United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EPA-450/4-84-007f
March 1984
Air
Locating And
Estimating Air
Emissions From
Sources Of Nickel
               45048400f

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                                  EPA-450/4-84-007f
                                         March 1984
Locating And  Estimating Air  Emissions
         From Sources Of Nickel
             U.S. ENVIRONMENTAL PROTECTION AGENCY
                  Office Of Air And Radiation
             Office Of Air Quality Planning And Standards
             Research Triangle Park, North Carolina 27711

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This report has been reviewed by the Office Of Air Quality Planning And Standards, U.S. Environmental
Protection Agency, and has been approved for publication as received from Radian Corporation. Approval does
not signify that the contents necessarily reflect the views and policies of the Agency, neither does mention of
trade names or commercial  products constitute endorsement or recommendation for use.

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                                  CONTENTS
List of Tables	    iv

List of Figures	..   vii

     1.  Purpose of Document	     1
     2.  Overview of Document Contents	v	     3

     3.  Background	     5
               Nature of Pollutant	     5
               Overview of Production and Use	    11
                 Nickel Production	    11
                 Nickel Uses	    25
               References for Section 3	    41
     4.  Nickel Emission Sources	    43
               Direct Sources of Nickel	    45
                 Nickel production	    45
                 Nickel ore mining and smelting	    46
                 Nickel matte refining	    52
                 Secondary nickel recovery	    59
                 Other secondary metals recovery plants	    63
                 Co-Product nickel recovery	    71
                 Ferrous and nonferrous metals  production	    73
                   Ferrous metals production	    74
                   Nonferrous metals production	    85
                 Electroplating	    94
                 Battery manufacturing	    98
                 Nickel chemical manufacturing	   102
                   (including catalysts)
               Indirect Sources of Nickel	   108
                 Coal and oil combustion	   108
                 Cooling towers at electric utility stations	   122
                 Cement production	   123
                 Municipal refuse and sewage sludge incineration...   129
                 Coke ovens	   139
                 Asbestos mining	   143
                 Coal conversion processes	   147
                 Petroleum processing	   148
                 Coal and oil supplying	   156
               References for Section 4	   159

     5.   Source Test Procedures	   169
               Literature Review of Sampling Methods	   169
               Literature Review of Analytical  Procedures	   172
               Suggested Sampling and Analytical Procedures........   174
               References for Section 5	   176
                                    iii

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                               LIST OF TABLES

Number                                                                 Page

  1       Physical Properties of Nickel	       6

  2       Physical Properties of Nickel Carbonyl	       8

  3       Property and Use Data for Several Miscellaneous  Nickel
            Compounds	       9
  4       Companies Identified as or Thought  to  be  Secondary Nickel
            Refiners or Reclaimers	       16

  5       List of Facilities Reported to be in the  Secondary Copper,
            Aluminum, Brass and Bronze,  Cadmium, Cobalt,  and Zinc
            Recovery Industries	       17

  6       Partial List of Firms Involved in Nickel  Plating
            Operations	       29

  7       List of Firms Producing Nickel Chemicals	       35

  8       Global Emissions of Nickel to  the Atmosphere  from Natural
            Sources	       44

  9       Nickel Emission Factors for the Primary Smelting
          - of Nickel Ore	       51

 10       Primary Nickel Emission Sources and Controls  at the AMAX
            Nickel Refinery	       56

 11       Annual Nickel Emissions for the AMAX Nickel Refinery
            in Braithwaite, Louisiana	       57

 12       Nickel Emission Factors for the Secondary Processing of
            Nickel-bearing Scrap	       62

 13       Nickel Emission Factors for Steel Manufacturing
            Operations	       79

 14       Distribution of Nickel Emissions from  Ferrous Metals
            Production by Geographic Region	       83

 15       Partial List of Domestic Firms Producing  Nickel-containing
            Ferrous Metals	       84

 16       Major Nickel Alloys and Their  Chemical Composition	       86
                                    iv

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                         LIST OF TABLES (Continued)

Number
                                                                        Page
 17       Representative Emission Control Equipment Used in Nickel
            Alloy Production	       91

 18       Nickel Emission Factors for Nonferrous Metals
            Production Sources	       92

 19       Nickel-Cadmium Battery Manufacturers in the
            United States	      103

 20       Nickel Catalyst Producers	      109

 21       Typical Nickel Content of  Domestic  Coals	      110

 22       Nickel Content of Various  Crude and Fuel Oils	      110

 23       Nickel Collection Efficiencies  for  Electrostatic
            Precipitators	      114
                                                                       »

 24       Nickel Collection Efficiencies  for  Fabric Filters	      114

 25       Nickel Collection Efficiencies  for  Wet  Scrubbers	      115

 26       Nickel Emission Factors for Oil Combustion	      117

 27       Nickel Emission Factors for Coal Combustion	      118

 28       Nickel Emission Factors for Fresh Water  Utility
            Cooling Towers	      124

 29       Nickel Emission Factors for Major Cement  Plant Sources	      128

 30       Design Temperature Profile  of a  Sewage Sludge Multiple-
            Hearth Furnace	      133

 31       Emission Factors for Nickel from Municipal Refuse and
            Sewage Sludge  Incinerators	      137

 32       Population of Municipal Refuse and  Sewage Sludge
            Incinerators  in the United States by State in 1978	      140

 33       Coke Plants in  the United States as of January 1980	      144

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                         LIST OF TABLES (Continued)

Number                                                                  Page

 34       Operations within a Coal Gasification and  Liquefaction
            Process that are Known or Suspected Nickel Emission
            Sources	      151

 35       Known or Suspected Nickel Emission Sources within Light,
            Intermediate, and Heavy Hydrocarbon Processing
            Operations	      155
                                    vi

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                             LIST OF FIGURES
iber

1
2


3
4
5
6

7


8

9

10

11

12

13

14

15

16


Nickel scrap flow diagram.
r 1 4 j £
^ickel"


w pattern for intermediate and end uses of

Intermediate use tree of nickel in 1978'
End use applications of nickel in 1978
Flow diagram of
Flow diagram of
refinery 	

Process flow di
recovery plant

Generalized flow
plant 	

Generalized flow
recovery plant,
Gep£ntUZed fl°W

Generalized flow

Generalized flow
plant 	

Generalized flow
plant 	

Generalized flow i
refinery 	

Representative pre
production faci]
R*»ni"oe AT*^ -»*--i *.«.
the Hanna Nickel Smelting Co. operations...
the AMAX hydrometallurgical nickel


gram tor a representative secondary nickel

diagram of a secohdary aluminum recovery

diagram of a secondary brass and bro

diagram of a secondary cadmium recovery

diagram of a secondary cobalt recovery

diagram of a secondary copper recovery

diagram of a secondary zinc recovery

diagram of an electrolytic copper

Jcess flow diagram of a ferrous me


"'nrrr^r* process tlow diagram of a nonferrous metal
nickel alloy production facility
17
Flow diagram for a typical nickel electroplating process...
Page
14


26
27
40
47

53


60

64

65

66

67

68

69

72

75

87
96
                               vii

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                                  SECTION 1

                             PURPOSE OF DOCUMENT

     The U. S. Environmental Protection Agency"(EPA), States, and local air
pollution control agencies are becoming increasingly aware of the presence
of substances in the ambient air that may be toxic at certain concentrations.
This awareness, in turn, has led to attempts to identify source/receptor
relationships for these substances and to develop control programs to
regulate emissions.  Unfortunately, very little information is available on
the ambient air concentrations of these substances or on the sources that
may be discharging them to the atmosphere.
                              *
     To assist groups interested in inventorying air emissions of various
potentially toxic substances, EPA is preparing a series of documents such as
this that compiles available information on sources and emissions of these
substances.-  This document specifically deals with nickel and nickel
compounds.  Its intended audience includes Federal, State, and local air
pollution personnel and others who are interested in locating potential
emitters of nickel and making gross estimates of air emissions therefrom.

     Because of the limited amounts of data available on nickel emissions,
and since the configuration of many sources will not be the same as those
described herein, this document is best used as a primer to inform air
pollution personnel about (1) the types of sources that may emit nickel,
(2) process variations and release points that may be expected within these
sources, and (3)  available emissions information indicating the potential
for nickel or nickel compounds to be released into the air from each
operation.

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     The reader is strongly cautioned against using the emissions
information contained in this document to try to develop an exact assessment
of emissions from any particular facility.  Since insufficient data are
available to develop statistical estimates of the accuracy of these emission
factors, no estimate can be made of the error that could result when these
factors are used to calculate emissions for any given facility.  It is
possible, in some extreme cases, that orders-of-magnitude differences could
result between actual and calculated emissions, depending on differences in
source configurations, control equipment, and operating practices.  Thus, in
situations where an accurate assessment of nickel emissions is necessary,
source-specific information should be obtained to confirm the existence of
particular emitting operations, the types and effectiveness of control
measures, and the impact of operating practices.  A source test and/or
material balance should be considered as the best means to determine air
emissions directly from an operation.

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                                  SECTION 2

                        OVERVIEW OF DOCUMENT CONTENTS

     As noted in  Section  1, the purpose of this document is to assist
Federal, State, and  local air pollution agencies and others who are
interested in locating potential air emitters of nickel and nickel compounds
and making gross  estimates of air emissions therefrom.  Because of the
limited background data available, the information summarized in this
document does not and should not be assumed to represent the source
configuration or  emissions associated with any particular facility.

     This section provides an overview of the contents of this document.  It
briefly outlines  the nature, extent, and format of the material presented in
the remaining sections of this report.

     Section 3 of this document provides a brief summary of the physical and
chemical characteristics of nickel, its commonly occurring forms, and an
overview of its production and uses.  A table summarizes the quantities of
nickel consumed in various end uses in the United States.   This background
section may be useful to someone who needs to develop a general perspective
on the nature of the substance and where it is manufactured and consumed.

     The fourth section of this document focuses on major industrial source
categories that may discharge nickel-containing air emissions.   Section 4
discusses the production of nickel and nickel compounds, the use of nickel
as an industrial feedstock, and the discharge of nickel from industrial
sources due to its being a trace contaminant in fossil fuels.   For each
major industrial source category described in Section 4, example process
descriptions and flow diagrams are given,  potential emission points are
identified, and available emission factor  estimates are presented that show

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the potential for nickel emissions before and after controls employed by
industry.  Individual companies are named that are reported to be involved
with either the production and/or use of nickel and nickel compounds based
on industry contacts and available trade publications.  Where possible, the
chemical form of nickel emissions is identified as this parameter is
important in considerations of health effects.

     The final section of this document summarizes available procedures for
source sampling and analysis of nickel.  Details are not prescribed nor is
any EPA endorsement given or implied to any of these sampling and analysis
procedures.  At this time, EPA has generally not evaluated these methods.
Consequently, this document merely provides an overview of applicable source
sampling procedures, citing references for those interested in conducting
source tests.

     This document does not contain any discussion of health or other
environmental effects of nickel or nickel-containing compounds, nor does it
include any discussion of ambient air levels or ambient air monitoring
techniques.

     Comments on the contents or usefulness of this document are welcomed,
as is any information on process descriptions, operating practices, control
measures, and emissions information that would enable EPA to improve its
contents.  All comments should be sent to:
               Chief, Source Analysis Section (MD-14)
               Air Management Technology Branch
               U. S. Environmental Protection Agency
               Research Triangle Park, North Carolina  27711

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                                 SECTION 3

                                BACKGROUND

NATURE OF POLLUTANT

     Nickel (Ni) is a lustrous white, hard, ferromagnetic metal found in
transition group VIII of the Periodic Table.  It has high ductility, good
thermal conductivity, high strength, and fair electrical conductivity.   It
constitutes approximately 0.009 percent of the earth's crust, making it the
                           2
24th most abundant element.   Nickel can achieve several oxidation states
including -1, 0, +1, +2, +3, and +4; however, the majority of nickel
compounds are nickel +2 species.   Nickel does not occur in nature as the
                                                2 3
pure metal but as a component of other minerals. '   The most prevalent
forms of nickel minerals are sulfides, oxides, silicates, and arsenicals.
Nickel sulfides, silicates, and oxides are the most important nickel
                                                       2
minerals from a mining and natural resource standpoint.   The most common
nickel sulfide mineral, pentlandite [(NiFe)QSa], accounts for the majority
                                    45
of the nickel produced in the world. '   Physical constants and properties
of nickel are presented in Table 1. '

     Nickel is an important metal because of its marked resistance to
corrosion and oxidation in both air and aqueous environments.  The corrosive
resistance of nickel to caustic soda and other alkalies is excellent, and it
is fairly resistant to corrosion by sulfuric acid, hydrochloric acid, and
organic acids.  Nickel is also relatively resistant to corrosion from
exposure to chlorine, fluorine, hydrogen chloride, and molten salts.
However, in the presence of a strongly oxidizing acid such as nitric acid,
nickel exhibits a poor resistance to corrosion.  Other compounds which are
corrosive to nickel include oxidizing and nonoxidizing acid salts and
oxidizing alkaline salts.

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                 TABLE 1.  PHYSICAL PROPERTIES OF NICKEL
                                                        4,6
Property
                                                                 Value
Molecular Weight
Crystal Structure
Melting Point, °C
Boiling Point, °C
Density at 20°C, g/cm
Specific Heat at 20°C, kJ/(kg-K)
Average Coefficient of Thermal Expansion x 10"
     at 20-100°C
     at 20-300°C
     at 20-500°C
Thermal Conductivity, W/(m-K)
     at 100°C
     at 300°C
     at 500°C
Electrical Resistivity at 20°C, yohm-cm
Latent Heat of Fusion, J/g
Latent Heat of Vaporization, J/g
Solubility
     in water
     in slightly dilute nitric acid
     in hydrochloric or sulfuric acid
Vapor Pressure, mm Hg
     1810°C
     2057°C
     2234°C
     2364°C
     2603°C
                                                per °C
          58.71
face centered cube
          1453
          2732
          8.908
          0.44

          13.3
          14.4
          15.2

          82.8
          63.6
          61.9
          6.97
          297.06
          6222

          insoluble
          soluble
     slightly soluble

            1
           10
           40
          100
          400

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     Nickel carbonyl  [Ni(CO>4] is a colorless or slightly yellow liquid that
 is  formed by the direct combination of metallic nickel and carbon monoxide
 (CO).  The compound is miscible in all proportions with most organic
 solvents but is essentially insoluble in water.  Nickel carbonyl is an
 extremely volatile compound having a vapor pressure at 20°C (68°F) of
 44  kPa.  Concentrations of nickel carbonyl in ambient air would tend to
 settle to ground level before being dispersed because its vapor density is
 about four times that of air.   Some of the more important physical
 properties of nickel carbonyl are presented in Table 2.4'7'8  The amount of
 nickel carbonyl that will form in a particular environment is directly
 proportional to total pressure and/or carbon monoxide content, and is
                                      q
 inversely proportional to temperature.   Once nickel carbonyl is formed it
 tends to remain as the metal carbonyl only in the presence of carbon
 monoxide.  In ambient air nickel carbonyl is relatively unstable and will
 dissociate to carbon monoxide and nickel metal.  The half-life of nickel
 carbonyl in air has been determined to be about 100 seconds.     Because
 nickel carbonyl readily decomposes at temperatures above 60°C (140°F), it
 can easily be destroyed by passing the stream through a furnace or other
 high temperature source.  The carbon monoxide is oxidized, leaving only
 elemental nickel particulate matter to be recovered.

     Miscellaneous physical/chemical property data and end use information
                                                            Q
 for several other nickel compounds are presented in Table 3.    Because most
 of these compounds are not produced in large quantities commercially,  only
 limited property data are available.   Apart from nickel oxide, most of which
 is used in metallurgical processes, the most significant nickel compound,
both in commercial importance and volume of production, is nickel sulfate
 (NiSO,).     The most widely used form of nickel sulfate is as the single
 salt, nickel sulfate hexahydrate (NiSO,»  6H-0).

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             TABLE 2.  PHYSICAL PROPERTIES OF NICKEL CARBONYL4'7'8
Property
  Value
Molecular Weight

Melting Point, °C

Boiling Point, °C

Density at 25°C, g/cm

Critical Temperature, °C

Decomposition Point, °C

Vapor Pressure, kPa
     -23°C
     -15.9°C
     -6°C
      0°C
     10°C
     20°C
     43°C
     60°C
  170.75

  -25

  42.6

  1.32

  200

  >60
   5.3
   7.9
  13.2
  19.2
  28.7
  44.0
 100.0
decomposes

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                 TABLE 3.  PROPERTY AND USE DATA FOR SEVERAL MISCELLANEOUS  NICKEL  COMPOUNDS8
    Compound
      Properties
                                                                                 Uses
 Nickel Acetate Tetrahydrate,
         302)2. 4H20
 Nickel Ar senate,
          )2» 8H20
 Nickel  Bromide,
  NiBr0
Nickel Carbonate,
  2NiC03«  3Ni(OH)2- 4H20


Nickel Chloride Hexahydrate,
Nickel Cyanide Tetrahydrate,
 Ni(CN)2- 4H20

Nickel Fluoride,
Nickel Formate Dihydrate,
 Ni(HCOO). 2H0
Nickel Hydroxide,
 Ni(OH)0
- Green crystalline powder
• Boiling point =  16.6°C
- Density =1.74 g/,cm

• Yellowish-green  powder
- Density =4.98 g/cm
• Highly insoluble in water

• Yellowish-green  crystals
• Very deliquescent
• Melting point =  963°C

• Green, odorless powder
 Soluble in acids and ammonium
 salts

 Green deliquescent powder
 Melting point =  1030°C
 Heat of fusion = 142.5 cal/g
 Soluble in water

 Highly poisonous
 Insoluble in water

 Green tetragonal crystals
 Sublimes in HF stream above
 1000°C

 Fine green crystals
 Decomposes to NiO at  180°C
 Density  =2.15 g/cm

 Light-green powder
 Extremely  insoluble in water
 Decomposes at 230°C
  Catalyst production, nickel
  electroplating, aluminum sealing
  Selective fat-hardening
  hydrogenation catalyst
- Nickel electroplating
  Catalyst manufacture, colored
  glass production, electroplating
- Nickel electroplating
  Chemical conversion of acetylene
  to butadiene
  Preparation of  fat-hardening
  nickel hydrogenation catalysts
  Manufacture  of nickel-cadmium
  batteries

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          TABLE 3.  (CONTINUED) PROPERTY AND USE DATA FOR SEVERAL MISCELLANEOUS NICKEL COMPOUNDS
                                                                                               8
   Compound
     Properties
                                              Uses
Nickel Iodide,
    [2
Nickel Nitrate,
 Ni(N03)2- 6H20
Nickel Oxide,
 NiO
- Blue-green, very deliquescent
  crystals
- Melting point = '797°C
- Density =5.83 g/cm

- Green, deliquescent crystals
- Melting point = 56°C
- Boiling point = 137°C
- Density =2.05 g/cm

- Green-black cubic crystals
- Melting point = 1990°C
- Density = 6.67 g/cm
- Insoluble in water
                                 - Catalyst and battery manufacture
                                   Catalyst production, alloy
                                   and stainless steel production,
                                   nickel salts and specialty ceramics
Trinickel Orthophosphate,
        )2- 7H20
Apple-green plates
Decomposes upon heating
Insoluble in water
                                     Steel coatings,  pigment for oil
                                     and water paints
Nickel Sulfate Hexahydrate,
Green transparent crystals
Density =2.03 g/cm
Decomposes above 800°C to
NiO and S0_
Highly soluble in water and
ethanol
                                     Nickel electroplating,  catalyst
                                     production
Nickel Subsulfide,
Lustrous, yellowish-bronze
metal              „
Density =5.82 g/cm
Melting point = 790°C
Insoluble in water
Heat of fusion = 25.8 cal/g

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OVERVIEW OF PRODUCTION AND USE

Nickel Production

     Nickel production in the United States is referred to as either primary
or secondary, depending on the source of the nickel raw material.  Primary
nickel production involves the smelting of natural nickel ores or the
refining of nickel matte.  Secondary nickel production involves the
reclamation of nickel metal from nickel-based or non-nickel-based scrap
metal.  Primary nickel production contributes about 40 percent to the
domestic nickel production total, while secondary production is responsible
for the remaining 60 percent.

     Presently, the only nickel ore mining and processing facility in the
United States is operated by the Hanna Mining and Nickel Smelting Company
                    12 13
near Riddle, Oregon.  '    Operations at this facility have been inter-
mittent since early 1982.  Consistent operation of the mine and smelting
plant is expected by the beginning of 1984.    The nickel ore mined and
processed by Hanna is known as garnierite.    The Hanna processing facility
produces nickel in the form of a ferronickel that is 50 percent nickel and
50 percent iron.    Ferronickels produced by foreign operations have nickel
contents ranging from 20 to 50 percent.

     The Hanna Company pyrometallurgical smelter uses an electric furnace to
recover selectively metallic nickel and iron from garnierite ore feed.   The
garnierite ore, which has been crushed and screened, is melted in an
electric furnace where nickel oxides, together with a controlled portion of
iron oxide, are selectively reduced by ladle mixing of the molten ore with
ferrosilicon.   The crude ferronickel that is produced is further refined in
an electric furnace and is cast into nickel pigs.

     Primary nickel is also produced domestically by AMAX Nickel,  Inc.  as a
co-product at its copper-nickel refinery in Braithwaite,  Louisiana.   In
addition to nickel,  the plant also produces copper, cobalt,  and ammonium
                                    11

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sulfate.  Approximately 25 percent of total domestic nickel production is
attributable to the AMAX refinery.    Feed material for the AMAX refinery is
not nickel ore but a nickel-copper-cobalt matte that is imported from South
Africa, Australia, and New Caledonia.    Matte is the name applied to an
impure metallic sulfide product obtained from the smelting of sulfides of
metal ores such as copper, nickel, and lead.  The nickel content of the
matte used by AMAX ranges from 40 to 75 percent.

     In contrast to the Hanna facility, AMAX uses a hydrometallurgical
process to refine their matte feed material.  '    In this process, a copper
sulfate-sulfuric acid solution is first used to leach the matte concen-
trates.    The leaching step dissolves the majority of the nickel and cobalt
components in the matte.  The resulting solution is purified and then
reacted with hydrogen under high temperature and pressure to reduce and
precipitate nickel.    The nickel powder produced by this process is about
99 percent pure.
     The smelting and refining processes used by Hanna and AMAX produce
nickel in forms that can generally be classified into two groups.  Group I
nickel materials are unwrought nickel with a purity of greater than
98 percent.  Materials in this group may be in the form of powder, pellets,
briquets, rondelles, and cathodes.  Group II nickel materials contain less
than 98 percent nickel.  Nickel oxide sinter (charge nickel), ferronickel,
Incomet, and Inco utility shot and pig make up this group.  Nickel salt
compounds are produced in much lower quantities and constitute a relatively
                                                    1 f\ 1 ft
small portion of the domestic primary nickel market.  '

     In the United States the secondary recovery and refining of nickel
scrap produces more nickel than ore processing and matte refining sources
combined.  In 1978 nickel from secondary recovery sources amounted to
approximately 53,600 Mg (59,100 tons), or 57 percent of domestic nickel
production.    The potential for increasing the quantity of nickel produced
by secondary means is substantial because only about 40 percent of the
                                    12

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 available nickel-bearing  scrap is currently being recycled.  The other
 60 percent, in  the form of batteries, spent nickel-base catalysts, and scrap
                           1Q 9fl
 metal,  is being landfilled.   '

     Nickel scrap refining generally involves melting it down in either an
 electric arc or reverberatory furnace, often in the presence of lime and an
 alloying agent.  The product of the smelting operation is often refined
                                                   9O
 further to produce a higher purity nickel material.    Two types of scrap,
 classified as obsolete and industrial, are used as raw materials in the
 secondary nickel recovery industry.  Obsolete scrap consists of alloys in
 the form of salvaged machinery, sheet metal, aircraft parts, and discarded
 consumer goods  such as batteries.  Industrial scrap refers to turnings,
 casting wastes, and solids from the manufacturing of alloy products.  About
 60 percent of the nickel scrap processed by secondary refiners is obsolete
      19
 scrap.    The flow of nickel-bearing scrap through the secondary processing
                                 12
 industry is depicted in Figure 1.    The basic products of the secondary
 nickel recovery industry include:

          stainless steels,
     -    low alloy steels,
          nickel-base alloys,
          copper-base alloys,
     -    aluminum-base alloys,
          nickel metal, and
     -    nickel in chemical compounds.

Generally, the nickel product of a scrap recovery facility is used to
produce the same type of good from which the scrap was generated.   For
example, recovered nickel-bearing alloy  scrap is used to manufacture new
nickel alloys.

     Information found in published sources is inconsistent concerning the
number of secondary nickel refiners operating in the United States.   A range
                                    13

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(— ^
1
1
1
-
Y r
Primary Primary Nonfer
Producers Imports Smelte
Refine


* ^ f ^
Alloy Foundries 4 Ste
Producers _ i">thor Manuf ac— -^ Mil
turing
Y Y Y
Runaround Runaround Runai
Scrap Scrap ~ — Scrs
j . , .

Consumers of Shapes and

1
u w
End Prompt Industrial
Products Scrap
Impoi
1 1
| 1
Old , I
Scrap 	 -^ 	 J 	
1 r
1 ' 1
Y t


Scrap Scrap i

1 1
Y Y *
Exports

rous 1
rs & i
rs
" •" 1
1
' * 1
a i
La ^
•* 1 ,
1 1
1 1
•ound | j
ip
1
1
1
!
1
1
1
1
1
!
P _,
ts -^n
i
1
1
— ^— — _ .^ ^^^
i
i
i
1

™ Indicates pattern
of primary consumption
Figure 1.  Nickel scrap flow diagram.
                                     19
                         14

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 of from 5 to 36 refiners has been indicated.19"21   The  confusion over the
 total number of refiners appears to have developed because  of problems in
 classifying what constitutes a secondary nickel  refiner.  Published data of
 secondary nickel producers have included:   (a) firms  that process nickel
 scrap,  but do not melt  or refine it;  (b)  firms that produce stainless steel;
 (c)  firms that primarily produce secondary  copper;  (d)  firms that only
 collect,  handle,  and  transport nickel  scrap;  (e) firms  that melt  and/or
 refine  nickel scrap;  and (f)  firms  that  produce  nickel  alloys in  a partially
 refined form.   Primary  nickel producers,  foundries, and other sources that
 recover their own captive scrap,  as well  as sources that only handle  or
 transport nickel  scrap,  are  not  considered  secondary nickel refiners.
 Table 4 presents  a list  of firms that  have been  identified  as being
 secondary nickel  refiners.   '

     There are  other  secondary metal recovery facilities, not  operated
 primarily for nickel  recovery,  that also produce varying quantities of
 nickel.   Secondary copper and  secondary aluminum recovery plants are
 examples  of  such  facilities.  Also, because they consume scrap containing
 varying amounts of nickel, the brass and bronze segments, the  cadmium
 segments,  the zinc segments, and  the cobalt segments of the secondary metals
 recovery  industry  may produce some nickel-bearing materials.   In several
 cases the  same  facility will recover nickel, aluminum, copper, and other
metals.   Generally however, a facility is categorized by the  type of metal
 that is produced  in the greatest quantity.  Table 5 presents a list of
 facilities that have been reported to be in the secondary copper, aluminum,
brass and bronze,  cadmium, and cobalt metals recovery industries.22'23  As
 shown in  the table, several facilities produce more than one metal.  Nickel
production data for the individual facilities are unavailable.  Through
their handling and processing of nickel-bearing materials,  the facilities
listed  in Table 5 may potentially emit nickel and nickel compounds to the
air.
                                    15

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              TABLE 4.  COMPANIES IDENTIFIED AS OR THOUGHT TO BE
                        SECONDARY NICKEL REFINERS OR RECLAIMERS  '*
               Company                            Location
International Metals Reclamation Co.         Ellswood City, PA
Alloy Metal Products, Inc.                   Davenport, IA
American Nickel Alloy Mfg. Co.               New York, NY
Advanced Metals Div. of ARMCO Steel          Baltimore, MD
Belmont Smelting Co.                         Brooklyn, NY
Frankel Co.                                  Detroit, MI
Mercer Alloy Corp.                           Greenville, PA
Metal Bank of America, Inc.                  Philadelphia, PA
Paragon Smelting Corp.                       Long Island City, NY
Riverside Alloy Metal Div. of
     H. K. Porter Co.                        Pittsburgh, PA
I. Schumann Co.                              Cleveland, OH
Utica Alloys, Inc.                           Utica, NY
Wai Met Alloys Co.                           Dearborn, MI
Whitaker Metals-Alloy Div.                   Greenville, PA
H. Keamer & Co.                              Chicago, IL
R. Lavin & Sons                              Chicago, IL
New Jersey Zinc Co.                          Bethlehem, PA
National Nickel Alloy Corp.                  Pittsburgh, PA
Metallurgical International, Inc.            Cartaret, NJ
American Nickel Alloy Mfg. Co.               Weehawken, NJ
International Wire Products                  Wyckoff, NJ
Nassau Smelting & Refining Co.               Tottenville, NY
Niagara Falls Metals & Minerals, Inc.        Buffalo, NY


NOTE:  This listing is subject to change as market conditions change,
       facility ownership changes, plants are closed down, etc.
       The reader should verify the existence of particular facilities
       by consulting current listings and/or the plants themselves.
       The level of nickel emissions from any given facility is
       a function of variables such as capacity, throughput, and control
       measures, and should be determined through direct contacts with
       plant personnel.
                                    16

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              TABLE 5.  LIST OF FACILITIES REPORTED TO BE IN THE SECONDARY COPPER, ALUMINUM,

                        BRASS AND BRONZE, CADMIUM, AND COBALT RECOVERY INDUSTRIES16'22"24
Company
Location
                   Secondary Recovery Segment
Copper    Aluminum    Brass & Bronze    Cadmium
                                                                          Cobalt  Zinc
Barth Smelting Corp.
Batchelder-Blasius, Inc.
Bay State Refining, Inc.
Joseph Behr & Sons, Inc.
Belmont Smelting &
 Refining Works
W.J. Bullock, Inc.
Cepro Corporate Brass Co.
Circuit Foil Corp.
Colonial Metals Co.
General Copper & Brass Co.
Samuel Greenfield Co.,
 Inc.
Holstead Metal Parts, Inc.
Benjamin Harris & Co.
Henning Brothers & Smith
K. Hettleman & Sons,
 Div. of Minerals & Chem.
Holtzman Metal Co.
H. Kramer & Co.
Metal Bank of America,
 Inc.
Nassau Smelting and
 Refining Co.
Phelps Dodge Refining
 Corp.
Riverside Alloy Metal
 Div. of H.K. Porter Co.
Roessing Bronze Co.
Newark, NJ
Spartanburg, SC
Chicopee Falls, MA
Rockford, IL

Brooklyn, NY
Fairfield, AL
Cleveland, OH
Bordentown, NJ
Columbia, PA
Philadelphia, PA

Brooklyn, NY
Zelienople, PA
Chicago Hgts, IL
Brooklyn, NY

Baltimore, MD
St. Louis, MO
Chicago, IL

Philadelphia, PA

Tottenville, NY

New York, NY

Pittsburgh, PA
Pittsburgh, PA

-------
            TABLE 5.  (CONTINUED) LIST OF FACILITIES  REPORTED TO BE IN  THE SECONDARY  COPPER,  ALUMINUM,
                                                                                     I /-  o o  O /
                            BRASS AND BRONZE,  CADMIUM,  AND COBALT RECOVERY INDUSTRIES  '
    Company
                           Location
                      Copper
         Secondary Recovery Segment
Aluminum    Brass & Bronze    Cadmium
Cobalt  Zinc
oo
I. Schumann & Co.
M. Seligman & Co.
SIPI Metals Corp.
U.S. Metals Refining Co.
R. Lavin & Sons
Cerro Copper Products,
 Inc.
Chicago Extruded
 Metals Co.
North Chicago Smelting
 & Refining
Alloy Metals, Inc.
Liberman and Glittlen
 Metal
Canton Smelting &
 Refining Co.
Chase Brass & Copper Co.
The Federal Metal Co.
The River Smelting &
 Refining Co.
•North American Smelting
 Co.
Lee Brothers, Inc.
Revere Copper & Brass,
 Inc.
Hyman Viener & Sons
New Jersey Zinc Co.
Whittaker Metals
Franklin Smelting &
 Refining Co.
Cleveland, OH
Chicago, IL
Chicago, IL
New York, NY
Chicago, IL

Saget, IL

Cicero, IL

North Chicago, IL
Troy, MI

Grand Rapids, MI

Canton, OH
Euclid, OH
Bedford, OH

Cleveland, OH

Wilmington, DE
Anniston, AL

Scottsboro, AL
Richmond, VA
Bethlehem, PA
Greenville, PA

Philadelphia, PA

-------
        TABLE 5.  (CONTINUED) LIST OF FACILITIES REPORTED TO BE IN THE SECONDARY COPPER, ALUMINUM,

                        BRASS AND BRONZE, CADMIUM, AND COBALT RECOVERY INDUSTRIES16'22"24
Company
                           Location
                   Secondary Recovery Segment
Copper    Aluminum    Brass & Bronze    Cadmium
                                                                          Cobalt  Zinc
Paragon Smelting Corp.
International Wire
 Products
Federated Metals
Semi-Alloys, Inc.
Rochester Smelting &
 Refining
Alloys & Chemicals Corp.
Aluminum Billets, Inc.
Aluminum & Magnesium, Inc.
Aluminum Smelters, Inc.
Aluminum Smelting &
 Refining Co.
Aurora Refining Co.
Barnum Smelting Co.
Bay Billets, Inc.
J.R. Elkins, Inc.
Excel Smelting Corp.
Firth Sterling, Inc.
General Smelting Co.,
 Div. of Wabash Smelting,
 Inc.
Gettysburg Foundries
Hall Aluminum Co.
Long Island City, NY

Wyckoff, NJ
Newark, NJ
Mt. Vernon, NJ

Rochester, NY
Cleveland, OH
Youngstown, OH
Sandusky, OH
New Allen, CT

Maple Hgts, OH
Aurora, IL
Bridgeport, CT
Sandusky, OH
Brooklyn, NY
Memphis, TN
Pittsburgh, PA
Philadelphia, PA
Gettysburg, PA
Chicago Hgts, IL
                                                   +
                                                   +
                                                   +

