22.
(5) Air Pollution Engineering Manual, U. S. Dept. HEW, NCAPA,
    Cincinnati, Ohio, p 307 (1967).

-------
                                  C-L06

          Reverberatory Sweating Process  (4).  This process is normally
used  to sweat scrap containing high  lead  content such as lead battery
plates.  The process  steps are the same as for Process 3.
          Energy required is  the fuel--gas or oil--to heat the furnace.
          Waste products from this process are atmospheric emissions
and solid wastes.  The atmospheric emissions are composed of gases and
particulate matter containing both fumes  and dusts.  The gases discharged
from  the furnace contain the  combustion products, sulfur oxides, unburned
fuel, and hydrocarbons from pyrolysis  of  the organic compounds present in
the scrap.  The fumes and dusts contain metallic materials such as lead,
antimony, and other heavy metals used  to  prepare the  lead alloys,  and
nonmetallic materials such the fluxes  and carbon or other organic
contaminants from the scrap.
          Although emissions  data are  lacking, it is estimated based on
data  from similar processes that raw emissions factor for the reverberatory
sweating process will range from approximately 30 Ib per ton of charge
                                     {3 4)
to 70 Ib per ton of metal processed.   '
          Unagglomerated lead oxide  fume  particles vary in diameter
from  0.07 to 0.04 micron with a mean diameter of about 0.3 micron.
The particle size of  the dust is expected to be much larger, normally
in the 5 to 20 micron or larger size range.
          The atmospheric emissions  are controlled by the same
system as is used for the smelting operation and discussed under
Process 5.
          Solid waste materials are  the residues remaining after removal
of the lead.  Composition of  these wastes may vary somewhat, but
generally will contain lead and other  heavy metals such as antimony.
          This process has a  high potential for the production of
pollution problems if emissions are  not controlled.

Smelting Operation

          Pretreated  scrap is partially refined, i.e., some of the
metallic and nonmetallic contaminants  are removed by the smelting

-------
                                    C-107

operation.  The individual processes (5 and 6) comprising the smelting
operation are shown in the attached flowsheet.

          Reverberatory Smelting Process (5).  Lead scrap (pretreated
or untreated, mixed) is partially purified and densified by the reverber-
atory smelting process.  This is achieved by the following process steps:
(a) charge the furnace with the lead scrap and flue dusts, (b) melt the
scrap, (c) allow the antimonical slag to rise to the surface of the melt,
(d) tap the antimonical slag to the blast furnace, and (e) tap the molten
lead melt to the refining/casting operation.  Alternately, the molten lead
may be poured and cast into ingots as a semisoft/hard lead product.
          The energy required for this step is from the fuel oil or gas to
smelt the scrap.
          Atmospheric emissions are produced by this process.  'No solid
or liquid wastes are produced.
          The atmospheric emissions are composed of gases and particulate
matter.  The gases contain the products from combustion of the fuel and
sulfur oxides along with any other gases from the scrap.  The particulate
matter (fume) is composed of oxides, sulfides, and sulfates of lead, tin,
arsenic,  copper, and antimony.  Recoverable lead from the charge is about
47 percent.  Approximately 46 percent of the charge is slag and 7 percent
is fumes  and dusts.
          The unagglomerated particulate matter was found to have a
particle  size range of 0.07 to 0.4 micron with a mean value of 0.3 micron.
The particle shape was essentially spherical.
          The reverberatory smelting process accounts for approximately
75 percent of the emissions from the lead segment of the secondary
nonferrous metals industry.  Particulate emission factor for reverberatory
smelting  is estimated at 130 Ib (uncontrolled) and 1.6 Ib (controlled)
per ton of metal processed.  Raw sulfur oxide emission factor is estimated
(6)  Air Pollution Engineering Manual,  U.  S. Dept. HEW, NCAPC,
    Cincinnati,  Ohio,  pp 301-302 (1967).

-------
                                  C-108

at 85.(/7>8>9)  ID  to  190^10^  Ib per  ton of metal processed.
          Particulate emissions from this process are controlled with
a baghouse, scrubber, or both.  The  baghouse is aorranged as the final
collector.  These  systems also include auxiliary items such as gas
cooling devices and settling  chambers.  Sulfur oxide emissions are
controlled  in some plants with a wet scrubber.
          The process produces significant quantities of atmospheric
emissions and is,  therefore,  a potential source of pollution problems.

          Blast Furnace Smelting  Process (6).  Semisoft/hard lead
which is a  product and an intermediate product, is produced from
pretreated  scrap,  antimonical slag  (reverberatory slag), and rerun slag
by the blast furnace  smelting process.  In this process the molten lead
flows almost continuously and the slag is tapped at intervals.   A '
typical charge which  is added as  the material melts down is:  4.5 percent
scrap iron; 3 percent limestone; 5.5 percent coke; and 82.5 percent
drosses, oxides, and reverberatory slag.  The drosses are miscellaneous
drosses consisting of copper drosses, caustic dross, and dry drosses from
the refining process  in the pot furnace.  Thus, the process steps are:
(a) add the charge with a composition as noted above, (b) continuously
remove the molten  lead, (c) remove the slag at intervals, and (d) cast
the lead ingots or transfer molten lead to the refining kettles.
          The energy utilized in this process is from coke, which also serves
as a reducing agent.
          Waste products produced by this process are atmospheric emissions
and solid wastes.  The atmospheric emissions consist of gases containing
carbon monoxide, hydrocarbons, sulfur oxides, nitrogen oxides,  and probably
(7)  Nance, J. T., and K. 0., Luedtke, Lead Refining, Air Pollution
     Engineering Manual, Danielson, J. A. (ed), U. S. DHEW, PHS,  National
     Center for Air Pollution Control, Cincinnati, Ohio, Pub. No.
     999-AP-40, pp 300-304 (1967).
(8)  Allen, G. L., et al., Control of Metallurgical and Mineral Dusts and
     Fumes in Los Angeles County, Dept. of the Interior, Bureau of Mines,
     Washington, D. C., Information Circular No. 7627, April, 1952.
(9)  Hammond, W. F., Data on Nonferrous Metallurgical Operations, Los
     Angeles County Air Pollution Control District, November, 1966.
(10) Unpublished work, Battelle's Columbus Laboratories (1972).

-------
                                  C-109
nitrogen.  The particulate matter in the emissions contains oil vapor,
smoke, fume, and dust.  The fume and dust are composed of lead, tin, zinc,
coke dust, sulfur, and other metals contained in the charge.  The fumes
are volatized and condensed from the charge, whereas the dusts are carried
from the furnace by entrainment in the furnace gases.
          Particle morphology of the particulate emissions are similar to
those from the reverberatory furnace.  Particle size ranges from 0 to 16
microns with approximately 15 percent between 0 to 1 micron, 45 percent
between 1 to 2 microns, 20 percent between 2 to 3 microns, 15 percent
between 3 to 4 microns, and 10 percent between 4 to 16 microns    .  No
data are available on particle shape; however, the dust is most likely
irregular and the fume (smaller size) is spherical.
          Emissions rate is high from the blast furnace smelting process.
Raw particulate emissions factor (uncontrolled) is estimated at'190 Ib per
ton of metal processed.  Sulfur oxide emissions factor is estimated at 90
                               (12 )
Ib per ton of metal processed.   '  Controlled emissions factors are 2.3
and 0.8 to 46 Ib per  ton of metal processed, respectively.
          The emissions are subject  to control.  The baghouse  is the most
acceptable device for controlling the particulate emissions.   The gas
stream containing the emissions is first passed through a series of water
or air cooled tubes and then to the baghouse.  To prevent tar  volatiles
from  blinding the bags, the temperature of  the baghouse is kept high.
Lime  is also added to the gas  stream to prevent the blinding action.  The
gas stream  from the baghouse is discharged  to a stack or possibly to an
electrostatic precipitator in  an attempt to  further clean the  gases before
                                 (13)
emitting  them to  the  atmosphere.
 (11) Air Pollution Engineering Manual, U. S. Dept. HEW, NCAPC,
     Cincinnati, Ohio, p 303  (1967).
 (12) Compilation of Air Pollutants Emission  Factors, 2nd  Ed., U.  S.
     EPA, Office of Air and Water Programs,  Research Triangle Park,
     North Carolina, p 7.11-2  (April,  1973).
 (13) U. S. Dept. of Commerce, Economic Impact of Air Pollution  Controls
     on the Secondary Nonferrous Metals  Industry, Washington, D.  C.,
     p 132  (1969).

-------
                                  C-110

          Wet  scrubbers may  be employed  to clean  the gaseous portion of
the stream.  The caustic  (NaOH)  scrubber  is more  effective  than the water
spray chamber  for removing sulfur  oxides  as.evidenced by  the fact that
caustic scrubbing reduced  the emissions  factor  from 90  Ib per ton of metal
processed to 0.8 Ib per ton  of metal  processed, whereas water scrubbing
                                                                     (14)
reduced the emission  factor  to only 46  Ib per ton of metal  processed.
          Solid wastes from  this process  are the  baghouse and flue dusts
and fumes, and the slag.   For the  most part, these are  recycled to the
process because of the high  lead content.
          Thus, uncontrolled, the  blast  furnacing process produces large
quantities of  atmospheric emissions and  solid wastes which  can cause serious
pollution problems, both  from the  atmospheric and water pollution aspects.

Refining/Casting Operation

          The  intermediate products from  the reverberatory  and blast furnace
processes--soft lead  and antimonical  lead--required additional purification
or refining to produce the desired products.  In  addition to the metal
products, some of the lead is converted  to lead oxide products.  The
processes employed to achieve conversion  of the impure  lead intermediate
products to the final products are processes 7  through  11 as shown in
the attached flowsheet.

          Kettle (Softening) Refining Process (7).  The intermediate
products from  the smelting operation may  contain  copper (generally not
present) and antimony which  makes  the lead hard.  Removal of these two
contaminants by the kettle (softening) refining process produces soft
lead--one of the products from the lead segment of secondary nonferrous
metals industry.  The process steps are:  (a) charge the preheated kettle,
(b) melt the charge,  (c) stir the molten  charge to mix  in the flux, (d)
remove the skimmings, (e) pour the molten metal,  and (f) cast into ingots
(bullion).  In some cases, the molten lead is poured directly from the
smelting operation to the refining kettle.
(14) Compilation of Air Pollutant Emission Factors, 2nd Ed., U. S. EPA,
     Research Triangle Park, North Carolina, p 7.11-2  (April,  1973).

-------
                                 C-lll
          Several fluxes or purifiers are used.  Included in this list
are sodium hydroxide, sodium nitrate, aluminum chloride, or aluminum.
Air is occasionally used to blow the melt.
          Source of energy for this process is generally gas to heat
the kettle indirectly and electricity to drive the equipment.
          Waste products produced are atmospheric emissions and solid
wastes (skimmings).  The atmospheric emissions containing mainly fumes
and possibly some dust are composed of such metals as lead, antimony,
sodium, and trace quantities of copper, zinc, arsenic, bismuth, and  tin.
The gaseous portion of the emissions contains primarily the fuel
combustion gases.
          Particle morphology should be similar to the fumes from the
reverberatory smelting process, i.e., the particle size is in  the
submicron range and the shape is generally spherical.
          Although the quantity of emissions from the refining process
is much less than from the other lead processes, for example,  0.8 lb
of particulates "per ton of metal processed as compared to 190  lb per ton
of metal processed for reverberatory smelting, the toxic or hazardous
nature of lead requires that the emissions  be  controlled.   The
most widely used device is the baghouse.  The fumes are collected via
a hood over the kettle.
          The solid wastes are skimmings containing the flux and
other metal values removed from the melt  during  the refining operation.
These wastes along with the particulate matter from the baghouse are
generally recycled to the blast furnace for  recovery of the  lead value.
          Thus, the kettle (softening) refining process produces waste
products which can cause pollution problems, if wastes are not collected
and disposed of in a nonpolluting manner.

          Kettle  (Alloy) Refining Process  (8).  Kettle  (alloy) refining
process involves  treatment and adjustment of the metals content  of  lead
to produce the desired lead alloy.  This  involves the  following  process
 (15)  Blythe, D. J., Ed.,  "Lead and Arsenic  Reports",  Journal  of  the
      Air Pollution Control Association,  10  (5),  p  940-944  (1955).

-------
                                   C-112
 steps:   (a) charging the preheated kettle, (b) melting the charge,
 if not  added molten, (c) stirring to mix the flux into the charge,
 (d) skimming to remove collected impurities,  (e) pouring,  and (f) casting.
 Alloying agents commonly used are antimony, copper, silver, and tin.
           Source of energy for this process is natural gas and electricity
 to drive the equipment.
           Emissions data—waste products produced,  emissions factor,
 control of emissions,  and particle morphology—are  essentially the same
 for this process as for Process 7.
           Thus, the process can be a source of environmental pollution.

           Kettle Oxidation Process (9).   Battery lead oxide (PbO
 containing approximately 20 percent lead metal) is  produced by the
 kettle  oxidation process.   The process steps  are:   (a) charge kettle
 with  molten lead from  a melting pot,  (b) rapidly agitate  (mechanically)
 the lead,  (c)  draw air  over the surface  of the melt through the duct
 leading to the baghouse,  and (d)  collect the  lead oxide (fumed from the
 surface of the melt) in the baghouse.
           Source of energy is  natural  gas to  heat the melt furnace and
 the oxidation  furnace,  and electricity to drive the equipment.
           Atmospheric emissions are produced  by'this  process.   These
 include (1)  the combustion gases  which are separate from those from the
melting chamber,  oxidation chamber,  and  the baghouse;  and  (2)  fumes and
dust  from  the  melting and  oxidation chambers  and  the  baghouse.   The gases
are composed of carbon  dioxide, carbon monoxide, sulfur oxides,  nitrogen
oxides,  and unburned fuel,  whereas  the particulate  matter  contains  lead
oxide,  lead metal,  and  other metal  values  from  the  melting and  oxidation
chambers and the  baghouse.
           The major  source  of  emissions  is  the  baghouse since  the  air
is  being swept  over  the oxidation  chamber  into  the  baghouse.   Emission
factor  for  the  baghouse will vary  somewhat, but  in  most oxide  collection
systems, collection efficiency  averages  greater  than  98 percent.   On this
basis,  emissions  factor is  estimated at  less  than 40  Ib of lead  oxide
per ton of oxide  produced.  Particle size  of  the oxide  is  in  the submicron
range (approximately 0.2 to 0.5 micron)  and particle  shape  is  spherical.

-------
                                  0113
          Thus, the kettle oxidation process is a source of pollution
problems.

          Reverberatory Oxidation Process (10).  The most widely used
lead oxide pigments are lead monoxide (PbO) and red lead (Pb-0,).  These
are produced by the reverberatory oxidation process.  The process steps
are:  (a) charge the hot reverberatory furnace with molten lead,
(b) agitate the melt while oxidizing the lead to lead oxide, and
(c) remove the lead oxide from the furnace and cool rapidly.  Lead
oxide (PbO) is produced by fully oxidizing the lead, whereas red lead
(Pb_0.)  is produced by over-oxidizing the PbO.
          Energy required for this process is from the fuel (natural
gas or fuel oil) to heat the furnace.
          Waste products produced by this process are atmospheric
emissions.  These emissions are gases containing the combustion gases,
excess air, and nitrogen and particulate matter containing lead oxide
along with the impurities found in the lead charge.  These emissions
are carried from the furnace by entrainment in the furnace gases or
from volatilization and condensation of the lead oxide fumes.  Particle
size is in the submicron range and the particles are spherical in shape.
          Emissions data are not available for the reverberatory
oxidation process.  However, it is estimated that the emission factor
will range from approximately 40 to 150 Ib per ton of lead oxide
produced.  These emissions are most likely controlled by a baghouse.
          Thus, the reverberatory oxidation process for producing lead
oxides can be a source of serious pollution problems.