-------
            TABLE 5.  (CONTINUED) LIST OF FACILITIES REPORTED TO BE IN THE SECONDARY COPPER,  ALUMINUM,

                            BRASS AND BRONZE, CADMIUM, AND COBALT RECOVERY INDUSTRIES16»22"24
    Company
                           Location
                                         Secondary Recovery Segment
                      Copper    Aluminum    Brass & Bronze    Cadmium
Cobalt  Zinc
NJ
o
Harco Aluminum, Inc.
Northwestern Metal Co.
Pioneer Aluminum, Inc.
George Sail Metals Co.
Siberline Manufacturing
 Co.
Sonken-Galamba Corp.
Superior Industries, Inc.
U.S. Aluminum Corp. of
 Pennsylvania
U.S. Reduction Co.
Wabash Smelting, Inc.
Allied Metals Co.
Precision Extrusions, Inc.
Metropolitan Metal Co.
Michigan Standard Alloys
Bohn Aluminum & Brass
Union Iron & Metal Co.
Easco Corp.
Ansam Metals Corp.
Tomke Aluminum
Atlantic Metals Corp.
Aluminum Smelters of
 New Jersey
Niagara Falls Metals &
 Minerals
Chicago, IL
Lincoln, NE
Los Angeles, CA
Philadelphia, PA

Langsford, PA
Kansas City, KS
Youngstown, OH

Marietta, PA
East Chicago, IN
Wabash, IN
Chicago, IL
Bensenville, IL
Detroit, MI
Benton Harbor, MI
Adrian, MI
Baltimore, MD
Baltimore, MD
Baltimore, MD
Baltimore, MD
Philadelphia, PA

Delair, NJ

Buffalo, NY
                                                                  +

                                                                  +

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        TABLE 5.  (CONTINUED) LIST OF FACILITIES REPORTED TO BE IN THE SECONDARY COPPER, ALUMINUM,

                        BRASS AND BRONZE, CADMIUM, AND COBALT RECOVERY INDUSTRIES16'22"24
Company
Location
                   Secondary Recovery Segment
Copper    Aluminum    Brass & Bronze    Cadmium
Cobalt   Zinc
Indium Corp. of America
U.S. Metal Products Co.
Magnolia Metal Co.
Lewiston Smelting &
 Refining
Freedman Metal Co.
Bunting Brass & Bronze Co.
Wolverine Metal Co.
United Refining & Smelting
 Co.
Frankel Co., Inc.
National Nickel Alloy
 Corp.
Metallurgical Inter-
 national, Inc.
American Nickel Alloy
 Mfg. Co.
Atomergic Chemetals Co.
Alloy Metal Products, Inc.
Max Zuckerman & Sons
The Himmel Bros. Co.
The Platt Bros. Co.
Philips Elmet Corp.
Associated Metals Co.
 of Oakland
Chemalloy Electronics
Globe Metals Co.
Edison, NJ
Erie, PA
Auburn, NE

Lewistown, PA
Brooklyn, NY
Toledo, OH
Detroit, MI

Franklin Park, IL
Detroit, MI

Greenville, PA

Cartaret, NJ

Weehawken, NJ
Carle Place, NY
Davenport, IA
Owings Mill, MD
Hartford, CT
Waterbury, CT
Lewistown, ME
Oakland, CA

Santee, CA
Oakland, CA

-------
            TABLE  5.   (CONTINUED) LIST OF FACILITIES REPORTED TO BE IN THE SECONDARY COPPER, ALUMINUM,
                                                                                    I x O O O /
                           BRASS AND BRONZE, CADMIUM, AND COBALT RECOVERY INDUSTRIES  '
    Company
                           Location
                      Copper
         Secondary Recovery Segment
Aluminum    Brass & Bronze    Cadmium
Cobalt   Zinc
to
Goldberg Metal
 Refining Co.
Vulcan Materials
Tri-Alloys, Inc.
M.P. Kirk & Sons
Pacific Smelting Co.
Bonanza Aluminum Corp.
Eugene Enterprises
Thorock Metals, Inc.
U.S. Reduction Co.
Zenith Metals, Inc.
Federated Metals Corp.
Levin Metals Corp.
Reynolds Metal Co.
Hi-Duty Alloys
Materials Reclamation Co.
R.D. Werner Co.
Electric Materials, Inc.
Johnson Bronze Co.
Metallurgical Products
Metchem Research
Delaware Valley Smelting
Superior Zinc Company
Signal Alloy Corp.
Florida Smelting Co.
Southwire Co.
Russell Anaconda
 Aluminum
Briel Industrial, Inc.
H&H Metals Co.
Berman Bros., Intl.
Gulp Smelting & Refining
M. Kimerling & Sons
Bay State Aluminum Co.
Gardena, CA
Corona, CA
Montclair, CA
Los Angeles, CA
Torrance, CA
Anaheim, CA
Los Angeles, CA
Compton, CA
Mira Loma, CA
Los Angeles, CA
San Francisco, CA
San Jose, CA
Phoenix, AZ
Seattle, WA
Seattle, WA
Greenville, PA
Erie, PA
New Castle, PA
West Chester, PA
Bristol, PA
Bristol, PA
Bristol, PA
Chattanooga, TN
Jacksonville, FL
Atlanta, GA

Miami, FL
Shelbyville, KY
Louisville, KY
Birmingham, AL
Attalla, AL
Birmingham, AL
Braintree, MA

-------
            TABLE 5.   (CONTINUED)  LIST OF FACILITIES  REPORTED  TO  BE IN  THE SECONDARY  COPPER,  ALUMINUM,

                            BRASS  AND BRONZE,  CADMIUM, AND  COBALT RECOVERY INDUSTRIES16'22"24
    Company
                           Location
                      Copper
         Secondary Recovery Segment
Aluminum    Brass & Bronze    Cadmium
                                                                                                     Cobalt   Zinc
KJ
OJ
Harry Butler & Co.
New England Smelting
 Works
Bay State Smelting
Anchor Alloys
Badger Aluminum Extrusion
 Corp.
White Metal Rolling
 & Stamp Co.
Ney Metals
Republic Metals
Freecast Alloys
Sitkin Refining &
 Plumbing
Friedman Metal Co.
Sidney Kronblum Metals
Hugo Neu & Sons
Anton Noll Metals
Eastern Alloys, Inc.
Kearney Smelting
Metropolitan Metals, Inc.
National Aluminum Division
Illinois Smelting &
 Refining
Jordan Co.
Meadowbrook Corp.
Sandoval Zinc Co.
Chemico Metals Co.
Hydrometals, Inc.
Gulf Reduction Corp.
Federated Metals
International Metal Co.
Federated Metals
Arkansas Aluminum
Alcoa
Boston, MA

Boston, MA
Somerville, MA
Brooklyn, NY

Brooklyn, NY

Brooklyn, NY
Brooklyn, NY
Brooklyn, NY
Brooklyn, NY

Brooklyn, NY
Brooklyn, NY
Brooklyn, NY
New York, NY
Long Island City, NY
Maybrook, NY
Belle Mead, PA
Camp Hill, PA
Pittsburgh, PA

Chicago, IL
Chicago, IL
LaSalle, IL
Chicago, IL
Afton, IL
Dallas, TX
Houston, TX
Houston, TX
Sapulpa, OK
Sand Spring, OK
Hot Springs, AR
Riverdale, IA

-------
           TABLE 5.  (CONTINUED) LIST OF FACILITIES REPORTED TO BE IN THE SECONDARY COPPER,  ALUMINUM,

                           BRASS AND BRONZE, CADMIUM, AND COBALT RECOVERY INDUSTRIES16'22"2
   Company
                           Location
                      Copper
         Secondary Recovery Segment
Aluminum    Brass & Bronze    Cadmium
Cobalt   Zinc
KJ
-p-
Diversified Metals
S-G Metals
Eagle-Picher Industries
American Alloys Corp.
Mackay Smelting Co.
U.S. Reduction Co.
Aluminum Billets, Inc.
Barmet Industries
Certified Alloys, Inc.
U.S. Reduction Co.
Eagle-Piher Industries
G.A. Avril Co.
ALCOA
Ireco Aluminum
U.S. Reduction Co.
Wabash Smelting
Arco
City Metals Refining
Grand Rapids Alloys
Gerox, Inc.
Gardiner Metal Corp.
Imperial Smelting Corp.
Inland Metals Refining
Clearing Smelting Corp.
Apex International
  Alloys, Inc.
Hazelwood, MO
Kansas City, KS
Galena, KS
Kansas City, MO
Salt Lake City, UT
Russellville, AL
Girard, OH
Akron, OH
Maple Heights, OH
Toledo, OH
Cincinnati, OH
Cincinnati, OH
Lafayette, IN
Plymouth, IN
East Chicago, IN
Wabash, IN
Detroit, MI
Detroit, MI
Grand Rapids, MI
Grand Rapids, MI
Chicago, IL
Chicago, IL
Chicago, IL
Chicago, IL
Cleveland, OH
Checotah, OK
Bicknell, IN
                                                                                                                   +
                                                                                                                   +
                                                                                                                   •f
                                                                                                                   +
                                                                                                                   +
   NOTE:  This listing is subject to change as market conditions change, facility ownership changes,
          plants are closed down, etc.  The reader should verify the existence of particular facilities
          by consulting current listings and/or the plants themselves.  The level of nickel emissions
          from any given facility is a function of variables such as capacity, throughput, and control
          measures, and should be determined through direct contacts with plant personnel.

-------
      In  addition to  primary and  secondary nickel production sources, nickel,
 in the form of nickel  sulfate  (NiSO^), is generated as a by-product or
 co-product  of copper and platinum metal refining.12'25  In 1975, 7.5 percent
 of the total domestic  nickel production was obtained from co-production
 during copper and platinum refining.  However, in 1976 the amount of nickel
 generated as a co-product was  insignificant compared to the amount produced
 by primary  nickel smelters and refiners and secondary refiners.  There is
 considerable uncertainty about estimating the level of nickel production
 achievable  from  co-production because there is no fixed relationship between
 the quantities of copper and platinum recovered and the quantity of nickel
         12,25
 produced.   '     Recent estimates of the amount of nickel produced by this
 method could not  be  determined.
Nickel Uses

     In 1978 approximately 162,700 Mg (180,700 tons) of nickel were consumed
in the United States in a wide variety of producer and consumer goods.
Nickel was consumed as pure unwrought nickel, ferronickel, nickel oxide, and
nickel salts.  The consumption of nickel has two components, an intermediate
consumption or use and an end or product use.  The major intermediate and
                                              26
end uses of nickel are summarized in Figure 2.    The largest intermediate
nickel use is in the manufacture of nickel-bearing alloys, including stain-
less and alloy steels, ductile and cast irons, cupronickels, and high nickel
alloys.
     Figure 3 presents a summary of the major intermediate uses of nickel on
a total weight and percentage basis.    Over 80 percent of all intermediate
nickel consumption goes into the production of steels and alloys.15'18  The
corrosion resistance, strength, and high ductility of nickel make it a
highly valuable alloying element.  Nickel alloys such as MoneiP,  which is
about 65 percent nickel and 30 percent copper, are stronger and more
corrosion resistant in certain environments than pure nickel, and therefore,
are prevalent in applications where extreme temperatures, stress, and
                                    25

-------
fo
               Nickel.
                                    Principal Intermediate Uses
                                  -Stainless  steel and heat resisting steel-
                                  -Alloy steel
                                  -Super  alloys-
                                  -Nickel-copper and copper-nickel alloys-

                                  -Pertnanent magnet alloys
                                  -Other nickel and nickel alloys'




                                  • Cast  irons

                                  -Electroplating

                                  -Chemicals and chemical uses ——
         Principal  End Uses

    Aircraft, trucks, railroad cars,
    decorative purposes, cryogenic equipment,
    household appliances, high temperature and
    ^corrosion resistance applications

    "Crankshafts, axles, gears, shafts, frames, and
    other parts for  trucks, cranes, cartmoving equipment,
    mechanic tool parts and frames, aircraft landing
    gear components, tnlssle parts, and rock drill parts
  "JTurbosupercharger and jet engine
    Food preparation and handling equipment,
    water meters, pumps, propellers and propeller
    shafts, condenser tubes, ice making equipment,
    pickling racks and baskets, tanning drums,
    paper making machine, soap making equipment,
    piping, tubing, pumps, and valves for machine
    _service, heat exchanger, condenser, evaporators
    Steam turbines, woven wire belting,
    skin covering of the .X-15 rocket research plane,
    pumps, valves, liners, shafts, digesters,
    distillation columns, process equipment for handling
    acid, alkaline, and bleach solutions
-^-Tiiick
   [etc.
Nickel sulfate, nickel chloride,  nickel nitrate,
                                  •Batteries, Ceramics, and others
                         Figure 2.  Generalized  flow  pattern  for  intermediate  and end uses  of nickel.
                                                                                                                26

-------
Nickel Consumption -
162,700 Mg(180,723 tons)
                                              Permanent Magnet Alloys

                                              740 Mg (818  tons), 0.5Z
                                              Super Alloys - 14,200 Mg
                                              (15,685 tons), 8.6Z
                                              Electroplating - 24,800 Mg
                                              (27,319  tons), 15.2Z
                                              Nickel-Copper & Copper-NicfceJ
                                              Alloys - 6,400 Mg(7,019 tons)
                                              3.9Z
Other Nickel Alloys -
36,000 Mg (39,633 tons),
21.91
                                              Stainless & Alloy Steel -
                                              69,900 Mg (77,640 tons),
                                              42.9Z
                                              Chemicals & Chemical Uses
                                              1,700 Mg (1,886 tons),  1Z
                                             Cast Irons - 3,900 Mg
                                             (4,279 tons), 2.4Z
                                             Other Uses -5,800  Mg
                                             (6,444 tons),  3.6Z
        Figure  3.  Intermediate use  tree  of  nickel in  1978.
                                                                            15
                                          27

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corrosive substances are found.  After metallurgical uses, the most
significant intermediate consumption sectors are electroplating and
chemicals.  These sectors are responsible for approximately 13 and
1 percent, respectively, of the nickel consumed.    A partial list of nickel
                                                                    27
platers, both electrolytic and electroless, is presented in Table 6.    A
list of firms consuming nickel and manufacturing nickel chemicals is given
           00
in Table 7.
     The principal end uses of nickel are in chemicals and allied products,
petroleum refining, fabricated metal products, aircraft parts, machinery,
household appliances, building construction, electrical equipment, motor
                                        12
vehicle construction, and ship building.    For end use applications, over
90 percent of all nickel used is in the form of metal, principally in
       12
alloys.    Petroleum refiners and manufacturers of chemicals and allied
products are the principal end users of nickel, chiefly in the form of metal
alloys applied in manufacturing equipment parts exposed to corrosive
chemicals.  In 1978 this end use consumed about 23 percent of the nickel
supply.  About 9 percent of the nickel consumed is used to manufacture
fabricated "metal products such as cutlery, handtools, hospital and kitchen
equipment, ductwork, general hardware, and sheet metal boilers.  The pro-
duction of aircraft parts accounts for approximately 8 percent of the nickel
end uses, primarily in the form of superalloys.  Jet engines, turbo-
superchargers, and gas turbines are the main aircraft parts composed of
                   12
nickel superalloys.

     About 8 percent of the nickel consumed is used in the construction of
general machinery.  Cast and wrought nickel alloy steels are used in
machinery to provide strength.  The manufacture of household appliances
consumes 7 percent of the nickel supply, principally in stainless steel and
electroplating.  Nickel-copper alloys are also used to manufacture food-
processing equipment.  Building construction constitutes about 9 percent of
all nickel consumption in the form of stainless steel or wrought and cast
alloy steels.   Nickel steels are preferred for structural members because of
                                    28

-------
    TABLE 6.  PARTIAL LIST OF FIRMS INVOLVED IN NICKEL PLATING OPERATIONS
                                                                         27
Electrolytic Nickel Platers
     Avalon Plating Co.
     Kotoff & Co., Inc.
     Electroforms, Inc.
     Alco-Cad Nickel Plating Corp.
     Bronze-Way Plating Corp.
     Cad-Nickel Plating Co., Inc.
     General Electroplating
     Precision Gage Plating Co.
     Chrome Nickel Plating Inc.
     Continental Plating Co.
     Haws Plating Works Inc.
     Lane Metal Finishers, Inc.
     Pacific Rustproofing Co.
     California Plating Co., Inc.
     Superior Plating Works
     Van Der Horst Corp.
     Oliver Wire and Plating Co.
     Ancidite Metal Finishing Div.
     Foss Plating Co.
     Artistic Polishing & Plating
     Anadite Metal Finishing Div.
     Sandia Metal Process Inc.
     Jennitfgs Plating Co.
     Emerik, Inc.
     Chrome Engineering,  Inc.
     Bridgeport Plating Co.
     J.  B.  Coggins Co.
     Frey Manufacturing Co.
     Trinacria Specialty Mfg. Co.
     Whyco Chromium Co.
     Summit Finishing Div.  of KBI,
     Southeastern Coatings,  Inc.
     Estes Plating Ltd.
     Hudson Wire Co.
     Waynesboro Industries,  Inc.
     Braco Industries
     Claytor Industries
     Imperial Plating Co.
     Sigoli Metal Plating Co.
     API Industries,  Inc.
     American Nickel Works
     Apollo Metals,  Inc.
     Century Plating Co.
     Chrome-Rite Co.,  Inc.
Inc.
Alhambra, CA
El Monte, CA
Gardenia, CA
Los Angeles, CA
Los Angeles, CA
Los Angeles, CA
Los Angeles, CA
Los Angeles, CA
Lynwood, CA
Oakland, CA
Oakland, CA
Oakland, CA
Oakland, CA
San Carlos, CA
San Diego, CA
San Francisco, CA
San Leandro, CA
Santa Clara, CA
Santa Fe Springs, CA
South El Monte, CA
South Gate, CA
Van Nuys, CA
W. Los Angeles, CA
Colorado Springs, CO
Bridgeport, CT
Bridgeport, CT
Meriden, CT
New Britain, CT
Norwich, CT
Thomaston, CT
Thomaston, CT
West Palm Beach, FL
Atlanta, GA
Trenton, GA
Waynesboro, GA
Chicago, IL
Chicago, IL
Chicago, IL
Chicago, IL
Chicago, IL
Chicago, IL
Chicago, IL
Chicago, IL
Chicago, IL
                                    29

-------
    TABLE 6.   (CONTINUED)  PARTIAL LIST OF FIRMS INVOLVED IN NICKEL PLATING

              OPERATIONS27
Electrolytic Nickel Platers
     Elkwood Plating Inc.
     Gilbertson, Inc.
     Graham Plating Works
     Handy Plating Co.
     James Precious Metals Plating Inc.
     Mechanical Plating Co.
     Metcil Plating Co.
     Modern Plating Corp.
     American Nickeloid Co.
     Anderson Silver Plating Co.
     State Plating Inc.
     Wayne Metal Protection Co.
     Artco Metal Finishing
     Emconite Division
     G&L Interstate Plating
     Summit Metal Finishing Div.  of
          KBI, Inc.
     Delaware Machinery &  Tool Co.
     Richmond Plating Co.
     Kitchen-Quip, Inc.
     Smith Jones, Inc.
     Tennis Plating Co., Inc.
     Production Plating, Inc.
     American Plating & Mfg. Co.
     Louisville Metal Treating Service
     A-l Plating Co.
     Davis & Hemphill Inc.
     D. L. Bromwell, Inc.
     Abercrombie and Co.
     Amesbury Metal Products Corp.
     Ames Plating Corp.
     Haverhill Plating Co.
     Globe Nickel Plating  Co., Inc.
     Esses Chrome Plating  Co.
     Norretco
     Advance Plating Corp.
     New England Plating Co., Inc.
     Barker Metal Corp.
     Bronson Plating Co.
     Certified Plating, Inc.
     General Plating Co.
     Masselink Electroplating Co.
     M & L Plating Co.
     Sarvis Mfg. Co.
Chicago, IL
Chicago, IL
Chicago, IL
Chicago, IL
Chicago, IL
Chicago, IL
Chicago, IL
Freeport, IL
Peru, IL
Elkhart, IN
Elwood, IN
Ft. Wayne, IN
Goshen, IN
Indianapolis, IN
Mishawaka, IN

Mooresville, IN
Muncie, IN
Richmond, IN
Waterloo, IN
Kellogg, IA
Sioux City, IA
Lexington, KY
Louisville, KY
Louisville, KY
Baltimore, MD
Elkridge, MD
Hyattsville, MD
Silver Spring, MD
Amesbury, MA
Chicopee, MA
Haverhill, MA
Maiden, MA
Methuen, MA
Ware, MA
Worcester, MA
Worcester, MA
Worcester, MA
Branson, MI
Detroit, MI
Detroit, MI
Grand Rapids, MI
Jackson, MI
Lansing, MI
                                    30

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    TABLE 6.  (CONTINUED) PARTIAL LIST OF FIRMS INVOLVED IN NICKEL PLATING

              OPERATIONS27
Electrolytic Nickel Platers
     Ductile Chrome Process Co.
     Electro Finishing Indus., Inc.
     Petroskey Mfg. Co. Inc.
     Plymouth Plating Works
     Michigan Plating of Detroit Inc.
     G&W Manufacturing Co.
     Silverstone Plating Co.
     Miller and Son
     De Troy Plating Works
     Talbot Commercial Plating
     Doerr Plating Co.
     Siegel-Robert Plating  Co.
     Cleveland Precious Metals
     Carlton-Cooke Plating  Corp.
     Cart-Wright Industries
     Astro Electroplating,  Inc.
     E.G. Electroplating, Inc.
     Mitronics Products
     PWF Corp.
     Alcaro & Alcaro Plating Co.
     Theromo National Industries
     New Brunswick Nickel & Chromium Works
     Orbel Corp.
     General Plating Corporation
     B&S Engraving Co.
     Marino Polishing & Plating
     Plated Plastic Industries
     Cohan-Epner Co., Inc.
     Control Electro-Sonversion Crop.
     Regent Metal Products  Inc.
     Technical Metal Finishing Corp.
     Val-Kro, Inc.
     Tonawanda Platers, Inc.
     H.M. Quackenbush, Inc.
     Sumereau, Eugene Co.,  & Sons
     Star Chromium Corp.
     Kings Automatic Plating Co.
     M.  L. Sheldon & Co., Inc.
     Spectranome Plating Co.,  Inc.
     Die Mesh Corp.
     Gibbs Machine Co.
     Akron Plating Co.
     Beringer Plating Inc.
     Ashtabula Bow Socket Co.
Livonia, MI
Oak Park, MI
P.etroskey, MI
Plymouth, MI
Southfield, MI
Southfield, MI
Ypsilanti, MI
Belleville, MD
Independence, MD
Neosho, MO
St. Louis, MO
St. Louis, MO
Merrimack, NH
Carlstadt, NJ
Engelwood, NJ
Farmingdale, NJ
Garfield, NJ
Gillette, NJ
Little Falls, NJ
Montclair, NJ
Newark NJ
New Brunswick, NJ
Phillipsburg, NJ
Trenton, NJ
Union, NJ
Brooklyn, NY
Brooklyn, NY
Brooklyn, NY
Brooklyn, NY
Brooklyn, NY
Brooklyn, NY
Buffalo, NY
Hamburg, NY
Herkimer, NY
Huntington Stn., NY
Long Island City, NY
Maspeth, NY
New York, NY
New York, NY
Pelham, NY
Greensboro, NC
Akron, OH
Akron, OH
Ashtabula, OH
                                    31

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    TABLE 6.  (CONTINUED) PARTIAL LIST OF FIRMS INVOLVED IN NICKEL PLATING

              OPERATIONS27
Electrolytic Nickel Platers
     Lake City Plating Co.
     U11 rakrome,  Inc.
     Auto Sun Products Co.
     Creutz Plating Corp.
     Advance Plating Co.
     Manufacturers Plating Co.
     Aetna Plating Co.
     Roster Plating Co.
     Precious Metal Plating Co.
     Bron-Shoe Co.
     Superior Plating Co.
     Industrial Platers,  Inc.
     Deyton Rust  Proof Co.
     Queen City Mfg. Co.
     Eastern Plating,  Inc.
     J. X. Kreizweld Plating Co.
     Shelby Standard,  Inc.
     Moore Chrome Products Co.
     Troy Sunshade Co.
     Clayton Plating Co.
     Garnet Chemical Corp.
     Multi-flex Spring &  Wire Corp.
     American Tinning & Galvinizing  Co.
     Klein Plating Works, Inc.
     Advance Specialty Co., Inc.
     Krometal Mfg. Corp.
     Philadelphia Rust-Proof Co.
     Pottstown Plating Works, Inc.
     Ametek, Inc.
     Gibbs Electronics, Inc.
     Sylvania - GTE
     High Quality Polishing & Plating
     Microfin Corp.
     Evans Plating Corp.
     Induplate, Inc.
     Felch-Wehr Co.
     Booth Electrosystems
     Carolina Plating & Stamping
     Arrow Plating Co.
     B&H Plating  Co.
     Texas Precision Plating, Inc.
     Chrome Platers of Houston
     Bronze-Art Casting & Plating Co.
     Schumacher Co., Inc.
Ashtabula, OH
Bedford, OH
Cincinnati, OH
Cincinnati, OH
Cleveland, OH
Cleveland, OH
Cleveland, OH
Cleveland, OH
Cleveland, OH
Columbus, OH
Columbus, OH
Columbus, OH
Columbus, OH
Dayton, OH
Hamilton, OH
Martins Ferry, OH
Salem, OH
Shelby, OH
Toledo, OH
Oklahoma City, OK
Allentown, PA
Clifton Hgts, PA
Erie, PA
Erie, PA
Lansdowne, PA
Philadelphia, PA
Philadelphia, PA
Pottstown, PA
Sellersville, PA
Somerset, PA
Warren, PA
Zionsville, PA
E. Providence, RI
N. Providence, RI
N. Providence, RI
Providence, RI
Greenville, SC
Greenville, SC
Ft. Worth, TX
Ft. Worth, TX
Garland, TX
Houston, TX
Houston, TX
Houston, TX
                                    32

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    TABLE 6.  (CONTINUED) PARTIAL LIST OF FIRMS INVOLVED IN NICKEL PLATING

              OPERATIONS27
Electrolytic Nickel Platers
     Lubbock Plating Works
     Kaspar Electroplating Corp.
     Vermont Plating, Inc.
     Alexandria Metal Finishers Inc.
     Royal Silver Mfg. Co., Inc.
     Allimac Stamping Co., Inc.
     Heath Tecna Corp., Plating Div.
     Asko Processing, Inc.
     ABC Metal Finishing Co.
     Alpine Plating Co.
     Huntington Plating Inc.
     Oconomowac Electroplating Co.
     Acme Galvanizing, Inc.
     Plating Engineering Co.
     Standard Plating Co., Inc.
     Vulcan Lead Products Co.
     Wacho Mfg. Co.,  Inc.
Electroless
     Plateronics Processing,  Inc.
     Mechmetals Corp.
     Chemplate Corporation
     Electro-Coatings, Inc.
     Chem-Nickel Co., Inc.
     Dixon Hard Chrome, Inc.
     Whyco Chromium Co., Inc.
     Mac Dermid, Inc.
     Har-Conn. Chrome Co.
     Chromium Industries, Inc.
     Graham Plating Works
     Grunwald Plating Co., Inc.
     Krell Laboratories, Inc.
     Precision Plating Co., Inc.
     Musick Plating Inc.
     Electro-Coatings, Inc.
     Electro Seal Corp.
     Ni-Mold, Inc.
     Electro-Coatings, Inc.
     Electro-Coatings, Inc.
     Cambridge Plating
     Hopewood Retinning Corp.
     Advanced Materials Systems, Inc.
     Fountain Plating Company  Inc.
     Plating for Electronics,  Inc.
     Electro-Coatings, Inc.
     G&W Manufacturing Co.
Lubbock, TX
Shiver, TX
Rutland, VT
Alexandria, VA
Norfolk, VA
Petersburgh, VA
Kent, WA
Seattle, WA
Seattle, WA
Tacoma, WA
Huntington, WV
Ashippun, WI
Milwaukee, WI
Milwaukee, WI
Milwaukee, WI
Milwaukee, WI
Milwaukee, WI

Chatsworth, CA
El Segundo, CA
Los Angeles, CA
Moraga, CA
South Gate, CA
Sun Valley, CA
Thomaston, CT
Waterbury, CT
W. Hartford, CT
Chicago, IL
Chicago, IL
Chicago, IL
Chicago, IL
Chicago, IL
E. St. Louis, IL
Maine, IL
Chesterton, IN
Indianapolis, IN
Indianapolis, IN
Cedar Rapids, IA
Belmont, MA
Maiden, MA
N. Attleboro, MA
W. Springfield, MA
Waltham, MA
Benton Harbon, MI
Southfield, MI
                                    33

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    TABLE 6.   (CONTINUED)  PARTIAL LIST OF FIRMS INVOLVED IN NICKEL PLATING

              OPERATIONS27
Electroless
     Tawas Plating Co.                        Tawas City,  MI
     Modern Hard Chrome Service Co.           Warren,  MI
     Cleveland Precious Metals               Merrimack, NH
     SGL Modern Hard Chrome Service
          Div. of SGL Industries Inc.         Caraden,  NJ
     Alcaro & Alcaro Plating Co.             Montclair, NJ
     Keystone Metal Finishers                Secaucus,  NJ
     Electro Coatings,  Inc.                  Woodbury Hgts, NJ
     Hardchrome Electro Processing Co.        Brooklyn,  NY
     Technical Metal Finishing Corp.          Brooklyn,  NY
     Keystone Corporation                    Buffalo, NY
   •  Queens Plating Co., Inc.                Long Island, NY
     Metallurgical Processing Corp.           Syosset, NY
     Electrolizing Corp. of Ohio             Cleveland, OH
     Lubrichrome, Inc.                        E.  Cleveland, OH
     Microfin, Corp.                         E.  Providence, RI
     Cahill Chemical Corp.                   Providence,  RI
     Booth Electrosystems                    Greenville,  SC
     Texas Precision Plating, Inc.           Garland, TX
     Bronze-Art Casting & Plating Co.         Houston, TX
     Electro-Coatings,  Inc.                  Houston, TX
     Alexandria Metal Finishees, Inc.         Alexandria,  VA
     Heath Tecna Corp.  Plating Div.           Kent, WA
     Electro Coatings,  Inc.                  Milwaukee, WI

NOTE:  This list is considered partial  because the reference cited does  not
       necessarily contain the name  of  each facility  plating nickel.
       Because of the number of sources involved, there is no single  authority
       that lists all facilities, therefore, it  is probable that more sources
       exist than are given in the table or that some of  those given  are no
       longer in operation.

       This listing is subject to change as market conditions change,
       facility ownership changes, plants are closed  down, etc.
       The reader should verify the  existence of particular facilities
       by consulting current listings  and/or the plants themselves.
       The level of nickel emissions from any given facility is
       a function of variables such  as  capacity, throughput, and control
       measures, and should be determined through direct  contacts with
       plant personnel.
                                    34

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              TABLE  7.  LIST OF FIRMS PRODUCING NICKEL CHEMICALS
                                                               28
 Chemical
                             Company
                                      Location
Nickel Acetate
 C.P.  Chems.,  Inc.
 Gulf  Oil Corp.
   Harshaw  Chem. Co.,  subsid.
    Indust. Chems. Dept.
 The Hall Chem. Co.
 Harstan Chem. Corp.
 Richardson-Vicks, Inc.
   J.T. Baker  Chem. Co";, subsid.
 The Shepherd  Chem. Co.
Nickel Acetylacetonate
MacKenzie Chem. Works,
  MacKenzie INTERVAR
The Shepherd Chem. Co.
Inc.
Nickel Ammonium Sulfate  McGean Chem. Co., Inc.
Nickel Bromide


Nickel Carbonate
Nickel Carbonyl
Nickel Chloride
The Hall Chem. Co.
Harstan Chem. Corp.

C.P. Chems., Inc.
Gulf Oil Corp.
  Harshaw Chem. Co., subsid.
    Indust. Chems. Dept.
The Hall Chem. Co.
McGean Chem. Co., Inc.
Richardson-Vicks, Inc.
  J.T. Baker Chem. Co., subsid.
The Shepherd Chem. Co.
Texasgulf Inc.
  M&T Chems. Inc., subsid.
United Catalysts Inc.

Pressure Chem. Co.

Allied Corp.
  Allied Chem. Co.
C.P. Chems., Inc.
Gulf Oil Corp.
  Harshaw Chem. Co., subsid.
    Indust. Chems. Dept.
The Hall Chem. Co.
Harstan Chem. Corp.
McGean Chem. Co., Inc.
                                                            Sewaren, NJ
                                                            Cleveland, OH
                                                            Wickliffe, OH
                                                            Brooklyn, NY

                                                            Phillipsburg, NJ
                                                            Cincinnati, OH
            Bush, LA
            Cincinnati, OH

            Cleveland, OH

            Wickliffe, OH
            Brooklyn,  NY

            Sewaren, NJ
            Cleveland,  OH
            Wickliffe,  OH
            Cleveland,  OH

            Phillipsburg, NJ
            Cincinnati,  OH

            Carrollton,  KY
            Louisville,  KY

            Pittsburgh,  PA
                                                            Claymont,  DE
                                                            Sewaren, NJ
                                                            Cleveland,  OH
                                                            Wickliffe,  OH
                                                            Brooklyn, NY
                                                            Cleveland,  OH
                                    35

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       TABLE 7.   (CONTINUED) LIST OF FIRMS PRODUCING NICKEL CHEMICALS28
Chemical
    Company
                                                               Location
Nickel Chloride
Nickel Dibutyldithio-
  carhamate
Nickel Di-isobutyldi-
  thiocarbamate

Nickel Dimethyldithio-
  carbamate

Nickel 2-ethylhexonate
Nickel Fluoborate
Nickel Fluoride
Nickel Formate
Nickel Halide
Richardson-Vicks,  Inc.
  J.T. Baker Chem. Co., subsid.
Texasgulf Inc.
  M&T Chems. Inc., subsid.

E.I. duPont de Nemours & Co., Inc,
  Polymer Prod. Dept.
R.T. Vanderbilt Co., Inc.
  Vanderbilt Chem. Corp., subsid.

R.T. Vanderbilt Co., Inc.
  Vanderbilt Chem. Corp., subsid.

R.T. Vanderbilt Co., Inc.
  Vanderbilt Chem. Corp., subsid.

Mooney Chems., Inc.
The Shepherd Chem. Co.