-------
                                  C-114
                 Population of Secondary Lead Processors
 (1)  Abrams Waste Materials Company
      1421 S. McBride Street
      Syracuse, New York

 (2)  Allie Smelting Corporation
      5116 W. Lincoln Avenue
      Milwaukee, Wisconsin  53219
      Telephone:  (414) 541-7830

 (3)  Cambridge Smelting Company
      100 Pacific Street
      Cambridge, Massachusetts

 (4)  Chicago Smelting and Refining Co.
      3701 S. Kedzie Avenue
      Chicago, Illinois

 (5)  Colinial Metals Company
      Columbia, Pennsylvania
      Telephone:  (717) 684-2311

 (6)  Crown Metal Company
      123 E. Washington
      Milwaukee, Wisconsin

 (7)  Detroit Lead Pipe Works, Inc.
      1701 Linden Avenue
      Detroit, Michigan

 (8)  Electric Storage Battery Company
      2  Penn Central Plaza
      Philadelphia,  Pennsylvania
      Telephone:  (215) 564-4030

 (9)  Florida Smelting Company
      2640 Capitola Street
      Jacksonville,  Florida
      Telephone:  (904) 353-4317

(10)  General Battery and Ceramic
        Corporation
    .  Post Office Box 1262
      Reading, Pennsylvania

 (11)   Industrial Metal Smelting Co.
      1508 Open Street
    ..  Baltimore, Maryland
(12)  Industrial Smelting Company
      19430 Mt.  Elliott & Marx Sts.
      Detroit,  Michigan

(13)  Inland Metals Refining Company
      651 E. 119th Street
      Chicago,  Illinois  60628

(14)  Lead Products,  Inc.
      Manchester,  Connecticut

(15)  Nassau Smelting and Refining
        Company, Inc.
      5  Nassau  Place
      Tottenville, New York
      Telephone  (212) 984-1970

(16)  National  Lead Company
      111 Broadway
      New York,  New York  10006
      Telephone:  (212) 732-9400

(17)  North American Smelting Company
      Terminal  (P. 0. Box 1952)
      Wilmington,  Delaware
      Telephone:  (302) 654-9901

(18)  Price Battery Corporation
      942 Grand  Street
      Hamburg,  Pennsylvania

(19)  Rochester  Lead  Works,  Inc.
      Exchange  and Ewell Sts.
      Rochester, New York

(20)  Schuylkill Products Co, Inc.
      Post Office  Box 3916
      Baton Rouge, Louisiana
      Telephone:  (504) 775-3040

(21)  Seitzinger's Inc.
      Post Office  Box 1336
      Atlanta,  Georgia
      Telephone:  (404) 876-3787

(22)  Southern  Lead Company
      2823 NW Moreland Road
      Post Office  Box 6195
      Dallas, Texas
      Telephone:  (214) 331-3241

-------
                                   C-115
(23)  U.  S.  Smelting Works
      American and Bristol Streets
      Philadelphia,  Pennsylvania

(24)  U.  S.  Lead Refinery, Inc.
      5300 Kennedy Avenue
      East Chicago,  Indiana
      Telephone:  (219)  397-1012

(25)  Hyman Viener & Sons
      Richmond,  Virginia  23205
      Telephone:  (703)  648-6563

(26)  Wenesley Metal Products Company
      1415 Osage
      Denver,  Colorado

(27)  Western  Lead Parts Company
      City of  Industry,  California

(28)  Willard  Smelting Company
      101 E. New Bern
      Charlotte, North Carolina

(29)  Winston  Lead Smelting Company
      Winston-Salem,  North Carolina

-------
• 7 | 6 5^4 3

!
REVIBIOMI
1=^ 	 -.„...„.,.. 	 h""' 1" "•
SCRAP PRETREATMENT SMELTING REFINING/CASTING '.
PA
•«««..—' s'c!K; *> . Tr^r5 p ^-^ rFUk p
' 	 ' BEVEBBERMWM /jo,, LŁM) \ ' X
' 	 1 	 ' VINCDT J ~ Rf FINING —
p x^^/ i 	 1
* ,^-U^ i— ALUMN6 At[Bt
DROSSES (, 	 • CRUSMIN6 vo.e .Hi)"—, _«rp,*j <, AC /^ v i— SULFUR
"ES10UŁS i LCADO.iots-^ F«R /u-n.-iffA 1 r"^"5' r
iiMinwi M O l-cwarionl ,H 1 1 fljŁ1- /
COKE-, , i | \ >-> l,"o 7 8 ^
(, V V / KtlTLt (ALLOrl V
' BLAST ruHNACC 0 	 f-*^ 	 ' »Ef™N6

	 (Lt*0 INEOTS1
MlPURt/SCfl) J
)
JLEAO IN6.M
T (ALLOT) I
1 /C;?V__ — ^r^] 	 •"•"'' ° ^ :
PYflOMEfALLURGlCAL 1 SCRAP 1 \- " / j «^ ^
^ \ ^/ 	 *S 	 	 . oxiOATion —
rUtl— '»»,,!* b
SMCATme 	 	 —
CABLE (WIRE.
fSs-^ p _ rAc,R c
DBOSS, LEAD • \ -li
OUDSSES t L «EVE«8Ell*rO(B O • lEvEBOERAIWi

UM THE AT ED
SCRAP (MXCOJ

LEGEND
O ATMisnCRic EMISSION;
A LIQUID WASfC
O SOUO WASTE
OPBDOUCI' Ot SrtJ«l«RY PAIU
MAICHIAir fCR UW m OTMEU SICKATUra »v
inojsrRiEs ^Jil. **
5."WWWH, •
fcic.
^ ^ -
1 IN Cl
^^ —
8 7 | 6 5^4 3
/LEAD \
_/OX!Ot )
"twirEirr 1
UEAOOnOtJ/
/RED LEAD \
) - 4 OUOE 1
! \»>3
-------
                                  C-L17
             PROCESS DESCRIPTION OF THE MAGNESIUM SEGMENT
                OF SECONDARY NONFERROUS METALS INDUSTRY
          Magnesium recovered from scrap constitutes approximately
10 percent of the U. S. production of magnesium metal..  In 1972, this
amounted to 15,662 short tons/1^ most of which was recovered from
aluminum alloys.  Emissions from the magnesium segment include minor
amounts of particulates and gases emitted to the atmosphere and solid
waste to the land.

                             Raw Materials

          Major sources of raw material to this segment include new
scrap (79 percent) and old scrap (21 percent).  Most of the new scrap
comprises magnesium-aluminum alloys generated in-house in the fabrication
and machining of  finished components.  The old scrap, also comprised of
magnesium-aluminum alloys, is generated from scrap automobile and aircraft
parts and, therefore, contains hand sortable ferrous and nonferrous
metallic parts.   Other sources of scrap include drosses and sludges.

                               Products

          Products from the magnesium segment of the secondary nonferrous
metals  industry include:
           (1)  Magnesium alloy ingot
           (2)  Magnesium alloy castings and shapes
           (3)  Aluminum-magnesium alloys
           (4)  Zinc and other alloys
           (5)  Cathodic protection  rods.
           Items (1) ,  (3), and  (5) constitute more  than 90 percent of  the
products.
 (1)   Telephone  conversation with  E.  Chin,  Chemist,  Division of Nonferrous
      Metals, USBM, Washington, D.  C.

-------
                                   C-118

                          Process Description

          The recovery of magnesium from scrap involves three manufacturing
operations:  (1) scrap pretreatment,  (2) smelting, and (3) casting.  These
operations and the individual processes under each operation are shown in
the flowsheet entitled "Magnesium Segment of The Secondary Nonferrous
Metals Industry"

Scrap Pretreatment Operation

          Magnesium scrap is hand sorted to separate the large and easily
identifiable pieces of other metals from the scrap magnesium parts as shown
in the flowsheet and discussed below.

          Hand Sorting Process  (1).   The process consists of separating
the magnesium and magnesium-alloy parts from all the other metals present
in the scrap.  The processing steps involve (1) spreading the scrap on
the floor and (2) hand picking  the  lightest pieces which are magnesium and
magnesium-alloys.  This hand picking  of light metal becomes second nature
to the person experienced in the process.
          The process does not  require any energy except human labor.
          Fine particles  left on the  floor constitute  the solid waste
generated by this process.  It  is usually insignificant as a source of
pollution.  Thus, the hand sorting  process does not offer any potential
for pollution.

S_melt_ing Operation

          The smelting of sorted scrap magnesium and the smelting  of
drosses and sludges are  the two processes under this operation.  However,
the same company does not necessarily do both  these operations.  The  scrap
melting facility finds it convenient  to ship its sludge  (slag) to  a sludge
processing facility, thus avoiding  a  potential solid waste disposal problem
at the scrap melting plant.

-------
                                  C-119
          Open Pot Melting Process  (2).  The sorted solid magnesium and
alloy scrap is transferred to a melt crucible of about  1000-lb capacity,
where the scrap is melted and the magnesium separated from the contaminants,
The process steps are:   (1) heat the crucible to melt the scrap,  (2) add
flux which is a mixture of calcium, sodium, and potass.ium chlorides,
(3) pour the molten metal into molds,  (4) cast the ingots, and (5) remove
the slag or sludge.
          Thermal energy is the main energy requirement of this process.
          The wastes generated are:  (1) gaseous effluents consisting of
chlorine, hydrogen chloride, smoke  from oil and grease, and particles of
dust, including small amounts of magnesium oxide (MgO); and (2) solid
waste as sludge containing slag which is sent for reprocessing at a sludge
smelter.  The estimated uncontrolled particulate emission factor  for a pot
                                           (2)
furnace is 4 Ib per ton of metal processed.
          This process has a moderate air pollution problem arising from
the gases generated.  In fact, the  in-house pollution is a greater threat
to the plant personnel than it is to the public by way of ambient air
pollution.   Some installations use  hoods to vent the gases to ambient air.
          The potential pollution from this process is significant by way
of air pollution if not controlled  properly.

          Sludge Smelting Process (3).   This  process recovers magnesium
from sludges produced in primary and secondary smelters.  The process
steps are:   (1)  heating, (2) flux addition, (3) slag removal,  and (4)
casting.
          Energy required for this  process is thermal energy.
          Potential pollutants from this process are solid wastes and
atmospheric emissions.  The solid waste--slag--contains the fluxes and
contaminants removed from the scrap.  The atmospheric emissions are
composed of chlorine and hydrogen chloride gases from the melting pot,
combustion gases,  and dust.
(2)  USEPA,  "Compilation of Air Pollution Emission Factors", Publication
     AP-42,  USEPA,  Washington, D.  C. (April,  1973).

-------
                                  C-120
          The atmospheric emissions, if uncontrolled, present an

atmospheric pollution problem, while the slags are a source of water

pollution if disposed of in an unapproved landfill.


Casting Operation


          Ingot Casting Process  (4).  The molten magnesium is cast into

ingots in this process.  The process steps are:  (1)  covering the melt

with a protective flux, (2) pouring the melt into casting dies, and

(3) casting the melt.

          Energy requirements of this process are not significant.

          Minor quantities of atmospheric emissions are generated.  Thus,

the quantity of emission is too small to represent any pollution potential,


              Population of Secondary Magnesium Processors
          (1)  American Smelting and Refining Company
               Federated Metals Division
               12 Pine Street
               New York, New York

          (2)  Apex Smelting Company
               Division of Amax Aluminum Company
               2515 West Taylor Street
               Chicago, Illinois
               Telephone:  (312) 332-2214

          (3)  Standard Magnesium
               Division of Kaiser Chemicals
               41st and Memorial Drive
               Tulsa, Oklahoma

          (4)  White Metal Rolling and Stamping Corporation
               84 Moultrie Street
               Brooklyn, New York

-------
        SCRAP PRETREATMENT
SCRAP fRQu OLD
fcUTOMOBtLES A
AIRCRAFT . ETC.
SMELTING
                                                                                       "    p
CASTING
                                                                                                                    LEGEND
                                                                                                                 LIQUID ««SIE
                                                                                                                 SOLID ««SIE
                                                                                                                    TOOOUCTS 0" SCCOKOWW RA»
                                                                                                                    ""TCBIALS «JB USE IN OIIC"
                                                                                                                    INDUSTRIES
                                                                                                                    iNTCRMEDuaC PTOOlXTS
                                                                 tlSNATUM 01V
                                                                                       AATTCLLC MCMORIAI. rNSTITUTE
                                                                                          COl-UMlu* UtKMATOMtCB
                                                                                      SCO KING AVC.. COLUMBIA. OHIO UZ01
                                                                                                                                                      ^MAGNESIUM SEGMENT OF
                                                                                                                                                     THE SECONDARY NONFERROUS
                                                                                                                                                      METALS INDUSTRY
                                                                                                                                                      D  79986
                                                                                                                                                                                      n
                                                                                                                                                                                      i •
                                                                                                                                                                                      10

-------
                                 C-122
             PROCESS DESCRIPTION OF THE MERCURY SEQ1ENT OF
               THE SECONDARY NONFERROUS METALS INDUSTRY
          The U. S. production of mercury by secondary recovery processes
was 12,139 flasks    in 1972, representing 62 percent of all mercury
produced in the U. S. in that year.  The salient statistics on the con-
sumption and production of mercury for the preceding two years are as
follows.(2)
                                              1971     1972
          Domestic consumption--flasks       52,275   52,907
          Production, primary processing     17,883    7,286
                      secondary processing   10,899   12,139
          Imports  (for consumption)          28,449   28,834
          The data indicate a sharp rise in mercury production by this
segment while production from the primary industry declined sharply,
probably due to a decrease in demand caused by the stringent mercury
                   (3)
emission standards    in December, 1971.
          Emissions to the land, water, or air from secondary mercury
processing, quantitatively speaking, are not significant.  However, the
extreme toxicity of the mercury vapor makes a careful study of this
industry worthwhile.  Due to the relatively high vapor pressure of mercury,
ambient mercury concentrations around open vessels can be sufficiently
greater than the threshold limit value (TLV) even at ordinary pressure and
temperature.  If good housekeeping in the secondary processing plants is
insured, mercury pollution will not reach significant levels.  The flowsheet
on the mercury segment of the Secondary Nonferrous Metals Industry provides
a flow of the processes and potential sources of emissions from each of the
processes.
(1)  Flask as used throughout this segment report refers to the 76-Ib flask.
(2)  Telephone conversation with V. Anthony Canunarota, Jr., Mercury
     Specialist, USBM, Washington, D. C.
(3)  Federal Register, National Emissions Standards for Hazardous Air
     Pollutants, Vol. 36, No. 234, pp 23,239-23,256 (December, 1971).

-------
                                  0123
                             Raw Materials

          Reported high volume sources of scrap for reprocessing include
the following:
          (1)  Salvage from instrument and electrical manufacturers,
               research laboratories (dirty liquid mercury from
               research organizations, educational institutions, etc.)
          (2)  Mercury battery scrap
          (3)  Industrial scrap
          (4)  Dental amalgam.
          The most common single source mentioned is dental amalgam,
though the absolute volume of this source is relatively small.  Obviously,
in this case, silver, rather than mercury, provides the primary incentive
             (4)
for recovery.
          Federal Effluent Standards for water considered to be in the
making may have created another source of scrap mercury.  The chlor-alkali
plant liquid effluent contains about 20 ppm mercury which needs to be reduced
to less than 5 parts per billion (ppb) which is considered to be the level
of mercury allowable by the regulations.  Rosenzweig  ' outlines the flow
schemes of two processes for mercury recovery from wastewater.  One of
them, the Osaka Soda Process, generates a resin as a solid waste containing
small amounts of recoverable mercury.  The solid waste generated is not
significant (about 1000 Ib per year).  Also, the amount of mercury recovered
by these processes is not significant enough to warrant further study as a
scrap recovery system.

                               Product

          The product from the mercury segment of the secondary metals
industry is liquid mercury.
(4)  ORNL Report, "Survey of the Mercury Reprocessing Industry 1968-1970",
     Report No. NSF-EP-22, ORNL, Oak Ridge, Tennessee 37830 (October, 1972).
(5)  Rosenzweig, Mark D., "Pairing Mercury Pollution", Chemical Engineering,
     pp 70-71, February 22, 1971.

-------
                                  C-124

                            Process  Description

           The recovery of mercury from scrap  involves  three manufacturing
 operations:   scrap pretreatment,  refining,  and bottling.   These  operations
 and  the individual processes under  each  operation are  shown on the  flowsheet
 entitled "Mercury Segment of the  Secondary  Nonferrous  Metals Industry".

 Scrap  Pretreatment Operation

           There  is no  pretreatment  of  the scrap when vacuum distillation
 is employed  as  the refining method.  The dirty liquid  mercury scrap  is
 fed  directly to  the distillation  vessel.  However,  during  transfer  of the
 scrap  mercury from the storage  to the  distillation  flask,  a small quantity
 of mercury may escape  as  vapor.   This  does  not constitute  any potential for
 widespread pollution.   Building ventilation at the  plant is sufficient to
 reduce the mercury levels  to below  the OSHA's  TLV of 100 ng/m  (Federal
 Register, Vol. 37,  No.  202,  October  18,  1972).

          Prefiltration Process (1).   This  is  a pretreatment operation used
 only with the oxygenation  process and  when  the mercury  scrap contains
 insoluble impurities that  need  to be removed before oxygenation  starts.  In
 fact,  this is the  only scrap  pretreatment operation in  the  entire secondary
mercury  industry.   The process removes insoluble  impurities by filtering
which  is a single  process  step.
          Energy,  mostly electrical, is required  for the filtration  process.
          The solid waste  (dirt) generated  is  sent  to  the  retorting  process
 for recovery of  trace  amounts of mercury that  may be present.
          The prefiltration process presents no potential  serious pollution
problem providing  the  area  is vented and gases  are cleaned  prior to  emitting
 to the atmosphere.

-------
                                  C-125

 Refining  Operation

           There  are  four different processes used  for  refining  scrap
 mercury.   The process  employed depends on  the  type  of  scrap.  Each of  the
 processes  (2 through 5) is  shown  in  the  flowsheet  on the mercury  segment
 and  discussed below.

           Vacuum Distillation Process  (2).  When the vapor pressure of  the
 impurities  is substantially  lower than that of mercury, purification by
 vacuum distillation which separates  a high purity mercury from  the impurities
 is employed.  The distillation unit  consists of a  still pot  for heating the
 impure mercury,  a water cooled condenser, and a pure mercury receiving
 vessel.  The processing steps are:   (1)  heating the still pot by  external
 heat  to vaporize the mercury at an absolute pressure of 0.01 torr (0.01 mm
 Hg Pressure), (2) condensing the  mercury in water-cooled condensers, and
 (3)  collecting the clean mercury  in  a receiver.  Afterwards, the  still
 residue is  removed for further processing.
          Energy requirements for this operation are:  (1) heat energy for
 heating the distillation still and (2) electrical energy to operate the
 vacuum pump and  associated equipment.
          The main source of potential pollution is the exhaust gas from
 the vacuum  pump.  Estimated maximum mercury emissions    by distillation
 are 0.02 Ib per  760 Ib of mercury produced.  Solid waste residue  from the
 still pot is normally recycled to other refining processes.  No liquid
 effluent is produced in this process.
          The process has no serious pollution potential if good  housekeeping
 practices are employed and precautions are taken to control emissions.

          Solution Purification Process  (3).   This process removes metallic
 and/or organic impurities contained  in the dirty liquid mercury by washing
with a dilute acid.   The processing  steps are (1)  leaching metallic
 impurities with dilute nitric acid using compressed air to mix the acid and
(6)  Battelle's Columbus Laboratories report to EPA, "Topical Report on
     Basis for National Emission Standards on Mercury", Battelle's Columbus
     Labs, Columbus, Ohio, June 15, 1971.

-------
                                   C-126

 mercury; (2) separating the mercury layer from the aqueous nitric acid slurry
 by decantation; (3) water washing to remove residual acid, and (4) filtering,
 probably through a bed of activated charcoal and silica gel, to remove last
 traces of water.  If the mercury contains organic impurities, the scrap
 mercury is treated in the same manner with organic solvents.
           Electrical energy is required to operate the compressor and
 associated equipment.  Pumping the mercury is avoided by use of gravity flow
 scheme from overhead tanks.
           Potential pollutants generated by this process are atmospheric
 emissions,  liquid  wastes,  and solid wastes.
           The atmospheric emissions containing mercury vapor result from
 sparging of the liquid mercury during the leaching step.  The spent leach
 liquor is the source of liquid waste,  while the solid waste consists  of the
 contaminated filter media.
           In view  of the hazardous nature of mercury, pollution problems
 can result.

           Oxygenation Process (4).   This process,  also called oxification,
 removes  the  metallic impurities contained in dirty liquid mercury by  oxidation
 with  sparging air.   The process steps  are;   (1)  sparging the dirty mercury
 with  air in  a closed,  agitated vessel  for several  hours  and (2)  filtration
 to  remove  solid metal oxides.   Finally,  the filtered  mercury is  bottled which
 is  discussed  in the  bottling  process.
          Electrical energy is required  for sparging  and water  scrubbing
 process  steps.
          Sparging air  which  contains  saturation  levels  of mercury at  77 F
 is  a  potential  atmospheric  pollutant.  However, before venting  to the
 atmosphere,  it  is generally water  scrubbed  and  filtered  through  a bed  of
 charcoal  to remove the  mercury.  The water  is  recycled many ti.nes before
 discharge because mercury settles out  of  the water.   In  most cases, the
 solid waste as  filter cake  is  sent  to  the retorting process.  Thus, the
 potential pollutants  from this process are  atmospheric emissions,  liquid
wastes,  and solid wastes.
          The potential  for pollution  from  this process  is  not significant,
 providing pollutants are treated before discharging to the  environment.

-------
                                  C-127
          Retorting Process (5).  This process produces pure mercury by
volatilization of the mercury contained in solid scrap.  Examples of scrap
are dental amalgams, mercury battery scrap, and distillation sludges.  The
process steps are:  (1) external heating of solid scrap in a closed still
pot or stack of trays to volatize the mercury, (2) cooling mercury vapor in
water-cooled condensers to condense the vapors, and (3) bottling which is
discussed in Process (6).
          Heat energy is required for volatilization of mercury and
electrical energy for cooling water circulation.
          Potential pollutants generated by the process are atmospheric
emissions from the retort, liquid wastes from the condenser, and cleaning
of the atmospheric emissions and solid wastes as the retort residue, each
containing mercury.  The degree of pollution can be reduced by scrubbing of
the process gases prior to emission to the atmosphere, packaging of the
retort residue and disposing of it in a hazardous landfill, and treating the
liquid wastes prior to disposal.
          Because of the hazardous nature of mercury,  this process can be.a
source of serious pollution problems.

Bottling Operation

          Bottling Process  (6).  Bottling of  the purified mercury is done to
enable marketing of the product in 76-lb flasks.
          The steps are  (1) pumping or manual pouring  of the mercury into
the 76-lb bottles and  (2) sealing the bottling.
          Electrical energy is used for pumping  the mercury to the bottles.
          The only waste emission is mercury vapor  (at 77 F), produced when
pumping or pouring mercury  into the bottle.   This is not a significant source
of air pollution but can cause high levels of mercury  vapor inplant.  Building
ventilation air is used  to  reduce the mercury  levels to below the TLV.
          The bottling process does not offer any potential for serious  air
pollution.

-------
                         C-128
     Population of Secondary Mercury Processors
 (I)  Florida Smelting Company
      2640 Capitola Street
      P. Box 3404
      Jacksonville, Florida
      Telephone:   (904) 353-9317

 (2)  Kahl Scientific Instrument Corporation
      737 West Main Street
      El Cajon, California  92022
      Telephone:   (714) 444-5944

 (3)  Metallurgical Products Company
      35th and Moore Streets
      Philadelphia, Pennsylvania  19148
      Telephone:   (215) 394-8300

 (4)  Wood-Ridge Chemical Corporation
      Park Place East
      Wood-Ridge, New Jersey  07075
      Telephone:   (201) 939-4600

 (5)  Eastern Smelting and Refining Corporation
      35 Bubier Street
      Lynn, Massachusetts  01901

 (6)  Martin Metals, Inc.
      1321 Wilson Street
      Los Angeles, California  90021

 (7)  Mallory (P.R.) and Company, Inc.
      3029 East Washington Street
      Indianapolis, Indiana  46206

 (8)  Bethlehem Apparatus, Inc.
      890 Front Street
      Hellerton, Pennsylvania  18055

 (9)  Dresher Metal Trading, Inc.
      Box 44
      Dresher, Pennsylvania  19025

(10)  D. F. Goldsmith Chemical and Metal Corporation
      109 Pither Avenue
      Evanston,  Illinois  60202

-------
                        C-129
(11)   Williams  Gold  Refining,  Inc.
      2978  Main Street
      Buffalo,  New York  14214

(12)   Merck and Company
      Metal Salts  Division
      Hawthorne, New Jersey

(13)   Iritox Chemical Company
      284 Hamilton Avenue
      Brooklyn, New  York  11231

-------
                                                                                                                                                       RKVIftlONl
         SCRAP   PRETREATMEIMT
D«TY LIQUID
UCRCURr
REFINING
                                                                                                          <(> SOLID WASTE
                                                                                                       O
                                                      BOTTLING

f«_TR*TION

P.
6

1 — am r LIOUC MEBCURT
| | — KCCCE& WIERft
VACUUM O
niSIIllATIOM

. — D«TY LIQUID MFfin«Y
(— Ot-UTt NITRC DCID
ORGAMC
1 p savon o
3 X
SOLUTION ' ^/
PURIFICATON

| — CHWOOAL
Ir^'"""*71^

• UK i(»Er«-«T &*
J
(SIU ) r^S^T^
^T^ 5 o
RL









LEGEND
O 'TVOSPMERC EMISSIONS
A LIQUD WASTE
                                     PftqOgCTS OR SECONDARY RAW
                                     MATERIALS FDR USE IN OT«n
                                     IMXJSTRIES
                                                                                                                INTEflMEOATE PTOOXTS
•ATTXLLC MEMORIAL IMVTITUTC
                                                                             KINO AVt. COLUMBUS, OHIO OBI
                                                                                                                                                  SECONDARY NONFERROUS
                                                                                                                                                  METALS  INDUSTRY
                                                                                                                                                  D 79986
                                                                                                                                                                                 O
                                                                                                                                                                                .  I

-------
                                  C-131
               PROCESS DESCRIPTION OF THE NICKEL SEGMENT
              OF THE SECONDARY NONFERROUS METALS INDUSTRY

          During 1971, this segment recovered 29,657 short tons of nickel,
mostly as alloys, from old and new scrap.  This recovery amounted to about
30 percent of total U.- S. nickel consumption.  It is estimated* that only
about 40 percent of the available scrap is recycled.  The remaining
60 percent, such as used nickel-cadmium batteries and spent nickel-base
catalysts, are disposed of in landfills.  Emissions to the environment
from this segment are atmospheric emissions and solid wastes.

                             Raw Materials

          Raw materials include old scrap (74 percent) and new scrap
(26 percent) both comprising of nickel-, copper-, and aluminum-base alloys.
The scrap originates as used burners (inconel), airplane parts, sheet
scrap,  electrical scrap,  and so on.  An exact percent breakdown of the
contribution of these sources is not available.

                               Products

          Products from the nickel segment are slag and the following
alloys:
          (1)   Stainless  steels (18/8 and other grades)
          (2)   Nickel-base alloys (cupronickel, nickel silver, etc.)
          (3)   Base alloys (low alloy steels)
          (4)   Nickel metal (quantitatively not significant).

                          Process Description

          The  recovery of nickel as nickel alloys from scrap involves
three manufacturing operations:  (1)  scrap pretreatment, (2) smelting,
(1)  Battelle's NASMI Report, "A Study to Identify Increased Solid Waste
     Utilization", Battelle's Columbus Laboratories, Columbus, Ohio  43201,
     (June, 1972).

-------
                                  C-132

 and  (3)  refining/casting.   These operations  and  the  individual  processes
 under  each  operation are shown  in the  flowsheet  entitled  "Nickel  Segment
 of The Secondary  Nonferrous Metals  Industry".

 Scrap  Pretreatment  Operation

          Hand  Sorting  Process  (I).  This  process  is done usually at  the
 scrap  merchant's  facilities rather  than  at the scrap smelting facilities.
          The process segregates the nickel  bearing  alloys  and  metals
 from the nickel-free components  in  the raw scrap.
          The process steps are:   (a)  spread the  scrap on  a platform and
 (b) separate the  nickel  scrap from  the nonmetallics  and nonnickel components.
          Manual  labor  is  the only  energy  requirement  for the process.
          Wastes  produced  are limited  to a small quantity of solid wastes
which  are composed  of dirt and nonnickel scrap.
          The pollution  potential of the waste is  insignificant.

Smelting Operation

          In the  smelting  operation, partial purification of the  nickel
scrap  is achieved or the nickel  scrap  is melted and mixed with  selected
alloying agents as  outlined in the  segment flowsheet by Processes 2 and 3.

          Electric  Arc Process  (2).  This  process  produces  a partially
purified product which is  purified  further in the  refining/casting
operation or nickel  alloys  which are cast  into alloy ingots.
          The process steps  are:   (a) charging the scrap  to the electric
arc furnace, (b) adding  a  reductant (lime),  (c) melting the charge,
(d) pouring into molds or  transferring the molten metal to  a reactor for
refining, and (e) removing  the slag.
          Electric  energy  is required in substantial quantities for this
process to operate  the furnace.  Additional energy is  required  to operate
the auxiliary equipment.

-------
                                  C-133

          Wastes generated are:  (1) atmospheric emissions consisting
of large quantities of dust particles and limited quantities of gases
and (2) solid wastes consisting of furnace slag.
          The off gases are invariably treated 'in a baghouse which removes
approximately 99 percent of the dust particles.  Hence, the gases are clean
when vented and do not' constitute any serious air pollution problem.
However, the collected dust (about 4 tons/day at a medium size facility)
is sent to a landfill and may be considered a potential source of water
pollution by leaching to surface and ground waters.  The metal value of
this dust is unknown and the industry would like to investigate possibilities
of recovery of any metals in the dust.*
          The slag may or may not be a waste as, in many cases, it is
ground at another facility for use in sandblasting or road surfacing
operations.*

          Rotary Reverberatory Furnace Smelting Process (3).  This process
is the same as Process (2) except a reverberatory furnace is used in place
of an electric arc furnace.  The process steps are:  (a) charging the scrap
to the furnace, (b) adding a reductant (lime),  (c) melting the charge,
(d) pouring the melt in the molds or transferring the melt to a reactor
for refining, and (e) removing the slag.
          Energy required for this process is from the fuel to operate
the furnace and other forms of energy to operate the auxiliary equipment.
          Potential environmental pollutants produced by this process are
atmospheric emissions and solid wastes.  The atmospheric emissions are
composed of dust particles and gases.  These are, in most cases, treated
in baghouses which collect approximately 99 percent of the particulate
matter.  The solid waste is generated as slag and, in most cases, is
ground at another facility for use in sandblasting or road surfacing
operations.
          Thus, the smelting process is a potential source of pollution
problems.  These problems may result from disposal of the baghouse dusts
* Conversation with Leonard Arness, ARMCO  Steel Advanced Metals  Division,
  P. 0.  Box  1697,  Baltimore, Maryland  21203.

-------
                                 C-134
via  landfill which  could  result  in  contamination of  the water system and
possibly contamination  of the atmosphere with gases  and particulate matter
from pollution abatement  equipment.  However, atmospheric emissions do
not probably constitute a serious pollution hazard.

          Reactor Finishing  (4).  This process, very similar to a
foundry operation,  purifies  the metal further and adjusts the composition
to the required values.
          The process steps  are:  (a) charging the molten metal to the
furnace; (b) adding cold  metals such as base scrap and pig nickel;
(c) adding lime, silica,  and trim (manganese, columbium, titanium, etc.,
in trace quantities as  required by  alloy composition);  (d) melting the
charge; (e) pouring into  molds, and (f) removing the slag.
          Large amounts of heat energy are required by the process.
          Potential pollutants generated by this process are atmospheric
emissions containing gases and particulate matter and solid wastes in the
form of slag.  The  atmospheric emissions are treated via a baghouse
which removes approximately  99 percent of the particles.  The slag is
sold as a product for use as a sandblasting material or in road surfacing
operations.
          Thus, the reactor  finishing process has a  low potential for the
production of serious pollution problems.