Allied Corp.
  Allied Chem. Co.
C.P. Chems., Inc.
Gulf Oil Corp.
  Harshaw Chem. Co., subsid.
    Indust. Chems. Dept.
Harstan Chem. Corp.
Pennwalt Corp.
  Chems. Group
    Ozark-Mahoning Co., subsid.
Thiokol Corp.
  Ventron Div.
    Alfa Products

Pennwalt Corp.
  Chems. Group
    Ozark-Mahoning Co., subsid.

The Hall Chem. Co.
The Shepherd Chem. Co.

Thiokol Corp.
  Ventron Div.
    Alfa Products
                                                            Phillipsburg, NJ

                                                            CarrolIton, KY
Deepwater, NJ
Murray, KY
Bethel, CT
Hurray, KY
Murray, KY

Franklin, PA
Cincinnati, OH
                                                            Claymont, DE
                                                            Sewaren, NJ
                                                            Cleveland, OH
                                                            Brooklyn, NY
                                                            Tulsa, OK
                                                            Danvers, MA
Tulsa, OK

Wickliffe, OH
Cincinnati, OH
                                                            Danvers, MA
                                     36

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       TABLE 7.   (CONTINUED) LIST OF FIRMS PRODUCING NICKEL CHEMICALS
                                                                     28
Chemical
    Company
                                                               Location
Nickel Hexamine
  Fluoborate
Nickel Hydrate

Nickel Hydroxide



Nickel Naphthenate

Nickel Nitrate
NickeloceneL (Dicyclo-
  pentadienylnickel)

Nickel Oxide, Black

Nickel Oxide, Green



Nickel Stearate
Nickel Sulfamate
Thiokol Corp.
  Ventron Div.
    Alfa Products
McGean Chem. Co., Inc.

C.P. Chems., Inc.

C.P. Chems., Inc.
The Hall Chem. Co.
The Shepherd Chem. Co.

Troy Chem. Corp.

C.P. Chems. Inc.
Gulf Oil Corp.
  Harshaw Chem. Co., subsid.
    Indust. Chems. Dept.
The Hall Chem. Co.

McGean Chem. Co., Inc.
Richardson-Vicks, Inc.
  J.T. Baker Chem. Co., subsid.
The Shepherd Chem. Co.
United Catalysts Inc.

Pressure Chem. Co.
McGean Chem. Co., Inc.

Richardson-Vicks, Inc.
  J.T. Baker Chem. Co., subsid.
United Catalysts Inc.

The Norac Co., Inc.
  Ma the Div.
Witco Chem. Corp.
  Organics Div.

Gulf Oil Corp.
  Harshaw Chem. Co., subsid.
    Indust. Chems. Dept.
Harstan Chem. Corp.
Danvers, MA
Cleveland, OH

Sewaren, NJ

Sumter, SC
Wickliffe, OH
Cincinnati, OH

Newark, NJ

Sumter, SC
Cleveland, OH
Arab, AL
Wickliffe, OH
Cleveland, OH

Phillipsburg, NJ
Cincinnati, OH
Louisville, KY

Pittsburgh, PA
Cleveland, OH
Phillipsburg, NJ
Louisville, KY
                                                            Lodi,  NJ

                                                            Chicago, IL
                                                            Cleveland,  OH
                                                            Brooklyn, NY
                                    37

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       TABLE 7.  (CONTINUED) LIST OF FIRMS PRODUCING NICKEL CHEMICALS
                                                                     28
Chemical
    Company
   Location
Nickel Sulfamate
Nickel Sulfate
McGean Chem. Co., Inc.
Texasgulf Inc.
  M&T Chems. Inc., subsid.
ASARCO Inc.
  Federated Metals Corp., subsid.
C.P. Chems., Inc.
Gulf Oil Corp.
Harshaw Chem. Co., subsid.
  Indust. Chems. Dept.
Harstan Chem. Corp.
McGean Chem. Co., Inc.
Richardson-Vicks, Inc.
  J.T. Baker Chem. Co., subsid.
The Standard Oil Co. (Ohio)
  Kennecott Corp., subsid.
   Kennecott Minerals Co., subsid.
    Utah Copper Div.
    Kennecott Refining Corp.,
     subsid.
Texasgulf Inc.
  M&T Chems. Inc., subsid.
Cleveland, OH

Carrollton, KY
Pico Rivera, CA
                                                            Whiting, ID
                                                            Sewaren, NJ
                                                            Cleveland, OH
                                                            Brooklyn, NY
                                                            Cleveland, OH

                                                            Phillipsburg, NJ
                                                            Salt Lake City, UT

                                                            Baltimore, MD

                                                            Pico Rivera, CA
NOTE:  This, listing is subject to change as market conditions change,
       facility ownership changes, plants are closed down, etc.
       The reader should verify the existence of particular facilities
       by consulting current listings and/or the plants themselves.
       The level of nickel emissions from any given facility is
       a function of variables such as capacity, throughput, and control
       measures, and should be determined through direct contacts with
       plant personnel.
                                    38

-------
their high strength-to-weight ratios.  Thirteen percent of nickel is used in
electrical equipment, primarily in the form of resistance alloys.  High
permeability nickel alloys and nickel-bearing glass-to-metals seals and
transistors account for the remainder of the nickel used in electrical
equipment.

     Motor vehicle construction consumes 6-11 percent of the nickel used
                     12 16
in the United States.  '    The majority of the nickel used goes into
electroplating the vehicle trim.  In trucks, vans, and buses, nickel-bearing
stainless steel is used to construct body parts, frames, and rocker panels.
Because of their resistance to corrosion, nickel alloys, cupronickels, and
nickel bronzes are used to build and repair ship hulls, frames, and other
parts exposed to saltwater.  Approximately 4 percent of total nickel
consumption is used in ship building actvities.

     The chemical properties of nickel allow it to be used in a variety of
other applications including catalysts, batteries, dyes and pigments, and
ceramics.  Nickel in a finely divided form, known as Raney nickel,  can
dissolve 17 times its volume of hydrogen.  This capability leads to the
extensive use of nickel in the hydrogenation of fats and oils.   Nickel is
used in batteries and fuel cells with iron, cadmium, and zinc,  and  it is
also applied in ceramics to form a bond between enamel and iron. The
combined miscellaneous uses of nickel constitute approximately  8 percent of
                  12
total consumption.
     Figure 4 presents a summary of the end use markets for nickel on a
total weight and percentage basis.
                                    39

-------
    Nickel Consumption -
    162,700 Mg (180,723 too*)
                                              Household Appliances -
                                              11,400 Mg (12,651 tons),
                                              7Z
                                              ?*trol«un Uses - 14,600 Mg
                                              (16,265  tons), 9Z
                                              Chemical  Uses - 22,800 Mg
                                              (25,300 tons), 14Z
                                              Ship Building & Repairs -
                                              6,500 Mg (7,229 tons), 4Z
                                              Aircraft  -  13,000 Mg
                                              (14,458 tons), 82
Fabricated Metal Products
14,600 Mg (16,265 tons),
9Z
                                              Motor Vehicles - 17,900 Mg
                                              (19,880 tons), 11Z
                                              Machinery - 13,000 Mg
                                              (14,458 tons), 8Z
                                              Electrical Equipment -
                                              21,100 Mg (23,494 tons),
                                              13Z
                                              Building Construction -
                                              14,600 Mg (16,265 tons),
                                              9Z
                                              Other Uses - 13,000 Mg
                                              (14,458 tons),  8Z
Figure  4.    End  use  applications of  nickel  in  1978.
                                                                         15
                                     40

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REFERENCES FOR SECTION 3

1.   Nriagu, J. 0. ed.  Nickel in the Environment.   John Wiley  and  Sons,
     Inc., New York.  1980.  p. 6.

2.   Sullivan, R. J.  (Litton Systems, Inc.)   Air Pollution Aspects of
     Nickel and Its Compounds.  NTIS No.  PB188070.   September 1969.  p.  18.

3.   Reference 1, p. 52.

4.   Kirk-Othmer Encyclopedia of Chemical Technology.   Third Edition.
     Volume 15.  John Wiley and Sons, Inc.  New York.   1980.  pp. 787-797.

5.   Reference 1, p. 55.

6.   Weast, R. C. ed. CRC Handbook of Chemistry and  Physics.  56th  edition.
     CRC Press, Cleveland, Ohio.  1975.   pp.  B-117,  118,  and D-185.

7.   Reference 4, p. 806.

8.   Reference 2, pp. 57, 66-69.

9.   Brief, R. S., et al.  Metal Carbonyls  in the Petroleum Industry.
     Archives of Environmental Health 23:   373-384,  1971.

10.  Stedman, D. H. and D. A. Hikade. Nickel Toxicology.   S. S. Brown and
     F.  W. Sunderman, Jr., editors.   Academic Publishing.   London.   1980.
     pp. 183-186.  (Proceedings of the International Conference on  Nickel
     Toxicology.  Swansea, Wales.   September  3-5, 1980.)
                                                                    #
11.  Production and Use of Nickel.  Versar, Inc.  EPA Contract No.
     68-01-3852, Task 16.  (Prepared for  U. S.  Environmental Protection
     Agency, Office of Water Planning and Standards, Washington, D.  C.)
     March 20 1980.  p.  28.

12.  Nickel.  Preprint from Bulletin 671.   Bureau of Mines,  U. S. Department
     of  the Interior.  1980.  pp.  1-13.

13.  Reference 11, pp. 1-9.

14.  Telecon.  Brooks, G. W., Radian Cororation with Doyle,  M. J.,  Hanna
     Mining Co.  October 14, 1983.  Status  of operations  at  the Hanna
     smelter.

15.  Matthews, N. A.  Mineral Industry Surveys, Nickel  in April 1979.
     U.  S. Department of Interior, Bureau of  Mines.  Washington, D.  C.
     1979.
                                    41

-------
16.  Letter and attachments from Warner, J. S., INCO to Lahre, T., U. S.
     Environmental Protection Agency.  September 27, 1983.  Comments on
     draft nickel report.

17.  Reference 4, p. 798.

18.  Reference 1, pp. 58-60.

19.  Burton, D. J., £t_ al_.  (Radian Corporation)  Process and Occupational
     Safety/Health Catalogue - Secondary Nonferrous Smelting Industry.
     NIOSH Contract No. 200-77-008.  July 1979.  p. 211.

20.  Nack, H., et_ al_.  (Battelle-Columbus Labs) Development of an Approach
     to Identification of Emerging Technology and Demonstration
     Opportunities.  EPA No. 650/2-74-048.  May 1974.  pp. C-131 to C-137.

21.  Coleman, R. T., et_ al.  Process and Occupational Safety and Health
     Review of the Secondary Nonferrous Metals Industry.  Radian
     Corporation.  Austin, Texas.  1976.

22.  Reference 19, pp. 269-294.

23.  Reference 20, pp. C-27 to C-136.

24.  Letter and attachments from Kucera, C. J., AMAX to Lahre, T., U. S.
     Environmental Protection Agency.  September 2, 1983.   Comments on draft
     nickel report.

25.  Reference 11, p. 13.

26.  Reference 11, p. 21.

27.  The Thomas Register of American Manufacturers and Thomas Register
     Catalog File.  70th Edition.  Thomas Publishing Company.  New York,
     New York.   1980.  pp. 8998-9030.

28.  SRI International  1982 Directory of Chemical Producers -
     United States.  Menlo Park,  California.   1982.  pp. 765-766.
                                    42

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                                  SECTION 4

                          NICKEL "EMISSION SOURCES

     Atmospheric nickel emissions occur both from natural and anthropogenic
sources.   Natural nickel sources include windblown soil and dust,
                                                                 1 2
volcanoes, vegetation, forest fires, sea salt, and meteoric dust. '
Estimates of global nickel emissions from natural sources are given in
Table 8.  These estimates are based on very limited data and should be
viewed as order-of-magnitude estimates at best.

     Anthropogenic nickel emissions occur from two broad categories of
sources:  direct and indirect sources.  The direct category primarily
includes sources that either produce nickel or consume nickel or a nickel
compound to manufacture a usable product.  The major sources within the
direct category are:

     -  nickel ore mining and smelting,
     -  nickel matte refining,
        secondary nickel recovery,
     -  co-product nickel recovery,
     -  ferrous and nonferrous metals production (nickel alloys
          and steels, cast irons, stainless steel),
     -  electroplating,
     -  battery manufacturing, and
     -  nickel chemical manufacturing.

     Indirect sources are generally those that do not produce nickel or
nickel-containing products and only inadvertently handle nickel because it
is present as an impurity in a feedstock or fuel.  The major indirect nickel
sources are as follows:

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           TABLE 8.  GLOBAL EMISSIONS OF NICKEL TO THE ATMOSPHERE

                     FROM NATURAL SOURCES1'2
Natural Source
Windblown Soil & Dust3
Forest Fires
Volcanoes0
Vegetation

Annual Emissions,
20
0.6
3.8
1.6

f 103 Mg
(22)
(0.66)
(4.2)
(1.8)

(103 tons)





Meteoric Dust

     TOTAL
 0.04   (0.044)

 0.18   (0.20)

26.2   (28.8)
                                                            .       .   ii
 Average concentration of nickel in soils was used to determine emissions.

 Emissions were calculated assuming average ash content of trees and
 foliage to be 4% and the average nickel content of the ash is
 200 yg/g.
£
 Emissions-were calculated assuming average nickel crustal abundance of
 75 yg/g and a 5-fold enrichment of nickel in volcanogenic particles.

 Emissions were calculated assuming average ash content of vegetative
 exudates to be 11% and the average nickel content of the ash is 25 yg/g.

 Emissions were calculated assuming nickel concentration in ocean water
 of 210 ng/liter and a nickel enrichment in atmospheric sea salt particles
 of 200-fold.

 Emission numbers are in terms of total nickel.
                                    44

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        coal and oil combustion,
        coke ovens
        municipal refuse and sewage sludge incineration,
        petroleum processing,
        coal conversion processes,
        cement manufacturing,
        coal and oil supplying, and
        asbestos mining.
Indirect sources, primarily coal and oil combustion, are estimated to
release
the air.
release from 85 to 94 percent of the total anthropogenic nickel emissions to
        3-5
     The following sections briefly describe the operations of both direct
and indirect nickel emission sources and the nickel emission points therein.
Where available, nickel emission factors are presented for each source.  For
some sources (e.g., coal liquefaction), atmospheric emissions of nickel have
been identified but the quantities have not been determined.

DIRECT SOURCES OF NICKEL

Nickel Production

     In the United States nickel is generated by three means:  nickel ore
smelting, the refining of imported nickel matte, and the recovery of nickel
from scrap metal.  As discussed in Section 3, the majority (60 percent) of
domestically produced nickel comes from secondary recovery operations.
Matte refining produces approximately 25 percent of the domestic total, with
primary nickel ore smelting producing the remaining 15 percent.  The
processes used in these nickel producing operations, and their resultant
nickel emissions, are discussed in detail in the following sections.
                                    45

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Nickel Ore Mining and Smelting

Process Description

     The only active nickel mine in the U. S. is located near Riddle, Oregon
and is currently operated by the Hanna Mining Company.  The raw ore obtained
from the mine is known as garnierite, and is approximately 0.96 percent
nickel.  The nickel content of the ore is expected to decline in future
production years.  The Hanna Nickel Smelting Company, also located in
Riddle, Oregon processes the garnierite to produce a ferronickel containing
50 percent nickel and 50 percent iron.  The step-by-step flow of nickel ore
from the mine to the final ferronickel product is depicted in Figure 5.
The initial step (pt. 1, Figure 5) in the ferronickel process is to screen
the raw ore into two fractions.  Material less than 14 cm (5.5 in) in
diameter is sent directly to a surge pile (pt. 2) and from there on to an
ore storage pile (pt. 4).  Material greater than 14 cm (5.5 in) is fed to a
crusher (pt. 3) and is then screened for a second time.  The undersized
material from the second screening is carried to the surge pile and from
there to the ore storage pile.  A belt conveyor delivers the ore from the
surge pile to tram cars which empty their contents into an ore storage
hopper.  Another belt conveyor is used to deliver ore material from the
hopper to the ore storage pile.  Oversized reject from the second screening
(which contains relatively small amounts of nickel) is stockpiled.

     The ore material from the storage pile is transferred by front-end
loaders into rotary dryers (pt. 5).  After drying, the ore is crushed and
screened to separate three size fractions (pt. 6).  The fines fraction is
delivered by belt conveyor to a fines storage bin (pt. 7).  Intermediate-
sized ore is also delivered by a belt conveyor to six ore storage bins (pt.
8), and oversized ore material is rejected and sent to a stockpile.  Fines
from the fines storage bin are fed to two vertical roasters (pt. 9) that are
fired by natural gas or diesel fuel.  The average composition of the feed to
the roasters is given below:
                                    46

-------
WOBBLER FEEDER
SCALPING SCREEN
JAW CRUSHER
Numbered points correspond to prcceaa
operation! «nd potential nickel mission
atreaas aa discussed In the text.
                                                                                                                    TRAMWAY
                                                                                                                    STACKER
                                                                              TRIPLE DECK SCREEN
                                                                              CONE CRUSHER
                                                                              BUCKET ELEVATOR

                                                                              FESI BIN
                                        ._HMr7-4MELTINO FURNACES

                                         '
                                                                                 I        frVF"*  FESII
      Figure  5.    Flow  diagram  of  the  Hanna  Nickel  Smelting Co.  operations.

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          Component                     Percent composition by weight

            A1203                                   1.9
            Si02                                   45.6
            Fe                                     10.1
            Ni                                      1.2
            MgO                                    27
          free water                                3.2
          chemically-bound water                    7.3

The figures for iron and nickel represent the percent composition for the
total level of these metals in the roaster feed.  Iron and nickel actually
exist as oxides in the ore feed.  Intermediate-sized ore is sent from its
storage bins into two rotary calciners (pt. 10), which are fired by natural
gas.  Both the roasters and calciners heat up the ore material to about
648°C (1200°F) to drive off chemically-bound water.  The roasters and the
calciners discharge hot ores into skiphoists (pt. 11) which feed into hot
ore bins.

     Nickel recovery is initiated by gravity feeding the roasted and
calcined ores into electric arc melting furnaces (pt. 12).  The electric arc
melt furnaces operate at approximately 1650°C (3000°F).  As molten ore is
tapped from the furnace into ladles, iron and nickel metal are extracted by
adding a ferrosilicon reductant to the ladle and mixing vigorously.  Mixing
is accomplished by pouring molten materials back and forth from one ladle to
another.  As the iron and nickel compounds undergo reduction (pt. 13),
metallic nickel and iron settle to the bottom of the ladle.  Slag is poured
off the ladle and granulated by high pressure water jets.  Part of the metal
that accumulates in the mixing ladle is poured into another ladle and is
transferred to a refining furnace.  The metal remaining in the mixing ladle
is known as "seed metal," serving as a metal collector for subsequent
reactions of molten ore with ferrosilicon.
                                    48

-------
      As  molten metal  is poured  into  the refining furnace  (pt.  14),  refining
 materials  (including  dolomite,  lime, and fluorspar) are added  to the furnace
 by  hand.   Chemical  reactions between the refining materials and the metals
 remove impurities from the molten ferronickel.  Refined ferronickel is cast
 into  12.7  kg  (28 Ib)  pigs on a  pig casting machine (pt. 15), or is  made into
 shot  by  pouring the molten material  through water jets (pt. 16).6

 Emission Factors

      Emissions  of nickel during mining operations are expected to be
 minimal.   Since the water content of the ore is relatively high, about
 20  percent, any dust  generated would settle quickly and in the vicinity of
           7—9
 the source.     However, as the ore dries in reject or stock piles,
 increases  in  fugitive dusts could be observed.  The nickel content of such
 dust would probably average that of the ore, about 0.96 percent.10  The
 nickel emitted  would be in the form of silicates as in the ore.

      In  ore smelting  the most significant sources of nickel-containing
 particulate emissions are:

     -   ore crushers,
     -   rotary  dryers,
     -   storage and surge bins,
     -  rotary  calciners,
     -  roasters,
     -  skiphoists,
     -  ore melting furnaces,
     -  the Fe-Si furnace, and
     -  refining furnaces.

All of these sources are currently controlled by a variety of  devices.
Fabric filters are used to control emissions from crushers, storage and
surge bins, skiphoists,  roasters,  ore melt  furnaces,  refining  furnaces, and
the Fe-Si furnace.   Rotary dryer emissions  are controlled  by first  passing
                                    49

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the stream through a two-stage cyclone and then onto a wet scrubber.
Calciner emissions are being reduced through the use of an electrostatic
precipitator (ESP).    The efficiencies of these control devices have not
been determined by testing; however, the same devices in operation on
similar industrial sources have demonstrated efficiencies ranging from 95 to
99 percent.
     The quantity of data available to estimate nickel emissions from the
Hanna mining and smelting operations is very limited.  The most reliable
information available appears to be emissions data that have been submitted
to the State of Oregon by the Hanna company.  These data, which are the
results of actual source tests and engineering estimates, are presented in
Table 9.10-12

     Very few data identifying the species or form of nickel emitted during
each of the Hanna operations were found in the literature.  Based on the
types of materials present and the nature of the operations, it seems
reasonable to estimate that emissions from crushers will contain nickel as
the silicate, as in the ore.  Nickel in dusts from dryers and calciners
would be present in the silicate mineral lattice because no chemical changes
are occurring during these operations.  Depending on the temperatures
reached during drying and calcining, some nickel on the surface of ore
fragments may become oxidized such that some small fraction of nickel may be
emitted as an iron-nickel oxide.  Nickel oxide or nickel in combination with
iron oxide as a ferrite or spinel are probably the dominant species emitted
during roasting and melting.    Both iron and nickel are transition metals
of Group VIII sharing similar properties such as atomic and ionic radii.
Both metals also use the same outer electron orbitals when forming complexes
such as silicates and oxides and prefer octahedral geometric configura-
      14
tions.    Therefore, iron and nickel may be found together in complex
oxides.  Since roaster feed material may contain about 10 percent iron by
weight and temperatures can reach 648°C (1,200°F), it is reasonable to
postulate that nickel and iron would be present as an oxide in particulate
                                     50

-------
          TABLE  9.   NICKEL  EMISSION FACTORS FOR THE PRIMARY SMELTING

                    OF NICKEL ORE10"12
 Source
Calciners0


Skip Hoists'
Control Device Used
 ESP
Emission Factor,
kg/Mg  (Ib/ton) of
Nickel Produced3
Rotary Dryers0




No.
No.
No.
No.
Crusher


Day



No.
No.
Binc
No.
No.
No.
1
2
3
4
House
1
2

1
2
3
Cyclone/Scrubber
Cyclone/Scrubber
Cyclone/Scrubber
Cyclone/Scrubber

Fabric Filter
Fabric Filter

Fabric Filter
Fabric Filter
Fabric Filter
0
0
0
0

0
0

0
0
0
.28
.26
.26
.021

.006
.046

.0009
.0009
.00033
(0
(0
(0
(0

(0
(0

(0
(0
(0
.56)
.51)
.52)
.042)

.012)
.092)

.0019)
.0019)
.00065)
0.23    (0.46)
No. 1
No. 2
Ore Melter/Roasterd
Combination
No. 1 •
No. 2
Refining Furnace '
OVERALL FOR THE PLANT
Fabric Filters
Fabric Filters
Fabric Filter
Fabric Filter
Fabric Filter

0.034
0.014
0.027
0.046
0.0065
1.2
(0.067)
(0.027)
(0.054)
(0.092)
(0.013)
(2.4)
 Emissions expressed as total nickel.
b
 No source test data available, emissions have been estimated.
c
 Nickel emissions from these sources are expected to primarily  be in the
 form of a nickel silicate as in the raw nickel ore.

 Nickel emissions from these sources are expected to be in the  forms of
 iron-nickel oxides and ferronickel.
                                    51

-------
matter.  An analysis of the thermodynamics of reactions of nickel-iron
oxides and silicates and oxygen shows that at temperatures of 727°-927°C
(1,340°-1,700°F), the oxide or silicate is the predominant form.

     In speciation studies of particulate matter trapped by control devices
during the melting of nickel alloys containing nickel, iron, and chromium
(Inconel Alloy 800,840), energy dispersive X-ray analysis (EDXA) of
particles revealed patterns which matched those of complex iron-nickel
oxides, and to a lesser extent nickel oxide.    The ferronickel melt
contains both iron and nickel, although not in the same proportions as the
alloy.  For lack of other data, it seems reasonable to assume that the
ferronickel melt would also emit particles containing iron-nickel oxides and
nickel oxide.

Nickel Matte Refining

Process Description

     The AMAX Nickel Refining Company in Braithwaite, Louisiana is the only
facility in the United States that is refining imported matte to produce
nickel.  In addition to nickel, the AMAX refining process also produces
copper, cobalt, and ammonium sulfate.  AMAX produces nickel by means-of
hydrometallurgical refining.  A simplified flow diagram of the AMAX
                                                                      1 £_1 Q
operation is presented in Figure 6 and the process is discussed below.

     To initiate the refining process, the semi-refined nickel-cobalt-copper
matte (containing about 40 percent nickel) is crushed to a material less
than 1.3 cm (0.5 in) in diameter (pt. 1, Figure 6) and sent to storage bins
(pt. 2).  A relatively small portion of the crushed matte (about 1300 kg/hr)
is drawn off to a sampling area (pt. 3) to analyze and monitor the metal
content of the matte.    The remainder of the matte is fed to a wet ball
mill (pt. 4) where it is ground to minus 200 mesh and then is sent to a
thickener and dewatered to 70 percent solids, by weight.  The slurry
material is then introduced to the atmospheric leaching circuit (pt. 5) of
                                    52

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                                             Imported Matte
                                    Nickel Emissions


                                         J	
                                     Q
        Matte
        Crusher
                                    Nickel Emissions
                                                Matte
                                                Storage
       1st Stage Pressure
           Oxidation
       2nd Stage Pressure
           Oxidation
                                             Blending and
                                                Grinding
                                              Atmospheric
                                               Leaching
                                                      Liquid
                                             Cobalt Removal
                                                      Solids
                                           Cobalt Purification
                                             (Pentaonine)
                                                      Liquid
                                             Nickel Removal
                                             Ion Exchange
Liquid
Matte
Sampler
                                                                                 Nickel Emissions
                                Number points correspond to process
                                operations and potential nickel emission
                                streams as discussed in the text.
                                                                              Nickel Emissions
                                                 Cobalt
                                               Reduction
                                                      Solids
                                            Cobalt Briquetting
                                             and Sintering
                                                 COBALT
                                                 METAL
                            INTERMEDIATE
                              SOLIDS
                                         Nickel Briquetting
                                           and Sintering
                                                 Scrip  _ To 1st
                                                         Stage
                                                         Digestion
                                                                           AMMONIUM SULPHATE
                                                                                PRODUCT
Figure   6.    Flow  diagram  of  the  AMAX  hydro-metallurgical  nickel
                  refining  process.   ',18
                                                 53

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the hydrometallurgical process, which consists of a series of agitated,
steam-heated, air-sparged tanks.  The atmospheric leaching step requires a
controlled reaction between the matte slurry and the nickel/copper
sulfate-sulfuric acid solution that is recycled from the first stage
pressure leach.  In the leaching step approximately 50 percent of the nickel
and cobalt are dissolved from the matte by the oxidizing conditions achieved
from sparging large volumes of air under pressure through the slurry.  The
reaction product from the leaching process is sent to a thickener to achieve
a solids-liquids separation.  Overflow from this operation contains only
nickel and cobalt sulfates in solution and is sent to the cobalt removal
stage (pt. 7) of the hydrometallurgical process.  Underflow from the
thickener is fed into the two-stage pressure leaching section (pt. 8) of the
        17,18
process.

     In the pressure leaching circuit, autoclaves operating at 204°C (400°F)
and 4130 kPa (600 psi) leach the remaining copper, nickel, and cobalt into
solution.  The product from the autoclaves is sent to a second-stage
pressure leaching section (pt. 9) for metal recovery.  The electrolyte feed,
which contains all the matte copper and a portion of the nickel and cobalt,
is directed to a series of electrowinning tanks (pt. 10) to produce a
finished copper cathode.  Spent electrolyte from this operation, which
contains nickel, cobalt, unplated copper, and sulfuric acid, is recycled
                                              17 18
(pt. 6)  back to the pressure leaching circuit.  '

     At  the cobalt removal phase of the process (pt. 7), the nickel-cobalt
solution from atmospheric leaching undergoes an oxidation reaction using
ammonium persulfate to precipitate cobalt hydroxide.  The cobalt hydroxide
slurry is pressure filtered to remove the hydroxides in cake form.  The
filtrate from this operation, a pure solution of nickel sulfate, is sent to
                                           17 18
the nickel recovery section of the process.  '

     The nickel recovery section at the AMAX process is a batch operation.
In this  step hydrogen gas is used to reduce and precipitate nickel metal
                                    54

-------
 from solution.   Anhydrous  ammonia  is used  to neutralize  the  sulfuric  acid
 formed  in this  process,  thereby yielding an ammonium  sulfate solution.   The
 precipitated  nickel  powder is  separated by decantation and is then washed,
 filtered,  and dried.  The  dried powder is  then packaged  as powder, or is
 pressed into  briquettes  and sintered prior to packaging  (pt. 12).  Residual
 nickel  in the liquor from  nickel reduction is sent to a  hydrogen sulfide
 scavenging step (pt.  13) and returned to first-stage digestion.17
 Multistage evaporators are then used to produce ammonium sulfate crystals
 from the purified ammonium sulfate solution.17'1**

      To initiate cobalt metal  recovery, the filter cake  precipitate from the
 cobalt  removal  phase  (pt.  7) is first treated with ammonia in an autoclave
 at 93°C (200°F).  This step dissolves the cobalt as an amine complex.  All
 traces  of  nickel are  removed from the cobalt amine solution by acidifying
 and  cooling the solution,  thereby yielding nickel double salts, and by
 subjecting the  resulting amine solution to an ion exchange circuit (pt.  15).
 The  purified  cobalt  solution is directed to a cobalt reduction step (pt. 16)
where hydrogenation  at elevated temperature and pressure is used to produce
 cobalt  metal.   The final cobalt metal product is packaged as a powder or is
 formed  into briquettes (pt. 17).

 Emission Factors

     In information submitted to the U.  S.  EPA and to the Louisiana Office
 of Environmental Affairs, AMAX Nickel lists ten primary sources of nickel
 emissions  from  its Braithwaite, Louisiana refinery.    These sources, and
 the  type of emission control device applied to each,  are delineated in
Table 10.  Particulate emissions from the majority of sources are collected
and  removed from the exhaust by a fabric filter.

     AMAX has also submitted estimates of total nickel emissions from each
of the sources given in Table 10.   These estimates are shown in Table 11.
Particulate emissions from operations occurring prior to the nickel
                                    55

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       TABLE 10.  PRIMARY NICKEL EMISSION SOURCES AND CONTROLS AT THE

                  AMAX NICKEL REFINERY16'18
Nickel Emission Sources
Source Identification   Control Device Applied
   From Figure 6        and Reported Efficiency
Matte Handling and Hopper
  Storage

Matte Sampling Process

Laboratory Matte Analysis

Matte Crushers

Storage Bins

Nickel Powder Dryer


Sintering Furnaces

Briquetting Process

Powder Packaging Process

Fugitive Emissions
    Points 1, 2


    Point 3

    Point 3

    Point 1

    Point 2

    Point 11


    Point 12

    Point 12

    Point 12

    Points 11, 12
Fabric Filter (99.5%)


Fabric Filter (97%)

Fabric Filter (99%)

Fabric Filter (97%)

Fabric Filter (97%)

Cyclone (97%) and
  Magnetic Filter

Uncontrolled

Fabric Filter (99%)

Fabric Filter (99.8%)

Fabric Filter (99%)
                                    56

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           TABLE 11.  ANNUAL NICKEL EMISSIONS FOR THE AMAX NICKEL
                                                        1 ft
                      REFINERY IN BRAITHWAITE, LOUISIANA
                                               Nickel Emissions3
Emission Source                                  Mg (tons)/yr
Matte Handling and Hopper Storage
Matte Sampling Process
Matte Crushers
Storage Bins
Nickel Powder DryerC
Sintering Furnaces
Briquetting Process0
Powder Packaging Process0
Fugitive Emissions0
Total Plant
~ 0.64
0.18
0.36
0.14
0.59
0.9
1.25
2.4
0.14
6.6
(0.71)
(0.20)
(0.40)
(0.15)
(0.65)
(1.0)
(1.39)
(2.7)
(0.16)
(7.4)
 All emissions estimates are expressed in terms of total nickel.

 Nickel emissions from these-sources are expected to be in the form of
 nickel subsulfide 
-------
reduction operation, such as matte handling, sampling, crushing, and
storage, contain nickel, copper, and cobalt compounds.  AMAX data indicate
that the mattes they process contain approximately 40 percent total
       18
nickel.    Nickel emissions from the matte handling and preparation part of
the AMAX facility are expected to be predominantly nickel subsulfide (Ni_S?)
because the nickel in the sulfide mattes processed is predominantly in this
     15 19 20
form.  '  '    Recent X-ray diffraction tests by AMAX have verified the
                                                                        20
existence of nickel subsulfide emissions from matte handling operations.
Matte handling, crushing, and grinding operations displace nickel
subsulfide-containing matte particles that are emitted to the ambient air.

     Following the hydrogen reduction nickel precipitation part of the AMAX
process, nickel emissions are predominantly in the form of metallic nickel.
Nickel emissions from the powder dryer, briquetting process, powder
packaging process, sintering furnace, and fugitive sources should be in the
                        15 19 20
form of metallic nickel.  '  '    Emissions from the sintering furnace are
also likely to contain nickel oxide since some of the input metallic nickel
powder is probably oxidized in the sinter furnace.