Casting Operation

          Ingot Casting (5).  In this process the molten alloy from the
reactor or electric furnace is cast into required shapes.
          The process steps are:  (a)  pouring into molds and (b) removing
the ingots from the mold  after they are cast by air cooling.
          Energy requirements of the process are minimal

-------
                                  C-135
          Wastes produced are minor amounts of metallic vapor which stays

inplant.
          The potential pollution of the wastes is insignificant.


                Population of Secondary Nickel Processors
          (1)  Alloy Metal Products,  Inc.
               626 Schmidt Road
               Davenport,  Iowa
               Telephone:   (319) 324-3511
          (2)  American Nickel Alloy Manufacturing Company
               30 Vesey Street
               New York, New York  10007

          (3)  ARMCO Steel Corporation
               Advanced Metals Division
               P. 0. Box 1697
               Baltimore,  Maryland  21203

          (4)  Belmont Smelting Company
               330 Belmont Avenue
               Brooklyn, New York  11207

          (5)  Frenkel Company
               19300 Filer Avenue
               Detroit, Michigan
               Telephone:   306-5300

          (6)  Mercer Alloy Corporation
               1 Alloy Road
               Greenville, Pennsylvania  16123

          (7)  Metal Bank of America, Inc.
               6801 State Road
               Philadelphia, Pennsylvania  19135
               Telephone:   (215) 332-6600

          (8)  Paragon Smelting Corporation
               36-08 Review Avenue
               Long Island City, New York  11101
               Telephone:   (212) 729-3641

          (9)  Riverside Alloy Metal
               Division of H. K. Porter Company, Inc.
               309, Porter Building
               Pittsburgh, Pennsylvania  15219
               Telephone:   (412) 391-1800

         (10)  I. Schumann Company
               Division of Ogden Metals Company
               22500 Alexander Road
               Cleveland,  Ohio

-------
                         C-136
(11)  Utica Alloys, Incorporated
      Box 53
      Utica, New York  13501

(12)  Wai Met Alloys Company
      7322 Oakman Boulevard
      Dearborn,  Michigan
      Telephone:  (313)  581-7200

(13)  Whitaker Metals
      Alloy Division
      P.  0. Box 607
      Greenville, Pennsylvania  16125

-------
SCRAP  PRETREATMENT
SMELTING
REFINING/CAST ING
                                                                                                    LEGEND
                                                                                             O n
                                                                                             A I-IQUHI »«s
                                                                                             ^ SOLID HHSTt
                                                                                          O
                                     PfCOuCTS OR SECOMMffr RAW
                                     MATERIALS FOR Utt 9t OT*H
                                     (NOUSTRiES
                                                                                                                    STAMBAUGH
                       awn
                                                                                                                                                                  o
                                                                                                                                                                  OJ
                                  BATTCLkŁ MCMOAIAL imTITVTI

                                  KtNC AVK.. COLUMBIA. OHIO 4
                                                                    ""NICKEL SEGMENT OF THE
                                                                      NONFERROUS METALS
                                                                      INDUSTRY
                                                                                                                                  D 79986

-------
                                  C-138
           PROCESS  DESCRIPTION  OF  THE  PRECIOUS METALS  SEGMENT
               OF THE  SECONDARY NONFERROUS METALS  INDUSTRY
           This  segment  includes  the  secondary  recovery methods for gold,
silver, and platinum group  of metals.  These are grouped together because
they derive from  the same scrap  and  the same general recovery operations
are used to obtain  the  individual metals from  the scrap.
           Exact statistics  on scrap volume are not available.  However,
estimates  are that  about 10,000  tons of scrap  are processed per year,
excluding  low grade scrap which  is disposed of in landfills at present.
These scrap estimates are corroborated by the  secondary platinum and silver
production figures, the silver consumption of  the electronic industry being
about 28 percent of the total U. S. silver consumption.  Production
statistics of this  segment  from  new and old scrap are as follows:


1971
Production of Precious Metals
Secondary

Gold
Silver
Platinum
Troy
2.2
47 x
103,
Ounces*
x IO6
io6
429
Tons
75.5
1597
3.55
Primary
Troy Ounces
1.5 x IO6
69 x IO6
10,198
Tons
51.2
2355
0.35
Percent**
1477.
68%
1014%
     *  One troy ounce is equal to   1.1 regular  (avdp.) ounce.
     ** Secondary as a percent of the primary production.

                             Raw Materials
          Electronic components such as gold-plated contacts and printed
circuit boards from military and civilian scrap equipment are the chief
source of scrap for this segment.  The second important source is scrap
from the dental industry.  Scrap jewelry usually goes to special smelters
as these do not require complicated processing.  Thus, raw materials to
this segment include:
          (1)  Electronic scrap consisting of relay contacts,
               switch contacts, wires, solders, etc.
          (2)  Dental analgams, inlays, dentures, and crowns
          (3)  New scrap generated in manufacturing.

-------
                                  C-139
                               Products

          Products from this segment include:
          (1)  Refined gold metal
          (2)  Refined silver metal
          (3)  Refined platinum metal
          (4)  Refined palladium and trace quantities of iridium
               and other metals.

                          Process Description

          The recovery of precious metals from scrap involves three
manufacturing operations:  (1) scrap pretreatment, (2) smelting, and
(3) refining/casting.  These operations and the individual processes under
each operation are shown in the flowsheet entitled "Precious Metals Segment
of The Secondary Nonferrous Metals Industry".

Scrap Pretreatment Operation

          Although a variety of processes are possible in scrap
pretreatment, only two processes are notably important for detailed
consideration.

          Hand Sorting and Crushing Process  (1).  Bulk precious metals
scrap consisting of identifiable aluminum contaminants (aluminum chasis)
is hand sorted to separate the aluminum from the scrap.  The aluminum-free
scrap is then crushed in a hammer mill.
          The process steps are:   (a) spread bulk scrap on floor,
(b) pick out aluminum parts, and (c) shred aluminum-free scrap in a
hammer mill shredder.
          The process requires electrical energy for crushing.
          Wastes generated consist of minor  in-house dust emissions during
charging and discharging of the shredder.
          The potential for pollution of wastes in this process is
insignificant.

-------
                                   C-140

           Incineration Process (2).  The crushed scrap is incinerated
 to burn off plastics and organic liquids and prepare a smelter feed.
           The processing steps are:  (a) charge to incinerator,  (b)  burn-
 off combustible constituents, and (c) discharge smelter feed.
           The process requires heat energy.
           Wastes generated are:  (1) atmospheric emissions consisting of
 organic vapors and dust particles and (2)  liquid waste if wet  scrubbing
 is used to control dust particles in the atmospheric emissions.
           Untreated wastes have considerable ambient air pollution
 potential.   However, the atmospheric emissions are treated in  an
 afterburner to complete combustion of organic matter.   Thus, the  effluents
 from the afterburner contain particles  of  dust and metal.   Usually a  wet
 scrubber or baghouse is used to collect these particles.   The  amount  of
 dust collected by either of these control  devices  is not sufficient  to
 constitute  serious solid waste problems.   Similarly,  any liquid waste
 generated is insignificant.
           Therefore, the wastes from this  process  have  no  serious
 pollution potential.

 Smelting  Operation

           Blast  Furnace  Smelting  Process  C3).   This  process purifies  the
 pretreated  scrap  to  produce  black  copper.
          The  process  steps  are:   (a) charging  the  segregated  scrap with
 coke and  flux,  (b) melting  the  charge,  (c) slagging  the melt,  (d) dis-
 charging  black copper, and  (e)  removing  the  slag.
          Heat energy  is  the main energy requirement of  the process.
          Copious  amounts of atmospheric emissions and moderate quantities
of solid waste—hard slag--are  generated in  the process.  The  atmospheric
emissions are  treated  in  a baghouse.  The collected dust is landfilled.
The hard  slag  is  crushed  and used in sand blasting operations.
          Therefore, the wastes generated in  this process do not have
significant pollution potential.

-------
                                  C-141
          Converter Purification (4).  The black copper is further
purified by oxidizing the contaminating metals with air blown through
the heated copper.  The end product is bullion (copper rich in precious
metals).
          The process steps are:  (a) charging the converter, (b) blowing
the melt, (c) removing the slag, (d) pouring the melt into molds, and
(e) casting the ingots.
          Heat energy is the main energy requirement.
          Wastes generated are:  (1) minor amounts of atmospheric emissions
and (2) slag metal oxides.  The slag metal oxides are recycled to the
blast furnace.
          Therefore, the process has no significant pollution potential
if the atmospheric emissions are controlled.

Refining/Casting Operation

          Electrolytic Refining Process (5).  The bullion from the
converter (as the anode) is electrolytically separated into pure copper
(cathode) and precious metal slimes.
          The process steps are:  (a) charging the electrolyte (copper
sulfate - CuSO,),  (b) electrolysis, and (c) slime recovery.
          Electrical energy is required in this process.
          Waste products are limited to minor amounts of gaseous hydrogen
and arsine.  Quantitatively, these wastes do not represent significant
potential for pollution.  Arsine is very much below TLV levels.

          Chemical Refining Process  (6).  The precious metals slime
from the electrolytic process  is refined to isolate each of  the  precious
metals by complex chemical processes.
          The process steps are:  (a) treating the slime with aqua regia
to dissolve the precious metals; (b) precipitate the gold, silver, and
platinum with suitable chemical solutions; and (c) melt or ignite to  collect
gold and silver as grains and  platinum and palladium as sponge.
          The process requires electrical and thermal energy  in  moderate
quantities.

-------
                                   C-142

          Wastes include waste liquor discharged to waterways and
atmospheric emissions generated during melting and ignition.

          The process has a low potential for the production of
atmospheric emission problems if emissions are controlled.  Discharge

of the spent liquor to the waterways could result in pollution problems,


           Population of Secondary Precious Metals Industries


          (1)  Joseph Behr and Sons, Inc.
               1100 Seminary Street
               Rockford, Illinois
               Telephone:  (815) 962-7721

          (2)  Eastern Smelting and Refining Corporation
               105 West Brookline Street
               Boston, Massachusetts  02118

          (3)  Handy and Harman
               850 Third Avenue
               New York, New York  10022
               Telephone:  (212) 752-3400

               (Refining of precious metal scrap is carried out in
               Fairfield, Connecticut and Los Angeles,  California)

          (4)  Hudsar, Inc.
               567 Wilson Avenue
               Newark, New Jersey  07105
               Telephone:  (201) 642-7334

          (5)  Metallurgical Products Company
               35th and Moone  Streets
               Philadelphia,  Pennsylvania  48300
               Telephone:  (215)  394-8300

          (6)  Pease and Curren,  Inc.
               780 Aliens Avenue
               Providence,  Rhode Island  02905
               Telephone:  (401)  461-6340

          (7)  Phelps  Dodge  Refining Corporation
               300 Park Avenue
               New York,  New York
               Telephone:  (212)  751-3200

          (8)  United  States Metals Refining Company
               1270 Avenue of  the Americas
               New York,  New York  10020
               Telephone:  (212)  757-9700

-------
SCRAP  PRE TREATMENT
                                                            SMELTING
                                                                                                                                      REFINING/CASTING
                                                                                                                                 COPPCft SULfATE
                                                                                                                                                                                                       n
                                                                                                                                                                                                       LO
                                                                                                                              LEGEND



                                                                                                                      O ATMOSACRC EMISSIONS

                                                                                                                      Ł LIQUIO WASTE

                                                                                                                        . SOLID WASTE
                                                                                                                            pwmcrs OR scccxcum RAW
                                                                                                                            MATERIALS FOR USE IN OTHER
                                                                                                                                ITRtES
                                                                                                                            INTERMEDIATE PROQUCTS
                                                                                                                                                  NACK
  OATTO-LC MEMORIAL rNSTITUTI

an KINO AVI.. OOLUMOU9. OHIO uat
                                                                                                                                                                   PRECIOUS NETALS SEGMENT OF
                                                                                                                                                                   THE  SECONDARY NONFERROUS
                                                                                                                                                                   METALS  INDUSTRY
                                                                                                                                                                   0 79986

-------
                                    C-144

                 PROCESS DESCRIPTION OF SELENIUM SEGMENT
                 OF SECONDARY NONFERROUS METALS INDUSTRY

           Tonnage-wise, the selenium segment constitutes one of the minor
 segments of the secondary nonferrous metals industry.  Based on 1971 data,
 30,000 Ibs or about 3 percent of the total U. S.  consumption was recovered
 from scrap.   Wastes from this segment are atmospheric emissions, liquid
 wastes, and  solid wastes.

                               Raw Materials

           Sources of raw materials for this segment, including both new and
 old  scrap, are:
           (1)   Selenium rectifiers (burned out and factory rejects)
           (2)   Spent catalysts
           (3)   Used xerographic plates.

                                 Products

          The  product  from this segment  is metallic selenium in the form of
 shot,  refined  powder,  and  selenium ingots.

                            Process  Description

          The  recovery of  selenium  from selenium scrap  involves three manu-
 facturing operations:   scrap  pretreatment, smelting/refining,  and casting
 (product formation).   These operations and the  individual  processes under
each operation are  shown  on the  flowsheet  entitled  "Selenium Segment of  the
Secondary Nonferrous Metals Industry".

Scrap Pretreatment

          Selenium  is  separated from the majority of  the other  scrap compo-
nents in the  scrap  pretreatment operation.

-------
                                   C-145
          Mechanical  Process  (1).  The selenium  is  separated  from  the other
 scrap components by hammer-mi11 ing,  shot blasting,  and  similar methods.  The
 recovered selenium is  further  processed or sold  as  a  selenium metal.
          Energy demand  is  that needed to drive  the equipment.
          The  process  produces atmospheric emissions  and. solid wastes.  The
 atmospheric emissions  contain  particulates of selenium  metal, compounds,
 alloys, and oxide, whereas  the solid wastes are  composed  of metallic and
 nonmetallic scrap.

 Smelt ing/Re fin ing Operation

          In the smelting/refining operation, the pretreated  scrap  is puri-
 fied to produce selenium metal for subsequent processing. The processes by
 which the purification is achieved are Numbers 2 through  4 on the  flowsheet.

          Retort Smelting Process  (2).  In retort smelting, partial purifi-
 cation of the  pretreated scrap is  achieved and the  scrap  is densified.  The
 process steps  are:   (1)  charging the retort,  (2) melting  the  scrap, (3) sep-
 arating the selenium  from the  impurities by distillation, and  (4)  discharging
 the residue from retort.
          The  energy  required  is that needed  to  heat  the  retort.
          Potential environmental  pollutants  are atmospheric  emissions, solid
 wastes, and liquid wastes.  The atmospheric emissions are composed  of gases
 and particulate matter containing  selenium.   The solid  wastes contain the
 impurities from the scrap selenium.  These wastes may go  to landfill.  The
 liquid waste is cooling water which may be recycled in  most cases.
          Thus, retort smelting has  the potential for producing atmospheric
 pollution problems as well  as water  pollution problems  from leaching  in the
 landfill.

          Hydrometallurgical Refining (3).   Hydrometallurgical refining also
achieves a partial purification of the scrap selenium.  The process steps
are:  (1)  dissolve the scrap selenium or the selenium from Process  2 in a

-------
                                    C-146

 suitable  solvent  such as aqueous  sodium  sulfite,  (2) remove insoluble impur-
 ities by  filtration, and (3)  precipitate  the selenium for further purifica-
 tion.
           The energy required is  that needed to heat the solutions and oper-
 ate the auxilliary equipment.
           Potential environmental pollutants are atmospheric emissions if
 gases are used to precipitate the selenium, liquid wastes, and solid wastes.
 The process has the potential for the generation of pollution problems.

           Distillation Process (4).   This process yields high-purity selenium.
 The process steps are:   (1) charge the distillation unit, (2)  melt and dis-
 till the selenium, (3)  condense  the  selenium vapors,  (4) transfer molten
 selenium to the product formation operation, and (5)  remove  residue.from
 the still.
           The  energy required is  that needed to operate  the  distillation unit.
           Potential  pollutants are atmospheric  emissions composed of distilla-
 tion wastes and particulates of  selenium, solid wastes,  and  liquid wastes.
 This process also has  the  potential  for  the  production of pollution  problems.

 Product  Formation Operation

           In product  formation, the molten selenium is converted  to  the  de-
 sired shape.  The  processes used  to achieve  this are  Processes 5  and  6.

          Quenching  Process (5).   The  quenching  process  produces  selenium
 shot and selenium  powder.   The process steps for the  production of selenium
 shot are:   (1) quench the selenium melt in a quenching liquid, (2) separate
 the  shot from the  cooling liquid,  and  (3) dry the shot.   Powder is produced
by quenching the selenium vapors from  the distillation unit.
          Energy required is  that  needed  to cool the quenching medium and
operate the auxilliary equipment.

-------
                                   C-147
          Potential pollutants are liquid wastes such as cooling water which
is recycled in most cases.  The process has a low potential for the produc-

tion of pollution problems.


          Casting Process (6).  By this process, the molten selenium is

cast into ingots or other shapes.  The process steps are:  (1) pour the

molten selenium into the molds and (2) solidify the melt.
          Energy is needed to operate the equipment.
          Essentially no pollutants are emitted.  Thus, the process has no

potential for the production of pollution problems.
               Population of Secondary Selenium Processors
          (1)  Kawecki-Berylco Industries
               Box 1462
               Tuckertown Road
               Reading, Pennsylvania  19603

          (2)  American Smelting and Refining Company
               3422 South 700 West
               Salt Lake City, Utah  84119

          (3)  U. S. Metals Refining Company
               Division of American Metals Climax, Inc,
               300 Middlesex Avenue
               Carteret, New Jersey

          (4)  Eastern Metal Converters, Inc.
               52 Wall Street
               New York, New York
               Telephone:  4-5778

          (5)  Kawecki-Berylco Industries, Inc.
               220 E. 42nd Street
               New York, New York

          (6)  Metallurgical Products Company
               35th and Moore Streets
               Philadelphia, Pennsylvania
               Telephone:  344-8300

-------
                          C-148
 (7)  Max Zuckerman and Sons
      Music Fair Road
      Owings Mills, Maryland  21117
      Telephone:  (301) 484-0400

 (8)  Phelps Dodge Refining Corporation
      300 Park Avenue
      New York, New York

 (9)  Belmont Smelting and Refining Works
      320 Belmont Avenue
      Brooklyn, New York  11207
      Telephone:  (212) 624-4004

(10)  Alloy Chem, Inc.
      641 Lexington Avenue
      New York, New York  10022
      Telephone:  (212) 421-6300

-------
8
                 SCRAP  PRETREATMENT
SMELT I'.JC/ REFINING
                                                                                                 PRODUCT  FORMATION
1
&& P !
2
RETORT
5UEL.TIMG
I
s.
^> 1
1
1
1
Ij-AQjEOuS SQQUM SULFiTE ,
;J^'C^'°EA (
3
*ETM.LUBClCAl
REFINING
6
i
j 1
1 P |



0 1
1
1
1















QUENCHING






6







-°A






-H



i
I



H



                                                                                                                                                                                 n
                                                                                                                                                                                 i
                                                                                                                                                                                 vO
8
                                                                                                     V
                                                                                                              LEGEND
                                                                                                          ATUOSFWC CUI&SIONS


                                                                                                          LIQUID WASTE


                                                                                                          SOLID WASTE
                                                                                                             POOOUCTS CR SCOMWTY RAW

                                                                                                             MATERIALS FOR USE W OTHER

                                                                                                             INDUSTRIES
                                                                                                              INTERMCOIAIE POOOUCTS
                                                                                                                                        MS X-CV3
                                                                                       bATTtXtC MXMOMIAt. INVTITUTT



                                                                                      09 KING AVL. COLUMBUS, OHIO US)
                                                                                                                                               SECONDARY 'CNF

                                                                                                                                               MFTA1S  IND-STRY
                                                                                                                                                                "OF
                                                                                   79986

-------
                                   C-L50
                PROCESS DESCRIPTION OF THE TIN SEGMENT OF
                THE SECONDARY NONFERROUS METALS INDUSTRY
           The importance of the tin segment of the secondary nonferrous
 metals industry is highlighted by the fact that virtually all U.  S.
 primary tin requirements (69,029 tons in 1972) are imported and that the
 secondary production constitutes about one-third of total U. S. production.
 In 1972,  this amounted to 20,180 long tons.  The forecast demand  for tin
 for the year 2000 is about 120,000 long tons.
           Additional salient tin recovery statistics for the U. S.^  '  are
 provided  below.
                                             1967     1971     1972
      Secondary tin recovered (long tons)    21,000   20,096   20,180
      U.  S.  tin consumption (long tons)      82,000   69,950   69,029
      Percent secondary tin recovery         25.6     28.7     29.2
      Percent as  primary tin                  16       10       10
      Percent as  alloy,  etc.
           Minor  sources of air  pollution  are the dross  smelting and  gas
 fired refining processes.   The  water  pollution potential from the chemical
 detinning  operation is  the major pollution problem of the tin scrap
 recovery  segment.

                              Raw Materials
          Major  raw  material  sources  for  scrap  recovery are  the  trimmings
and rejects  from the can  companies  and  rejected plating coils  from  the
steel industry.   Although  the used  food cans and containers  constitute
a vast potential source of raw material,  their  present contribution  to the
recoverable  scrap is only  one percent.  Even this one percent  is collected
by the ecology minded groups  like the Isaac Walton group, etc.   Other than
these groups, there  is no  organized method of used can collection for
scrap recovery.   Almost 99 percent  of the used  cans find their way  to
municipal incinerators.
(1)  U. S. Bureau  of Mines, Washington, D. C., Telephone Conversation
     with Keith Harris.

-------
                                   C-151
          The recovery of scrap from used cans is not expected to exceed
the current level because of the aluminum and plastic used in production of
cans.   The high cost of segregating the 'tin and iron metal portion from
the garbage and the difficulties in processing the metal cans to recover
the tin in the presence of aluminum are negative incentives to increased
usage of used cans in scrap recovery.  Thus, the raw materials are mostly
new scrap consisting of:
          (1)  Tin drosses and sludges
          (2)  Solder drosses and sludges
          (3)  Can rejects from can companies
          (4)  Rejected plating cells
          (5)  Bronze used parts and rejects
          (6)  Type metal scrap.

                               Products

          Products from the tin segment of  the secondary nonferrous
metals industry include:
          (1)  Pig tin
          (2)  Solder and type metal (tin-lead alloy with
               varying amounts of antimony)
          (3)  Tin oxide
          (4)  Fire-refined tin
          (5)  Sodium stannate
          (6)  Stannous sulfate and other tin chemicals
          (7)  Babbit metal.

                          Process Description

          Three manufacturing operations are employed  to  recover tin from
scrap:   (1) scrap pretreatment,  (2) detinning/smelting, and  (3)  refining/
casting.  These operations and the associated processes are  shown in the
process  flowsheet for the tin segment  of the secondary nonferrous metals
industry.

-------
                                   C-152

 Scrap Pretreatment Operation

           The pretreatment process varies  according  to the  type  of  scrap.
 The  individual pretreatment processes  are  Numbers  1  and 2 on the segment
 flowsheet.

           Dealuminization Process  (1).   This  process is conducted only
 if the  scrap  tin  cans  are suspected  to  contain  substantial  quantities of
 aluminum  ends.  About  90  percent of  the time  dealuminization is  not  done.
           This  process removes  aluminum as sodium  aluminate in solution.
 The  steps are:   (a)  leach the  scrap  in  hot sodium  hydroxide,  (b)  remove
 the  sodium  aluminate solution,  (d)  pump it to Process  No.  (7) of the
 refining  operation for recovery of soluble tin  values,  and  (d) recover
 dealuminized  tin  scrap for Process No.  (3).
          Heat  energy  for alkali solution  and electrical energy  for
 pumping are required.
          The  process  produces  no wastes;  hence, there  is no potential
 pollution from  this process.

          Batch Mixing  Process  (2).  This  mechanical operation mixes
 the drosses with  limestone  and  coke  to  prepare  a feed  suitable for smelting.
          Mixing  is the only process step  involved.
          Electrical energy  for the  rotary  drum mixer  is required.
          Dust emissions  are produced.  However, these  are  collected by
baghouses and recycled.   The process, therefore, has no pollution potential.

Detinning-Smelting Operation

          By  the  detinning-smelting  operation,  the tin  values in  scrap
are separated from metallic  and nonmetallic impurities  or contaminants.
Two types of  operation--hydrometallurgical  and  pyrometallurgical--are used.
The individual  processes  are numbered 3 through 5  in the flowsheet.

-------
                                   C-153
           Chemical  Detinnlng  Process  (3).   The  process  extracts  the  tin
 value  in  the  scrap  as  sodium  stannate  solution  and  also generates  detinned
 steel  scrap  for  use in secondary  ferrous' metallurgy.
           The  process  steps are:   (a)  addition  of hot alkali (NaOH)  and
 sodium nitrite or nitrate  (NaNCL  or NaNO^)  solution to  the scrap,  (b)
 draining  and  pumping the solution to the refining/casting  operation  after
 the  reaction  is  complete,  and (c)  washing  the detinned  scrap with  water
 sprays (as many  as  four) to obtain clean scrap  for  the  steel industry.
 Three  of  the  sprays are pumped  to the  crude sodium  stannate solution tank
 and  the fourth spray is used  for  recycle.
           Heat energy  is required to heat  the caustic solution and
 electrical energy for  pumping stannate solution and spray  water.
           No  significant quantities of wastes are generated in the process
 and  hence  there  are no serious  pollution problems.

           Dross  Smelting Process  (4).   This process partially purifies
 the  drosses and  produces "crude furnace metal".
           The  process  steps are:   (a)  charging  the  furnace,  (b)  melting
 the  charge,  (c)  tapping the "crude furnace  metal",  and  (d)  tapping matte
 and  slag.
                                                               (2)
          Heat energy  is required  in smelting.   It  is reported    that
 90 gallons of  fuel  oil per ton  of  charge are used in the process.
          The matte  produced  is shipped to  the  copper smelter.   The  slag
 is discarded if  low  in metal  values.   Cooling water is  recycled  in a
 closed  loop operation.  Hence,  the only wastes  are  minor atmospheric wastes
 and  major amounts of slag.  Almost 99.9 percent  of  dust in the furnace
 gases  is collected  in  an electrical precipitator and leached in  Process (5).
          The process has  reasonable potential  for  solid waste pollution.

          Dust Leaching and Filtrajion Process  (5_).  The tin and  chlorine
 values  in  the Cottrel  dust collected in Process  (4) are separated  from
 the  dust by sulfuric acid  leaching.  The process steps  are:   (a)  leaching
(2)   Earl  R.  Marble,  Jr.,  "Redesigning a Secondary Smelting Plant", Journal
  of Metals, pp 218-222, March,  1951.

-------
                                   C-154

the Cottrel dust with dilute sulfuric acid to remove zinc and chlorine,
(b) filtering to remove acid and dissolved zinc and chlorine, (c) drying
the leached dust, and (d) conveying the drred leached dust to Process  (2).
          Energy required for this process is electrical energy and that
derived from fuel oil.
          Potential environmental pollutants generated by this process
are atmospheric emissions from handling of the dust and drying of the
leached dust, liquid.wastes from the leaching and filtering steps, and
solid wastes collected via a baghouse from the atmospheric emissions.
          Thus, the process has a potential for the production of
pollution problems if the pollutants are not collected and disposed of
in an acceptable manner.

Refining/Casting Operation

          Via this operation, the tin is recovered as sodium stannate  of
commerce, as stannic oxide, as pure metallic tin, and as tin alloys.   The
individual processes to produce these products are 6 through 13 as noted
in the flowsheet.

          Settling and Leaf Filtration Process (6).  This process produces
a purified stannate solution from which tin can be recovered by a number
of processes.  The impurities — silver, mercury, copper, cadmium, some
iron, cobalt, and nickel--are precipitated as metal sulfides.
          The process steps are:  (a) addition of sodium sulfide with
agitation, (b) settling, (c) decantation, and  (d) filtration.
          Electrical energy is required for agitation and filtration steps,
          The process has marginal potential for solid waste disposal
problems.  These solid wastes are generated as metal sulfides.

          Evapocentrifugation (7).  This process produces a sodium
stannate of commerce (Na^SnO-) product.
          The process steps are:  (a) heating the solution to concentrate
the' sodium stannate solution, (b) crystallization of sodium stannate,  and
(c) recovery of the stannate by centrifugation.

-------
                                  C-155

          Thermal energy for evaporation and electrical energy for
centrifugation are required.
          The wastes produced are atmospheric emissions consisting of
water vapor and liquid wastes.
          The process has no substantial pollution potential.

          Electrolytic Refining Process  (8).  This process produces
cathodic pure tin metal from the purified sodium stannate solution.  The
process steps are:   (a) passing the alkaline electrolyte  (sodium stannate
solution) through a  cascade of cells at about 190 F, a characteristic
condition with an initial concentration of 110-120 g/1 of tin; (b) removal
of cathode as tin builds up; and (c) stripping the tin from the cathode.
          Electrical energy is required for electrolysis and to operate
auxiliary equipment.
          Spent electrolyte, an alkaline solution, is generated as a
liquid waste.  This waste has moderate water pollution potential.

          Acidification and Filtration Process (9).  The process produces
"tin hydrate" which  is subsequently processed to tin and stannic oxide.
          The process steps are:  (a) acid neutralization with sulfuric
acid to form "tin hydrate" and (b)  filtration to separate the hydrate as
filter cake.  The filtrate is recycled to Process (6).
          Electrical energy is used for stirring and filtration.
          No wastes per se are generated in the process and hence the
process has no pollution potential.

          Fire-Refining (10).   This process produces purified tin from
cathodic tin.   Natural gas is the heat source.  The process steps are:
(a) charging the furnace,  (b)  melting of the charge, (c) removing the
impurities  as  slag and dross,  (d)  pouring of the molten metal, and
(e) casting of the metallic tin.
          Energy required  for this  process is that derived from natural gas.

-------
                                  C-156

           Potential pollutants are atmospheric emissions--gases and
 metallic fume--and solid wastes.  The solid wastes are recycled for
 metals recovery.  Thus, the process is not a source of serious pollution
 problems.

           Smelting Process (11).  This is an alternate route to producing
 pure tin when electrolysis is not feasible.  The process converts the tin
 hydrate to tin metal by reducing the stannic oxide (SnCL)  with a reducing
 agent.
           The process steps are:  (a)  heating the hydrate,  (b) adding
 the  reducing agent, (c) reducing the tin hydrate, (d)  melting  the tin,
 (e)  skimming the dross, (f) pouring the molten metal,  and  (g)  casting
 the  metal.
           Heat energy derived from the fuel is the main energy requirement
 of  the process.
           Potential pollutants are solid wastes,  liquid wastes,  and
 atmospheric  emissions.   The solid waste produced  as dross  is recycled.
 The  water  used to cool  castings is recycled although eventually  some  of
 it is  rejected to the waterways.   Atmospheric emissions are  collected via
 baghouses  or wet scrubbers.
           The pollution potential of the process  does  not appear  to be
 significant.

          Calcining Process  (12).   This  process converts tin hydrate  to
 anhydrous stannic  oxide  (SnCL).   The process  steps  consist of:   (a)
 charging the  calciner,  (b)  calcining the  tin  hydrate,  and  (c)  removing
 and  packaging  the  stannic  oxide.
          Energy  required  is  thermal energy.
          The  primary pollutant  is atmospheric emissions consisting of
water vapor, dusts, and  fume.   Solid wastes generated  are those collected
 in the baghouse.
          Thus,  this process has  a potential  for  the production of
pollution problems.