     Potentially a minor amount of nickel carbonyl [Ni(CO,)] could be
produced from the hydrogen reduction step of the nickel recovery process at
AMAX if carbon monoxide was present as a contaminant in the hydrogen used.
Nickel powder and nickel salts have been shown to react to form nickel
                                            21
carbonyl in the presence of carbon monoxide.    No information is available
on possible carbon monoxide in the process hydrogen or on nickel carbonyl
formation and release during nickel precipitation.  If nickel carbonyl was
formed, it is unlikely that it would eventually be found in ambient air
around the plant considering that the half-life of nickel carbonyl in air is
                       22
only about 100 seconds.
                                    58

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 Secondary Nickel Recovery

 Process Description

      As discussed in Section 3,  the  secondary  nickel  scrap  recovery industry
 is  a significant component  of domestic  nickel  production.   The  basic
 processes conducted at  a  secondary nickel  recovery plant  include  scrap
 pretreatment,  smelting, refining, and casting  of  the  nickel-based product.23
 All secondary  nickel plants do not,  however, necessarily use each of these
 processes.   For  example,  plants  receiving  relatively  clean  nickel scrap may
 not need to  carry out a degreasing pretreatment step.  The  generalized flow
 pattern of nickel materials through  a representative  secondary  nickel
 recovery facility is illustrated in  Figure 7.24

      Unless  nickel scrap  is exceptionally  clean and homogeneous when it
 enters  the recovery  facility,  it must first undergo some degree of  pretreat-
 ment.   Pretreatment  generally  involves  inspecting and sorting the  scrap and
 cleaning or  degreasing the  scrap.  Sorting is performed manually  to  separate
 nickel-bearing scrap from non-metallic  and non-nickel materials.  Pieces of
 nickel  scrap are  then segregated with respect to cleanliness and physical
 form.   Clean scrap may be charged directly to the smelting  furnace while
 dirty scrap undergoes degreasing.  Nickel scrap is generally degreased by
 using trichloroethylene solvent.  No atmospheric nickel emissions occur
                                 o /   o c
 during  nickel scrap  pretreatment.  '

      In  the smelting  step of the recovery process, nickel scrap is either
 (1) partially purified prior to further refining,  or (2)  melted with
 alloying agents to form specific alloys.  In either case, the scrap  is
 charged  to a furnace, lime  is usually added, and the charge is melted.  The
molten metal is poured into ingot molds or is sent directly into another
 reactor  for refining.  Both electric arc and rotary reverberatory furnaces
are used to accomplish scrap melting.  The effects on the scrap are the same
regardless of the  furnace  type used.   Both types of furnaces are sources of
                                    59

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       PRETREATMENT
'SMELTING
REFINING
                                                                                              CASTING
NICKEL
SCKAP
                                                      G"T
                                                        Alloying A«u[.Cil

                                                         - electricity
                                                      electric
                                                      Arc
                                                      Furnace
                                                                Nickel E>l»lofui
                                                         Alloying
        Figure  7.   Process flow diagram  for a  representative  secondary nickel
                     recovery  plant.  '

-------
 atmospheric nickel emissions,  generally in the form of  nickel oxide and
 other more complex forms of oxidized nickel.19'25   Fabric  filter control
 devices are predominantly used to control the dust  emissions  from the
                   25
 smelting furnaces.

      If higher purity material is required than can be  achieved  in the
 smelting furnace,  the molten product of smelting is sent to a refining
 reactor.   In the  refining reactor,  cold base  scrap  and  pig nickel are added
 to  the molten metal.   To this  mixture are added lime, silica,  and specified
 quantities of alloying metals.  The alloying  metals (e.g., manganese,
 titanium,  and columbium)  are added  to produce the required alloy
 composition.   The  total  charge  is then  melted and poured into  molds.  The
 processes  carried  out in the refining reactor generate  nickel  emissions
 similar to those produced in the  smelting step.  Fabric filter control
 devices are  routinely used to  reduce  the  release of  these emissions  into the
 air.25

     The final step  in the  secondary  nickel recovery process involves
 casting the molten product  alloys into  ingots.  After pouring  the molten
 metal  into molds,  solidification  is accomplished by air cooling.  The ingot
 alloys  are then removed  from the molds  and packaged for consumption by the
 metallurgical  industry.   Although no  atmospheric nickel emissions occur
 during  the casting process, minor amounts of metallic vapor are released
 into the work  environment, which are  likely to be oxidized very
 rapidly.19'25

 Emission Factors

     Emission  factors  specifically applicable to secondary nickel recovery
 plants  are very limited.   The factors that are available apply only to scrap
melting furnaces and are  presented in Table 12.  The accuracy of the factors
 given in Table 12 has not been determined by testing.
                                     61

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            TABLE 12.  NICKEL EMISSION FACTORS FOR THE SECONDARY
                       PROCESSING OF NICKEL-BEARING SCRAP26
Scrap Source
            Emission Factor
                                                         a,b
Stainless Steel
Nickel Alloy Steels
Iron & Steel Scrap6
Other Nickel Alloys
Copper Base Alloys
Electrical Alloys
Cast Iron
5 kg/Mg (10 Ib/ton) of nickel charged
               or
0.3 kg/Mg (0.6 Ib/ton) of steel produced'
5 kg/Mg (10 Ib/ton) of nickel charged
0.0008 kg/Mg (g.0015 Ib/ton) of iron and
steel produced
1 kg/Mg (2 Ib/ton) of nickel charged
1 kg/Mg (2 Ib/ton) of nickel charged
1 kg/Mg (2 Ib/ton) of nickel chargedd
10 kg/Mg (20 Ib/ton) of nickel charged8
 Nickel is primarily emitted as complex oxides of nickel and other metals.
 The emission factors apply to individual melting furnaces.
Q
 Emission factor based on questionnaire survey results.
 Controlled emission factors.  Although specific controls for these
 factors are not known, the industry generally uses fabric filters for
 emissions control.
 Emission factors based on material balances.
 Emission factors based on engineering judgement.
 Uncontrolled emission factors.
                                    62

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 Source Locations

      The locations of firms believed  to  be  engaged  in  the  secondary recovery
 of nickel metal are given in Table  4  of  Section  3.

 Other Secondary Metals Recovery  Plants

 Process Description

      Secondary  aluminum,  copper,  cadmium, cobalt, brass and bronze,  and  zinc
 recovery facilities have  the potential to emit nickel because they  process
 scrap containing varying  amounts  of nickel.  Nickel compounds, probably
 nickel-containing  oxides,  are emitted as a minor component of the total
 particulate  emission stream from  each of these source categories.
 Figures 8-13 present flow  diagrams that are representative of secondary
 metal recovery  processes performed in the United States.  The basic
 processes  involved in all  these source categories are so similar that to
 detail  each  separately would be repetitive.  Generally, there is a  scrap
 pretreatmerit step,  a smelting step, a refining step, and a product  casting
 step.

      Typically,  scrap  metal  is brought into the recovery facility,  sorted by
 type, and pretreated according to the physical and chemical nature of the
 scrap.   In zinc  recovery plants,  for example, pretreatment of scrap can
 involve  crushing and  screening, furnace sweating, or sodium carbonate
 leaching, depending  on the nature of the input scrap.   In comparison,
 secondary copper scrap pretreatment can involve crushing and grinding, kiln
 drying,  furnace  sweating, or sulfuric acid leaching.  As shown in
 Figures  8-13, similar pretreatment operations exist in all the secondary
                           27
metals  recovery  facilities.    Atmospheric nickel emissions potentially
 occur from the pretreatment processes used in the secondary aluminum,
 copper, brass and bronze, and zinc segments of the metals recovery industry.
Wet scrubbers, fabric filters, ESPs and cyclones have  been used to control
                                                              7 7
particulate emissions from the various pretreatment processes.
                                    63

-------
            SCRAP  PRETREATMENT
SMELTING/REFINING
                 MECHANICAL
Sheet.Castings
Clippings
electrical Con
ductors
Sheet. Castings,
Clippings
Borings. Turnings ,>i
Drosses, Skimmings
Fuel, Organic-
Cent aminaLed
Scrap
Fuel, High Iro
Scrap
Water, Drosses_
Skimmings. Slags
     	 Allaying  Agent
       	Nitrogen
           Chlorine
                                                                                 " " Y t
    (Chlorine)
    Reverb Furnace
        Aluminum Fluoride
        	Nitrogen
          	 Alloying Agent
         r  ,..,

         Ur""
              Fuel
              ,	 Flux
                                                                                (Fluoride)
                                                                                Reverb Furnace
        Alloying Agent
        	Nit rogen
             Chlorine
              Fuel
                Flux
              r
                                                                                     Alloying Agent
                                                                                      Electricity
                                                                                   r	
                                                                                     Fuel
                                                                                      Flux
                                                                                Rotary Furnace
           Figure  8.    Generalized  flow diagram  of  a  secondary  aluminum recovery  plant.
                                                                                                                     27

-------
Ul
                SCRAP PRETREATMENT

                       MECHANICAL
SMELTING/REFINING
Electrical Conduc=^
tors

Turnings. Borings,


Electrical Conduc-


Turnings. Borings,


Fuel , Lead. Solder^
nated Scrap



Fuel, Organic- 	 ^
Contaminated Scrap

Fuel, Borings, ^
Turnings

Air. Flux, Coke ,
Water .Slags , ^
Residues , Ski ma Ings


Water, Slags.
Skimmings
Stripping


Brlquett Ing


Shredding


Magnet 1 z Ing

PYRONETALLURGICAl
Sweat Ing

/i\
/Solder \
Ifiabhltt 1

Burning


Drying


Cupolaing



Gravity Separa-
tion

















	 , 	 ^




s~ ^\
	 1 Melt I 	 ^
\ /
\^_^/






:










/Treated^
















Al loy Ing Agent
1 . 	 Flux

1 i — Alr
r v t 1

*" *"

1 	 Alloying Agent
1 I Fl"X
1 1 T— F"el

* *
	 Alloylnj Agent
1 Flux
![>'•"
Crucible
" ^ Furnace • •• V

I Agent
1 I 	 Electric! y
[ i f-F1UX
Electric I
	 ^Crucible — -^«
Furnace 1
1
1 1

















f Alloy
Vlx













       Figure 9.   Generalized flow diagram of a secondary  brass and bronze  recovery
                   plant.27

-------
               PRETREATMENT
                                                   SMELTING /REFINING
                                                                                  CASTING
  SCRAP ALLOYS

SOLVENT VAPORS

 COOLINO WATER

SCRAP
OECREAliMQ



fPRETREATEDl
SCRAP ME! At






rMEAT
ALLOY
SMELTWO/REfMINa

*"
rHEAT
RETORT
DISTILLATION

I 	 CHLORINE
1 r— Nf At

DEZINCIMO


*
COOLINO
T WATER



H
                                                                                                    C4DUWM
                                                                                                    •ALLS AND |
                                                                                                     STICKS
          Figure 10.   Generalized flow  diagram of  a secondary cadmium recovery  plant.  '

-------
                                       PRETREATMENT
                                  IOIVCNI MCAI
COBAl I •
• (AHINO-
(CHAP
              Figure 11.   Generalized  flow diagram of  a  secondary cobalt  recovery plant.
                                                                                           27

-------
        SCRAP PRETREATMENT
SMELTING
                                                                                          REFINING/CASTING
       MECHANICAL
Conductor*
                                                    icrap    TT^
                                                       U*car—I

                                                        Cok*	I
                                       .Natural C»m

                                         _Cr«n Pol..


                                         |	Reducing Ag«nc


                                          (	High Grade Scrap

                                             .Flux


                                               ,Air

Oxyg.n 	
\ "^
\ ""^n
V-f] I !
X-»
.1.K IrJ S"ltt"«






/ Shoe \
1 Copper I




'Sulrurlc. .Acid)
          Figure  12.    Generalized  flow diagram  of  a secondary copper recovery  plant.
                                                                                                          27

-------
         SCRAP  PRETREATMENT
                                                        REFINING
                      MECHANICAL
Ski••Ings/Residues
Flux, Fuel, Castings,
Scrap,  Top Drosses,—
Sklnlnga
Flux,  Fuel, Nixed
Scrap
Fuel,  Die-Cast Sc
Electricity, Clean.
Scrap,  Flux
Flux,  Fuel, Mixed
Scrap
Water, Sodlu» Carbonate
Sklnlngs, Residues
Crush ing and
Sc reen Ing
PYROHETALLURGICAL
Kettle Sweating

Reve rbe ratory
Sweating

r



i
                       Rotary Sweating
                       Electric  Sweating
Muffle Sweating
                      IIYDROHETALLURCICAL
Sodium Carbonate
Leaching
                                          Fuel
                                                                               r
                                                                                  Fuel
                                                                               Retort
                                                                               Distillation
                                                          .Fuel
                                                                              Muffle
                                                                              Distillation
                                                           Fuel
                                                          r"'
                                                                              Retort
                                                                              Distillation/
                                                                              Oxidation	
                                                       I>
    Fuel

      Ir
Muffle
Distillation/
Oxidation
    Flux Cover

     -Alloying Agent
          uel
   I	Alloyl

   I  I	 Fue
"It
                                                                              Alloying
                                                                               r:
                                                                                  Electricity
                                                                              Graphite
                                                                              Resistor
                                                                              Distillation
    Figure  13.   Generalized  flow  diagram  of  a  secondary  zinc  recovery  plant.
                                                                                                             27

-------
     The smelting step in secondary recovery facilities is performed by
using electric arc furnaces, reverberatory furnaces, blast furnaces, or
converters.  Figures 8-13 detail the specifics of each segment's smelting
process, including a description of the alloying agents and fluxes used in
each.  A smelting step is performed in all of the secondary recovery
operations except zinc.  In secondary zinc facilities, scrap is melted
during pretreatment and is only refined to produce a final product.  All of
the other smelting processes, except those carried out in the cobalt
segment, have the potential to emit nickel particulates.  Control of these
sources is generally achieved by using fabric filters.  In the cobalt
segment, a vacuum smelting process is used which traps metal emissions and
                                  27
prevents them from being released.

     As shown in Figures 8-13, the processes used to refine the various
metals are often similar and closely related to the smelting step processes.
In some segments such as aluminum, brass and bronze, and cobalt, the
smelting and refining processes are the same.  Regardless of the particular
process configuration, all of the secondary refining processes, except those
used in the cobalt segment, have the potential to emit nickel-containing
particulate.  Fabric filters, ESPs, and wet scrubbers have been applied to
                                                             27
control the particulate emissions of these various processes.

     The metal casting operations in the secondary smelting plants involve
pouring molten alloys into molds, which are air cooled to form ingots.  No
                                                                27
nickel emissions are generally associated with these operations.

Emission Factors

     No quantitative emission factor data have been determined to estimate
the level of nickel emissions from secondary metal smelting processes.

     No measured nickel speciation data exist for secondary nickel recovery
plants; however, the forms of nickel potentially emitted from these
facilities can be theorized from speciation results of other nickel
                                     70

-------
 metallurgical operations  and a knowledge  of  the  conditions  existing  within
 the recovery processes.   Because  of  the high temperatures involved in the
 smelting and refining  furnaces, the  majority of  nickel present  should be
 oxidized.   Data taken  from a nickel  alloy metallurgical plant indicate that
 nickel  would exist  predominantly  as  oxides of nickel and other  metals and
 not pure nickel oxide  although some  is possible.15  Some metallic nickel may
 also be present in  the emissions  from reasons connected with reaction
 kinetics.   Data from the  nickel alloy plant  tests confirm that  some  metallic
 nickel  is possible  from a high temperature metallurgical environment
 involving nickel.

 Source  Locations

     The locations  of  firms which practice secondary recovery of metals,
 including aluminum, copper, zinc, cobalt, cadmium, and brass and bronze, are
 given in Table  5 of Section 3.  These firms have been identified as  having
 the  potential to emit  nickel  compounds.

 Co-Product Nickel Recovery

 Process  Description

     As  discussed in Section 3, nickel,  in the form of nickel sulfate, is
 produced in varying quantities as a co-product of electrolytic copper and
 platinum metals refining plants.  A representative electrolytic copper
 refinery flow diagram  is presented in Figure 14 to illustrate how nickel
                     28
 sulfate  is generated.     As shown in Figure 14,  impurities in
 smelter-generated blister copper are separated from the copper product by
 electrolytic dissolution at an anode. Usually the electrolyte used is a
 solution consisting of copper sulfate and sulfuric acid.   The electrolyte
 serves to dissolve the impurities in the  copper anode.   Those impurities not
dissolved fall to the  bottom of the electrolytic cell  as a slime.   In the
electrolytic cell a portion of the dissolved copper is  generally not  trans-
ferred to the cathode.   Therefore, a gradual increase  occurs in  the copper
                                    71

-------
                       Blicter Copper
                                            Recovery


                                     Heated Eleetrolvt
                                                       Copper Product
                                                          Decopperized
                                                          Electrolyte
                    Nickel Emissions-^
                                         Nickel Sulface
Figure  14.   Generalized  flow  diagram of  an electrolytic  copper
              refinery. 28
                                    72

-------
 concentration of the electrolyte.   The  concentration  of  copper  and
 impurities  in the electrolyte  is  controlled by  continuously  or
 intermittently withdrawing  a portion  of the used  electrolyte and  replacing
                        28
 it with a new solution.                                                  _

      Copper is recovered from  the electrolyte solution at the liberator
 cells.   These liberator cells  are similar to the  electrolytic refining
 cells;  however,  insoluble iron or lead  anodes are used in place of  copper
 anodes.  After the copper has  been  recovered in the liberator cells, the
 remaining solution is transferred to  an open or vacuum evaporator and then
 to a  centrifuge  for  the concentration and recovery of nickel sulfate.
 Nickel  sulfate recovered from  the centrifuge is dried and sold as a product,
 or is redissolved and recrystallized  to  produce a higher purity product.28

 Emission Factors

     Nickel emissions from electrolytic  copper and platinum  refining
 primarily occur from the evaporation  and nickel sulfate drying operations.
 The evaporation operation produces nickel-containing aerosols, while the
 drying operation  produces nickel sulfate particulate matter.   Emissions are
 estimated to be low because (1) relatively few refiners practice nickel
 sulfate recovery, and (2) the most widely used evaporator systems are
 enclosed so that  any emitted nickel aerosol is captured and recycled to the
        29
process.    No other quantitative data are available on nickel emissions
                     28
 from these processes.

Ferrous and Nonferrous Metals Production

     As discussed in Section 3, metallurgical uses constitute the largest
demand for nickel.  Nickel is used to produce two main categories of metal
alloys:   ferrous and nonferrous.   Important  ferrous nickel alloys include
cast irons (which are produced in foundries),  stainless steels,  and alloy
steels.   Nonferrous nickel alloys include nickel-copper alloys,
                                    73

-------
copper-nickel alloys, superalloys, and electrical alloys.  Although
individual plant configurations and techniques may vary between
manufacturers, the basic processes used to produce either the ferrous or
nonferrous materials are the same.  In the following paragraphs process
descriptions are presented that are representative of ferrous and nonferrous
nickel metal production facilities.  A discussion of the level of nickel
emissions from each metals category and the location of ferrous and
nonferrous facilities is presented after each process description.

     Ferrous Metals Production

Process Description

     The general flow process for the production of a nickel stainless steel
or steel alloy is depicted in Figure 15.  As shown in the figure, the
process is initiated by charging scrap metal (similar in composition to the
metal being produced), alloying materials, and a lime fluxing agent to
either an electric arc or high frequency induction furnace for melting
(pts. 1 or~2).  The majority of steels produced are melted by electric arc
furnaces.  The types and quantities of alloying materials added are
dependent upon the type of steel to be produced.  Ferronickel, ferro-
chromium, pure unwrought nickel, nickel oxide, ferrosilicon, ferromanganese,
and manganese silicon are examples of typical alloying materials.

     After the furnace charge has been melted, the molten steel is
mechanically transferred from the furnace by a ladle to the argon oxygen
decarburization (AOD) process (pt. 3).  The ADD process is a step to refine
the molten steel.  In 1978 over 80 percent of all domestically produced
stainless steel was refined by the AOD process.  Other, less frequently used
refining techniques include vacuum arc remeltirig, electroslag remelting, and
vacuum decarburization.  In the AOD process, controlled amounts of oxygen
and argon, and in some cases nitrogen, are blown through the bottom of the
AOD vessel to remove excess carbon.  During the AOD operation, the
                                     74

-------
                          Nickel
Ln
0 I
Electric
^ Arc Melt
Furnace
SCRAP 	

ALLOYS OR
LIME & FLUX- ,|lgh Fre_
~~ Induction
Furnace
© f
Nickel
Emissions
Cold

Nickel
Emissions
© f


Pickling
Refining
Argon/Oxygei
tlon Vessel

Annea
oven
© © ©
Annealing
*" Oven *•
Pickling

Micke]
Emlssi
01

— r*"
Nlcki't 1
Emission
Hug


L
ona

Continuous
Casting Process

Nickel
Emissions
	 ^fc- Powdpr
Torch

— *- STEEL SLAB
Ingot Mold
Casting Process
a

Rinse and |
*" Dry
•

Hot
Rolling

OR B1LLE
Ingot fS\
*~ Rolling 	 ^

Rehe.it
"* 	 Furnace -« 	 Surf
Grin
1

ace
ding

1
. Nirkel
Emissions
FINAL PRODUCT AS:
COIL
STRIP
                                                                                 PLATE
                                                                                 SHEET
Numbered points correspond to process
operations and potential nickel emission
streams as discussed in the text.
                       Figure  15.   Representative  process flow diagram of  a ferrous metal production
                                     laci-Lity.

-------
temperature of the molten metal is about 1565°C (2850°F).  The refined,
extremely hot metal is poured from the AOD vessel into a ladle.  At that
point it is either cast in a continuous casting machine or cast into ingots
using conventional cast iron molds.

     In a typical continuous caster (pt. A), the molten steel is poured into
a vertical, water cooled copper mold where the metal begins to solidify and
emerges as a continuous slab.  The solidified steel is then cut into
sections using an iron powder torch (pt. 5).  In conventional mold pouring
operations known as teeming (pt. 6), a special ladle is placed directly over
the open tops of the ingot molds.  A nozzle on the bottom of the ladle is
connected to a stopper mechanism which controls the flow of metal from the
ladle into the mold.  The molten steel is allowed to flow into a series of
molds until the supply is exhausted.  The ingot molds are then left to cool,
allowing the steel to solidify.*  Once the ingot is solidified, an overhead
crane is used to strip the steel from the molds.  The thickness of the
semi-finished steel is then reduced by running it through a rolling mill
operation (pt. 7).  The steel slabs produced (pt. 8) by rolling are
generally about 15 cm (6 in) thick, 0.61 m (2 ft) wide, and 2.4 m (8 ft)
.    30
long.

     Slabs made by either the continuous casting or ingot method have
surface blemishes and an oxide coating that must be removed by surface
grinding (pt. 9) before any further rolling or metal forming can take place.
Ingot slabs are ground on all sides, while continuous-cast slabs are usually
ground on only two sides.  Because continuous-cast slabs do not require
initial rolling to reduce thickness, fewer surface defects are present on
the slab sides, and less grinding is needed to prepare these slabs for
further processing.

     To resume the metal forming process after grinding is complete, the
steel slabs must be reheated to a temperature of 1200-1260°C (2200-2300°F).
Reheat furnaces (pt. 10) or soaking pits are used for this purpose.  Once
                                     76

-------
 the  slab  is malleable,  it passes  through a series of reduction and  finishing
 mills  (pts. 11,  14)  of  widely varying design among manufacturers.   The  final
 required  product determines  the number of mills used.

     Two  important processes that are conducted during the reduction and
 finishing operation  are annealing and pickling.  Hot rolling of stainless
 steel  to  a desired thickness produces distortion in the metal grain
 structure and builds up internal stresses in the metal.  The high
 temperature annealing operation (pts. 12, 15) recrystallizes the grain
 structure, relieves  the internal stresses, and dissolves any chromium
 carbides  present.  It also produces an oxide film on the surface of the
 metal known as scale.   Scale is removed by pickling (pts. 13, 16), which
 involves  immersing the  steel in specialized acid baths.  The pickling baths
 may be either hot or cold operations.  Following the final pickling
 operation the steel product is rinsed, dried, and removed to a storage area.

     The  production process described above (and shown in Figure 15) for
 stainless and alloy steels is generally applicable to basic iron and steel
 (carbon steel) plants except for differences in the types of melt furnaces
used.  Iron and  steel plants employ basic oxygen, open hearth, or electric
 furnaces  to melt the charge materials.  High frequency induction furnaces
 are not used.

Emission  Factors

     In the production of nickel stainless and alloy steels and cast irons,
 the charge melting furnace (pts. 1,  2) is a major source of nickel-
                                 2fi  on
containing particulate emissions.   '    Tapping and material transfer
operations at  the furnace generate considerable fugitive particulate
emissions which also contain nickel  and nickel oxides.   The steel industry
generally controls furnace emissions by the use of collection hoods and
standard particulate control devices such as fabric filters or ESPs.  A
second important source of nickel  emissions is the ADD process vessel
                                    77

-------
(pt. 3).  As is the case with the melt furnaces, considerable
nickel-containing, fugitive particulate emissions are released during
tapping and material transfer operations from the ADD vessel.  Hooding and
induced draft roof designs are used to capture the particulate emissions.
Fabric filters are successfully being used to control the collected
  .   .    31,32
emissions.

     A third major source of nickel emissions is the surface grinding
operation (pt. 9).  As the grinding wheel contacts the metal surface,
particles are displaced and emitted.  Different manufacturers use various
hooding designs to capture the emitted particulates, which are then directed
to a fabric filter or other particulate removal device for control.

     Other less significant nickel emission sources include the casting
operations (pts. 4,6) and the iron powder torch cutting operation (pt. 5).
As molten metal is transferred to the continuous caster or the teeming
ladle, fumes evolve that may contain nickel.  Hooding and the induced draft
roof system are used to remove the fumes from the work area.  A similar
situation exists with the torch cutting operation.  As the slabs are cut,
fumes are released which potentially contain nickel.  Downdraft hoods, which
are placed beneath the steel being cut, are used to remove these fumes from
the work area.

     Potential nickel emission points, including fugitive emission sources,
are indicated in Figure 15.  With the exception of the AOD operation, basic
iron and steel plants contain the same potential nickel emission sources
that have been described above for nickel stainless and alloy steel
facilities.

     Nickel emission factors for the steel industry have been estimated
based on steel industry particulate emission factors and data on the nickel
content of emitted particulates.       The calculated factors are presented
in Table 13.  Both the particulate emission factors and the nickel content
data are based on the results of many source tests in the steel industry.
                                    78

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                      TABLE 13.   NICKEL EMISSION  FACTORS  FOR STEEL MANUFACTURING OPERATIONS
                                                                                           33-36
VO
                    Source
Controls in Place*
Emission Factor, kg (Ib) Ni per
   Mg (ton) of steel produced
                                                                      kg/Mg
                                            Ib/ton
Open Hearth Furnace
Open Hearth Fugitive Emissions
Basic Oxygen Process Furnace
Basic Oxygen Process Fugitives
Electric Arc Furnace (Carbon Steel)
Electric Arc Furnace (Carbon Steel)
Electric Arc Furnace (Alloy Steel)
Electric Arc Furnace (Alloy Steel)
Electric Arc Furnace Fugitive Emissions
(Carbon Steel)
Electric Arc Furnace Fugitive Emissions
(Alloy Steel)
Electric Arc Furnace Fugitive Emissions
(Carbon Steel)
Electric Arc Furnace Fugitive Emissions
(Alloy Steel)
Electric Arc Furnace (Stainless Steel)
Electric Arc Furnace (Stainless Steel)
Electric Arc Furnace Fugitive Emissions
(Stainless Steel)
Electric Arc Furnace Fugitive Emissions
(Stainless Steel)
Argon Oxygen Decarburization Vessel
(Stainless Steel)
Argon Oxygen Decarburization Vessel
(Stainless Steel)
ESP
None
Scrubber
None
None
FF
None
FF
None

None

Hoods & FF

Hoods & FF

None
FF
None

Hoods & FF

None

FF

0.00009
0.000025
0.000009
0.00005
0.0042
0.000007-0.000042
0.013
0.00002-0.00013
0.00027

0.0008

0.00006

0.00016

0.15
0.0015
0.018

0.0036

0.16

0.032

(0.00018)
(0.00005)
(0.000018)
(0.0001)
(0.0083)
(0.000013-0.000084)
(0.025)
(0.000039-0.00025)
(0.00054).

(0.0016)

(0.00011)

(0.00032)
;
(0.3)
(0.003)
(0.036)

(0.0072)

(0.32)

(0.064)

        a
         ESP = electrostatic precipitator
         FF = fabric filter

         Emissions are expected to be in the form of complex oxides of nickel and other metals,
         nickel oxide, nickel sulfate, and metallic nickel.  All factors are expressed in terms
         of total nickel.

-------
Factors are only available for melting furnaces and furnace fugitive
emissions.  No emission factor data were available to characterize other
steel sources such as grinding and casting processes.

     One other set of emission factor data has been developed in a study by
Purdue University for this source category.    In that study an open hearth
furnace was tested for both controlled and uncontrolled nickel emissions.
The average controlled nickel emissions from the ESP system controlling the
melt furnace were 0.00055 kg/Mg (0.0011 Ib/ton) of steel produced.  The
average emission factor for uncontrolled emissions from the furnace was
0.0042 kg/Mg (0.0085 Ib/ton) of steel produced.37

     In the high temperature metallurgical processes occurring in
steelmaking furnaces, the majority of nickel present would be expected to be
oxidized.  Data from the steelmaking industry and from the related nickel
alloy industry confirm that the majority of nickel present in emissions from
metallurgical melting furnaces is in the form of complex oxides of nickel
                 15 38
and other metals.  '    In one test of nickel emissions from an EAF
producing stainless steel, only 5 percent of the total nickel present was
              38
water soluble.    The nickel in the insoluble phase was determined to exist
as an alloyed element in iron oxide particles.  In the same series of tests
nickel emissions from surface grinding of stainless steel were determined to
exist as metallic nickel, while emissions from manual metal arc and metal
                                                                      38
inert-gas welding of stainless steel contained nickel as nickel oxide.

     Tests of the emissions from an EAF producing carbon steel identified
nickel oxide to constitute from 0 to 3 percent of total particulate
emissions.  Similar work on the emissions from an AQD vessel handling
specialty steel produced one sample where nickel oxide constituted
                                           35 39-42
3.1 percent of total particulate emissions.  '

     Data taken from tests of EAF's in a high-nickel alloy plant support the
observations made from the steelmaking industry tests.  Dust samples taken
                                    80

-------
 in these  tests were  analyzed  primarily by X-ray  diffraction  and  also  some
 selected  samples  were  analyzed by  energy dispersive X-ray analysis.   All
 samples were  viewed  under  a scanning  electron microscope.  Nickel  in
 particulate emissions  from melting furnaces was  found  to exist mainly as
 oxides of nickel  and other metals  (primarily iron) followed  by lesser
 amounts of metallic  nickel and nickel oxide.15»^3

     Although these  results cannot be extrapolated directly  to nickel
 emissions from steel manufacturing, the indications are clear that nickel in
 high temperature  metallurgical environments is predominantly oxidized and
 combined  with other  metals present  (if stoichiometry permits) to forn
 complex oxides of nickel and  other  metals.  From available data it is
 difficult to  predict the extent to  which metallic nickel would be found in
 steelmaking particulate emissions.  However, because metallic nickel  is
 unstable  relative to nickel oxide over a wide temperature range, any  non-
 oxidation of  the  metallic  nickel present is probably due to a specific
 feature of the  overall steelmaking  process reaction kinetics.1^

     The  only  sulfur compound of nickel expected to be emitted from
 steelmaking processes is nickel sulfate.   Generally,  in these metallurgical
 operations attempts are made  to exclude sulfur from the reactions;  however,
 small amounts  can be present.   If sulfur is present (usually as sulfur
 dioxide),  sulfate and consequently nickel sulfate can and would be  formed
 over nickel sulfide or nickel subsulfide because it is thermodynamically
more stable under these types of temperature conditions than either of the
 sulfide compounds.  Essentially the reactions shown below would not occur
because sulfur pressures present would not be sufficient to bring about the
reaction.
     (1)  3Ni(s) + 2S02(g)  •>  Ni3S2(s) + 202(s)
     (2)  Ni(s) + S02(g)  *  NiS(s) + 02(g)
                                    81

-------
Sulfate and chloride anions have been identified in the small water soluble
portion of steelmaking dusts such that it is likely that a minor part of the
emissions generated from steelmaking contain nickel sulfate and nickel
 ui  4J  15,43
chloride.

Source Locations

     Because of the large number of plants involved in this category of
nickel emission sources, it is not feasible to present an individual plant
listing.  However, the national distribution of nickel emissions from
                                               44
ferrous metals production is shown in Table 14.    Directories such as The
Thomas Register, Dunn and Bradstreet, or Standard and Poor's could be used
to identify individual site locations.  The necessary SIC codes to access
published directories are given below:

     -  SIC 331, Blast Furnaces, Steel Works, and Rolling and
        Finishing Mills
     -  SIC 332, Iron and Steel Foundries

In addition, the following trade associations should have listings of
domestic ferrous metals production facilities from a compilation of their
membership.

     -  American Iron and Steel Institute (Directory of Iron and Steel Works
        of the United States and Canada)
     -  The Ferroalloys Association
     -  American Foundrymen's Society
     -  Cast Metals Federation

A partial list of firms identified under the ferrous metals category is
given in Table 15.
                                     82

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          TABLE  14.  DISTRIBUTION OF NICKEL EMISSIONS FROM FERROUS

                     METALS PRODUCTION BY GEOGRAPHIC REGION44
Geographic                          Percentage of Nickel Emissions
  Re8ion                            From Ferrous Metals Production

New England                                    0.48%

Middle Atlantic                               22.8%

East North Central                            26%

West North Central                             2.4%

South Atlantic                                13.2%

East South Central                            20%

West South Central                             2.5%

Mountain                                       5.8%

Pacific                                        6.9%
                                    83

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             TABLE 15.  PARTIAL LIST OF DOMESTIC FIRMS PRODUCING
                                                        30
                        NICKEL-CONTAINING FERROUS METALS
Stainless Steel
Melting Firms
   Alloy Steel
   Melting Firms
Allegheny Ludlum
Al-Tech Specialty
Armco
Babcock and Wilcox
Carpenter Technology
Crucible Steel
                   o
Cyclops Corporation
Eastern Stainless
Electroalloy Corporation
Ingersoll
Jessop Steel3
Jones and Laughlin
Jorgenson
Josyln Stainless
McLouth Steel3
National Forge
Republic3
Simonds Steel
Timken
U. S. Steet3
Washington Steel Corporation
Bethlehem Steel Corporation
Braeburn Alloy Steel
Columbia Tool Steel Company
Teledyne Vasco
 Also produces carbon steel.
NOTE:  This listing is subject to change as market conditions change,
       facility ownership changes, plants are closed down, etc.
       The reader should verify the existence of particular facilities
       by consulting current listings and/or the plants themselves.
       The level of nickel emissions from any given facility if
       a function of variables such as capacity, throughput, and control
       measures, and should be determined through direct contacts with
       plant personnel.