-------
                                 C-157


          Kettle Refining Process (13).  This process purifies the

"crude furnace metal".  The process steps are:  (a) dry dressing to remove

the impurities as slag and matte, (b) decopperizing using sulfur, (c)
removing antimony using aluminum, and (d) casting into required shapes.
          The process uses large amounts of heat energy as derived from

fuel oil.
          The waste products generated are atmospheric emissions and

solid wastes.  The solid wastes are slag and matte from the purification
of the crude furnace metal.  Atmospheric emissions consist of gases from
combustion of the fuel and fume and dust entrained in the gases.
          These wastes constitute reasonable potential for pollution if
not collected and disposed of by an approved method.


                Population of Secondary Tin Processors
          (1)  Colonial Metals Company
               Columbia, Pennsylvania
               Telephone:  (717) 684-2311

          (2)  K. Hettlemen & Sons
               Division of Minerals & Chemicals
               Phillip Corporation
               9th Street & Patapsco Avenue
               Baltimore, Maryland  21225
               Telephone:  (301) 355-0770

          (3)  Holtzman Metal Company
               5223 McKissock Street
               St. Louis, Missouri  63147
               Telephone:  (314) 244-3820

          (4)  Industrial Smelting Company
               19430 Mt. Elliot at Marx Street
               Detroit, Michigan
               Telephone:  (313) 892-5300

          (5)  Inland Metals & Refining Company
               651 East 119th Street
               Chicago, Illinois  60628
               Telephone:  (312) 928-6767

          (6)  M & T Chemicals
               Rahway, New Jersey

-------
                       C-158
(7)   North American Smelting Company
     Marine Terminal P. 0. Box 1952
     Wilmington, Delaware
     Telephone (302) 654-9901

(8)   United States Metal Products Company
     P.  0. Box 1067
     Erie, Pennsylvania  16512
     Telephone:  838-2051

(9)   Vulcan Materials Company
     Metallics Division
     Edison, New Jersey
     Telephone:  (201) 225-3838

-------
                                       SMELTING / DETINNING
REFINING/CASTING
SCRAP  PRETREATMENT
                                           SOOUU NITBITt •
                                         [—S001UH HrtJBOxlOE
                                         b-sa,    Q
                                                                                                                                   I— REDUCING U3LH1
                                                                                                                                    f~ ..ltd    (-V
                                                                                                                                     (-FVJEL    tt.
TIN DR05SCS.SLUDOCS.
•NO SOLOES CWSSES-*
                                                                                                             /	«.  TOODUCTS OR SŁC-
                                                                                                             /     \ OND'Rr RAW
                                                                                                             /       \UATEHIlLrORUSE
                                                                                                             I       I IN OT^CK INOUSTR-
                                                                                                                                               """TIN SEGMENT OF THE
                                                                                                                                               SECONDARY  NQN.FERROUS
                                                                                                                                               METALS  INDUSTRIES
                                                                                                                    JWTEB^EOIATE
                                                                                                                    (PfiOOuMS
                                                                                                                                                                             Ul
                                                                                                                                                                             VO

-------
                                   C-160
            PROCESS DESCRIPTION OF THE TITANIUM SEGMENT OF THE
                   SECONDARY NONFERROUS METALS  INDUSTRY
           The titanium segment of the secondary  nonferrous  metals  industry
 constitutes one of the minor segments.   Annual recovery of  titanium is
 approximately 8000 tons.   Because of the nature  of  the  operations,  this
 segment  has a low potential for the production of serious atmospheric
 emission problems.  However, problems resulting  from water  pollution could
 be  significant.

                               Raw Materials

           Raw materials to this segment  include  the following:
           (a)   Bulk scrap  (trim sheets,  plate sheets, cuttings,  etc.)
           (b)   Noncarbide  machine turnings and borings
           (c)   Carbide-containing machine turnings  and  borings.
                This scrap  is generated by the use of carbide
                tools  in machining.

                                 Products

           Products include titanium alloy ingots and electrodes.

                         Population of Companies

           The  following companies  are known to be involved  in titanium
 scrap processing:
           (1)  RMI Company
               Niles,  Ohio
               Telephone (216)  652-9951
           (2)  Titanium Metals  Corporation of America
               West Caldwell, New  Jersey
           The Air  Force Materials  Laboratory (AFML)  of The Wright-Patterson
AFB is also pursuing recovery of  the titanium values in scrap.  Mr. Lee
Kannard  (Telephone 513-255-2413)  is  working to recovery (by contracts to

-------
                                  C-161
processors) titanium from low-grade scrap generated during machining of
parts for aircraft.

                           Process Description

          The recovery of titanium alloys from scrap titanium involves
three operations:  (1) scrap pretreatment, (2) smelting, and (3) casting.
These are shown in the flowsheet entitled "Titanium Segment of the
Secondary Nonferrous Metals Industry".

Scrap Pretreatment Operation

          Two processes are used in this operation: vapor degreasing and
acid pickling.  Normally, if the scrap is not contaminated by oxides,
acid pickling is not necessary and degreasing will suffice to produce a
clean scrap.

          Vapor Degreasing (1).   This process removes grease and cutting
oils from machine turnings and borings.
          The process steps are: (1) vaporizing a solvent such as tri-
chloroethylene, (2) mixing the vapors with the scrap, (3) condensing the
oil-bearing vapor, (4) filtering the condensed solvent, and (5) removing
the scrap for subsequent processing.  As the solvent goes through this
cycle, the oil dissolves in the solvent and gradually lowers the boiling
point of the solvent mixture.   Eventually, the oil-solvent mixture is discarded
due to loss of deoiling ability of the solvent or the solvent is regenerated.
          Heat energy is required by the process for vaporizing the oil
and electrical energy for water circulation through condenser.
          Wastes generated are the oil-solvent mixture, minor amounts of
solvent vapor and insignificant quantities of solid dust particles.
          The oil-solvent mixture has a considerable water pollution
potential.   Atmospheric emissions and solid wastes generated are
negligible and thus,  present no serious pollution problems.

-------
                                  C-162
          Acid Pickling Process  (2).  This process is done only when the
scrap is known to contain oxide-scale formed during machining and storage.
The process  follows vapor degreasing and consists of treating the scrap
with a mixture of hydrochloric and  hydrofluoric acids.  The process steps
are: (1) leach the scrap with the mixed acid to remove the oxide,
(2) remove the acid from the scrap  with a water wash, and (3) dry the
scrap for further processing.
          Energy requirements are not significant.  The major waste
generated is a liquid waste consisting of the spent acid mixture.  This
spent acid is normally disposed  of  by neutralization.
          The process has little potential for the production of serious
atmospheric  problems.  However,  the potential for water pollution by spent
acids could be significant.

Refining Operation

          The scrap pretreatment operation removes primarily the surface
impurities such as the oils and  the oxide.  Via the smelting refining
operation the scrap is densified and the internal impurities are removed
by vaporization as shown in the  segment flowsheet by Process 3.

          Vacuum Electric Arc Melting Process (3).  In this process, the
clean scrap  is melted to obtain  molten alloys and the volatile impurities
are removed.  The process steps  are: (1) charging clean scrap to the
electric furnace, (2) melting the scrap, (3) vaporizing the impurities,
and (4) pouring the molten metal.
          Energy required is electricity to operate the process.
          The process is conducted  in a completely closed system and
wastes generated are well controlled.  Therefore, the process has little
potential for the production of  pollution problems.

Casting Operation

          Casting Process.  By this process the molten metal is cast
into ingots.

-------
                                  C-L63
          The process consists of: (1) pouring the molten alloy into
molds and (2) casting.
          Energy requirement is that necessary to operate the equipment.
          Wastes generated are insignificant and do not present any
pollution problem.


             Population of Secondary Titanium Processors
          (1)  RMI Company
               Niles, Ohio
               Telephone:  (216) 652-9951

          (2)  Titanium Metals Corporation of American
               1140 Bloomfield Avenue
               West Caldwell, New Jersey
               Telephone:  (201) 575-9400

          (3)  Kawecki Berylco Industries, Inc.
               220 East 42nd Street
               New York, New York

-------
.8
      SCRAP   PRETREATMENT
                                                                           SMELTING/REFINING
                                                                                                                       CASTING
     SOLVENT V*PO
     BULK «RAP_
WITRlC *CO bwOj)	


MYWOPUJQRlC »CIO fr*1 —

WATER —^—^-^
                                                                               VACUUM
                                                                               ELECTRIC ARC
                                                                               MELTING
                                                                                                                                                                                     o
                                                                                                                                                                                      I
                                                                                                                                                                                     I-*
                                                                                                                                                                                     0\
                                                                                                                                                                                     •p-
                                                                                                                  LEGEND
                                                                                                            O «"«3»tne EUCSCNS

                                                                                                            & LiauitJ W«3IE

                                                                                                            ^ SOLID *ASIE
                                                                                                                  PRODUCTS OR SGCCVOART RAM

                                                                                                                  MATERIAL TOR U5C IN OTIC"
                                                                                                                  INTERMEOU1E PRODUCTS
                                                                                                                                     •SSfu
                                                                                                                                                           UTTCLU MtMOfnAL INVTTTUTE
                                                                                                                                                      TITANIUM SEGMENT OF
                                                                                                                                                    THE SECONDARY NDNFER -
                                                                                                                                                    ROUS METALS INDUSTRY
                                                                                                                                                    D  79986

-------
                                  C-165
                PROCESS DESCRIPTION OF ZINC SEGMENT OF
               THE SECONDARY NONFERROUS METALS INDUSTRY
                             Introduction
          The zinc segment of the secondary nonferrous metals industry
consists of those plants that process discarded and scrap materials
for the purpose of recovering zinc.  In 1969,^   376,400 tons of zinc
were recovered.  In the recovery of the zinc, waste products—atmos-
pheric emissions, liquid wastes, and solid wastes—are generated which
can cause serious pollution problems.

                             Raw Materials
          The principal sources of zinc scrap as classified by the
Bureau of Mines^ ' are:
                          New clippings
                          Old zinc
                          Engravers' plates
                          Skimmings and ashes
                          Sal skimmings
                          Die-cast skimmings
                          Galvanizers1 dross
                          Diecastings
                          Rod and die scrap
                          Flue dust
                          Chemical residues.
In addition  to  containing metallic zinc or compounds  and alloys,  thereof,
the  scrap contains a wide variety of organic materials  such as oil,
grease,  lubricants, and electric insulation.  Alloying  elements commonly
found  in the scrap are aluminum, copper,  and lead.
 (1)   Moulds,  D.  E., Minerals  Yearbook,  1969,  U.  S,  Dept.  of  Interior,
      Bureau  of Mines,  p  1148  (1971).

-------
                                    C-166
                                Products

           Products from the zinc segment of the secondary nonferrous
 metals industry are:  (1) specification zinc alloys, (2) zinc ingots
 (slab) containing essentially .100 percent zinc, (3) zinc dust,  (4) zinc
 oxide approaching 100 percent purity, and (5) crude zinc oxide  for
 reduction to zinc metal by the primary smelters.

                           Process Description

           The products from the zinc segment are  recovered from the
 various types of scrap zinc employing two manufacturing operations--
 scrap pretreatment and refining.   These operations and  the individual
 processes in each operation are shown in the attached segment flowsheet.

 Scrap Pretreatment Operation

           Zinc scrap is  pretreated prior to  refining to remove  a  portion
 of  the metallic and nonmetallic impurities and to  physically  prepare
 the material for further processing.   Three  types  of preprocessing
 (hydrometallurgical,  pyrometallurgical,  and  mechanical)  are used.
 The pretreatment varies  depending on the type of scrap.   The  individual
 pretreatment processes are  numbers 1  through 6, as  shown in the segment
 flowsheet.

           Crushing/Screening Process  (1).  The concentration  of
metallic  zinc in skimmings/residues  is  increased by the  crushing/
 screening  process.   The  process steps  involved are:   (a)  pulverizing
or crushing  the  skimmings/residues to  separate the  metallic zinc  from
 the flux,  and (b)  screening  or  pneumatically treating the crushed
material  to  separate  zinc from  nonmetallic constituents.
           Energy required is that  to drive the equipment.

-------
                                   C-167

           The process  generates  atmospheric emissions and solid wastes.
 The atmospheric  emissions  are composed of dusts  from both the
 pulverizing (crushing)  process step  and the screening step.   These
 emissions contain,  in  addition to zinc, those materials--nonmetallic
 constituents, metallic  values such as  zinc, aluminum, copper, iron,  lead,
 cadmium,  tin, and chromium and fluxes--separated from the scrap zinc
 during the sweating process.   Emissions data are not available; however,
 based on  studies conducted of other  industries,  the raw emissions
 factor is estimated to range  from 0.9  to 7.5 lb  per ton of skimmings/
 residues  processed.
           The solid wastes generated by this process are nonmetallic
 constituents from the  screening  operation and baghouse dusts, if
 emissions from crushing and screening  process steps are controlled.
           This process  produces  a small quantity of emissions and is,
 therefore, a minor source  of  pollution.

           Kettle  Sweating  Process  (2).   The kettle  sweating process
 separates  the metallic  zinc from metal  attachments,  having higher
 melting points,  and from nonmetallic residues.   This  is  achieved by  the
 following  process steps:   (a)  charging  the  scrap  into the furnace con-
 taining generally a molten heel,   (b) melting  of  zinc  fraction of  the
 scrap, (c) working  of charge  to effect  separation of  the  zinc,
 (d) fluxing to aid  in the separation, and (e) skimming to remove
 impurities removed by the flux.  Afterwards the molten metal may be
 removed and cast in blocks for further processing,  fed to a
 distillation  furnace or alloyed to obtain specification  composition  and
 then cast into ingots.   Operating  temperatures of the kettle-sweating
 baths range from 800 to 1000 F.  Production is batchwise, with one
 batch requiring 6 to 8 hours to complete one  heat.
         Energy required is the electricity  to drive  the  equipment
 and the fuel, generally, natural gas, to melt and keep the zinc
molten.  Fuel oil is used as fuel  in some cases.

-------
                                  C-168

           The process produces significant quantities of potential
 environmental pollutants.  Atmospheric emissions consist of:
 (1) combustion gases (which are separate from the emissions from the
 molten metal), and (2)  emissions consisting of gases and particulates
 from the molten metal.   Solid.wastes generated are metal attachments
 and skimmings or slag from the flux present in the scrap or that added
 to purify the zinc metal and baghouse dusts.
           Composition of the particulate atmospheric emissions  varies
 somewhat depending on the charge.   However, in most cases,  the  emissions
 contain ammonium chloride,  zinc,  aluminum,  tin,  nickel,  copper,  iron,
 lead,  cadmium, magnesium, manganese, and chromium.   A typical analysis
 is shown in Table C-3.   The gases are composed of, in addition to the
 combustion products,  carbonaceous  materials from the rubber, plastic,
 and other organic impurities or contaminants  in the scrap.  Some
 carbonaceous materials  are  also mixed with  the particulate  emissions.
           Emissions factors also vary depending on  the composition of '
 the charge.   When sweating  metallic scrap*  with  zinc chloride as the
 flux,  raw emissions factor  was reported  to  be  10.8  Ib/ton of scrap
 processed.   These particulate  emissions  contained 4,  77, 4, 4,  and 10
 percent,  respectively,  of zinc chloride,  zinc  oxide,  water, other  metal
 chlorides and oxides, and carbonaceous materials.   In other cases, the
 raw emissions factor  for sweating  residual  scrap**  (the  flux was
 residual  zinc chloride)  was reported at  24.5  Ib/ton of scrap processed.
 Composition  of particulate  emissions was  similar to that from the
 sweating  of  the metallic scrap.
          Morphology  of  the particles is  dependent  on the type of  scrap.
 For  example,  the  particle size of  the emissions  from sweating of residual
 scrap  ranged  from less  than 1  micron to greater  than 20 microns, whereas
 those  from sweating of metallic scrap were  less  than 2 microns.  Particle
 shape  is  acicular and/or irregular.   Those  emissions  that are predominately
 zinc oxide are  composed  of  primarily acicular  particles which is the
*  Metallic scrap consists of metallic items, generally in the same
   shape as when manufactured or used.
** Residual scrap is composed of residues, skimmings, and other low
   grade scrap.

-------
                       C-169
 TABLE C-3.   ANALYSES OF PARTICULATE EMISSIONS
             FROM ZINC SWEAT PROCESS ING(2)
 Component                             Percent


ZnCl2                                14.5 - 15.3

ZnO                                  46.9 - 50.0

NH4C1                                1.1 - 1.4

A1203                                1.0 - 2.7

Fe203                                0.3 - 0.6

PbO                                  0.2

H20 (in. ZnCl2-4H20)                  7.7 - 8.1

Oxides of Mg, Sn, Ni, Si, Ca, Na     2.0

Carbonaceous Material                10.0

Moisture (deliquescent)              5.2 - 10.2
(2) Herring, W. 0, Secondary Zinc Industry,
    Emission Control Problem Definition Study,
    Part 1, Technical Study, APCO, EPA,
    Durham, North Carolina.

-------
                                  C-170
 characteristic shape of zinc oxide.   Low zinc emissions  have  an
 irregular shape or are composed of a mixture of particle shapes.
           Generally, the atmospheric emissions are controlled or
 collected using baghouses with orlon filter  medium.   Collection
 efficiencies  of approximately 96 percent are reported.
           No  liquid wastes are generated by  the kettle sweating
 process  unless possibly some cooling water.   However, significant
 quantities of solid wastes are generated.  These wastes  are:   (1)  slag
 (skimmings or drosses), (2)  high melting attachments, and  (3) baghouse
 dusts.
           Thus, the kettle sweating process  is a source  of potential
 pollution problems if the wastes are not collected and disposed of
 properly.

           Reverberatory Sweating Process (3).   This process separates
 or  recovers zinc metal from  mixed zinc  scrap.   The recovered  impure
 zinc  is  processed  further to obtain  specification alloys or fed to a
 distillation  furnace for refining.   The  process steps are:  (a) charging
 of  furnace,  (b) melting of zinc,  and (c)  removal of unmeltables.   In
 this process  the zinc flows  from the furnace as it melts and  is collected
 in  vessels or allowed to flow to the next process  in operation.
           Energy required for this process is  the  electricity to drive
 the equipment and  the gas or fuel oil to fire  the  furnace.  The
 reverberatory furnace is direct-fired whereas  the  kettle furnace is
heated indirectly.
           Both  atmospheric emissions and solid  wastes are generated.
 The atmospheric emissions are composed of the  combustion gases, gases
or vapors  from  burning  of the organic content  of the scrap, and volatile
metallic materials.   The particulate emission  is  the fume volatilized
from, the  furnace and  dust carried from the furnace by the entrainment
of particles  in the  furnace  exit  gases.
          Composition of the  atmospheric emissions varies depending  on
the source and  type  of  scrap.  However,  in general, the particulate
emission will contain such metals as  zinc, aluminum, copper,  iron, lead,

-------
                                  C-171
cadmium, manganese, and chromium, in addition to carbonaceous materials
and components from the residual fluxes.  The gases contain primarily
carbon dioxide, nitrogen, oxygen, and water, and possible sulfur oxides,
chlorides, and fluorides.
          Particulate emission factors vary depending on the type of
scrap.  For metallic scrap, raw emissions factor was reported to be
approximately 13 Ib of particulate matter per ton of charge processed,
whereas raw emissions factor for residual scrap was reported to be
                                            (3)
approximately 32 Ib per ton of feed process.     Baghouses with orIon
filter media are used to control these emissions.
          Particle morphology of atmospheric emissions is the same or
comparable to the morphology of emissions from the kettle furnace.
          No liquid wastes are generated.  Solid wastes from this
process are:  (1) baghouse dusts; (2) skimmings, drosses or slag; and
(3) unmeltable attachments.
          The process does produce significant quantities of atmospheric
emissions and solid wastes which could cause pollution problems.

          Rotary Sweating Process (4).  Zinc metal is separated from
zinc scrap such as die-castings by the rotary sweating process.  During
the sweating, the furnace is rotated on its axis.  The zinc metal is
collected in a kettle (outside the furnace) and the residue is skimmed
off the molten metal.*  The process steps are:  (a) charging of furnace,
(b) melting of zinc values, (c) removing (skimming) of residue, and
(d) removing the unmeltables from the furnace.  Afterwards, the impure
zinc melt is transferred to a distillation furnace or alloyed and cast
into ingots.
          Energy required is the electrical energy to rotate the furnace
and fuel (gas or oil) to heat the furance which is direct fired.
(3) Herring, W. 0.,  "Secondary  Zinc  Industry,  Emissions  Control  Problem
    Definition  Study,  Part  1-Technical  Study", NASMI,  APCO,  EPA,
    Durham, North  Carolina.
'(4) Air Pollution  Engineering Manual, U.  S. Dept.  HEW  NAPCA,  p  307  (1967)
* No fluxes are added.

-------
                                   C-172
           Potential environmental  pollutants  generated  by  this process
 are:   (1)  atmospheric emissions, and (2)  solid wastes.   The  atmospheric
 emissions  include both gases  and particulate  emissions.  The gases  are
 composed of those produced by combustion  of  the  fuel and burning  of
 organic  matter contained in the scrap.  The particulate  emissions
 generally  are  composed of such metal values as are  found in  the emissions
 from  the reverberatory sweating process.   Included  in this list are zinc,
 aluminum,  copper,  iron,  lead,  cadmium, manganese, and chromium.
           Particulate emission factor data are not  available.  However,
 based  on reported values from other  sweating  processes,  it is estimated
 the raw  emission factors will range  from  11 to 25 Ib of  particulate
 matter per ton of feed.
           Particulate morphology of  the particles should be  similar to
 the morphology of the particles from other sweating processes.
           The  solids  generated by  this process are  skimmings, unmeltable
 attachments, and baghouse dusts.
           The  process produces significant quantities of atmospheric
 emissions  and  solid  wastes and, therefore, is a  potential  source  of
 atmospheric and  water pollution problems.

           Electric-Resistance  Sweating (5).   This process is employed
 in small plants  to  recover  zinc from clean scrap.   The process steps
 are:   (a)  charging  of furnace,  (b) sweating of zinc, (c) pouring of
 zinc melt  for  subsequent processing,  and  (d)  removing residue from
 furnace.
           Energy  required is  the electricity  to  sweat the zinc.
           Potential environmental pollutants  are:   atmospheric
 emissions  and  solid wastes.  Atmospheric emissions  are composed of
primarily  fume and dust  since  only clean scrap is used as the source
of zinc and no combustion products are formed.   The fume and dust contain
primarily  zinc oxide  from the  oxidation of zinc vapor along with trace
quantities of  other heavy metals and  possibly a  small quantity of
chloride and fluxing materials.  The  gaseous  portion of  the emissions
 is primarily nitrogen.   Emissions are controlled with baghouses,  if
pollution  controls are used.

-------
                                  C-173
          Particle morphology is the same as that of emissions from
other processes.
          Emissions factor is probably low, <10 Ib of fume and dust
per ton of feed processed.
          Solid wastes from this process are drosses, if fluxes are
used, unmeltable components of the scrap, and baghouse dusts.
          Although this process produces small quantities of atmos-
pheric emission, there is potential atmospheric and water pollution
problems associated with disposal of these materials and with the
process.

          Muffle Sweating Process (6).  Zinc metal is recovered from
zinc scrap materials by the muffle sweating process.  The process steps
are:   (a) charging of furnace, (b) sweating of zinc values,  (c) tapping
of furnace to remove molten zinc for subsequent refining or alloying,
and  (d) removing residue with a shaker screen to separate the dross
from the unmeltable attachments.
          Energy required is the fuel--gas or oil--to heat the muffle
furnace which is indirectly fired.
          Potential pollutants from this process are:   (1) atmospheric
emissions composed of gases from the combustion of the  fuel and from the
sweating chamber and particulate emissions from the sweating chamber,
and  (2) solid wastes--drosses and unmeltable attachments.  The gaseous
emissions include those from the combustion chamber which are emitted
separately to the atmosphere and those from the sweating chamber.  The
combustion gases contain primarily carbon .dioxide, nitrogen, unburned
fuel,  and possibly trace quantities of heavy metals and sulfur oxides
if oil is used  as the source of fuel.  Those from the sweating chamber
are  composed of a small quantity of gases  from air leaking into the
chamber and from combustion or decomposition of organic compounds added
with the scrap.
          Composition of  the particulate emissions from the  sweating
chamber will vary depending on the type of scrap but, in general,
contains the metals found in particulate emissions from other  sweating
processes, with the major component being  zinc.

-------
                                   C-174

           Particle morphology of the participates is the same as that
 of emissions from other processes.
           Emission factors for the muffle furnace process are not
 available.  However,  they are estimated to range from approximately
 10.8 to 32 Ib per ton of feed processed.   Baghouses are used to control
 the emissions.   A cyclone may be used in  series with the baghouse.
           The solid wastes generated are  drosses, baghouse dusts,  and
 unmeltable attachments.
           The process generates a considerable quantity of atmospheric
 emissions and solid wastes,  and thus is a source of pollution problems.

           Sodium Carbonate Leaching Process (7).   The sodium carbonate
 leaching process removes the nonmetallic  contaminants from skimmings
 and residues and converts the zinc values to zinc oxide which can be
 reduced to zinc metal.   The  process steps are:   (a)  crushing to make
 the scrap more  amenable  to leaching, (b)  washing with water to separate
 nonmetallic  contaminants and recover metallic zinc,  (c)  treating the
 aqueous stream  with sodium carbonate to precipitate  the zinc values,
 (d)  drying the  precipitate to remove the  water,  and  (e)  calcining  to
 convert zinc hydroxide  to zinc oxide.   The product (zinc oxide)  is
 shipped to a primary  smelter for reduction to zinc metal.
           Energy required for this process is electrical energy to
 drive  the equipment and  fuel,  either gas  or oil,  to  dry and calcine
 the  zinc  hydroxide.
           The process produces waste products — atmospheric  emissions,
 liquid  wastes and  solid  wastes—in modest quantities.   The  atmospheric
 emissions  consisting  of  both  gases  and  particulate matter  are  produced
 during  the crushing,  drying,  and  calcining process steps.   The  gases  are
 from the  crushing  step and present  no problem since  they primarily
 consist of air.  Those from  the  drying  and calcining  steps  contain
 primarily  the combustion gases and  water  vapor.   Since  any  residual zinc
 chloride  is  vaporized during  the  calcination,  the  gases  may also contain
hydrogen  chloride  and zinc chloride.  The  particulate matter  consists
primarily of  zinc  oxide  fume  contaminated  with other metal  values either

-------
                                  C-L75
vaporized with the zinc oxide or entrained in the gaseous stream.  The
atmospheric emissions are controlled with baghouses.
          Liquid wastes are generated in steps (b) and (c).   These
wastes contain sodium chloride, sodium carbonate, and other water-
soluble compounds not precipitated by the sodium carbonate.
          Because of the corrosive nature of the atmospheric emissions,
allowing them to escape to the environment could cause pollution
problems.  Liquid wastes may cause water pollution problems if not
treated before discharge.

Refining Operation

          The pretreated zinc scrap still contains a wide variety of
metallic and nonmetallic contaminants which are removed in the refining
operation to produce pure zinc ingots, zinc dust, zinc oxide, and
specification zinc alloys.  These products are produced by the processes
8 through 12 as shown in the attached flowsheet entitled "Zinc Segment
of the Secondary Nonferrous Metals Industry".

          Retort Distillation Process (8).  This process produces pure
zinc ingots and pure zinc dust from pretreated zinc scrap--molten
zinc-rich metal from the sweat furnace or cast zinc-rich metal ingots
from a sweating process--and/or zinc dross.  The process steps are:
(a) charging the furnace with the pretreated zinc scrap or dross,
(b) melting the charge,  (c) distilling the zinc,  (d) condensing  the
zinc vapor rapidly to produce zinc dust or slowly to produce pure
liquid zinc.  Afterwards, the zinc metal is removed and cast into
ingots (slabs).  Zinc dust, if the final product, is removed and packaged.
          The energy required for this process is the fuel--gas  or oil--
to heat  the furnace which is indirectly fired.
          This process produces significant quantities of atmospheric
emissions and solid wastes.  Sources of atmospheric emissions are the
retort opening,- combustion chamber, the condenser,  and casting of ingots.
Emissions as zinc oxide  fumes are evolved from the  retort opening

-------
                                   C-176
 (charging port) during removal of the hot residue from the retort after
 a distillation heat and recharging of the retort for the next distillation.
 These emissions contain primarily zinc oxide along with aluminum, copper,
 and other metal values found  in the residues.  Raw emissions factor from
 this source and the condenser as discussed below are estimated to be 45 Ib
 of particulates per ton of zinc distilled.     Emissions factor may be
much higher due to leaks  in the grout seal around the condenser neck.
          Particle size of the fumes is estimated to range from approxi-
mately 0.05 to 1.0 micron.  Since the fumes are primarily zinc oxide
 resulting from air oxidation  of zinc metal, particle shape is acicular,
 the characteristic shape  of zinc oxide.
          Combustion gases which are emitted separately from the other
 emissions contain carbon  dioxide, unburned fuel and nitrogen, and  .
possibly trace quantities of heavy metals if oil is used as the fuel.
          During distillation of zinc, the condenser must be kept
positive pressure to prevent air from entering the condenser and con-
 taminating the zinc metal with oxygen.  To ensure that there is a
positive pressure, a small hole, called a "speise" hole,  is provided
 through which a small amount of zinc vapor is allowed to escape contin-
uously into the atmosphere where it reacts with oxygen.  These emissions
 (fumes) are essentially 100 percent zinc oxide.  The particles, acicular
 in shape, are extremely fine, i.e., approximately 0.05 to 1 micron.
          Only a small amount of atmospheric emissions is formed during
the pouring and casting processing steps.  Emission factors are estimated
to range from 0.4 to 0.8  and 0.2 and 0.4 Ib of particulates, respectively,
per ton of zinc produced.  These data are based on similar operations in
other industries.   These  emissions are emitted as fine particulates with
the same particle size and shape as those from the condenser.
          Solid wastes generated by the retort distillation process are
the distillation residues and the particulate matter, if collected, in
the atmospheric emissions.  The atmospheric emissions are primarily zinc
(5)  Vandegriff, A. E., et al., Particulate Pollutant System Study,
     Volume 1-Mass Emissions, Midwest Research Institute, Kansas City,
     Missouri, p 179 (May 1, 1971).

-------
                                   C-177
 oxide,  whereas the distillation residues are composed of heavy metals
 such as residual zinc (10 to 50 percent) not removed by the distillation
 process and contaminants such as aluminum,  copper,  lead, and fluxes not
 removed during the pretreatment process.
           In view of the quantity of atmospheric emissions  and solid
 wastes  generated by the  retort distillation process,  serious pollution
 problems may arise if the atmospheric emissions  are not collected  and
 the  wastes  are not disposed  of by a  nonpolluting method.

          Muffle Distillation Process (9).   This process produces  pure
 zinc ingots, generally from  pretreated zinc scrap.   However, in some
 cases,  untreated scrap such  as zinc  die-castings may  be substituted for
 pretreated  scrap.   This  process  may  be operated  continuously whereas the
 retort  distillation process  is batch.   The  process  steps  involve:
 (a)  continuously adding  molten zinc  from a  melting  pot  or a sweating
 furnace to  the muffle  section,  (b) continuously  distilling  and  condensing
 the  pure  zinc,  (c)  periodically  tapping  the zinc from the condenser  into
 the  molds,  (d)  casting the zinc ingots,  and (e)  periodically removal
 of residue  from  muffle.
          Energy utilized  by  this  process is  fuel oil or gas  to  supply
 the  heat  for vaporization  of  the  zinc.
          The process  produces  significant  quantities of atmospheric
 emissions and solid wastes.   Sources  of  atmospheric emissions are  the
 combustion gases, distillation residues, pouring and casting  of  the
 ingots,  and  the  orifice  in the condenser.   Emission factors,  composition
 of emissions, and morphology  of particulates are the same for both
 distillation processes.  Atmospheric emissions may be controlled with
 baghouses alone or in series  with cyclones.
          Solid wastes generated are distillation residues and baghouse
dusts which are essentially of the same composition as the solid wastes
from the retort distillation  process.
          Thus, the process is a source of pollution problems.