       This is considered a partial list because the reference cited does
       not necessarily contain the name of each company making nickel-
       containing steel.  Because of the size and diversity of this
       industry, it is possible that more companies are involved than are
       given here.
                                     84

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      Nonferrous  Metals  Production

 Process Description

      Many nickel alloys are produced in this category, including
 copper-nickel, nickel-copper, electrical, super, and permanent magnet
 alloys.  Each alloy  is  designed and manufactured to have a composition  that
 facilitates  its  final end use in an environment that is generally corrosive,
 stressful, or hot.   Table 16 presents a list of the more prominent nickel
 alloys and their chemical composition.

     ^Nonferrous  nickel  alloys are produced in the form of rods, sheets, and
 tubes.  These semifinished materials are then used to fabricate finished
 products.  The production of all nickel alloys starts with a common process
 step  in which melting (and in some cases refining) of the input materials is
 performed.  From this point the processing differs depending on the type of
 alloy produced.   Further processing steps include casting, hot and cold
 working, and powder  production.

     A generalized flow diagram is given in Figure 16 depicting the possible
 methods of nickel alloy production.  Initially, the charge materials
 consisting of pure nickel pellets, alloy scrap, and other alloying agents
 are added to the melt furnace.  Primary melting of the charge materials is
 accomplished by using one of several types of furnaces including an electric
 arc, vacuum induction, vacuum arc, or electron beam furnace (pt. 1,
           46
 Figure 16).     Electric arc furnaces are prevalent in this industry;
however, vacuum induction furnaces are used in melting alloys with highly
 oxidizable metals, and electron beam furnaces are used for alloys containing
highly refractory metals.

     As the melting process in an electric arc furnace is carried out,  slag
tapping is accomplished through a tap spout on one side of the furnace.
Slag is poured into a slag pot and transported to a cooling area where  it
                                    85

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                                 TABLE 16.   MAJOR  NICKEL  ALLOYS  AND THEIR CHEMICAL COMPOSITION
                                                                                                        45
oo

Alloy8
Nickel 200
Monel Alloy 400
Monel Alloy K-500
Ni chrome
Inconel Alloy 600
Hastelloy Alloy B-2
Hastelloy Alloy G
Hastelloy Alloy C-276
Inconel Alloy 718
B-1900

Mar-M200

Uaspaloy
Udimet 500
Udimet 700
Nimonic Alloy BOA
Nlmonic Alloy 115
Rene' 41
Inconel Alloy 754
Mi
99.5
66.5
65.0
77.0
76.0
65.4
42.0
55.4
52.5
64.0

60.0

58.0
54.0
53.0
76.0
60.0
55.0
78.0
Fe
0.15
1.25
1.0
0.5
8.0
2.0
19.5
5.0
18.5











Cr Cu
0.05
31.5
29.5
20.0
15.5
1.0
22.0 2.0
16.0
19.0
8.0

9.0

19.5
18.0
15.0
19.5
14.3
19.0
20.0
Chemical Composition, wt. percent
Mo Mn Si C Al





28.0
6.5
16.0
3.0
6.0



4.3
4.0
5.2

3.3
10.0

0.25
1.0
0.6
1.0
0.5
1.0
1.5
1.0
0.2







0.3



0.05
0.25
0.15
1.0
0.2
0.1
1.0
0.08
0.2







0.3



0.06
0.15
0.15
0.06
0.08
0.02
0.05
0.02
0.04
0.1

0.15

0.08
0.08
0.08
0.06
0.15
0.09
0.05


2.8





0.5
6.0

5.0

1.3
2.9
4.3
1.4
4.9
1.5
0.3
Ti


0.5





0.9
1.0

2.0

3.0
2.9
3.5
2.4
3.7
3.1
0.5
Other





2.5 Co
2.5 Co, 2.0 (Cb+Ta),1.0
2.5 Co, 4.0 W
5.1 Cb
10.0 Co, 4.0 Ta, 0.015
0.1 Zr
10.0 Co, 12.0 W, 1.0 Cb
0.015 B, 0.05 Zr
13.5 Co, 0.006 B, 0.06
18.5 Co, 0.006 B, 0.05
. 18.5 Co, 0.03 B
0.003 B, 0.06 Zr







W


B,

,

Zr
Zr


13.2 Co, 0.16 B, 0.04 Zr
11.0 Co. 0.005 B
0.6 Y 0


                &Monel,  Duranlckel, Inconel, Incoloy and Nlmonic are trademarks  of INCO companies; Hastelloy  is a trademark of the
                 Cabot Corporation; Udimet is a trademark of the Special Metals  Corporation, Mar M is a trademark of the Martin
                 Marietta Corporation; Rene 41  is  a trademark of Teledyne Allvac; and Waspaloy is a trademark of United
                 Technologies Corporation.

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                                                   Nickel Emissions
oo
vj
 Nickel Euissions

(D
I
Nickel Emissions
1

NICKEL PELLETS ^ Primary Charge
ALLOYING ^
ACEHTS
1
Slag
— Dotted lines indicate potential
process pathways.
W 1 	 • 	
Argon/Oxygen ._____^ Refining
^->____-^ Decarburizatlo i Furnace
Defining 	
Enlsslo
' t©
Emissions >•• Hot Working
_ A r 	 *- Proce88
® J_ i_
_ Mold
^^ Cau Ling — ' •
i
L T ^, Cold
Working
Nickel Nickel
Emissions Emissions
|®
Metal
	 *- Powder . ^> ALLOY POWDRR
Production PRODUCT
na Nickel Emissions
© f
Scale
Removal . . nv
(Grinding) 	 >- PRODUCT
^ A1.LOY
PRODUCT
Surface ^^ ALLOY
Cleaning *" PRODUCT
® 1
* Nickel
Emissions
*
Numbered points correspond to process
operations and potential nickel emission
streams as discussed In the text.
                       Figure  16.   Representative process flow diagram of a nonferrous  metal,

                                    nickel alloy production facility.46

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may undergo further processing to reclaim metal values.  After the com-
pletion of slag tapping, the furnace is tilted forward and the melted metal
alloy is poured into a ladle.  If sufficient impurities are not carried out
in the slag, the molten metal may require further refining in an ADD unit
(pt. 2).  The refining process in the AOD vessel is performed in the same
manner as AOD refining in the ferrous metals production process.  Alloy
ingots produced by the AOD operation may then be sent directly to the hot
working process (pt. 4) or they may require secondary refining.  In the
secondary refining operation (pt. 3), cast ingots are remelted in either an
electroslag or vacuum arc remelting furnace.  The remelt process is
conducted in a mold so that as the ingot melts, the molten metal is
contained in the mold.  After the remelting and refining is complete, the
molten metal is again poured into ingots.  The ingots resulting from
secondary refining are subjected to hot working processes to determine their
product form.

     The hot working process involves physically changing and forming the
shapes that the alloy products will take.  The process is carried out at
temperatures high enough to maintain the plasticity of the metal being
formed.  The alloys may undergo rolling, drawing, extruding, forging, and
pressing during the hot working process.  During the hot working process,
scale may develop on the metal surface, thereby requiring grinding,
sandblasting, or pickling to be performed prior to the alloy becoming a
finished product (pt. 5).  The amount of scale formed is related to the
degree and number of times an alloy is shaped or deformed.

     As the nickel alloy from hot working approaches its final shape, the
alloy may be shifted into a cold working process (pt. 6).  As the name
implies, this operation of metal forming is not carried out at  elevated
temperatures.  Cold working has certain advantages in that as the metal is
worked, it holds its dimensional shape better and scale problems are
avoided.  In some cases the metal may be too hard for certain cold working
operations and annealing is performed to reduce hardness.  After annealing,
pickling may be needed to clean the metal surface (pt. 7).
                                    88

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      If the molten alloy from the primary melt  furnace  does  not  require
 further refining,  it may be sent  directly to  casting  (pt.  8)  or  to  the metal
 powder production  process (pt.  9).   Casting essentially consists of pouring
 molten metal into  a mold to form  a useful shape.   The molten metal  in the
 mold is generally  allowed to air  cool.   If necessary, the  cooled product
 from casting may undergo further  forming or shaping in  either the hot or
 cold working processes.

      For alloys  that,  because of  their particular  physical properties,  are
 very hard to work,  powder metallurgy is  often employed  to  produce the
 required alloy shapes.   Powder  metallurgy (pt.  9)  involves atomizing  the
 molten metal from  the  primary melt  furnace to form spherical  metal  droplets.
 The  most frequently used atomization method is  the inert gas  atomization
 method,  with argon  as  the usual inert gas.  Nickel alloy droplets are formed
 by impacting the molten  metal with  a high velocity argon stream.  Alloy
 powders  formed in  this way can  more  easily be compressed to form the
 required shapes  and products.

 Emission Factors

      The primary nickel  emission  sources within a  nickel alloy facility are
 the  melting  furnaces (pts.  1, 3), the casting process (pt. 8), the hot and
 cold working processes,  the powder production process (pt. 9), and  the scale
 removal  (surface grinding) process  (pt. 5).    These various  emission points
 are  indicated in Figure  16.  The  emissions from these points  are  in the form
 of dust  and  fumes.    '  '    The method generally employed  throughout  the
 industry  for  the control  of the alloy-generated nickel emissions  involves
 collecting them by  the use of various hooding designs and directing the
 collected particles to a  fabric filter system.  Fabric filters in this
 application have estimated control efficiencies in excess of 99 percent.46
Most  important, however,  in an alloy facility's overall nickel control
 system is the ability of  the hooding system to collect emissions
 efficiently.  Sidedraft,  canopy, and full roof hooding designs have been
                                    89

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shown to be effective in this industry.  Table 17 presents a description of
the controls used at one nickel alloy facility that is considered to be
                               46
representative of the industry.

     In Table 18, nickel emission factors are presented for several types of
nickel alloy facilities.  The emission factors presented apply only to a
facility's individual melt furnaces.  No emission factor data were available
to characterize other sources such as the AOD vessel, powder production, hot
and cold working processes, and casting processes.

     Very few specific data were found which identified the species or form
of nickel in emissions generated during alloy production.  The International
Nickel Company (INCO) has, however, performed several analyses of dusts
collected during the manufacture of high nickel alloys using X-ray
diffraction, scanning electron microscopy (SEM), and energy dispersive X-ray
analysis.    Particles collected during the melting of Monel® 400 and K-500
alloys which contain about 66.5 percent nickel, 1 percent iron, and
30 percent copper, were spherical, which was considered typical of metal
that has condensed from the vapor state.  The X-ray diffraction pattern of
the dust was compared to several patterns in a reference library; patterns
for nickel oxide and a complex copper-nickel oxide closely matched that of
the unknown dust.  Of the particles examined using EDXA, none were found to
be copper-free, therefore, the existence of nickel oxide as a separate
species in the particles is doubtful.

     Using the same techniques, dusts collected during melting of Inconel
800 and 840 were thought to contain complex nickel-iron oxides, nickel-
chromium oxides,  and nickel oxide.  These alloys contain approximately
32 percent nickel, 46 percent iron, and 21 percent chromium.  Similarly,
dusts from melting Inconel 600 (76 percent nickel, 8 percent iron,
15..5 percent chromium)  were thought to contain nickel oxide and a complex
iron-nickel oxide.  EDXA indicated the presence of substantial amounts of
                                    90

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            TABLE 17.  REPRESENTATIVE EMISSION CONTROL EQUIPMENT
                       USED IN NICKEL ALLOY PRODUCTION
                                                      ,46
Part of the Alloy
Process Controlled
  Control Equipment
    Configuration
Electric arc melt furnace
  and AOD vessel
Secondary refining in an
  induction furnace
Surface grinding for scale
  removal
Water-cooled, side draft hoods
on the furnaces
Canopy hood in building roof to
collect particulate emissions
during tapping operations
All hoods vent to a fabric filter
system

Traversing hood positioned over
the furnace
Hood vents to a fabric filter

Fixed hoods placed directly over
grinders to collect fine
particulate emissions
Hoods vent to a fabric filter
                                    91

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          TABLE 18.  NICKEL EMISSION FACTORS FOR NONFERROUS METALS

                     PRODUCTION SOURCES
Facility Type
    Emission Factors"
Nickel-Copper,
  Copper-Nickel

Superalloys
Permanent Magnet
  Alloys

Electrical Alloys
Other Nonferrous
  Alloys
1 kg/Mg (2blb/ton) of Ni
   charged

1 kg/Mg (2bIb/ton) of Ni
   charged

1 kg/Mg (2 Ib/ton) of Ni
   charged

1 kg/Mg (2 Ib/ton) of Ni
   charged

1 kg/Mg (2 Ib/ton) of Ni
   charged
 All factors are engineering estimates from Reference 26 and represent
 controlled emissions from fabric filters.   Emissions are expected to be
 in the form of metallic nickel, complex oxides of nickel and other
 metals, nickel oxide,  and nickel sulfate.   The factors apply to individual
 melting furnaces at each type of facility.

 Reference ~19 reports nickel emissions from a high nickel alloy
 manufacturing plant as less than 0.25 kg/Mg (0.5  Ib/ton) of nickel charged.
 The types and levels of control are not specified.
                                    92

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copper in the particles analyzed.  The copper was probably present as a
contaminant and does not indicate the presence of nickel-copper oxides from
an alloy containing little or no copper.

     A specialized Br./alcohol leaching technique was used to substantiate
                                      /TJs
the absence of alloy or metal in Monel^ 405 dusts.  This method dissolves
the metal but leaves oxides relatively intact.  It was found that
5-10 percent of the nickel was present as the metal.    Dusts from Inconel
600 and Incoloy 800 were found to contain 7.8 and 4.1 percent metallic
nickel, respectively.

     Grinding dust was also examined and determined to be coarser than
melting dusts and similar in composition to the parent material.  Oxides
were present on particle surfaces, but the particles were primarily
metallic.

     Based on these analyses, nickel emitted during alloying is likely to be
present as a complex oxide of nickel, iron, and other metals present in each
particular~alloy such as chromium.  Smaller amounts of metallic nickel and
possibly some nickel sulfate may also be emitted.

Source Locations

     Specific locations of the numerous firms producing nickel alloys can be
found in the Thomas Register, keying on specific nickel alloy names
including Moner*, Inconel®, Hastelloy®, Nimonic®,  and Udimet .  In published
manufacturing directories indexed by SIC code, SIC 335 (Rolling, Drawing and
Extruding of Nonferrous Metals)  can be used to locate possible nickel alloy
producers.
                                    93

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 Electroplating

 Process Description

     Nickel  is plated  onto metal by  several means  to provide  decoration,
 corrosion  resistance,  electrical conducting properties,  and mechanical
 wearing properties.  Nickel plating  is performed using both electrolytic and
 nonelectrolytic processes.  Electrolytic plating of nickel includes
 electroplating and electroforming processes.  Nonelectrolytic,  chemical
 coating processes used in the  industry include displacement coating  (simple
 immersion) and autocatalytic reduction (electroless plating).   For
 categorization purposes, the broad term electroplating is used  to refer to
 the collection of all  these plating  processes, even though electroplating is
 a distinct type of plating technique.  Each electrolytic and nonelectrolytic
 technique  is discussed in the  following paragraphs.

     Electrolytic nickel plating basically consists of electrically
 depositing a thin coating of nickel  on an object for decoration or
 protection"purposes.   The material or surface to be plated is generally
 treated prior to plating.  Pretreatment may include polishing or grinding,
 solvent degreasing, electrolytic cleaning, or acid dipping to remove
 alkaline residues.  Between pretreatment steps the surface being plated is
 rinsed.  Frequently during pretreatment, an undercoat of copper is applied
 to the plating surface to facilitate better nickel coverage.

     Most electrolytic electroplating operations are conducted in an
 electroplating tank with a cathode and an anode immersed in electrolyte.
 Generally, the part to be plated functions as the cathode, and the anode is
 a bar or slab of nickel metal.   The electrolyte solution contains ions of
 the metal to be deposited and other additives such as sulfuric or fluoboric
 acid.   The function of the acids is to improve the electrical conductivity
 of the electrolyte bath.   Nickel sulfate and nickel chloride are the primary
nickel compounds used to prepare electrolyte solutions.
                                    94

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     To accomplish the plating process, low voltage direct current is passed
through the electrolyte bath.  Electrolytic decomposition of water in the
bath occurs, thereby releasing hydrogen gas at the cathode and oxygen at the
anode.  As these gases rise to the surface of the bath, a mist of
electrolyte is formed and nickel metal is deposited on the part.  During
plating, the pH and temperature of a sulfamate bath are 3-4 and 40-68°C
(104-154°F), respectively.  The equivalent values for a fluoborate bath
during plating are 2.7-3.5 and 35-65°C (95-149°F).  Figure 17 illustrates
the basic process steps that are found in a representative electroplating
facility.48'51

     A specialized application of the electrolytic electroplating process is
known as electroforming.  Electroforming is the production of an article by
electro-deposition upon a mold that is subsequently separated from the
deposited material.  The mechanics of the electroforming process are
essentially the same as the electroplating process previously described.
The main difference between the two processes is that the electroforming
process requires more time to accomplish the material deposition.  To speed
up the process, electroforming baths are operated at the highest possible
electrical current density.  The increased current density creates a greater
potential for electrolyte misting than is found in standard electroplating.

     The displacement or nickel immersion plating process is generally known
as nickel dip plating.  The process basically involves the replacement of
the surface atoms of a solid base metal with nickel from solution.  As the
base metal dissolves, it provides electrons to reduce the nickel ions.  A
dilute solution of nickel sulfate with a pH of 3-4 and a temperature of 70°C
(160°F) is used for the displacement bath.  The only large-scale operation
where this method of nickel plating is prominent is the coating of steel in
the ceramic enameling industry.  '

     The process of autocatalytic reduction, or electroless plating,
involves coating metallic parts with an ultra-micro crystalline
                                    95

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       Nickel
       Emissions
                         Pretreatment Step
                        (Polishing,  Grinding,
                         Degreasing)
                                 }
                        Alkaline Solution
                        Soaking Step

                        (2-8 min. at  40-95°C)
                                   Rinse
                        Alkaline Solution
                        Electrocleaning Step

                        (2-8 min. at 40-95°C)
                                    Rinse
                                 1
                        Acid Dip in Dilute
                        Acid Solution
                       (0.25-2 min. at 20-
                        60°C)
                                   Rinse
                           Strike Plating
                           of Copper
                           (2-5 min.)
                                   Rinse
Electrolytic
Nickel Plating
(10-30 min.)
                                 T
-Hydrogen &
 Oxygen Gases
         Rinse
                              NICKEL PLATED
                                PRODUCT
Figure  17.  Flow diagram for  a typical nickel  electroplating
              process.48-51
                                96

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nickel-phosphorus alloy.  The plating is performed through the controlled
autocatalytic reduction of cations (Ni++) at the surface of the base metal.
Hypophosphite anions  [(H-PO-)"] in an aqueous medium are employed as
reducing agents, and no external electric current is used.  The probable
chemical reactions occurring during plating can be represented by the
following equations:
 (H2P02)~ + H20       -    »» H  + (HP03)~ + 2H (Catal.) (1)

Ni++ + 2H(Catal.) - ^- Ni° + 2H+                    (2)

 (HP0)~ + H(Catal.) - ^- H0 + OH~ + P             (3)
Active hydrogen atoms, after being loosely bonded by the catalyst
(Equation 1), reduce the nickel ions to metallic nickel while they are being
oxidized to^ hydrogen ions (Equation 2).  Simultaneously, a small portion of
the hypbphosphite anions are similarly reduced by active hydrogen and
adsorbed on the catalytic surface, yielding elemental phosphorus, water, and
hydroxyl ions (Equation 3).  The hypophosphite reducing anions are also
catalytically oxidized to acid orthophosphite anions, with the evolution of
hydrogen gas (Equations 1,4).

Emission Factors

     Nickel emissions potentially occur from nickel plating shops during the
handling of nickel salts used to prepare plating baths, the plating of
nickel, and grinding, polishing, and cutting operations performed on the
finished product and scrap metal.  Emissions of nickel from the handling of
nickel salts are fugitive in nature and are generally contained within the
occupational environment.  During electrolytic nickel plating, hydrogen and
                                    97

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 oxygen gases can be generated such that  nickel  salts  from the  plating  bath
 can be entrained and emitted as  a  mist.   Nickel emissions from misting are
 generally very low or nonexistent  due  to the  low temperature and  low current
 densities used in nickel plating baths.   ~    Most  nickel emissions
 generated in this manner probably  remain in the workplace area.   Potentially
 the largest  amount of nickel emissions from nickel  plating would  occur
 during grinding,  polishing,  and  cutting  operations  performed on plated
 products  and scrap metal.  These operations displace  metallic  nickel
 particles into the occupational  environment with atmospheric release being
 possible  as  a result of  work area  ventilation.   In  all  instances  in the
 literature,  nickel air emissions are reported as negligible.   >>52   No
 emission  factors  for nickel  air  emissions from  electroplating  are given.

 Source Locations
                                                    *
     An extensive,  though incomplete,  listing of nickel electroplating
 facilities is  given  in Table  6 of  Section 3.  Published directories of
 manufacturing  firms  may  be used  to  identify more  nickel electroplaters
 within SIC code 3471,  Electroplating,  Plating, Polishing, Anodizing and
 Coloring.  Names  and locations of nickel electroplaters may also be
 available from the membership roll  of  the technical group known as the
 American  Electroplaters1 Society,  Inc.

 Battery Manufacturing

 Process Description

     The primary use of nickel in the battery manufacturing industry is in
 the production of nickel-cadmium (Ni-Cd)  batteries.   Nickel is used in Ni-Cd
batteries as the active material for the  positive electrode and as a binder
for some types of battery plate construction.   Nickel use in another type of
battery, the nickel oxide-zinc storage battery,  is expected to grow in the
near future as the technology for electric vehicles  develops.   One plant
producing nickel oxide-zinc batteries is  scheduled to go on line in the mid
1980's.53"67

                                    98

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     Batteries consist of one or more cells.   There are two major cell
categories known as sealed cells and vented cells.  Batteries constructed
with sealed cells commonly have small cylindrical, rectangular, or button
configurations which have application in calculators, toys, radios, and
other types of consumer products.  Even though they are classified as
sealed, most sealed cell batteries have a safety vent to relieve pressure
                                                        CO —£ ~1
within the cell if gas builds to a near-explosive level.  ~    In contrast,
vented cell batteries are designed to release gases as part of their normal
operation.  Vented cells are filled with excess electrolyte and are suitable
for constant charging/discharging and applications where the orientation of
the battery can be maintained.

     Sealed and vented Ni-Cd battery cells can be made by similar processes.
In each, negative and positive electrodes are assembled alternately with a
separator between the electrodes to hold the  electrolyte in place and to
isolate the negative and positive electrodes.  Minor assembly differences
between manufacturers may be noted.

     Although the production of the overall Ni-Cd cells is similar
throughout the industry, the production of the cell electrode plates is not.
Two basic types of electrode plate construction are found in the U. S.,
sintered plate and pocket plate.  Because sintered plate construction
predominates in the U. S., it is discussed in detail in the following
process description.

     The sintered plate process basically involves binding of the cell's
active materials to the nickel-plated base structure.  In the process,
binder materials such as nickel powder are heated to very high temperatures
causing the contact points of each grain to weld together.  This mechanism
provides a very porous medium which is bound  to the base structure.  The
void space in the binder material is then impregnated with nickel and
cadmium nitrate salts (active material) by soaking the sintered base in
either a nickel or cadmium salt solution.  The impregnated plate is then
                                    99

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 submerged  in  a potassium  hydroxide  solution  causing  the nickel  and  cadmium
 nitrate  to convert  to  the hydroxide  form.  The plate material is  then
 washed,  dried in  an oven, and  cut into  individual plates  for cell assembly.
 Figure 18  presents  a flow diagram of this  impregnation process  and  the major
 operations involved in Ni-Cd battery manufacture.

 Emission Factors

     The forms of nickel  most  likely to be emitted by a Ni-Cd battery plant
 are metallic  nickel, nickel oxide, nickel nitrate, and nickel hydrate.  All
 nickel compounds  emitted  by Ni-Cd battery plants are in the form  of
 particulate matter.  Emissions of metallic nickel powder  in the
 manufacturing of Ni-Cd batteries are primarily fugitive in nature as a
 result of  material  handling and transfer operations.  Fugitive  emissions of
                                       «
 this type  occur mainly in connection with sintering  operations  performed
 during battery plate production.  Process nickel emissions from the
 sintering  operation  exist primarily  as nickel oxide  since during  sintering
 metallic nickel powder is subjected  to very high oxidizing temperatures in
 order to cause the  contact points of  each grain to weld together.

     Fugitive emissions of nickel nitrate from material handling and
 processing operations are possible during the preparation of nickel salt
 impregnation  solutions used in electrode plate production.  Nickel hydrate
 emissions  from the production of Ni-Cd batteries also occur during plate
 formation.   When the nickel nitrate  impregnated plate is submerged in a
potassium hydroxide solution, nickel nitrate is converted to the hydroxide
form.  As water is evaporated from the nickel hydroxide material during the
drying operation,  nickel hydrate crystals are formed and emitted.  Fugitive
nickel hydrate particles can also be emitted during  the plate cutting
operation.

     There  are no  organized estimates available on the level of nickel being
emitted into the air nationally from Ni-Cd battery plants.  Emissions are
                                   100

-------
                           Nickel
                           Powder

           Nickel
           Placed
            Steel

     Nickel
     Emissions
Nick
Nitr
Satu
Sintered St
el Nitrat, Formation
ic Acid
rated Solution "
W V
Nickel
Impregnation
rip 	 ^-E
Cadmium
»•"•'-«
Saturat
i 1 X
Impregnation
missions
Nitrate
c Acid
td Solution
                Potassium
                Hydroxide
                Solution
Immersion
                                     i
                                  Washing
                                     i
                                Oven Drying
                                     I
                                Final Caustic
                                   Soak
                                Hot Deionized
                                Rinse Water
                                     i
                                  Forming in
                                   Caustic
                                     I
                                Final Brushing
                                 and Rinse
               Felted Nylon
               Cellulose	
               Separator
               Potassium
               Hydroxide,	^
               Lithium Hydroxide
  Assembly
                                     I
 Plastic or
'Nickel Plated
 Steel Case
Electrolyte
 Addition
                                Test and Pack
                                    BATTERY
                                    PRODUCT
Figure  18.   Flow diagram of  typical production operations  in
               impregnation sintered plate nickel-cadmium battery
               manufacture. 53-70
                                   101

-------
expected to be low because battery manufacturers attempt to control nickel
emissions  (and other metals like cadmium) to the extent economically
                                                         £Q
possible because of the high cost of these raw materials.    Hooding and
vacuum systems ducted to fabric filters are the predominant control methods
used  in the industry.  Tests at one plant, which controls a majority of the
sealed cell Ni-Cd battery market, indicated a total nickel emission level of
approximately 28.1 kg (62 lb)/yr.
     The only available nickel emission factor for battery manufacturing
describes total plant emissions on an uncontrolled basis.  Separate factors
for process and fugitive emissions have not been developed.  The factor of
4 kg (8.8 Ib) of nickel emissions/Mg (ton) of nickel processed is based on
                                             26
industry responses to a questionnaire survey.    This factor expresses
emissions as total nickel and not any particular nickel species.  The
majority of these emissions are expected to occur from the sintering
operation.

Source Locations

     The manufacture of Ni-Cd batteries falls within the general SIC code
3691, Storage Batteries.  Those manufacturers identified as producers of
Ni-Cd batteries are listed in Table 19.  Additional information on Ni-Cd
battery producers may be obtained from the Independent Battery Manufacturers
Association and the Battery Council International trade groups.

Nickel Chemical Manufacturing (Including Catalysts)

Process Description

     As shown in Table 7 of Section 3,  at least 28 types of nickel chemicals
(including catalysts) are produced domestically.   The largest volume and
most commercially significant nickel chemical, nickel sulfate, has the
greatest potential for nickel air emissions because its production consumes
                                    102

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  TABLE 19.  NICKEL-CADMIUM BATTERY MANUFACTURERS IN THE UNITED STATES53"67


      Company                                       Location

General Electric                                  Gainesville, FL

GouldE                                            St. Paul, MN

Union Carbide                                     Cleveland, OH

Saft America                                      Valdosta, GA

Marathon Battery                                  Waco, TX

McGraw Edison                                     Greenville, NC

NIFE                                              Lincoln, RI

Eagle-Picher                                      Colorado Springs, CO

^Recently purchased by Saft America, announced plans are to shut down
 the nickel-cadmium battery operations.

NOTE:  This listing is subject to change as market conditions change,
       facility ownership changes, plants are closed down, etc.
       The reader should verify the existence of particular facilities
       by consulting current listings and/or the plants themselves.
       The level of nickel emissions from any given facility is
       a function of variables such as capacity, throughput, and control
       measures, and should be determined through direct contacts with
       plant personnel.
                                    103

-------
 the largest quantity of nickel raw material.    Nickel sulfate production
 is, therefore, described below to illustrate a representative nickel
 chemical manufacturing process.

     Figure 19 illustrates a representative process flow diagram for a
 nickel sulfate production facility.    Nickel sulfate can be produced from
 several raw materials:  pure nickel powder, nickel oxide, or spent nickel-
 plating solutions.  If pure nickel or nickel oxide is used, the first step
 of the process involves dissolving the nickel compound in sulfuric acid
 (pt. 1, Figure 19).  For a different nickel salt, such as nickel chloride, a
 different acid solvent would be used such as hydrochloric acid.  The
 resulting solution is filtered (pt. 2) and either packaged as a product, or
 processed further to recover the solid nickel sulfate hexahydrate.  The
 sludges produced by filtration can also be further processed (pt. 3) to
 generate additional nickel sulfate.

     When spent nickel-plating solutions are used as the starting raw
material, digestion with sulfuric acid is the initial step in the nickel
 sulfate process (pt. 4).  In a series of subsequent steps, the resulting
 solution is treated with oxidizers, lime, and sulfides to remove impurities.
 The purified nickel sulfate solution is filtered and sold or processed
 further to generate a solid nickel sulfate product.

     To recover the solid product in either the spent nickel-plating
 solution process or the pure nickel process, the nickel sulfate solution is
 first concentrated (pt. 6).   After concentration, the soluton is filtered
again and sent to a crystallizer (pt. 7).  The product of the crystal-
lization process is fed to a classifier (pt. 8) where the solid nickel
sulfate product is recovered.   To facilitate final packaging, the nickel
sulfate is dried (pt.  9), cooled, and screened.  Nickel sulfate dusts
generated during drying are  generally controlled by wet scrubbers, with the
resulting nickel-containing  scrubber water being recycled to the process
                                   104

-------
                              Nickel   Nickel
                              Oxide    Powder

                               J	L_
                Soda    Spent Plating
                Ash    Solution
                 NICKEL SULFATE
                 SOLUTION
                 PRODUCT
                                Dlgastor
• Steam

• Sulfuric
 Acid
                 tsh    Solul

                  I      I
                                                                   Digestor
©
streams as discussed in the text.
'ATE

1
@
^ Liq
Filter Filter
process
Spent Nickel
Catalv.f ^
Steaa 	 ^»
S ul f ur iCm_^B»
Acid
St-.au. ^
Air ^

Lime 	 ^
(?)
0
jor
to process
ckel emission (7)
text .
"| i i
Dlgeator
*
Treating Tank
i
Filter
Procee*
*
Treating Tank
*
Filter
Process
» X
* 1
Concentrator
t
Filter
Process
*
Crystal lirer
I
Classifier
*
Dryer
i
Cool, Screen,
and Package
Process
E
.*( 	 Spent Nickel
Residues
i
«y Sulfuric Acid
et Oxidizer
„(—__ Calcic*
^ Slud»«
NICKEL SULFATE
	 »-SOLUTIO» PRODUCT
^ Sludge
	 * Stean
© 	 ~j

;
* Cooling
^ Water
\ i
(fluent
H
vaporatlon
Tank

Holding
(?) T*011
M
Nickel
Dusts '


.. ._ |
Nickel *
i

-------
 (pt.  10).  Nickel-containing sludges from the filtrations  (pt.  11) and the
 liquor  from the classifiers (pt. 12) are also recycled to  the process.

      A  subcategory of nickel chemical production is nickel catalyst
 manufacture.  Nickel catalysts are commonly used in a number of applications
 including hydrogenation and dehydrogenation of organic compounds, artificial
 aging of liquors, cracking of ammonia, manufacture of hydrazine from urea,
 and catalytic combustion of organic compounds in auto exhausts.  Nickel
 catalysts are produced in several different ways depending on the type of
 catalyst needed.  The methods used to manufacture three currently used
 catalysts are briefly described below.

      To produce a fine nickel powder catalyst known as Raney nickel, a
 nickel-aluminum alloy is first ground to a fine powder.  The aluminum
 components of the powder are then leached by using a caustic solution.  The
 resulting product is a spongy nickel material with a very high surface area.
 To make the nickel sponge material more suitable for industrial application,
 it is slurried with water.  If necessary for a particular application, other
 metals such as molybdenum, chromium, cobalt, and copper may be incorporated
                                      72-75
 into  the nickel catalyst as promoters.

      The production of a second type of nickel catalyst involves two major
 steps, precipitation and reduction.  The process begins with the mixing of a
 nickel salt solution and an alkaline promoting agent solution.  Upon mixing
 the solutions, the nickel and the promoting agent co-precipitate as a
 material known as green catalyst.  The green catalyst slurry is then
 agitated and sent through a filtering mechanism.  The collected green
 catalyst is then dried with hot air and formed into tablets.   The final
processing occurs when the green catalyst tablets are fed into a reactor and
 reduced at high temperature with steam and hydrogen.   The product nickel
                                                                72—75
catalyst is then slurried in vegetable oil and packaged for use.
                                    106

-------
     In the manufacture of supported nickel catalysts, the starting material
is generally nickel powder or briquettes.  In preparation for adsorption
onto the support medium, the catalyst material is ionized and solubilized.
The nickel catalyst is then adsorbed onto a support medium which may be
alumina or some other refractory material.  The supported nickel catalyst is
then oxidized to complete the preparation process.  In some instances this
technique is modified so that prepared nickel oxide is combined directly
                      72-75
with a support medium.

Emission Factors

     In the production of nickel sulfate (Figure 19) the primary points of
potential nickel (or nickel compound) emissions are the nickel powder/nickel
oxide handling and preparation steps (pt. 1, Figure 19), the solid nickel
sulfate drying operation (pt. 9), and the nickel sulfate packaging operation
(pt. 13).  The emissions from nickel powder/nickel oxide handling and nickel
sulfate packaging are primarily fugitive dusts caused by material
displacement.  Local exhaust hooding is used to collect these dusts.  The
collected nickel material is either sent to a control device (wet scrubber
or fabric filter) from which it can eventually be recycled to the process or
vented to the atmosphere.  Nickel sulfate emissions from the product dryers
are also collected and directed to wet scrubbers or fabric filters for
control.  Again, the collected nickel material is usually recycled to the
process.  Though other nickel chemical plants may have slightly different
configurations from those shown in Figure 19, materials handling and product
drying are expected to be the primary sources of potential nickel emissions
in each facility.

     In the production of nickel catalysts, nickel preparation and handling
                                                           72-75
steps are the most significant sources of nickel emissions.       Crushing,
grinding, and screening of nickel prior to catalyst production all generate
nickel dust emissions.  The emission control techniques applied in the
catalyst operations are very similar to those used in the basic nickel
                                   107

-------
chemical processes. Local exhaust hooding is used to capture and convey
nickel emissions to a scrubber or fabric filter particulate control
A   •   72-75
device.
     Available references report that nickel emissions from nickel chemical
or nickel catalyst production processes are negligible.  '       In all
cases either no nickel emission factors were given or they were listed as
                 26
being negligible.
Source Locations

     The domestic producers of basic nickel chemicals are presented in
Table 7 of Section 3.  This list represents the population of nickel
chemical producers as of mid 1982.  A partial listing of nickel catalyst
producers is given in Table 20.  This list was taken from the Thomas
Register of Manufacturers and the McGraw-Hill Chemical Buyers' Guide.  Only
catalyst manufacturers specifically noted as producing nickel catalysts are
reported.

INDIRECT SOURCES OF NICKEL

Coal and Oil Combustion

Process Description

     Nickel is a trace element common in most coals and oils.  Tables 21 and
22, respectively, summarize the nickel contents of typical coals and oils
used in this country.  The average nickel content of U. S. coals ranges from
about 5 to 21 ppm, whereas the average nickel content of U. S. crude oils is
15 ppm.  Residual oils appear to have higher nickel contents, on the
average,  than crude oils as a result of the refining process.  A heavy metal
such as nickel has a very low vapor pressure and exists as a low vapor
                                   108

-------
                TABLE 20.  NICKEL CATALYST PRODUCERS19'76'77
     Company                                 Location
United Catalyst                         Louisville, KY

Union Carbide                           Tarrytown, NY

American Cyanamid                       Wayne, NJ

De Gussa                                Teterboro, NJ

Davison Div. of W. R. Grace             Baltimore, MD

Mallinckrodt, Inc.                      Erie, PA

Harshaw Chemicals                       Cleveland, OH

Activated Metals & Chemicals            Sevierville, TN

Houdry Div. of Air Products &           Allentown, PA
  Chemicals


NOTE:  This listing is subject to change as market conditions change,
       facility ownership changes, plants are closed down, etc.
       The reader should verify the existence of particular facilities
       by consulting current listings and/or the plants themselves.
       The level of nickel emissions from any given facility is
       a function of variables such as capacity, throughput, and control
       measures, and should be determined through direct contacts with
       plant personnel.
                                   109

-------
                                                               78
            TABLE 21.  TYPICAL NICKEL CONTENT OF DOMESTIC COALS
                                   Average Nickel          Range of Nickel
Coal Source                         Content, ppm            Content, ppm
Eastern United States
(Appalachia)
Midwestern United States
15
21
6.3
7.6
- 28
- 68
(Illinois Basin)

Western United States                     5                  1.5 - 18a

Average of Total U.S.                    20                    3-80

 uata presented in reference 79 show measured nickel levels in an
 unwashed and washed western coal to be 100 ppm and 170 ppm, respectively.
      TABLE 22.  NICKEL CONTENT OF VARIOUS CRUDE AND FUEL OILS26'81"84

Average Nickel
Oil Source/Type Content, ppm
United States/crude
Foreign/ crude
United States/residual No. 6
United States/residual No. 5
United States/residual No. 4
Foreign/residual No. 6
United States/distillate No. 2
15
25.6
48. 53
31
18
36.3
NA
Range of Nickel
Content , ppm
1.4 - 64
1.8 - 59
NAb
NA
NA
4 - 61.2
< 0.02 - 1.7
 Reference 86 indicates that this value is probably accurate for regular
 sulfur fuel oil,  but that it is too high for low sulfur fuel oil,  the
 use of which became important around 1970.   Low sulfur fuel oil has  a
 total nickel content that averages 10 ppm.   The two types of oil are
 used currently in roughly equal amounts.

 NA means data not available.
                                   110

-------
 pressure  organo-metallic  complex with  the higher molecular weight
 hydrocarbons  in  crude  oil.  As  such, the metal concentrates in the heavy
                                              Oft
 residual  part of the crude as it is distilled.

     This concentration phenomena explains why nickel contents of distillate
 oils are  generally much lower than residual and crude oils.  In analytical
 tests of  several distillate oils by a major oil refiner, nickel was not
                                          81
 found at  a limit of detection of 0.02 ppm.    Other measured values of
 nickel in distillate oil  have ranged from < 0.1 ppm to 1.7 ppm.82~84  In
 contrast,  however, measured levels of nickel in some distillate oils have
                       85
 been as high  as  23 ppm.    There are no data in the literature to reconcile
 this inconsistency, except that the analytical method used in these tests
 (spark source  emission spectrometry) is known to sometimes encounter
 interferences  when measuring nickel.  These higher than expected values for
 nickel in distillate oil  that have been reported may be the result of a
                            Q£
 faulty analytical procedure.

     The  amount  of nickel emitted to the atmosphere during coal and oil
 combustion "is  dependent primarily on the following factors:

     -  the nickel content of the fuel,
     -  the type of boiler used and its firing configuration,
     -  the partitioning of nickel between fly ash and bottom ash,
     -  the degree of nickel enrichment on fine fly ash, and
     -  the nickel removal efficiency of any controls that may be present.

The effect of  each of these factors is described in the following
paragraphs.

     The  concentration of nickel in coals and oils has been determined to be
the major factor affecting uncontrolled nickel emissions from combustion
        87
sources.     The greater the nickel concentration in the fuel, the higher the
uncontrolled rate of nickel emissions.   For the combustion of coal,  the type
                                    111

-------
 of boiler  and  its  firing  configuration both  affect nickel  emissions  by
 affecting  the  amount  of coal  ash  that ends up  as bottom ash.   The  bottom ash
 contains some  concentration of nickel that will not be  emitted to  the
 atmosphere.  The combustion of oil produces  essentially no bottom  ash,
 minimizing the effect of  boiler type and  firing configuration  on the level
 of nickel  emissions from  oil  fuels.

     The emission  of nickel from  coal or  oil combustion is generally ex-
 plained by the volatilization/condensation mechanism  (VCM) theory.   The
 theory basically states that, in  the firebox of a boiler or furnace, peak
 temperatures of approximately 1650°C (3000°F) volatilize fuel  elements such
 as nickel.  The hot flue  gases from the combustion process then undergo
 cooling through convective heat transfer  and other mechanisms, condensing
 the volatilized species.  Volatilized nickel may condense  or adsorb  onto
 existing particles in the exhaust stream  according to the  available
 particulate surface area, or may homogeneously condense  into fine nickel-
                     go
 containing particles.    Through  this procedure, the nickel concentration in
 the bottom ash is depleted, while the concentration in  the fly ash is
 enriched.   This phenomenon occurs because the fly ash has more relative
 surface area for condensation than the bottom ash and because  the bottom ash
 does not come  in contact with the volatilized nickel long enough for it to
         88 89
 condense.   '    As an example, tests of three coal fired utility boilers
 showed that 18  percent of the fuel nickel deposited in the bottom ash
                                              90
whereas 82 percent entrained onto the fly ash.

     The degree of partitioning and small particle enrichment  that goes on
during the volatilization and condensation of nickel has been  studied by
several researchers, especially for coal combustion.   These researchers have
devised several classification schemes to describe the partitioning and
enrichment behavior of many trace elements,   including nickel.   One of the
                                                                  88 89
more simplistic, but useful classification systems is given below:
                                    112

-------
           Class  1.  Elements which are approximately equally distributed
           between fly ash and bottom ash, showing little or no enrichment
           onto small particles.
           Class  2.  Elements which are enriched in fly ash relative to
           bottom ash, or show increasing enrichment with decreasing particle
           size.
           Class  3.  Elements which are intermediate between Classes 1 and 2.
           Class  4.  Elements which are emitted entirely in the gas phase.

Nickel emissions from coal combustion have been shown to demonstrate the
behavior of Classes 1, 2, and 3, and are usually categorized under Class 3.
Class 3 elements such as nickel are apparently not totally volatilized
during the coal  combustion process, and, therefore, exhibit a capability for
bottom ash or fly ash deposition.  Nickel emissions from oil combustion
demonstrate the  behavior of Class 2 elements, primarily because little
bottom ash is produced in oil fired boilers.

     Nickel emissions from both coal and oil combustion show preferential
                                     89 91
enrichment"on fine fly ash particles.  '    Because of this enrichment
factor, the type of control device used plays an important role in
determining how much nickel is removed from the flue gas exhaust.  Control
devices not designed to remove fine particulates do not perform as well on
nickel emissions as devices which are so designed.   A summary is given in
Tables 23-25 of  the collection efficiencies for nickel that have been
determined for ESPs, fabric filters,  and wet scrubbers.  In addition to
control devices, fuel cleaning has also been shown to be an effective method
of reducing nickel and other trace element emissions from combustion pro-
cesses.  Physical coal cleaning has been shown to remove from 12 to
50 percent of the nickel in coal, depending on the  source of the coal.
Physical cleaning is 40-50 percent efficient on eastern and midwestern
coals, but is only 12 percent efficient on western  coals.   Hydrotreating
processes are very effective at removing nickel from oil.   Removal
efficiencies of greater than 95 percent have been achieved.92
                                   113

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        TABLE 23.  NICKEL COLLECTION EFFICIENCIES FOR ELECTROSTATIC
                   PRECIPITATORS92

Source Identification
Power Plant A
Power Plant B
Power Plant C
Power Plant D
Power Plant E
Power Plant F
Power Plant G
Power Plant H
Fuel
Coal
Coal
Coal
Coal
Coal
Coal
Coal
Coal
Percent Collection Efficiency
96.3
99.4
99.7
99.8
98
96.4
98.7
78.5
       TABLE 24.  NICKEL COLLECTION EFFICIENCIES FOR FABRIC FILTERS
                                                                   92
Source Identification
Fuel
Percent Collection Efficiency
Power Plant A
Power Plant B
Steel Mill
Coal
Coal
              99.6
             100
             100
                                    114

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      TABLE 25.  NICKEL COLLECTION EFFICIENCIES FOR WET SCRUBBERS
                                                                 92,93
-
Source Identification
Power Plant A
Power Plant B
Industrial Boiler A
Industrial Boiler A
Power Plant C
Fuel
Coal
Coal
Coal
Oil
Coal
Percent Collection Efficiency
95a
90.8 - 98b
95C
83C
>97d
.Controlled by a venturi scrubber.
 Controlled by a horizontal scrubber.
.Scrubber was designed primarily for S02 control.
 The scrubber is preceeded by an ESP.
                                    115

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 Emission  Factors

     Nickel  emission  factors for coal and oil combustion are presented  in
 Tables  26 and 2T.   In both tables, calculated and measured emission factors
 are given.   For oil combustion, calculated factors have been developed  by
 determining  the amount of nickel in the fuel and then by assuming that
 100 percent  of the  nickel is emitted.  This approach results in an emission
 factor  that  is theoretically the maximum for the fuel under analysis.   The
 only means by which actual emissions could be greater than the calculated
 value are that nickel is added to the emission stream from metal erosion in
 the boiler or control device, or nickel is present in combustion air at a
 significant  level.  Calculated emission factors for oil combustion are
 generally much greater than the same factors determined by testing.  In one
 series  of tests, calculated nickel emission factors were consistently two
 times higher than what was determined by actual emissions testing.85

     Calculated nickel emission factors for coal combustion also rely on the
 amount  of nickel in the fuel as a primary input.  The application of average
 nickel  enrichment ratios (which have been estimated by testing) and average
 control device efficiencies are also an integral part of the calculation.
 For coal combustion,  particularly sources controlled by an ESP, measured
 nickel  emission factors were found to be greater than the amount of nickel
 that could be calculated to be emitted based on fuel nickel levels.  This
 inconsistency again indicates an influx of nickel into the emission
       94
 stream.    Measured nickel emission factors for oil and coal combustion are
based on actual emissions generated during source testing and analysis of a
boiler and a knowledge of the quantity and-characteristics of the fuel
burned.

     As shown in Tables 26 and 27,  wide variability exists in some of the
emission factor estimates for coal and oil combustion.   Although it is
beyond the scope of this document to reconcile all the reasons for these
large ranges, available data suggest that the most important factor
                                   116

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                           TABLE 26.   NICKEL EMISSION FACTORS FOR OIL COMBUSTION
                                                                                94-98
     Oil Type
         Uncontrolled Nickel
          Emission Factors
Type of Factor
Domestic Crude
Foreign Crude
Residual //6
Residual #5
Residual #4
Residual (No. Unspecified)
Residual (No. Unspecified)
Distillate #2

Distillate #2
Distillate //2
2-5 kg/10  liters (20 - 500 lb/10  gal)'
20 kg/106 liters (200 lb/106 gal)a
9.9 kg/106 liters (83 lb/106 gal)a
7.7 kg/106 liters (64 lb/106 gal)3
5.6 kg/106 liters (48 lb/106 gal)a
63 - 1,056 pg/Jb
57 - 63 Pg/Jb'd
0.046 .- 0.049 kg/106 liters
     (0.38 - 0.41 lb/10b gal)3'6
290 Pg/Jb
13 - 446 pg/Jb
Calculated
Calculated
Measured  -,
Measured
Measured
Calculated
Calculated
Measured

Measured
Calculated
 Emission factor expressed as total nickel emitted per  mass of oil fired.
 Emission factor expressed as total nickel emitted per  unit of heat energy contained in the  fuel.
£
 Calculated emission factors have been developed  by determining the nickel content of the oil and  making
 the assumption that all nickel in the fuel is emitted.   Measured emission factors have been determined by
 actual emissions source testing and sample analysis combined with a knowledge  of  the amount of fuel burned.
 These emission factors represent controlled emissions.   The 57 pg/J factor represents control With an ESP,
 while the 63 pg/J factor represents control with a scrubber.
"Reference 81 indicated the pg/J equivalent of this emission factor would  be 1.25  - 1.35 pg/J, assuming that
 all the nickel present in the emissions came from the  fuel.  This factor  is significantly lower than the
 other measured value for distillate oil combustion of  290 pg/J.   This difference  can basically be reconciled
 by examining the nickel content of the fuels burned.   In the case of the  lower emission factor, the fuel
 nickel level was about 0.05 ppmw.  The fuel nickel content in the tests that produced the higher  value ran as
 high as 23 ppmw.                                                                              <
 Nickel emissions from oil combustion are most likely to exist as nickel sulfate,  complex oxides of nickel
 and other metals, and nickel oxide.

-------
TABLE 27.  NICKEL EMISSION FACTORS FOR COAL COMBUSTION79'82'91'92'94"96'98'104
Coal Type
Anthracite
Anthracite
Anthracite
Bituminous
Bituminous
Bituminous
Bituminous
Bituminous
Bituminous
M Bituminous
i (
oo Bituminous
Bituminous
Bituminous
Bituminous
Bituminous
Bituminous
Bituminous
Bituminous
Bituminous
Bituminous
Bituminous
Bituminous
Lignite
Lignite
Lignite
Lignite
Lignite
Lignite
Lignite
Boiler Type
Stoker
Stoker
Pulverized
Pulverized
Pulverized
Pulverized
Pulverized
Pulverized
Pulverized
Pulverized
Pulverized
Cyclone
Cyclone
Cyclone
Cyclone
Cyclone
Cyclone
Stoker
Stoker
Stoker
Stoker
Stoker
Pulverized
Pulverized
Pulverized
Pulverized
Pulverized
Cyclone
Cyclone
Control
Device3
None
MC
ESP
None
None
MC
MC
ESP
ESP
WS
WS
MC
ESP
ESP
None
WS
WS
None
None
MC
MC
FF
MC
MC
ESP
ESP
WS
ESP
ESP
Nickel Emission
Factors, pg/Jb'd
135 - 470
29
30
130 - 2,900
1,045
709 - 870
16
50 - 62
4.3 - 2,480
213 - 227
0.48 - 133
147
2-11
429 - 1,330
470
38
20
400 - 2,200
13 - 1,463
670
13 - 2,230
71
228
115 - 263
8.3 - 13
< 68
161
4.5
< 47
Type of Factor0
i
Measured
Calculated
Calculated
Calculated
Measured
Calculated
Measured
Calculated
Measured
Calculated
Measured
Calculated
Calculated
Measured
Measured
Calculated
Measured
Calculated
Measured
Calculated
Measured
Measured
Calculated
Measured
Calculated
Measured
Calculated
Calculated
Measured

-------
              TABLE 27.  (CONTINUED) NICKEL EMISSION FACTORS FOR COAL COMBUSTION79'82'91'92'94"96'98'104
VO


Coal Type
Lignite
Lignite
Lignite
Lignite

Boiler Type
Cyclone
Cyclone
Stoker
Stoker
Control
a
Device
WS
MC
MC
ESP
Nickel Emission
Factors, pg/J '
87
221 - 320
276
< 38

£
Type of Factor
Calculated
Calculated
Measured
Measured
 The key for the control device  abbreviations is as follows:
     MC  - multicyclones
     ESP - electrostatic precipitator
     WS  - wet scrubber
     FF  - fabric filter

 Emission factors expressed  as total nickel emitted per unit for heat energy in the fuel.
r»
"Calculated emission factors have been developed using average fuel nickel contents, average nickel
 enrichment ratios,  and demonstrated average control device efficiencies.  Measured emission factors
 have been determined by actual  emissions source testing and sample analysis combined with a knowledge
 of the energy content of the fuel burned.
 Nickel emissions from coal  combustion are most likely to exist as nickel sulfate, complex oxides of
 nickel and other metals, and nickel oxide.

-------
 Influencing  the  situation  is  the nickel  content of  the  fuel.98  A  problem of
 inconsistent information regarding  fuel  nickel levels was- pointed  out
 previously in connection with distillate oil.

     Limited nickel emission  factors are also available for the combustion
 of wood.  In one  set of tests for five furnaces burning wood, measured
 nickel emission  factors ranged from 2-65 pg/J with  the average being
 29 pg/J.  Other measured nickel emission factors for wood have ranged from a
 low of 3.6 pg/J  to 110 pg/J.82'96

     Several recent studies have produced results strongly indicating the
 forms of nickel occurring  in  emissions from coal and oil combustion.  In fly
 ash samples  collected from the stacks of five oil fired utility boilers, the
 nickel components were found  to be  60-100 percent water soluble.99  In the
 analysis of  leachate from  the solubility test, sulfate anion was the only
 anion present at more than trace levels.  With this information it can be
 postulated that the form of nickel  in the fly ash emissions and ambient air
 from oil fired combustion  is  predominantly nickel sulfate.  This theory was
 eventually confirmed after the fly  ash and the soluble and insoluble
 fractions of  the samples were analyzed by Fourier transform infrared (FT-IR)
              100
 spectroscopy.

     In another study of stack fly ash and scale samples taken from the
 reducing and oxidizing sections of an oil fired utility boiler, nickel was
 found to exist as nickel ammonium sulfate [Ni(NH,)2(SO )  •  6H20].101  These
 samples were analyzed by Raman spectroscopy.  The water soluble fractions
 from the previous study (Reference 99)  that determined nickel sulfate to be
present were not analyzed  for ammonium (NH,  ).  Therefore, the results from
 the Raman spectroscopy analysis do not necessarily conflict with those of
Reference 99.

     In the  insoluble fraction of the fly ash samples from oil fired
boilers,  nickel was determined by X-ray diffraction (XRD)  to potentially
                                    120

-------
                      99
exist as nickel oxide.    However, with X-ray diffraction patterns it is
frequently difficult to distinguish between pure nickel oxide and complex
metal oxides involving nickel.  In addition, nickel oxide is known to have
an affinity for oxides of iron, aluminum, vanadium, and magnesium, all of
                                                         102
which are compounds found in fly ash combustion products.     Potentially,
the nickel component of the insoluble fraction could exist as complex nickel
oxides such as ferrites, aluminates, and vanadates, a combination of complex
metal oxides involving nickel and nickel oxide, or purely nickel oxide as
the X-ray diffraction results.

     The authors of Reference 99 have performed solubility and component
analysis studies for fly ash from coal combustion similar to those discussed
above for oil combustion.  Samples of fly ash emitted from coal fired
utility boilers controlled by electrostatic precipitation were water leached
and the fraction of nickel found to be soluble ranged from 20-80 percent.
For a boiler controlled by a limestone scrubber, 100 percent of the nickel
                                99
present was found to be soluble.    As in the case of oil combustion,
sulfate was the only major anion present, therefore, in the soluble fraction
of fly ash from coal combustion, nickel probably exists as nickel sulfate.
Various metal sulfates were identified in the soluble fraction of the coal
combustion fly ash by XRD and FT-IR, but specific compounds were not
         99
reported.    The insoluble fractions of the coal fired combustion fly ash
were determined by XRD to contain metal oxides, although neither nickel
oxide nor complex oxides containing nickel were specifically indicated as
being present.  Considering the experience with the insoluble fraction of
oil fired fly ash samples, it would be reasonable to expect that nickel
oxides would be present in the insoluble fraction of coal fired fly ash.

     Reference 103 examined the 100-200 ym size fraction of fly ash captured
by electrostatic precipitators from coal fired utility boilers.  Using
magnetic separation and hydrochloric and hydrofluoric acid leaching steps,
the fly ash was separated into a glass matrix, a mullite-quartz matrix, and
a magnetic spinel matrix of composition Fe« oAln 70..  Analysis by XRD and
                                          Z • j  U. / H
                                    121

-------
 X-ray  fluorescence  (XRF) of the separated matrices indicated that
 approximately 90 percent of the nickel present was associated with the
 spinel.  The theory was put forth that nickel probably existed as a
                                          103
 substituted spinel of the form Fe.3_xNix04.  J  Data gathered in this study
 reemphasized that while nickel is oxidized during the combustion process, it
 is probably not oxidized to pure nickel oxide.

 Source Locations

     Due to the large number of combustion sources in the U. S., individual
 source listings are not attempted here.  However, data on the location of
 large emitters such as power plants and industrial boilers are available
 through published government data bases maintained by EPA and DOE, the
 Electric Power Research Institute (ERPI), and the American Boiler
Manufacturers Association.

Cooling Towers at Electric Utility Stations

     Wet cooling towers used by the electric utility industry are sources of
nickel emissions because nickel-containing biocides and corrosion
inhibitors, usually in the form of hydrated nickel sulfate salts, are used
in the cooling tower water.   In 1978 cooling towers were used for
20.6 percent of the total installed capacity for all power plants.  Older,
mechanical draft type towers comprise about 54 percent of the total tower
population, while modern,  closed-cycle type towers make up the remaining
,,         98
46 percent.

     The emission of nickel  from cooling towers is proportional to the water
recirculation rate, the drift fraction (the fraction of cooling water
emitted as drift droplets),  the concentration of nickel in the cooling water
(which is highly variable),  and the ratio of the nickel concentration in the
drift fraction to that in the cooling water.
                                    122

-------
     The form of nickel emitted from cooling towers would vary depending on
the concentration of ligands and anions in the water and on water quality
                                          2+
(pH and hardness).  Nickel sulfate is a Ni   species that is readily soluble
in water.  Therefore, nickel may be present in cooling tower drift emissions
         2+
as the Ni   ion or bound to other ions such as hydroxide.  If chlorine is
also used to control biofouling, as is common practice, nickel chloride may
be formed and emitted.
     Nickel emission factors for utility cooling towers are presented in
Table 28.  These emission factors are based on measured emission rates
obtained from tests of three utility cooling towers.   The towers tested were
designed for drift losses in the 0.1 to 0.2 percent range, which is
representative of  older, mechanical draft cooling towers.  Estimates of
nickel emissions from newer (closed-cycle) cooling towers with drift losses
of 0.002 to 0.005 percent were obtained by a linear adjustment of the test
                                          98
results to reflect the lowered drift loss.

Cement Production

Process Description

     The production of cement is a potential source of nickel emissions
because nickel can be a component of both the process feed materials and the
fuels such as coal and oil that are burned in cement  process kilns and
dryers.  In 1981, approximately 67.6 million Mg (75.1 million tons) of
cement were produced in the U. S.  Cement is produced by either a wet or dry
method.  In the dry method, feed materials are sent to the processing steps
in a dry solid form.  In the wet method, feed materials are mixed with water
and sent to the processing steps as a slurry.  Of the total domestic cement
production, about 42 percent or 28.4 million Mg (31.2 million tons), is made
by the dry method, and 58 percent, or 39.2 million Mg (43.9 million tons),
by the wet method.
                                    123

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        TABLE 28.  NICKEL EMISSION FACTORS FOR FRESH WATER UTILITY
                                 no
                   COOLING TOWERS
                     Nickel Emission Factors, pg/Ja'b

         Drift Loss Range                    ..    Drift Loss Range
          of 0.1 to 0.2%                        of 0.002 to 0.005%


                16                                      0.34


Emission factors are expressed as weight of pollutant per thermal energy
input to the power plant associated with the cooling tower.

Emission factors are based on source tests of three separate cooling
towers.
                                  124

-------
     The basic process flow diagram for cement production by the wet and dry
methods is shown in Figure 20.  The raw materials used to make cement can be
divided into four basic categories:  lime, silica, alumina, and iron.
Approximately 1,600 kg (3,520 lb)' of dry raw materials are required to
produce 1 Mg (1.1 ton) of cement.     Following quarrying, raw materials are
crushed to a suitable size for processing and are entered into either the
wet or dry processing loop.  In both wet and dry processes the materials are
proportioned, ground, and blended prior to initiating the primary cement
production steps.

     In the dry process, the moisture content of the raw material is reduced
to less than 1 percent either before or during the grinding operation.  The
dried materials are then ground to a powder, blended, and fed directly into
an inclined rotary kiln.  The powdered raw materials are fed into the upper
end of the kiln and travel slowly to the lower end.  The kilns are fired
from the lower end so that hot gases pass upward and through the raw
materials.  Drying, decarbonating, and calcining are accomplished as the
material travels through the heated kiln, finally burning to incipient
fusion and forming what is known as clinker.  The clinker is then cooled,
mixed with about 5 percent gypsum by weight, and ground to a final product
size.  The cement product is then stored for packaging and shipment.

     In the wet process, a slurry is made by adding water to the raw
materials at the initial grinding operation.  After blending and mixing,
excess water is removed and the slurry is adjusted to achieve the proper
composition.  The homogeneous mixture which is fed to the kilns is usually
either a slurry of 30 to 40 percent moisture or a wet filtrate of about
20 percent moisture.  The remaining kiln burning, clinker cooling, and
gypsum addition steps are carried out the same as in the dry process.
                                    125

-------
                                                                      Nickel Emissions
Quarrying Raw
Materials
                                              Wet
                                              Process
                                                                      Water
                                                                              Nickel Emissions



Dry Mixing
and
Blending

Slurry Mixing
and








Storage



Nickel Eaiaslons
t'T
	 ^- Kiln


Nickel Emissions
1
Clinker
Cooler




Storage

Gyp
1
i
sum
Air
Separator
1
Grinder "•*•




Nickel
Emissions
                                                                                                         .CEMENT
                                                                                                          PRODUCT
                                                                                              106
 Figure  20.   Basic process  flow diagram  for wet and  dry cement production plants.   «

-------
Emission Factors
     The primary nickel emission sources in cement production are the rotary
kilns and grinding mills.     The majority of the cement industry uses  -
controls such as multicyclones, ESPs, ESPs with cyclones, and fabric filters
to reduce particulate, and consequently nickel emissions, from these
sources.  Typical collection efficiencies for control devices in these
   , .            106
applications are:
     -  multicyclones, 80 percent
     -  ESPs, 95 percent
     -  ESPs with cyclones, 97.5 percent
     -  fabric filters, 99.8 percent.

     Nickel emission factors for wet and dry cement processes have been
developed based on actual source testing of controlled cement plants.
Table 29 summarizes the nickel emission factors for major cement plant
sources.

     Few data were found which identified the nickel content of particles
from cement processing.  Nickel emitted from preliminary crushing and
grinding would be in the same form as it is found in raw materials, most
likely as a trace constituent of silicate minerals.  Nickel emissions from
kilns are probably in the forms of oxides of nickel and other metals, nickel
oxide, and to a lesser extent nickel sulfate because of the high
temperature, oxidizing conditions present in kilns.  Nickel emissions from
the clinker cooler would be in the same forms as those emitted from the
kilns because the nickel particles would not be undergoing any reactions in
the cooler.  During milling and packaging, nickel would also be emitted in
the forms that are produced in the kiln.  Nickel emitted from the combustion
of fossil fuels and dryers should be in the forms of nickel sulfate, complex
oxides of nickel and other metals, and nickel oxide, as discussed previously
in the combustion section.
                                    127

-------
     TABLE  29.  NICKEL EMISSION FACTORS FOR MAJOR CEMENT PLANT SOURCES
                                                                       26
Source Category  „
Controlled Nickel Emission Factors,
  kg/103 Mg (lb/103 tons)f'8
                                  c,h
Dry Cement Process3

     Kiln0'1
     Feed to Initial Grinding Mill
     Air Separator After Initial
       Grinding Mill0'
     Raw Material Grinding Mills0' .
     Feed to Finish Grinding Mill0'1
     Air Separator After Finish
       Grinding Mill0'1

Wet Cement Process

     Kiln*1'1
     Clinker Cooler0'
     Clinker Cooler '.
     Clinker Cooler6'1
     Finishing Grinding Mill After
       Air Separator0'
         0.2
         0.005
(0.3)
(0.01)
                                                0.0005 (0.001)
                                                0.0003 (0.0006)
                                                0.005  (0.01)

                                                0.002  (0.006)
                                                0.1 to 1 (0.2 to 2)
                                                0.002  (0.004)
                                                0.05   (0.1)
                                                0.1    (0.2)

                                                0.002  (0.004)
 Emission factors based on source testing of two plants with particulate
 sample analysis by emission spectroscopy.

 Emission factors based on source testing of three plants with particulate
 sample analysis by spark source mass spectrograph and optical emission
 spectrograph.
 Source controlled by a fabric filter.
 Source controlled by an ESP.

 Source controlled by two fabric filters in parallel.
 All factors expressed in terms of the amount of raw material feed input.
8Emission factors are expressed as total nickel.

 Nickel emissions from this source would be in the form of nickel silicate
 minerals.

 Nickel emissions from this source are expected to be in the forms of
 complex oxides of nickel and other metals, nickel oxide, and to a lesser
 extent nickel sulfate.
                                    128

-------
Source Locations

     In 1981 there were 201 cement plants in the United States.  The
majority of plants were located in California, Texas, Pennsylvania,
Michigan, and Missouri.     Individu;
from a variety of sources including:
Michigan, and Missouri.     Individual plant locations can be determined
     -  cement trade associations (e.g., Portland Cement Association)
     -  published industrial directories (e.g., Thomas Register,
        Standard & Poor's)
     -  the EPA National Emissions Data System (NEDS).

For sources indexed by SIC code, SIC 3241 should be used for cement
manufacturing.

Municipal Refuse and Sewage Sludge Incineration

Process Description

     Nickel is released during the incineration of municipal refuse and
wastewater sewage treatment sludge because these materials contain varying
quantities of nickel.  The nickel content of municipal refuse ranges from
4-50 ppm, with an average content being 15 ppm.   '     Dry sewage treatment
sludges have nickel contents ranging from 0-2800 ppm, with the average
                                109
content equalling about 410 ppm.     A description follows of the workings
of refuse and sewage sludge incinerators and of factors affecting nickel
emissions.

     The majority of municipal refuse incinerators have either
refractory-lined or water-walled combustion chambers that are equipped with
a grate upon which refuse is burned.  The grate can be stationary,
travelling, or vibrating, depending on the design of the incinerator.  In
most cases, natural draft or slight induced draft is used to pull air up
                                    129

-------
 through  the  grate  to  carry out the primary refuse combustion process.  The
 combustion gases from the primary chamber pass through a flame port where
 they  are reheated  and mixed with air to achieve more complete oxidation.
 Exhausts from the  secondary combustion chamber are either vented directly to
 the atmosphere or  to  a control device.  The basic configuration of a
 representative municipal refuse incinerator is given in Figure 21.110

      Sewage  sludge incineration refers to the oxidation of sludge material
 generated by wastewater sewage treatment plants.  The most prevalent types
 of incinerators for sludge oxidation are multiple-hearth and fluidized-bed
 units.   Multiple-hearth incinerators are relatively simple pieces of
 equipment, consisting of a steel shell lined with refractory.  The interior
 of the incinerator is divided by horizontal brick arches into separate
 compartments or hearths.  Alternate hearths are designed with openings to
 allow solid material  to drop onto the hearth below.  At the center of the
 unit, a  shaft rotates rabble arms that are located on each hearth.  To
 enable the incinerated material to move inward and then outward on alternate
 hearths,  teeth on  the rabble arms are placed at an angle.  As sludge is fed
 through  the roof of the incinerator, the rotating rabble arms and rabble
 teeth push the material across the hearth to drop holes where it falls to
 the next  hearth.  This process continues until the sterile ash produced by
 the oxidation steps is discharged from the bottom of the incinerator.
 Figure 22 presents a  schematic diagram of a typical multiple-hearth sewage
 sludge incinerator.