-------
                                   C-178
           Retort  Distillation/Oxidation  Process  (10).  Zinc oxide
produced  by  the retort  distillation/oxidation process  involves vapor
oxidation of zinc metal.  The  process  steps  in this process are the
same as for  the retort  distillation process  except zinc vapor from the
retort is discharged  through an orifice  into a stream  of air where zinc
oxide is  formed inside  a  refractory-lined chamber.  The combustion gases
from oxidation of the metallic zinc vapors and excess  air carry the
zinc oxide to a baghouse  collector where the zinc oxide is collected.
The combustion gases and  excess air pass through the baghouse into the
surrounding  atmosphere.
           Energy  required for  this process is the fuel--gas or oil--to
vaporize  the zinc metal.
          Waste products  from  this process are atmospheric emissions and
solid wastes.  The atmospheric emissions, which consist of gases and
fumes, are emitted to the atmosphere from the retort opening (charging
port), baghouse, and combustion (furnace) chamber.  Those from the retort
opening result from oxidation of the hot residue removed after a dis-
tillation heat and upon charging of the retort with molten zinc for the
next distillation heat.   See the discussion  on the retort distillation
process for  pertinent data on composition of emission, emission factors,
and morphology of the particles.
          Combustion gases from the retort furnace consist of primarily
carbon dioxide, nitrogen, and unburned fuel.  If oil is used as the
fuel, the gases may also contain sulfur oxides, chlorides, and trace
amounts of heavy metals.
          Atmospheric emissions from the baghouse contain pure zinc
oxide fume and the gases  from burning of the zinc with air.  The zinc
oxide may contain trace quantities of heavy metals such as cadmium,
depending on the purity of the feed.  The particles of zinc oxi.de are
very small,  ranging in size from approximately 0.05 to about 1.0 micron.
The particle shape is predominantly acicular, i.e., needle-like.
          Emission factors for the baghouse  are estimated at 20 to 40 Ib
of zinc oxide per ton of oxide produced.  These data are calculated based
on a collection efficiency of 98 to 99 percent.

-------
                                  C-179

          Solid waste generated is the distillation residue remaining
in the retort after removal of the zinc.  This residue contains 10 to 50
percent zinc and contaminants — aluminum,' copper, lead, and residual
flux--not removed from the zinc scrap during the pretreatment operation.
          Thus, the retort distillation/oxidation process is a source of
potential environmental pollutants which can cause problems.

          Muffle Distillation/Oxidation Process (11).  This process
produces zinc oxide from pretreated zinc scrap.  The process steps are
the same as for the muffle distillation process except that in the
production of zinc oxide, zinc vapors are allowed to escape through an
orifice at the top of the first chamber of the condenser and are burned
or oxidized in the air.  The resulting zinc oxide is transported by the
combustion gases and excess air through conduits and collected in a
baghouse.
          Energy required for this process is gas or oil to heat the
muffle furnace.
          The potential environmental pollutants are:  (1) atmospheric
emissions, and  (2) solid wastes.  Sources of atmospheric emissions are:
(1) the furnace combustion chamber which is separate  from the other
sources as the furnace is indirectly  fired, (2) muffle opening
(charging port), and  (3) baghouse.  See discussion on the muffle
distillation process  for details  concerning composition of emissions,
emission factors and morphology on particulates from  sources  (1) and
(2),  and the above discussion on  the  retort distillation/oxidation
process for pertinent data on composition of emissions, emission factors,
and morphology of particles  for conversion of  zinc to zinc oxide and
subsequent collection of the zinc oxide.
          Solid waste generated by the muffle  distillation/oxidation
process is the distillation  residue from the muffle.  This residue has
the same composition  as  the  residue from the retort  distillation/
oxidation process.
          Based on these data,  this process is  a  source of pollution
problems.

-------
                                   C-180
           Alloying Process (12).   The alloying  process  produces  zinc
 alloys  from pretreated scrap.   The process  steps  are:   (a) melting  the
 pretreated scrap,  (b)  adding  the  alloying agent to molten metal,
 (c)  homogenizing the mixture,  (d)  pouring the melt into ingot molds,
 and  (e)  casting the ingot. In many cases,  the  alloying process  is
 combined with the  sweating process,  whereby the molten  pretreated scrap
 is used  directly to produce the alloy.
          Energy requirement for the Alloying Process is fuel—oil or gas
to keep the melt molten or  to melt pretreated scrap ingots.
           The process  produces atmospheric  emissions and solid wastes.
 If alloying is carried out using molten  zinc from a  sweating furnace,
 the  atmospheric emissions  contain  zinc oxide, small  amounts of the
 alloying agent,  and the  flux  cover.   If  pretreated scrap ingots  are
 used as  the source of  zinc, the atmospheric emissions will contain,
 in addition to the particulate matter, gaseous  emissions from combus-
 tion of  the fuel.   Particulate matter may be controlled using a  baghouse;
 however,  in many cases,  no pollution control is employed.
           Solid waste  is the  flux  cover  used to protect the melt.  Flux
 covers commonly  used are carbon or  zinc  chloride.
           The  process  produces  minor  quantities of emissions and solid
wastes and,  therefore, is  not  a major source of pollution.

           Graphite  Rod Resistor Distillation Process (13).  This process
 produces  zinc  dust  from pretreated  scrap  ingots.  The process steps are:
 (1)  charge  the  ingot or melt to furnace,  (2) heat with  electric  power,
and  (3) collect zinc dust  as distillate  using closed-loop water  cooling
 system.
          Electric  energy  is used  in  significant  quantities to vaporize
 the  zinc.

-------
                                   C-L81
          The process generates vapors containing traces of zinc, zinc
oxide,  lead,  and lead oxide.
          The pollution potential of these vapors is not significant because
the metal content is recovered in baghouses and returned to the process.
          The process has no pollution potential.

-------
                                  C-182
                  Population of Secondary Zinc Processors
 (1)   Apex Smelting Company
      Division of AMAX Aluminum Company
      2515 West Taylor Street
      Chicago, Illinois
      Telephone:  (312)  332-2214

 (2)   Belmont  Smelting and Refining
        Works, Inc.
      320  Belmont Avenue
      Brooklyn,  N.Y.  11207

 (3)   Colonial Metals Company
      Columbia,  Pennsylvania
      Telephone:  (717)  684-2311

 (4)   Empire Metal Company
      820  E. Water Street
      Syracuse, New York 13210
      Telephone:  (315)  478-6950

 (5)   Florida  Smelting  Company
      2640 Capitola Street
      Jacksonville, Florida
      Telephone:  (904)  353-4317

 (6)   Freedman Metal  Company
      310 McGinnis Boulevard
     Brooklyn, N.Y.  11222
     Telephone: EV9-4131

(7)  General Copper  and Brass Company
     Post Office Box 5353-D
     Philadelphia, Pennsylvania
     Telephone:  (215) SA6-7111

(8)  General Smelting Company
     Division of Wabash Smelting, Inc.
     2901 EW Moreland Street
     Philadelphia, Pennsylvania
     Telephone: GA3-3200

(9)  Gettysburg Foundry
     Specialties Company
     Post  Office Box 421
     Gettysburg,  Pennsylvania 17325
     Telephone:  335-5616
 (10)   Gulf  Reduction Corporation
       6030  Esperson Street
       Houston,  Texas

 (11)   Holtzman  Metal Company
       5223  McKissock Avenue
       St. Louis, Missouri 63147
       Telephone: (314) CI1-3280

 (12)   Inland Metals Refining Co.
       651 E. 119th Street
       Chicago,  Illinois 60628

 (13)   Jordan Company
       Salvage Reclamation Division
       5000  S. Merrimac Avenue
       Chicago,  Illinois 60638
       Telephone: (312) P07-6570

 (14)   Metchem Research, Inc.
       Radcliff  and Monroe Streets
       Bristol,  Pennsylvania
       Telephone: (215) 848-0820

 (15)  National Metal and Smelting
        Company
       210 NW Fourth Street
      Fort Worth, Texas

 (16)  North American Smelting
        Company
      Marine Terminal
      Post Office Box  1952
      Wilmington, Delaware
      Telephone: OL4-9901

(17)  Pacific Smelting Company
      22219  Southwestern Avenue
      Torrance,  California
      Telephone: SP5-3421

(18)  Paragon Smelting Corporation
      36-08  Review  Avenue
      Long Island City,  N.Y.  11101
      Telephone: (212)  RA9-3481

-------
                                  C-183
(19)   Roth Smelting Company
      Thompson Road
      Syracuse, New York

(20)   George Sail Metals Company, Inc.
      2255 East Butler Street
      Philadelphia, Pennsylvania 19137
      Telephone: (215) PI3-3900

(21)   Sandoval Zinc Company
      3649 South Albany Avenue
      Chicago, Illinois 60632
      Telephone: FR6-1900

(22)   SIPI Metals Corporation
      1722 N.  Elston Avenue
      Chicago, Illinois

(23)   Solken-Galamba Corporation
      Second and Riverview Streets
      Kansas City,  Kansas 66118
      Telephone: (913) MA1-4100

(24)   St.  Joseph Lead Company
      250  Park Avenue
      New  York 10017
      Telephone: YU6-7474

(25)   U.S. Metal Products Company
      Post Office Box 1067
      Erie, Pennsylvania 16512
      Telephone: (814) 838-2051

(26)   Hyraan Viener  & Sons
      Post Office Box 573
      Richmond, Virginia 23205
      Telephone: (703) 648-6563

-------
S 7 6 5 + 4 3 2 1
SCRAP PRE TREATMENT
MECHANICAL
P
i X
SUMMIN6VIS9DUES 	 trSmlSc6
3»EE 6
PYRQ METALLURGICAL
FLUI.FUCL — J,rIT, , X
CASTINGS .FABRICATING c !riri»r V
SCRAP, OE CASTINGS, TOP — SWEATING
0
PLUJI.FUEL^— 3 X
M»EO SCRAP 	 - REVCRBERAIOPT C>

Q PBŁTRCAJEO\ 	
DIE -CAST SCRAP 	 "'[Hint • 	
0
ELECTRICITY-— 5 X
CLEAN SCRAP — 	 	 ftT^'rAhCC -
("LU* — • SWEAflNC
0
FLUI.FUCl 	 -6 X
"'«» **"• 	 SMAI.M 	 	 J
HYOBOMETALLURGlCAL
O O
* SOOIUM X /CRUDE \
SWUM CARBOItATt 	 CABBCWATE V CALONER J jjjj.1" j

REFINING
i — FUEL


e
RETORT
OtSTTLLATWl
FUEL—)






MUFFLE
OSTILLATION
I— FUEL
1 {-**
°fiCTOHI
OXIDATION
i-fWL
'MUFFLE
OSTILLATIOV
E'LUJ COVER
ALLOWS AGCN
— FUEL
ALLOTINE
r-
'(&™*?1
t»v,,uW


,
P X^X
X I IHlt \
V | 	 : 	 ^ OUST )
( f UNO \
	 J INGOT 1
V IPUREI J
^^ jX
P - :
6
/CT^ ;
/"^ \ y
X ! ^— *^
Tp
©.
-
LEGEND j
O ATMOSPHERIC EMISSCTS 3
A LI8U1D WASTES
O SOLID WASTES
MATfmA! *! FW IIV n r)THTP MCNATVM MV OATI j^\ •ATTCUJ HEMOHIAL iMmn/n
WOUSrnES JJgJp M SWGn ^^ n KIHO «vc.. rriin»n OHIO OBI
SHF6" ' " ""ZINC SEGMENT OF THE

OM btLAjNUWHT NUnrtKnUUb
METALS INDUSTRY
tNTEW*0«ll PTOOUtl s- — .U. -ST=- =T5 	 W
"i*— 0 799tt«
_ — T |_
	 8 7 8 B A 4 J 2 1

-------
                                 C-185
             PROCESS DESCRIPTION OF THE ZIRCONIUM SEGMENT
              OF THE SECONDARY NONFERROUS METALS INDUSTRY
          There are two zirconium processors in the United States.  Most
of their product is used in nuclear reactors in the civil and military
applications.
          The scrap zirconium market is very small.  In fact, the two
processors do not, as a rule, purchase any scrap except those routinely
generated in their regular customer operations.  This state prevails
because scrap from unknown sources makes the control of product quality
very difficult.
          Production volume of zirconium (primary and secondary) is a
proprietary secret.  Estimates, however, range from 3 to 5 million pounds.
The product sells at about 10 to 15 dollars per pound.
          As in the case of indium, hafnium, and beryllium, currently
employed product process details are not available.  However, since the
total market is very small and the product is very expensive, the processors
are economically constrained to maximize recovery.  This insures low
ambient or indoor emissions of zirconium.
          Zirconium is not a toxic material.
          U. S. producers of zirconium do not seem to be interested in
outside help in their research and development activities.  This trend may
not change in the foreseeable future.

              Population of Secondary Zirconium Processors
           (1)  Amax Specialty Metals Division
               American Metal Climax, Inc.
               6000 Hake Road
               Akron, New York  14001
               Telephone:   (716) 542-5454
           (2)  Teledyne Wha Chang
               P. 0. Box 460-T
               Albany, Oregon

-------
                                     C-186

                                 TECHNICAL REPORT DATA
                          (Please rcail Imimctions on llic reverse before
 I. REPORT NO.
  EPA-650/2-74-048
                            2.
                                                       3. RECIPIENT'S ACCESSION NO.
 4. TITLE AND SUBTITLE
 Development of an Approach to Identification of
     Emerging Technology and Demonstration
     Opportunities	
                                 5. REPORT DATE
                                  May 1974
                                 6.PERFORMING ORGANIZATION CODE
 7. AUTHOR(S)
 H.Nack, K. Murthy, E.Stambaugh,  H. Carlton, and
     G. R.Smithson, Jr.
                                 8. PERFORMING ORGANIZATION RtPORT NO.
 9. PERFORMING ORGANIZATION NAME AND ADDRESS
 Battelle--Columbus Laboratories
 505 King Avenue
 Columbus, Ohio  43201
                                                       10. PROGRAM ELEMENT NO.
                                  1AB015; ROAP 21AFH-016
                                 11. CONTRACT/GRANT NO.
                                  R-802291
 12. SPONSORING AGENCY NAME AND ADDRESS
 EPA, Office of Research and  Development
 NERC-RTP, Control Systems Laboratory
 Research Triangle Park, NC 27711
                                 13. TYPE OF REPORT AND PERIOD COVERED
                                   Final; Through 5/25/74
                                 14. SPONSORING AGENCY CODE
 15. SUPPLEMENTARY NOTES
 16. ABSTRAC1
 The report gives results of a study to develop methodology for characterizing
 major industries from the standpoint of their present environmental impact and
 for assessing the probable effect of emerging process technology on environmental
 considerations. It describes a systematic method for separating the industries into
 process modules.   It demonstrates the applicability of this approach,  using as
 examples the petroleum refining and secondary nonferrous metals industries, each
 with substantially different characteristics.  It also reports an approach utilizing
 expert opinion for rapid identification of emerging technology, and discusses
 technology being developed in the two industries.
 7.
                              KEY WORDS AND DOCUMENT ANALYSIS
                 DESCRIPTORS
                                           6.IDENTIFIERS/OPEN ENDED TERMS
                                             C.  COSATI Picld/Croup
 Air Pollution
 Environmental
  Engineering
 Processing
 Industries
 Petroleum Refining
Metal Industry
Industrial Wastes
\ir Pollution Control
Stationary Sources
Methodology
 nvironmental Impact
 merging Technology
Secondary Nonferrous
 Metals
13B,  11F

05E

05C
13H
 8. DISTRIBUTION STATEMENT
 Unlimited
                                           19. SECURITY CLASS (This Report)
                                           Jnclassified
                                              21. NO. OF PAGES
                                                273
                                           20. SECURITY CLASS (Thispage)
                                           Unclassified
                                                                    22. PRICE
EPA Form 2220-1 (9-73)

-------