      The  majority of multiple-hearth incinerators have three distinct
 operating zones.  The first zone includes the top hearths where the
water-laden sludge feed is partially dried by rising hot combustion gases.
 The second operating zone is the incineration/deodorization zone where
 temperatures of 760-980°C (1400-1800°F) are reached and maintained.   The
 third zone of the multiple-hearth unit is the cooling zone where hot ash
 from  incineration releases heat to incoming combustion air.  The design
 temperature profile of a typical multiple-hearth incinerator is given in
                                                    112
 Table 30  to illustrate the break in operating zones.
                                    130

-------
X
x
X
x
X
X
X
X
X
X
X
X
X
X
X
         Charging
          Chute
                                        Superstructure
                       \\\\
                   V \ \ \ \ \ V\ VA A \ \
                              Curtain
                              Wall
          Curtain
         -Wall
Inclined Charging and
   Burning Grate
\:
                      V \ \ \ \ \ \ \
Nickel-Containing
Exhaust Flue Gases
                  Combustion Chamber
                          Ash and Clinker
                                Discharge
                         Horizontal Burning Grate
Furnace
Access
Door






       Figure 21.  Basic configuration of a municipal refuse incinerator.
                                                                   110

-------
  Nickel-containing
  Flue Gases  Out
                                    ooling  Air Discharge

                                   Floating Damper
                                             Sludge Inlet
  Drying  Zone
Combustion  Zone
  Cooling  Zone
  Ash Discharge
                                                 Rabble Arm  at
                                                 Each Hearth
                                                 ^Combustion
                                                  Air Return
                                               Rabble Arm
                                               Drive
       Cooling Air Fan'
   Figure 22.  Schematic diagram of a typical multiple<-hearth sewage
             sludge  incinerator.^
                              132

-------
          TABLE 30.  DESIGN TEMPERATURE PROFILE OF A SEWAGE SLUDGE

                                            112
                     MULTIPLE HEARTH FURNACE
Furnace Hearth No.a                  Nominal Design Capacity, °C (°F)




1 (Sludge drying zone)                       427   (800)



2                                            649  (1200)



3                                            900  (1650)



4                                            788  (1450)



5                                            649  (1200)



6 (Ash cooling zone)                         149   (300)




Dearth 1 is at the top of the furnace and 6 is at the bottom.
                                    133

-------
      The  second  technique used to oxidize sewage sludge is fluidized-bed
 incineration.  Figure 23 represents the basic operations found in a
                    112
 fluidized-bed unit.     In this operation dewatered sludge is introduced
 into  the  freeboard  area of the incinerator just above the fluidized bed -
 material  (which  is  usually sand).  Hot combustion gases rising from the bed
 evaporate remaining water in the sludge and sludge solids and then enter the
 fluidized bed.   The organic constituents of the sludge are oxidized to
 carbon dioxide and water vapor, which exit the system as exhaust gases.
 During this reaction, the bed is vigorously mixed and the bed temperature is
 maintained at 704-816°C (1300-1500°F).  Remaining inorganic sludge material
 either deposits  on.the bed sand particles and is removed from the bottom of
 the reactor, or  it  can be made to exit with the exhaust gases.  Air velocity
 through the bed  is used to control the method of inorganic sludge material
 removal.  Nickel emissions from this type of system are dependent on air
 flow velocity through the bed and the nickel content of the sludge.112

 Emission Factors

     The primary factors affecting nickel emissions from municipal refuse
 incinerators are the nickel content of the refuse and the manner in which
 combustion air is supplied to the combustion chambers.  The manner in which
 air is supplied can affect the combustion temperature achieved and conse-
 quently the degree of nickel species volatilization and the level of fly ash
 emissions.   '     The types of control devices used to reduce overall
 incinerator particulate emissions have some effect on reducing nickel
 emissions.  The configuration of controls found in the U.  S.  varies from
 simple settling chambers and baffle plates to more sophisticated ESP, wet
 scrubber, or fabric filter systems.   No information was found in the litera-
 ture describing the performance of municipal refuse incinerator controls on
nickel emissions.

     Nickel emission factors have been determined based on several U. S. EPA
 tests.  The emission factors for nickel from municipal refuse incinerators
                                    134

-------
                                                          Nickel-Containing
                                                         • Emissions
        Sludge
         Feed
                                                   Fluidized Media  (Heated by
                                                   Combustion  Gases)
                                             ;•••   Gas Distribution
                                          Solids Outlet
Figure 23.   Schematic diagram of a fluidized-bed sewage sludge incinerator.
                                                                           112
                                    135

-------
and  sludge incinerators are given in Table 31.  Recent studies of refuse
incinerators across the country concluded that these sources are not major
nickel emitters.116'117

     Nickel emissions from sewage sludge incinerators are influenced by the
nickel content of the sludge, the combustion temperature of the incinerator,
and  in fluidized-bed units, the method of inorganic material removal from
        109 112
the  bed.   '     Wet scrubber control devices are extensively used with good
success to control multiple-hearth and fluidized-bed sewage sludge
             109 112
incinerators.    '     Table 31 presents nickel emission factors for
multiple-hearth and fluidized-bed sewage sludge incinerators, based on
testing performed by the U. S. EPA.

     A recent study has also estimated nickel emissions from controlled
sewage sludge incinerators, but the results are basically semi-quantitative.
An examination of source tests from eight multiple-hearth incinerators
controlled by wet scrubbers showed that nickel emissions were generally less
than 1 percent of the amount of nickel entering with the sludge.   The test
results of one fluidized-bed incinerator controlled by a wet scrubber showed
that only about 0.1 percent of the nickel in the sludge was eventually
        109
emitted.     These results support the order of magnitude emission factor
difference given in Table 31 between the two types of controlled  sewage
sludge incinerators.

     The potential types of nickel compounds found in the emissions of
refuse and sludge incinerators are related to the kinds of waste  entering
the incineration systems.  Municipal refuse is generally high in  plastics
content such that chloride ions are likely to be prevalent.  Sewage
treatment sludge is affected by the kinds of discharges entered into the
publicly owned treatment works (POTW's).  Phosphates from human wastes and
detergent use can be significant in sludges to be incinerated.  Local
industry can also greatly affect the kinds of nickel compounds  found in
                                    136

-------
      TABLE 31.  EMISSION FACTORS FOR NICKEL FROM MUNICIPAL REFUSE AND

                 SEWAGE SLUDGE INCINERATORS26'114'115
                                 •Nickel Emission Factor, kg/Mg (Ib/ton)-
Emission Source                      of Solid Waste Incinerated3

Municipal Refuse Incinerators

     Refuse OnlyC                          0.002    (0.003)d

     Refuse and Sludge0                    0.003    (0.005)d

Sewage Sludge Incinerators6

     Multiple Hearth0                      0.002    (0.003)f'g

     Fluidized Bedc                        0.0002   (0.0003)8>h

     Uncontrolled Multiple-Hearth
       or Fluidized-Bed Unit               0.07     (0.15)


 All factors expressed in terms of total elemental nickel.

 Nickel emissions are expected to be in the forms of nickel chloride,
 nickel sulfate, and complex oxides of nickel and other metals.
c
 Source is controlled by a wet scrubber.

 Emission factors determined from U.S. EPA testing and analysis of one
 municipal incinerator.

 Nickel emissions are expected to be in the forms of nickel sulfate,
 nickel phosphate, nickel chloride, nickel nitrate, and complex oxides
 of nickel and other metals.

 Emissions found to range from 0.0003 to 0.004 kg/Mg (0.0006-0.008 Ib/ton).
o
"Emission factors determined from U.S. EPA testing and analysis of three
 sewage sludge incinerators.

 Emissions found to range from 0.0001 to 0.0002 kg/Mg (0.0002-0.0003 Ib/ton)
                                    137

-------
 sludge,  particularly  if plating or nickel chemical facilities exist that
                       1 1 R
 discharge  into POTW's.

     An  absolute  species characterization of potential nickel emissions from
 incinerators  is difficult because the compositions of waste streams vary so
 greatly  between units  and even daily within the same unit.  Recent tests,
 however, on the fly ash emissions of three different refuse incinerators and
 three different sludge incinerators have produced results that greatly aid
 in estimating the species of nickel potentially being emitted.  Fly ash
 emissions  from refuse  and sludge incineration were determined to be one-
 third to one-half water soluble.  The soluble phase of refuse incinerator
 fly ash  contained principally chloride and sulfate ions.118  The fraction of
 total nickel from refuse incinerator fly ashes that was water soluble ranged
                                118
 from less  than 47 to 84 percent.     Nickel compounds in the water soluble
 phase of these emissions are probably nickel chloride and/or nickel sulfate,
 although this was not  confirmed during these analyses.  The insoluble
 portion of these ashes contained primarily oxide and silicate salts of
 various metals.  Although not specifically identified, complex oxides of
 nickel and other metals (mainly iron) are probably the prevalent forms of
 nickel that would exist.

    .The water soluble phase of the sludge incinerator fly ash was found to
 contain predominantly sulfate ions, although chloride, nitrates, and
 phosphates were present at much lower levels.   The fraction of total nickel
 that was water soluble in sludge incinerator fly ash ranged from 34 to
           118
 52 percent.     It is reasonable to expect that nickel emissions present in
 the water soluble phase of sludge incinerator emissions are predominantly
 nickel sulfate, with potentially much lesser amounts of nickel chloride,
nitrate, and phosphate.  The insoluble phase of sludge incinerator fly ash
 emissions was similar to  that from refuse incinerator emissions.
 Principally oxide, silicate, and phosphate salts of various metals were
 identified, such that the probability is great that nickel exists as complex
                                    138

-------
oxides of nickel and other metals.  It is highly likely that nickel was
combined with iron to form a spinel; however, such a conclusion was not
explicitly determined.

Source Locations

     In 1979, there were 108 municipal refuse incinerators and 358 sewage
                                119 120
sludge incinerators in the U. S.   '     Table 32 presents a breakdown of
the number of incinerators of each type found by state.  Additional
information on the specific locations of these facilities can be obtained
from the Compliance Data System maintained by U. S. EPA Regional offices.

Coke Ovens

Process Description

     The production of metallurgical coke is a potential source of nickel
emissions because of nickel in the coal being processed.  Coke production
involves the destructive distillation of coal by heating it in a low oxygen
atmosphere, driving off gases generated by the decomposition of organic
compounds in the coal.  After distillation only the relatively involatile
coke remains.  The primary method of coking in the U. S. is the byproduct
                                                             121
method, which accounts for 98 percent of domestic production.

     The byproduct method is designed to recover gases generated during the
coking process.  A coke battery comprises a series of 40 to 70 narrow
rectangular, slot-type coking ovens interspersed with heating flues.
Figure 24 illustrates the arrangement of a typical coke oven battery.  Coal
is charged into ports on the top of the ovens by a device called a larry
car.  After charging, the ports are sealed, and heat is supplied to the
ovens by the combustion of gases passing through the flues between ovens.
The fuels used in the combustion process are natural gas, coke oven gas, or
gas from an adjacent blast furnace.  Inside the ovens, coke is first formed
near the exterior walls and then the process progresses toward the oven
                                    139

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TABLE 32.  POPULATION OF MUNICIPAL REFUSE AND SEWAGE SLUDGE
           INCINERATORS IN THE UNITED STATES BY STATE IN
      '    1978119'120 "
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
District of Columbia
Florida
Georgia
Hawaii
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
South Carolina
No. of Municipal"
Refuse Incinerators
0
0
0
0
0
0
16
1
0
8
0
0
0
. 4
1
0
0
0
3
0
1
0
3
0
0
2
0
0
0
2
7
0
31
0
0
6
0
0
10
1
0
No. of Sewage
Sludge Incinerators
1
6
0
2
18
0
11
0
0
3
8
2
0
6
10
' 4
4
4 -
6
1
7
15
55
11
0
16
0
2
3
5
17
0
32
5
0
27
2
1
21
5
3
                          140

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   TABLE 32.  (CONTINUED)POPULATION OF MUNICIPAL REFUSE AND SEWAGE SLUDGE

               INCH

               19781
INCINERATORS IN THE UNITED STATES BY STATE IN
   ,119,120
                             No. of Municipal         No. of Sewage
State                      Refuse Incinerators      Sludge Incinerators

South Dakota                         0                       0
Tennessee                            2                       9
Texas                                0                       9
Utah                                 2                       0
Vermont                              0                       0
Virginia                             2                      15
Washington                           0                       5
West Virginia                        0                       3
Wisconsin                            4                       4
Wyoming                            	0_                     	0

          TOTAL                    108                     358
                                    141

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Ni
                   Potential Nickel
                   Emission Sources
                  (l) Pushing emissions
                  (2) Charging emissions
                  (3) Door emissions
                  @ Topside emissions
                  © Battery underfire emissions
                                    Figure 94.   Metallurgical  coke oven  battery
                                                                                   121

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center, where temperatures of 1150°C (2100°F) can be reached.  The complete
coking process takes 16 to 20 hours.  Once the process is complete, coke-is
removed from the oven simply by pushing it out with a ram into a quenching
car.  The quenching car full of extremely hot coke is moved into the quench
tower and cooled by applying several thousand gallons of water.  The coke is
then allowed to dry before being separated into various size "fractions for
, ^         121
future uses.

Emission Factors

     The possible process related nickel emission points from a coke oven
battery are indicated in Figure 24.  Nickel emissions may also be generated
during quenching operations and from materials handling operations involving
                                     121
coal unloading, crushing, and sizing.     The form of nickel emissions from
these coking sources has not been determined and expressed in the
literature.

     Only one emission factor for nickel from metallurgical coke production
is available from the literature.  The level of uncontrolled nickel
emissions from coke ovens are estimated by this factor to be 0.008 kg/Mg
                                  122
(0.0016 Ib/ton) of coal processed.

Source Locations
     Table 33 presents the complete listing of coke production plants in the
                                 123
United States as of January 1980.

Asbestos Mining
     The mining and milling of asbestos minerals such as chrysotile can be a
potential source of nickel emissions because chrysotile contains 1.5-1.8 mg
nickel/g of chrysotile.  Dusts generated during the milling of chrysotile to
recover asbestos fibers can therefore contain small quantities of nickel.
                                    143

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       TABLE  33.   COKE  PLANTS  IN THE UNITED  STATES AS OF JANUARY  1980123
 Company Name
 Plant Location
Armco,  Inc.
 Bethlehem Steel Corp.
CF&I Steel Corp.
Crucible Steel, Inc.
Cyclops Corp.  (Empire-Detroit)
Ford Motor Co.
Inland Steel Co.
Interlake, Inc.
J&L Steel Corp.
Kaiser Steel Corp.
Lone Star Steel Co.
National Steel Corp.
Republic Steel Corp.
U. S. Steel Corp.
Hamilton, OH
Houston, TX
Middletown, OH  (2)

Bethlehem, PA
Burns Harbor, IN
Johnstown, PA
Lackawanna, NY
Sparrows Point, MD
Pueblo, CO

Midland, PA

Portsmouth, OH
Dearborn, MI

E. Chicago, IN  (3)

Chicago, IL

Aliquippa, PA
Campbell, OH
E. Chicago, IN
Pittsburgh, PA
Fontana, CA

Lone Star, TX
Granite City, IL
Detroit, MI
Weirton, WV
Brown's Island, WV
Cleveland, OH (2)
Gadsden, AL
Massillon, OH
S. Chicago, IL
Thomas, AL
Warren, OH
Youngstown, OH

Clairton, PA (3)
Fairfield, AL
                                    144

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         TABLE 33.  (CONTINUED) COKE PLANTS IN THE UNITED STATES AS
                                   123
                    OF JANUARY 1980
Company Name
Plant Location
Wheeling-Pittsburgh

Alabama By-Products Corp.
Allied Chemical Corp.
Carondelet Coke Company
Chattanooga Coke and Chemical Comp,
Citizens Gas and Coke Utility
Detroit Coke
Donner-Hanna Coke Corp.
Empire Coke Comp.
Erie Coke and Chemicals
Indiana Gas and Chemical
Ironton Coke Corp. (McLouth Steel)
Keystone Coke Comp.
Jim Walter
Koppers Co., Inc.

Milwaukee Solvay
Philadelphia Coke
  (Eastern Assoc. Coal Corp.)
Fairless Hills, PA
Gary, IN
Lorain, OH
Provo, UT
E. Steubenville, WV
Monessen, PA
Tarrant, AL
Ashland, KY
St. Louis, MO
Chattanooga, TN
Indianapolis, IN
Detroit, MI
Buffalo, NY
Holt, NY
Painesville, OH
Terre Haute, IN
Ironton, OH
Swedeland, PA
B irmingham, AL
Erie, PA
Toledo, OH
Woodward, AL
Milwaukee, WI
Philadelphia, PA
                                    145

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         TABLE 33.  (CONTINUED) COKE PLANTS IN THE UNITED-STATES AS
                                   1
                    OF JANUARY 1980
Company Name                                 Plant Location


Shenango, Inc.                               Neville Island, PA
Tonawanda Coke Co.                           Buffalo, NY


lumbers in parentheses indicate the number of plants at that location.
 If no number is indicated, only one plant exists at that location.

NOTE:  This listing is subject to change as market conditions change,
       facility ownership changes, plants are closed down, etc.   The
       reader should verify the existence of particular facilities by
       consutling current listings and/or the plants themselves.
       The level of nickel emissions from any given facility is  a
       function of variables such as capacity, throughput, and control
       measures, and should be determined through direct contacts with
       plant personnel.
                                    146

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An analysis by the U. S. EPA of an asbestos mill producing 36,300 Mg
(39,930 tons)/yr indicated an annual asbestos emission rate of 180 kg
(396 Ib).  If it is assumed that the asbestos emissions contain 1.8 mg
nickel/g of asbestos, an annual nickel emissions rate of 0.32 kg (0.71 Ib)
can be calculated.  Milling dusts at the facility are controlled by a fabric
filter system.  A controlled nickel emission factor for asbestos milling
operations, in terms of total asbestos produced, is 0.000009 kg/Mg
(0.000018 lb/ton).124'125

     Other sources of nickel emissions from asbestos operations are dry
waste piles of chrysotile tailings.  These tailings are generated from the
asbestos fiber recovery processes.  Generally, the waste piles are open and
exposed to winds which can dislodge and transport nickel-containing tail-
ings.  Because the recovery efficiency of asbestos fiber from chrysotile is
low (5 to 50 percent), a large amount of nickel-containing chrysotile is
present in the tailings for possible wind distribution.  The levels of
                                                                    124 125
nickel emissions from waste tailings piles have not been determined.   '

     Currently, there are four asbestos mining and milling operations in the
United States.  These operations are located in Arizona, California, and
        126
Vermont.

Coal Conversion Processes

     The category of coal conversion processes includes coal gasification
and coal liquefaction plants.  The existence of nickel compounds in the air
emissions of these facilities has qualitatively been determined; however, no
                                                     127
data are available quantifying such nickel emissions.     Nickel metal,
nickel carbonyl, and nickel subsulfide have either been found or are sus-
pected in several unit process emission streams from gasification and
liquefaction plants.
                                    147

-------
      The process flow sheets  given  in  Figures  25  and 26  represent  typical
 gasification and liquefaction plants.  The  operations within each  process
 that are known or suspected nickel  emission sources are  denoted by dotted
 lines,  and they are  listed individually  in  Table  34.  The only confirmed
 nickel  emission sources  are hydrotreating and  hydrocracking operations  in
 liquefaction plants  (nickel metal emissions) and  the methanation reaction
 operation in gasification plants (nickel carbonyl emissions).  More testing
 and  characterization of  emissions from these types of facilities are
 required to confirm  and  quantify the severity  of  nickel  emissions.

      The number of gasification and liquefaction  plants  in the United States
 is relatively small.  The majority of  plants are  demonstration or  pilot
 scale plants geared  to be research tools for a particular gasification or
 liquefaction technology.

 Petroleum Processing

      The  petroleum processing category includes refineries conducting light,
 intermediate,  and heavy hydrocarbon processing.  Several sources within
 these hydrocarbon processing operations have qualitatively been determined
                             128
 to have nickel  air emissions.     No data quantifying these emissions are
 available; however, nickel metal and nickel carbonyl are known or suspected
 to be present.

      The process flow sheets given in Figures 27,  28,  and 29 are basic
 representations of light, 'intermediate, and heavy  hydrocarbon processing
 operations,  showing which sources have nickel air  emissions.  Known and
 suspected nickel emission sources from all three types  of hydrocarbon
processing are summarized in Table  35.   All three  of these processing
 operations also have nickel emissions as a result  of using oil fired process
heaters.  Emission factors  presented in the oil combustion section are
applicable to oil fired process heaters.
                                    148

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VO
        0
                                                                                                     Known or Suspected
                                                                                                     Nickel Emission
                                                                                                     Sources
             Figure  25.   Representative  flow  diagram  for  a  coal  gasification process.
                                                                                                 127

-------
1



H Separation

\
I 	 1
                                                                                   riant Fuel J—^•
•    * Known or Suspected
•—»•• Nickel Emission
     Sources
      Figure  26.   Representative flow diagram  for  a  coal  liquefaction process
                                                                                            127

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      TABLE 34.   OPERATIONS WITHIN A COAL GASIFICATION AND LIQUEFACTION

                 PROCESS THAT ARE KNOWN OR SUSPECTED NICKEL EMISSION

                 SOURCES127
Coal Conversion
    Process
    Source of
Nickel Emissions
Nickel Species
 Status
Gasification
Liquefaction
Gasification,
Liquefaction
Quenching and
Direct Cooling

Fixed-bed Catalyst
Regeneration (Hydro-
treating and Hydro-
cracking)

Sulfur Recovery
Plant
Nickel Metal
Nickel Metal
Nickel Carbonyl
Nickel Metal
Suspected
Known
Suspected
Suspected
Liquefaction
Gasification


Coal Slurry Reactor
Oxygen Blower
Gasifier
Methanation Reactor
Air-blown Gasifier
Nickel Metal
Nickel Metal
Nickel Metal
Nickel Carbonyl
Nickel Metal
Suspected
Suspected
Suspected
Known
Suspected
aThe status column refers to the designation of whether the nickel species
 indicated is known to exist, based on some type of test data, or is
 suspected to be present, based on a knowledge of process materials and
 conditions.
                                     151

-------
Ul
                                                                          __J Known or Suspected
                                                                              Nickel Emission Sources
                    Figure  27.  Typical  flow diagram for a light hydrocarbon processing facility.128

-------
Cri
U>
                                                                                                                         1
                                                                      •j""~l«l7N67l7~"l
                                                                      J  C*T. t(IACM«  *

                                                                      —T-'
                                                 \l\l\t
                                                INICUKDIAU  I
                                              NYDRKMBON STOR-I
                                              >C[ t BUKBIHG  f

                                               4 t,  t,
_f
                                                                      •J  WUIYTIC   !
                                                                      •j HVDftOCMKING  J'
                                                                                                            Known or Suspected
                                                                                                            Nickel Emission Sources
                   Figure  28.   Typical flow diagram  for an  intermediate  hydrocarbon processing facility..128
                                                    \

-------
Ul
.p-
                                                             Known or Suspected
                                                        '——' Nickel Emission Sources
           Figure  29.  Typical  flow diagram for  a heavy hydrocarbon  processing  facility
                                                                                                   128

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       TABLE 35.  KNOWN OR SUSPECTED NICKEL EMISSION SOURCES WITHIN

                  LIGHT, INTERMEDIATE, AND HEAVY HYDROCARBON PROCESSING
                            1 ?R
                  OPERATIONS

Source of Nickel Emissions
Light Hydrocarbon Processing
Naphtha Hydrodesulfurization

Intermediate Hydrocarbon Processing
Kerosene Hydrodesulfurization

Gas Oil Hydrodesulfurization

Fluidized-bed Catalytic Cracker
Moving-bed Catalytic Cracker
Catalytic Hydrocracking

Heavy Hydrocarbon Processing
Lube Oil Hydrodesulfurization

ResiduaLOil Hydrodesulfuri-
zation

Lube Oil Processing

Fluid Coker Offgas
Decoking-Visbreaking
Asphalt Air Blowing
Nickel Species
-
Nickel Metal
Nickel Carbonyl

Nickel Metal
Nickel Carbonyl
Nickel Metal
Nickel Carbonyl
Nickel Metal
Nickel Metal
Nickel Metal
Nickel Carbonyl

Nickel Metal
Nickel Carbonyl

Nickel Metal
Nickel Carbonyl
Nickel Metal
Nickel Carbonyl
Nickel Metal
Nickel Metal
Nickel Metal
Status3

Known
Suspected

Known
Suspected
Known
Suspected
Known
Known
Known
Suspected

Known
Suspected

Known
Suspected
Known
Suspected
Known
Known
Known
The status column refers to the designation of whether the nickel species
indicated is known to exist, based on some type of test data, or is
suspected to be present, based on a knowledge of process materials and
conditions.

While hydrodesulfurization processes may use nickel-containing catalysts,
nickel emissions would not be expected to be emitted during normal
operation.  These processes are totally enclosed systems operating at
elevated temperatures and pressures.  The only possible sources of nickel
emissions from these processes would be fugitive catalyst dust emissions
during catalyst loading or unloading operations, which occur only once
every 2 to 3 years.  These operations are normally conducted so as to
control dust emissions and thus limit worker exposure.
                                   155

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     As of January 1, 1982 there were 273 active refineries in the United
States.  Although 39 states have refineries, almost 50 percent of the total
                                                                     129
number are located in three states, California, Louisiana, and Texas.     A
complete listing-of all domestic-refineries and their capacities is given in
Reference 129.

Coal and Oil Supplying

     This category of nickel emission sources consists of processes or
operations associated with supplying coal and oil to consumers.  For the
supply of coal, operations such as extraction, transportation, preparation,
distribution, and storage constitute the primary sources of nickel
emissions.  Extraction operations consist of underground, surface (basically
strip), and auger (another form of surface mining)  mining.  Transportation
operations include hauling the coal from the mining site to the coal
preparation site.   Trucks, rail cars, and conveyors are predominantly used
for this purpose.   The type of transportation used  is generally dependent on
the type of mining being conducted.  Trucks are used primarily at surface
and auger mines, while rail cars and conveyors are  used at underground
mining sites.

    .Once transported to a preparation site, coal can be processed in a
variety of ways including:

     -  crushing and screening to a maximum desired size,
     -  cleaning to remove dust and non-coal material, and
     -  drying to prepare the coal for shipment or  use.

The particular chemical and physical characteristics of a coal dictate the
amount of preparation required.

     Distribution operations involve the shipment of coal from the
preparation site to the point of consumption.  Rail cars, barges, trucks,
                                    156

-------
 slurry pipelines,  and conveyors  are  the  predominant means  of  coal
 distribution.   Lastly,  storage operations  involve  the open storage of coal
 in piles  or  the storage of  coal  in enclosed  silos  or bins  at  the consumption
  ...  130
 site.
      Nickel  emissions  from coal  supplying activities occur as part of the
 dusts associated with  the  coals.  Nickel emissions from coal dusts vary by
 region of  the  country  because  coal nickel content varies by region (see
 Table 23).   Most emissions of  this type are fugitive in nature and result
 from  wind  action on  the coal piles and coal loading/unloading activities.
 No nickel  emissions  or emission  factor data have been developed for these
 fugitive sources.  Nickel  emissions may also occur due to nickel-containing
 oil products being burned  to power trucks, trains, barges, and other heavy
 equipment used to supply coal.     Emission factors and national emissions
 associated with the  combustion of oil and petroleum products are discussed
 in the  section entitled, Coal and Oil Combustion.

      The process of  supplying oil has many of the same nickel-emitting
 operations as supplying coal, including extraction, transportation, distri-
 bution, and  storage.   Oil  processing or refining operations are also a
 component of the oil supply matrix; however, nickel emissions associated
 with  these operations  have been discussed in a previous section entitled
 Petroleum Processing.  The remaining oil supply nickel-emitting operations
 are briefly  described below.

      In the  supply of oil, extraction refers to onshore or offshore drilling
 operations.  Transportation involves moving the oil from the drilling site
 to the processing or refining site.  Pipelines, tankers,  and barges are used
 for this purpose.   Oil distribution from the processing site to the consump-
 tion market is generally accomplished by pipeline, barge,  or tank truck.
Oil supply storage operations refer to the storage of crude oil or refined
oil products in tanks.   Storage activities can occur at the refining site
and at the site of product consumption.
                                    157

-------
     Nickel emissions from supplying oil and oil products result mainly from
fuel combustion in trucks, barges, and other equipment used in extraction,
transportation, and distribution operations.  Again,  nickel emissions of
this type have been previously considered in the section, Coal and Oil
Combustion.
                                   158

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REFERENCES FOR SECTION 4

1.   Nriagu, J. 0.  Global Inventory of Natural and Anthropogenic Emissions
     of Trace Metals to the Atmosphere.  Nature.  Volume 279.  May 31, 1979.
     pp. 409-411.

2.   Nriagu, J. 0., editor.  Nickel in the Environment.  John Wiley & Sons.
     New York, New York.  1980.  pp. 94-101.

3.   Source Assessment:  Noncriteria Pollutant Emissions (1978 Update).
     United States Environmental Protection Agency, Research Triangle Park,
     NC.  EPA-600/2-78-004t.  July 1978.  pp. 94-95.

4.   Systems Applications, Inc.  Human Exposure to Atmospheric Concen-
     trations of Selected Chemicals - Volume II.  Appendix A-21-Nickel.
     (Prepared for U. S. Environmental Protection Agency, Research Triangle
     Park, NC.)  p. 21-21.

5.   Goldberg, A. J.  A Survey of Emissions and Controls for Hazardous and
     Other Pollutants.  EPA-R4-73-021.  (Prepared for U. S. Environmental
     Protection Agency, Washington, D.C.)  February 1973.  p. 115.

6.   Matthews, N. A.  Mineral Industry Surveys, Nickel in April 1979.
     U. S. Department of Interior, Bureau of Mines.  Washington, D. C.
     1979.

7.   Versar, Inc.  Production and Use of Nickel.  (Prepared for U.  S.
     Environmental Protection Agency, Washington, D.C.) Contract No.
     68-01-3852, Task 16.  March 20, 1980.  p. 7.

8.   Matthews, N. A.  Mineral Commodity Profiles - Nickel.   U.  S. Department
     of Interior, Bureau of Mines, Washington, D.C.  1979.

9.   Donaldson, H. M.; Canady, M.; Jones, J. H.  Environmental Exposure  to
     Airborne Contamination in the Nickel Industry, 1976-1977.   NIOSH
     Publication No. 78-178.  1978.

10.  Letter and attachments from Doyle, M. J., Hanna Mining Company to
     Lahre, T., U. S. EPA.  September 2, 1983.  Comments on the draft nickel
     emissions document.

11.  Air Contaminant Discharge Permit.  Oregon Department of Environmental
     Quality.  Permit No. 10-0007.  Permit Issued to The Hanna Mining
     Company and The Hanna Nickel Smelting Company.  July 23, 1981.

12;  Application for Air Contaminant Discharge Permit.   Oregon Department of
     Environmental Quality.  Hanna Mining Company.   Riddle, Oregon.  Permit
     No. 10-0007.  August 22, 1980.
                                    159

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 13.  Warner, J. S.  Occupational Exposure to Airborne Nickel in Producgin
     and Consuming Primary Nickel Products.  In press for the IARC Monograph
     on Nickel in the Human Environment.  INCO LIMITED, Toronto, Ontario,
     Canada.  1983.

 14.  Nielsen, F.^H.  Interactions of Nickel with Essential Minerals.  In:
     Nickel in the Environment, Nriagu, J. 0., ed.  Wiley-Interscience, New
     York, NY.  1980.  pp. 611-634.

 15.  Letter and attachments from Page, J. H., INCO to Sivulka, D., U. S.
     EPA.  July 14, 1983.  Comments on draft nickel health assessment
     report.

 16.  Letter and attachments from Swofford, Jr., W. G., AMAX Nickel to
     Cooper, K. D., U. S. Environmental Protection Agency.  April 24, 1981.
     Environmental inventory questionnaire.  39 pages.

 17.  Reference 7, pp. 9-13.

 18.  Letter and attachments from Kucera, C. J., AMAX Environmental Services
     to Lahre, T., U. S. EPA.  September 2, 1983.   Comments on the draft
     nickel emissions document.

 19.  Letter and attachments from Warner, J. S., Inco to Lahre, T. F.,
     U. S. EPA.  September 27, 1983.  Comments on  the draft nickel emissions
     document.

 20.  Letter and attachments from Gordy, B., AMAX Nickel to Cruse, P. A.,
     Radian Corporation.  February 20, 1984.  Nickel species in AMAX
     emissions.

 21.  Antonsen, D. H.   Nickel and Nickel Compounds.  In: Kirk-Othmer
     Encyclopedia of Chemical Technology, Volume 15.  John Wiley and Sons,
     New York, NY.  1980.  pp. 801-819.

 22.  Stedman, D.  H.  and D. A. Hikade.   Nickel Toxicology.   In:  Proceedings
     of the International Conference on Nickel Toxicology, September 3-5,
     1980, Swansen,  Wales.  Brown, S.  S. and F. W. Sunderman,  Jr.,  eds.
     Academic Publishing, London.  1980.  pp. 183-186.

 23.  Matthews, N. A.  and S. F. Sibley, Bureau of Mines. Nickel - A Chapter
     from Mineral Facts and Problems.   Preprint from Bulletin  671.   1980.
     U. S. Department of the Interior, Washington, D.C.

24.  Burton, D.  J.,  et al.  (Radian Corporation) Process and Occupational
     Safety/Health Catalogue - Secondary Nonferrous Smelting Industry.
     (Prepared for National Institute  for Occupational Safety  and Health,
     Cincinnati,  Ohio).   NIOSH Contract No.  200-77-0008.  July 1979.
     pp.  211-220.
                                    160

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 25.  Nack, H., et al.   (Battelle-Columbus Laboratories) Development of an
     Approach to Identification of Emerging Technology and Demonstration
     Opportunities.  EPA-650/2-74-048.   (Prepared for U. S. Environmental
     Protection Agency, Washington, D.C.)  May 1974.  pp. C-131 to C-137.

 26.  Anderson, DT  Emission Factors for  Trace Substances.  EPA-450/2-73-001.
     U. S. Environmental Protection Agency, Research Triangle Park, N. C.
     December 1973.  pp. 8-1 to 8-9.

 27.  Reference 25, pp. C-12 to C-29, C-39 to C-9b, and C-165 to C-184.

 28.  Reference 7, pp. 13-16.

 29.  Developmental Document for Interim  Final and Proposed Effluent
     Limitations Guidelines and New Source Performance Standards for the
     Primary Copper Smelting Subcategory and the Primary Copper Refining
     Subcategory of the Copper Segment of the Nonferrous Metals
     Manufacturing Point Source Cat'egory.  U. S. Environmental Protection
     Agency, Washington, D.C.  EPA-440/1-75/0326.  1975.

 30.  Radian Corporation.  Industry Profile - Phase I Study of Nickel,
     Volume I.  (Prepared for Occupational Safety and Health Administration
     under Contract No. J-9-F-9-0007.)  August 31, 1980.  pp. 90-105.

 31.  Kaplan, K. J., £Jt al.  Feasibility and Cost Study of Engineering
     Controls for Nickel Exposure Standards.  Performed by Industrial Health
     Engineering Associates, Inc.  Minneapolis, Minnesota.  1979.

 32.  Envirex.  An Evaluation of Occupational Health Hazard Control
     Technology in the Foundry Industryl.  (Prepared for NIOSH.)  NIOSH
     Publication No. 79-114.  Milwaukee, Wisconsin.   1978.

 33.  Letter and attachments from Young, E. F., Jr.,  American Iron and Steel
     Institute to Lahre, T. F., U. S.  EPA.  November 3,  1983.  Comments on
     draft nickel emissions document.

 34.  Compilation of Air Pollutant Emission Factors,  AP-42.  Third Edition.
     Supplement 14.   U.  S. Environmental Protection Agency.   Research
     Triangle Park,  N.  C.   May 1983.   pp. 7.5-8.

 35.  Electric Arc Furnaces and Argon-Oxygen Decarburization Vessels in the
     Steel Industry - Background Information Document.   EPA-450/3-82-020a.
     U. S. Environmental Protection Agency.   Research Triangle  Park,  N. C.
     July 1983.   pp.  3-37, 4-3, and 4-23 - 4-24.

36.  Characterization,  Recovery,  and Recycling of EAF Dust.   U.  S.  Depart-
     ment of Commerce.   Project No.  99-26-09886-10.   February 1982.
                                    161

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37.  Jacko, R. B. and D. W. Neuendorf.   Trace Metal Particulate Emission
     Test Results from a Number of Industrial and Municipal Point Sources.
     Journal of the Air Pollution Control Association.   Volume 27, October
     1977.  pp. 989-994.

38.  Koponen, M., et al.  Chromium and  Nickel Aerosols  in Stainless Steel
     Manufacturing, Grinding, and Welding.  American Industrial Hygiene
     Journal.  42: 596-601.  August 1981.

39.  Emission Test Report, Al Tech Specialty Steel Corporation.  U. S.
     Environmental Protection Agency, Research Triangle Park,  NC.  EMB
     report no. 80-ELC-7.  1981.

40.  Letter and attachments from Andolina, A. Y., Al Tech Specialty Steel to
     Iverson, R. E., U. S. EPA.  August 20, 1980.  Emissions data from
     stainless steel manufacturing.

41.  Sahagian, H., et al-.  Inspection Manual for Enforcement of New Source
     Performance Standards - Steel Producing Electric Arc Furnaces.  U. S.
     Environmental Protection Agency, Washington, DC.  EPA report
     no. EPA-340/1-77-007.  1977.

42.  Brough, J. R. and W. A. Carter.  Air Pollution Control of an Electric
     Furnace Steel Making Shop.  Air  Pollution Control  Association Journal.
     22: 167-171.  1972.

43.  Law, S. L., et al.  Characterization of steelmaking dusts from electric
     arc furnaces.  Bureau of Mines,  Avondale Research  Center, Avondale, MD.
     Report of investigations 8750.  1983.

44.  Reference 4, pp. 21-13 to 21-15.

45.  Kirk-Othmer Encyclopedia of Chemical Technology.  Third Edition.
     Volume 15.  John Wiley & Sons, Inc.  New York.  1980.  p. 789.

46.  Reference 30, pp. 125-134.

47.  Phillips, N. (Radian Corporation).  Summary of Nickel Emissions.
     Contract No. 68-01-3249, Task 10.   (Prepared for U. S. Environmental
     Protection Agency.  Washington,  D. C.).  September 30, 1976.

48.  Graham, A. K., Editor.  Electroplating Engineering Handbook, Third
     Edition.  Van Nostrand Reinhold  Company.  New York.  1977.

49.  Patty, F. R.  Industrial Hygrene and Toxicology, Third Edition -
     Volume I.  Wiley Interscience Publishing.  New York.  1978.

50.  Material provided by Harshaw Chemical Company to A. V. Simonson, Radian
     Corporation.  Salt Lake City, Utah.  June 1980.
                                    162

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 51.   National  Institute  for Occupational  Safety  and Health.   Health  Hazard
      Determination  Report  No.  78-96-595.  May  1979.

 52.   Reference 7, pp.  26-27.

 53.   Trip Report".   Hunt, D.  and  Fjeldsted,  B., Radian  Corporation  to General
      Electric  Battery  Plant.   Gainesville,  Florida.  April 28,  1980.

 54.   Catotti,  et. .al..   Nickel-Cadmium  Battery Application; Engineering
      Handbook.   Second Edition.  General  Electric Company Battery  Business
      Department.  Gainesville, Florida.   1975.

 55.   Telecon.   Hunt, D., Radian  Corporation with Rohbam, D.,  Gould.
      October 24, 1979.  Use  of nickel in  battery manufacturing.

 56.   Gould, Inc.  NICAD Batteries Catalogue.  Portable Battery Division.
      St. Paul,  Minnesota.   1976.

 57.   Telecon.   Hunt, D., Radian  Corporation with Smith, E., Union  Carbide.
      October 18, 1979.  Use  of nickel in  battery manufacturing.

 58.   Telecon.   Hunt, D., Radian  Corporation with Patterson, R. L., Union
      Carbide.   October 18,  1979.  Use  of  nickel  in battery manufacturing.

 59.   Telecon.   Hunt, D., Radian  Corporation with Northern, P., Saft America.
      October 19, 1979.  Use of nickel  in  battery manufacturing.

 60.   Telecon.   Hunt, D., Radian  Corporation with Pierce, D., Marathon.
      October 19, 1979.  Use of nickel  in  battery manufacturing.

 61.   Health Hazard Elevation Determination  - Marathon Battery Company, Waco,
      Texas.  National Institute  for Occupational Safety and Health.  Report
      No. 74-16-272.  March 1976.

 62.   Telecon.   Hunt, D., Radian  Corporation with Merta, R., McGraw Edison.
      October 19, 1979.  Use of nickel  in battery manufacturing.

 63.   Telecon.   Hunt, D., Radian  Corporation with Stutzback, R., Nife.
      October 4, 1979.  Use of nickel in battery manufacturing.

 64.   Telecon.   Campbell, J., Radian Corporation with Devour, V., Eagle
      Pitcher.  March 7, 1980.  Use of nickel in battery manufacturing.

65.  Telecon.  Hunt, D.,  Radian Corporation with Bradley, M., General
     Electric.   October 4,  1979.   Use of nickel in battery manufacturing.

66.  Telecon.  Hunt, D.,  Radian Corporation with Barkis,  W., Gates Energy.
     November 1979.   Use of nickel in battery manufacturing.
                                   163

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67.  Assessment of Industrial Hazardous Waste Practices:  Storage and
     Primary Batteries Industries.  Versar, Inc.  Springfield, Virginia.
     (Prepared for U. S. Environmental Protection Agency, Washington,
     D. C.).  1975.

68.  Letter and attachments from Radakovich, R., McGraw-Edison to McRorie,
     A., North Carolina Division of Environmental Management.  November 15,
     1978.  Responses to permit application.

69.  Air Pollutant Survey, General Electric Company, Battery Business
     Department, Hague, Florida.  Sholtes and Koogler, Inc.   Gainesville,
     Florida.  1981.

70.  Reference 7, pp. 31-33.

71.  Reference 7, pp. 27-30.

72.  Submission No. 51 to Occupational Safety and Health Administration
     Docket H-110.  Metal Finishers Suppliers' Association.

73.  Multi-media Assessment of the Inorganic Chemicals Industry.   Versar,
     Inc.  Springfield, Virginia.  (Prepared for U.  S. Environmental
     Protection Agency, Washington, D. C.).  1979.

74.  International Agency for the Research of Cancer.  IARC  Monographs
     11.75-112, Nickel and Nickel Compounds.  1976.

75.  Antonsen, D. H. and Springer, D. B.   Kirk-Othmer Encyclopedia of
     Chemical Technology.  Volume 13.  John Wiley &  Sons, Inc.  New York.
     pp. 753-763.

76.  1982 Chemical Buyer's Guide.  Published by McGraw-Hill, Inc.  New York,
     New York, 1981.  pp. 9-40.

77.  The Thomas Register of American Manufacturers and Thomas Register
     Catalog File.  70th Edition.  Thomas Publishing Company.  New York, New
     York.  1980.  pp. 1953-1954.

78.  Edwards, L. 0., e± al_. (Radian Corporation). Trace Metals and Station-
     ary Conventional Combustion Sources  (SCCPs).  (Prepared for U.S.
     Environmental Protection Agency, Research Triangle Park, NC.)  EPA
     Contract No. 68-02-2608.  April 1980.  pp. 3-1  to 3-12.

79.  DeAngelis, D. G. (Monsanto Research).  Emissions from Coal-fired
     Residential Combustion Equipment. Paper No. 79-60.3, Presented at the
     72nd Annual Meeting of the Air Pollution Control Association.
     Cincinnati, Ohio, June 24-29, 1979.
                                   164

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80.  Letter from Blum, E. D., Union Oil to Lahre, T., U. S. EPA. January 18,
     1984.  Nickel and chromium levels in oils.

81.  Letter and attachments from Blum, E. D., Union Oil to Lahre, T., U. S.
     EPA.  February 27, 1984.  Nickel and chromium levels in distillate
     oils.      '                "

82.  Surprenant, N. F., et al.  Emissions Assessment of Conventional
     Stationary Combustion Systems:  Volume IV..  Commercial/Institutional
     Combustion Sources.  October 1980.  (Prepared for IERL, U. S. EPA,
     Research Triangle Park, NC).  EPA Contract No. 68-02-2197.

83.  Cato, G. A., et al.  Field Testing:  Application of Combustion
     Modifications to Control Pollutant Emissions from Industrial Boilers -
     Phase 1.  EPA-650/2-74-078a.  October 1974.

84.  Barrett, R. E., et al.  Field Investigations of Emissions from
     Combustion Equipment for Space Heating.  EPA-R2-73-084a and API
     Publication 4180.  June 1973.

85.  Surprenant, N. F., et_ _ali.  Emissions Assessment of Conventional
     Stationary Combustion Systems; Volume 1.  Gas- and Oil-fired
     Residential Heating Sources.  EPA-600/7-79-0296.  May 1979.  p. 6.

86.  Letter from Holt, E. L., Exxon to Cruse, P. A., Radian Corporation.
     March 23, 1984.  Nickel emissions from oil combustion.

87.  Baig, S., et_ al.  (TRW, Inc.) and T. Hurley, e± al. (Radian).  Conven-
     tional Combustion Environmental Assessment.  (Prepared for U. S.
     Environmental Protection Agency, Research Triangle Park,  NC.)  EPA
     Contract No. 68-02-3138.  July 1981.  p. 3-51.

88.  Reference 87, pp. 3-7 to 3-15.

89.  Lim, M.  Y.  Trace Elements from Coal Combustion - Atmospheric
     Emissions.  IEA Coal Research Report No. ICTIS/TROS.   London, England.
     May 1979.  pp. 17-24.

90.  Reference 78, p. 4-18.

91.  Reference 87, p. 3-53.

92.  Reference 87, pp. 5-11 to 5-23.

93.  Reference 78, pp. 4-29 to 4-55.
                                    165

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94.  Shih, C. C., et al.  Emissions Assessment of Conventional Stationary
     Combustion Systems:  Volume III, External'Combustion^Sources for
     Electricity Generation.  (Prepared for Industrial Environmental
     Research Laboratory, U. S. EPA, Research Triangle Park,  NC).  EPA
     Contract No. 68-02-2197.  November 1980.

95.  Krishnan, E. R. and G. V. Hellwig.  Trace Emissions from Coal and Oil
     Combustion.  Environmental Progress.  1(4):  290-295.   1982.

96.  Surprenant, N. F., et al.  Emissions Assessment of Conventional
     Stationary Combustion Systems:  Volume V, Industrial  Combustion Sources
     (Draft Final Report).  (Prepared for Industrial Environmental Research
     Laboratory, U. S. EPA, Research Triangle Park,  NC).  EPA Contract No.
     68-02-2197.  October 1980.

97.  Levy, A., et al.  A Field Investigation of Emissions  from Fuel Oil
     Combustion for Space Heating.   API Publication  4099.   November 1, 1971.

98.  Reference 95, pp. 4-1 to 4-66.

99.  Henry, W. M. and K. T. Knapp.   Compound Forms of Fossil  Fuel Fly Ash
     Emissions.  Environmental Science and Technology.   14(4):  450-456.
     1980.

100. Gendreau, R. M., et al.  Fourier Transform Infrared Spectofscopy for
     Inorganic Compound Speciation.  Environmental Science and  Technology.
     18(8): 990-995.  1980.

101. Blaha, J. J., et al.  Raman Microprobe Analysis of Stationary Source
     Particulate Pollutants.  Reports of EPA Contracts  EPA-1AG-D7-F1186 and
     EPA-1AG-78-D-F0367.  Available from NTIS, Springfield, Virginia,
     PB80-202708.

102. Letter and attachments from Page, J. H., Inco to Sivulka,  D.  J., U.  S.
     EPA.   July 14, 1983.  Comments on nickel health document.

103. Hulett, L. D., Jr., et al.   Chemical Species in Fly Ash  from
     Coal-buring Power Plants.  Science.  210: 1356-1358.

104. Klein, D. H., et al.  Pathways of 37 Trace Elements Through  Coal-fired
     Power Plants.  Environmental Science and Technology.   9(10):  973-979.
     October 1975.

105. The 1982 U. S. Industrial Outlook for 200 Industries  with  Projections
     for 1986.  January 1982.   U.  S.  Department of Commerce,  p.  14.

106. Compilation of Air Pollutant Emission Factors.   Third Edition.   U.  S.
     Environmental Protection Agency, Research Triangle Park, NC.   August
     1977.  pp. 8.6-1 to 8.6-4.
                                    166

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107. Reference 78, p. 3-20.

108. Marr, H. E. et_ a±.  Trace Elements in the Combustible Fraction of Urban
     Refuse.  U. S. Bureau of Mines.  College Park Metallurgy Research
     Center, College Park, Maryland.

109. Gerstle, R. W. and D. N. Albrinck.  Atmospheric Emissions of Metals
     from Sewage Sludge Incineration.  Journal of the Air Pollution Control
     Association.  32(11): 1119-1123.

110. Helfand, R. M. (Mitre Corp.).  A Review of Standards of Performance for
     New Stationary Sources-Incinerators.  EPA-450/3-79-009.  (Prepared for
     the U. S. Environmental Protection Agency, Research Triangle Park, NC).
     March 1979.  p. 4-10.

111. Helfand, R. M. (Mitre Corp.).  A Review of Standards of Performance for
     New Stationary Sources - Sewage Sludge Incinerators.  EPA-450/2-79-010.
     (Prepared for the U. S. Environmental Protection Agency, Research
     Triangle Park, NC).  March 1979.  p. 4-11.

112. Environmental Engineers' Handbook, Volume 3 - Land Pollution.  Edited
     by Liptak, B. G.  Published by Chilton Book Company,  Radnor,
     Pennsylvania.  1974.  pp. 253-267.

113. Reference 106, p. 2.1-3.

114. Nagda, N. L., et_ ad.  Emission Factors and Emission Inventories for
     Carcinogenic Substances.  Paper presented at the 72nd Annual Meeting of
     the Air Pollution Control Association, Cincinnati, Ohio.  June 24-29,
     1979.

115. Cross, Jr., F. L., et_ a^.  Metal and Particulate Emissions from Incin-
     erators Burning Sewage Sludge and Mixed Refuse.  Paper presented at the
     1970 National Incinerator Conference of the American Society of Mechan-
     ical Engineers.

116. Greenberg, R. R., e± a±.  Composition and Size Distribution of Parti-
     cles Released in Refuse Incineration.  Environmental Science and
     Technology.  12(5): 566-573.

117. Greenberg, R. R., ej^ al.  Composition of Particles Emitted From the
     Nicosia Municipal Incinerator.   American Chemical Society.   12(12):
     1329-1332.

118. Henry, W. M., et  al.  Inorganic Compound Identifications of Fly Ash
     Emissions from Municipal Incinerators.  (Prepared for Environmental
     Sciences Research Laboratory, U. S.  EPA, Research Triangle Park, NC).
     EPA Contract No.  68-02-2296.   1982.
                                    167

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119. Reference 110, pp. 4-2 to 4-3.

120. Reference 111, pp. 4-4 and 5-2.

121. Compilation of Air Pollutant Emission Factors.  Third Edition - Supple-
     ment 11.  Ul S. Environmental Protection Agency, Research Triangle
     Park, NC.  October 1980.  pp. 7.2-1 to 7.2-4.

122. Reference 4, p. 21-16.

123. Coke Wet Quenching - Background Information for Proposed Standards,
     Draft Report.  Emission Standards and Engineering Division,  U.  S.
     Environmental Protection Agency, Research Triangle Park, NC. May  1981.
     pp. 9-18 to 9-21.

124. Telecon.  Acurex Corporation with Clifton, R.  A., U.  S.  Bureau  of
     Mines.   July 1980.  Asbestos emissions.

125. Telecon.  Acurex Corporation with Wood,  G., U. S. Environmental Pro-
     tection Agency.  July 1980.   Asbestos emissions and controls.

126. Laney,  M. N. and L.  A. Conrad.  Review of National Emission  Standard
     for Asbestos (Draft).  (Prepared for Emission  Standards  and  Engineering
     Division, U. S. EPA, Research Triangle Park, NC).  EPA Contract No.
     68-02-3056.   October 1981.

127. Cavanaugh, G., et al.  Potentially Hazardous Emissions from  the Ex-
     traction and Processing of Coal and Oil.   EPA-650/2-75-038.   (Prepared
     for the U. S. Environmental  Protection Agency, Research  Triangle Park,
     NC). April 1975.  pp. 84-108.

128. Reference 127, pp. 10-61.

129. Oil and Gas Journal.  Volume 80, No.  12.   March 22,  1981.  pp.  130-151.

130. Toxic Trace Pollutant Coefficients for Energy  Supply  and Conversion.
     Hittman Associates,  Columbia, Maryland.   (Prepared for Energy Research
     and Development Administration,  Washington, D.C.)   Contract  No.
     EX-77-C-03-1296.   September  1977.
                                    168

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                                  SECTION 5

                           SOURCE TEST PROCEDURES

     Specific sampling and analysis source test procedures have not been
published by the U. S. EPA for suspected nickel emissions sources.  The
sampling and analysis methods presented in this section represent a
collection of nickel air emission detection and quantification techniques
that have been published in the open literature as viable methods.  The
presentation of these published methods in this report does not constitute
endorsement or recommendation or signify that the contents necessarily
reflect the views and policies of the U. S. EPA.

LITERATURE REVIEW OF SAMPLING METHODS

     Trace amounts of nickel can be determined using a sampling train
                             1 2
developed by Hamersma, et al. '   This system is designed to sample under
high pressure environments under isokinetic conditions.  The sampling train
consists of (1) a modified ASTM liquid sampling probe, (2) an impinger for
condensing water and oil vapors in an ice bath under pressure, (3) a
pressure reduction mechanism, and (4) a second impinger series where nickel
and its compounds are expected to be found.  The contents of the second set
of impingers are:  3M H^ in the first; 3M H20, 0.2 M (NH^^Og, and
0.02 M AgNO. in the second and third; and Drierite for drying the sampling
gases in the fourth.  The sampling train is capable of operating at temper-
atures up to 500°C (932°F) and pressures greater than 2000 kPa (300 psig) .
                           3           3
Sampling rates of 2 to 10 m  (71-353 ft ) of gas over a 1 to 4 hour period
                                                                    o
are used.  The detection limit for nickel in a gas stream is 60 yg/m .
                                    169

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     A  similar  system  for  flue gas sampling for trace inorganic materials at
atmospheric pressures  was  designed by Flegal, £t_ al.1'3  The sampling  train
consists of a standard Aerotherm high volume stack sampler  (HVSS) modified
in three areas:  ,_(!) the probe is. lined with a removable -inner liner made of
Kapton  polyimide film  to prevent nickel, chromium, and other components in
the stainless steel probe  from contaminating the particulate catch; (2) a
Gelman  Spectrograde type A glass fiber filter is used as the filtering
medium, and (3) a special  oxidative impinger system is used to sample
vapors.  The oxidative system consists of four impingers:  one impinger with
3M H202, two impingers with 0.2 M (NH^^Og plus 0.02 M AgN03» and a fourth
impinger with Drierite.  The impinger nozzles are coated with Teflon to
prevent corrosion of the stainless steel components due to the oxidative
solutions.  The system is  designed to operate in a flue gas stream at
temperatures up to 270°C (518°F) and a sampling rate of up to 90 liters per
minute  (3 cfm).

     EPA Method 5, as modified effective September 19, 1977, has been used
                      4
to sample nickel dust.   This train consists of the following components:  a
stainless steel or glass probe nozzle with an appropriate liner (e.g.,
borosilicate or quartz glass) capable of maintaining a gas temperature at
the exit of 120°C ± 14°C (248°F ± 57°F), an S type pitot tube,  a
differential pressure gauge, a borosilicate glass filter holder, a filter
heating system capable of maintaining a temperature of 120°C ±  14°C during
sampling, and a condenser system consisting of four impingers for
determining the stack gas moisture content.  The first and second impingers
in the condenser system are of the modified Greenberg-Smith design and
contain known amounts of water;  the third is the same design but empty; and
the fourth is a regular Greenberg-Smith impinger filled with a  desiccant
(silica gel, calcium sulfate, or any other appropriate material).   The
system also includes a metering system consisting of a vacuum gauge,
leak-free pump,  thermometer, and a volume measuring gas meter,  a barometer,
and gas density determination equipment.   The sample is recovered from the
                                    170

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system by washing the nozzle and probe liner with acetone and combining the
wash eventually with the participate matter collected on the filter and
filter holder.

     Peters, et_ al. proposed and tested a sampling train similar to Method 5
for particulate sampling.   This system is all glass in order to avoid metal
contamination.  Stack emissions are isokinetically sampled from the source
                                      3                    3
at an appropriate rate [(0.014-0.028 m /min), (0.49-0.99 ft /min)] and for a
sufficient period to collect a 24-hour representative sample (recommended
minimum sampling period is 2 hours).  The main components in the system are
a stainless steel or glass nozzle with sharp, tapered leading edge; a
sheathed borosilicate glass probe with a heating system capable of
maintaining a minimum gas temperature in the range of the stack temperature;
a pitot tube type S, or equivalent, attached to probe to monitor stack gas
velocity; a differential pressure gauge to measure velocity head to within
10 percent of the minimum value; a filter holder made of borosilicate glass;
four Greenberg-Smith impingers; a metering system; and a barometer.  The
first two impingers contain 0.1 M nitric acid, the third impinger is left
empty, and the fourth contains 200 g (0.44 Ib) of preweighed silica gel.
The filter is a high efficiency Gelman Microquartz fiber filter (99.95
percent efficiency on 0.3 dioctyl phthalate smoke particles.)

     EPA Level 1 Environmental Assessment Flue Gas Sampling Trains (SASS)
has been the most widely used system for sampling inorganics, including
nickel and nickel compounds.   It is mainly designed to collect large
quantities of particulate matter, size classified in the ranges of > lOp,
3-10y, l-3y and ly in diameter, as well as inorganic volatile species that
can be liquid absorbed.  The sampling train consists mainly of a stainless
steel probe, which enters an oven module containing the three size
fractionating cyclones and a filter, an impinger system containing
(NH.KS-S, AgNO.,, high purity water and H_0?, and a high volume vacuum pump.
It is designed to operate up to 205°C (401°F) in flue gas streams and to
operate unattended.
                                    171

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       A high-volume filtration sampler used by the National Air Sampling
  Network was found to be applicable for particulate sampling, but does not
  catch volatile compounds like nickel carbonyl.7

  LITERATURE REVIEW OF ANALYTICAL PROCEDURES

       Nickel can be detected  colorimetrically'using dimethylglyoxime  as  the
  complexing agent.    West,  et  al.  adapted  the  ring-oven technique  for the
  determination  of nickel  particulates using dimethylglyoxime  as the
  complexing agent.    Neutron activation analysis (NAA) is used to  determine
  nickel levels  at the microgram  level, and  has a detection limit of 0.7 yg.10
  Atomic absorption  spectrophotometry (without flame) (AAS) or X-ray
  fluorescence spectrometry  (XRF) have even  lower detection limits.  X-ray
  fluorescence^spectrometry is fast and has a detection limit of
 0.01 yg/cm  .    Flame Emission Spectrophotometry (FES) is also used,  and
 capable of detecting 0.03 pg/ml nickel in solution.12

      Atomic Absorption Spectrophotometry with flame (AAF)  is by  far the  most
 popular technique for measuring nickel in solution.  The  reported detection
 limit is  0.005  yg/ml,   and the linear range  for accurate measurement is
 reported  as 0.2-5 yg/ml at  a  232.0 nm  wavelength setting and  an oxidizing
 air/acetylene flame are used.13   In a  10 ml sample,  the mass  required for
 accurate  measurement is 2.50  pg.   The  analysis by AAF  is especially appro-
 priate  for  nickel because there  are no known interferences.   However,  it was
 reported  that a hundred fold excess of iron, manganese, chromium,  copper,
 cobalt or zinc  may  decrease the  absorbance  recorded  for nickel by  as much  as
 12 percent.     Proper burner elevation and  use of an oxidizing flame can
minimize  this effect.  High solids content  in the aspirated solution will
cause increased nonspecific absorbance at the 232 nm line setting.14
Thompson, et al.15 reported that the National Air Pollution Control
Administration found that the minimum detection limit for nickel by AAS is
0.004 yg/m  based on a 2,000 m3 (70,600 ft3) air sample.
                                    172

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     Inductively coupled argon plasma  (ICAP) has gained prominence recently
as a fast and reliable analytical tool for nickel determination when multi-
element analysis is required.16  The detection limit using the 231.6 nm line
is 15 ug/1.17

     For the determination of volatile nickel carbonyl, Brief, et. al. has
described the following methods:18

     (1)  An air sample can be drawn through a saturated solution of sulfur
          in trifluoroethylene.   The sulfur reacts  with nickel to form a
          precipitate.   Spectrographic examination  is sensitive to
          0.0003 ppm nickel carbonyl.
     (2)   An air sample may be drawn through a  tube  containing red mercuric
          oxide  at  200°C  (392'F),  and  the  liberated  mercury may be de-
          termined  spectrographically.  A  parallel stream  of  air  is drawn
          through an oxidizing reagent  to  convert the CO to CO ,  and the
          stream is passed  over mercuric oxide; the  liberated  mercury is
          again  determined  spectrographically.  The  difference  in  the
          amounts of mercury vapor measured corresponds to the nickel
          carbonyl content  in  the air.  A sensitivity of 0.0014 ppm is
         reported.
    (3)  Nickel carbonyl may be absorbed in chloramine.  The nickel deter-
         mination is accomplished colorimetrically using dimethylglyoxime.
         For a 30-minute sample,  at the suggested sampling rate of
         0.5 liters per minute,  a sensitivity of  0.01 ppm is obtained.
    (4).  Another colorimetric method uses  iodine  in carbon tetrachloride as
         the collection medium.   The nickel is  colored  with  dimethyl-
         glyoxime.   A  sensitivity of 0.1 ppm to nickel  carbonyl is claimed.
    (5)   Nickel  carbonyl may be collected  in dilute  sulfuric  acid followed
         by  spectrophotometry using  sodium diethyl-dithiocarbamate as  the
         coloring agent.
    (6)  Nickel  carbonyl may  be collected  in  dilute  hydrochloric  acid in a
        midget  impinger [0.0028 m3/min (0.1  ft3/min) for  30 minutes].  The
                                  173

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           nickel is complexed with alpha-furildioxime and extracted with
           chloroform, and the content is determined speetrophotometrically.
           The method is sensitive to 0.0008 ppm.

      A field method described by Kobayashi appears to be appropriate for
 analysis of nickel carbonyl in a sampling train.19  The sample is drawn
 through a tube filled with silica gel impregnated with 0.5  percent gold
 chloride.  In the presence of nickel carbonyl,  the silica gel  changes  from
 light yellow to bluish-violet.   The  concentration of nickel carbonyl is a
 function of the length of  the colored layer.  The useful range of a 100 ml
 sample is 200 to 600  ppm.   By measuring  the minimum volume  of  test gas
 needed to color the silica gel at  a  constant  sampling  rate,  the concen-
 tration of nickel carbonyl to 3  ppm  can  be determined.

      In another method, the test air  is  drawn at  0.5 liter per minute
 through an absorption  tube containing  two 15 mm diameter filter papers  and
 then  through  two absorption vessels with porous plates.20  Each plate
 contains  3 ml of a  1.5 percent solution of chloramine-B in alcohol.  The
 chloramine-B  solution retains the nickel carbonyl vapor.  The colored vapor
 is compared with standards.  The sensitivity of the method is 1 g of nickel
 carbonyl, and the error does not exceed 10 percent.

SUGGESTED SAMPLING AND ANALYTICAL PROCEDURES

     The modified EPA Method 5 combined with atomic absorption  with flame is
the suggested approach because:

          The sampling train is  capable of collecting both the  volatile  and
          nonvolatile  nickel compounds.
          Based on nine replicate experiments  the  precision  of  the nickel
          measurement  is 11.4  percent and the  accuracy  3.9 percent at about
          100  jag level.
                                    174

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          The quartz filter used is effective in trapping nickel parti-
          culate.
          The impinger system (0.1 M HNCL) is appropriate for nickel
          sampling and allows for modification without additional cost if
          special trapping solutions are to be used for organometallic
          components.
          AAF detection method is interference free and accurate for nickel
          analysis using air/acetylene and the 232.0 nm line.

Reference 21 cautions that if nickel-containing particulate matter
originates from high temperature processes, they are likely to be very
refractory, in which case, nitric acid alone is not an adequate treatment.
Perchloric acid or a fusion is often required to get high nickel recovery.
                                    175

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REFERENCES FOR SECTION 5                                 -

1.   Technical Manual for Inorganic Sampling and Analysis.   U.  S.  Department
     of Commerce.  NTIS, PB-266 842.  TRW Defense and Space Systems Grouji,
     Redondo Beach, CA.

2.   Hamersma, J. W., and S. R. Reynolds.  Tentative Procedures for Sampling
     and Analysis of Coal Gasification Processes.  TRW Systems  Group,  EPA
     Contract Number 68-02-1412. March 1975.

3.   Flegal, C. A., M..L. Kraft, C. Lin,  R. F.  Maddalone, J. A. Starkovich,
     and C. Zee.  Procedures for Process  Measurements of Tract  Inorganic
     Materials.  TRW Systems Inc.  EPA Contract Number 68-02-7393.  July
     1975.

4.   Federal Register.  42(160) :41776. August  8, 1977.

5.   Peters, E. T., J. R. Valentine, and  J. W.  Adams.  Metal Particulate
     Emissions from Stationary Sources-Volume 1.  Arthur D. Little, Inc.
     EPA Contract Number 68-02-1219.  1977.

6.   Duke, K. M., M. E. Davis, and A.  J.  Dennis.  IERL-RTP  Procedures
     Manual:  Level 1.  Environmental Assessment Biological Tests  for  Pilot
     Studies.  EPA-600/7-78-201.  U. S. Environmental Protection Agency,
     Research Triangle Park, North Carolina.  1978.

7.   Air Pollution Measurements of the National Air Sampling Network-
     Analysis of Suspended Particulates,  1957-1961.   U.  S.  Department  of
     Health, Education, and Welfare.  No. 978.   1962.

8.   Kielczewski, W., and J. Supinski. Determination of Microgram
     Quantities of Nickel by the Impregnated-Paper Method.   Chem.  Anal.
     (Warsaw), 10(4):667, 1975.

9.   West, P. W., et^ al_.  Transfer, Concentration, and Analysis of Collected
     Air-Borne Particulates Based on Ring Oven  Techniques.   Anal.  Chem.
     32(8):943-946, 1960.

10.  Activation Analysis, Gulf General Atomic,  San Diego, CA.

11.  Wagman, J., R. L. Bennett, and K. T. Krepi.  X-ray Fluorescence for
     Rapid Elemental Analysis of Particulate Pollutants. EPA-600/2-76-033.
     U. S. Environmental Protection Agency.

12.  Pickett, E. E., and S. R. Lpirtyoham.  Emission Flame  Photometry-A  New
     Look at an Old Method.  Anal. Chem.  41:29A. 1969.

13.  Chritian, G. D., and F. J. Feldman.   Atomic Absorption Spectroscopy.
     Wiley-Interscience, New York. 1970.
                                    176

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 14.  Occupational Exposure to Inorganic Nickel.  National Institute of
     Occupational Safety and Health.  1977.

 15.  Thompson, R. J., G. B. Morgan, and L. J. Purdue.  Analyses of Selected
     Elements in Atmospheric Particulate Matter by Atomic Absorption.
     Preprint presented at the Instrument Society of America Symposium, New
     Orleans, LA, May 5-7.  1969.

 16.  Federal Register.  44(233):69559.  December 3, 1979.

 17.  Inductively Coupled Plasma Optical Emission Spectroscopy Prominent
     Lines.  EPA-600/4-79-017.  U. S. Environmental Protection Agency.

 18.  Brief, R. S., F. S. Venable, and R. S. Ajemian.  Nickel Carbonyl:   Its
     Detection and Potential for Formation.  Am. Ind. Hyg.  Assoc.  J.  26:72.
     1965.

 19.  Kobayashi, Y.  Rapid Method for the Determination of Low Concentrations
     of Nickel Carbonyl Vapor.  Yuki Gosei Kayaku Kyokai Shi.   15:466.
     i y j / •

20.  Belyakov, A.  A.   The Determination of Microgram Quantities of Nickel,
     Nickel Tetracarbonyl and Its Solid Decomposition Products in  Air
     Zavodsk.  Lab.  26:158.   1960.

21.  Letter and attachments  from Warner, J.  S.,  Inco to  Lahre,  T.,  U. S.
     EPA.  September 27, 1983.  Comments on draft final  nickel report.
                                    177

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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
 . REPORT NO.
  EPA-450/4-84-007f
                              2.
                                                            3. RECIPIENT'S ACCESSION NO.
 .. TITLE AND SUBTITLE
  LOCATING AND  ESTIMATING AIR EMISSIONS FROM SOURCES  OF
  NICKEL
             5. REPORT DATE
              Mareh 1984
             6. PERFORMING ORGANIZATION CODE
 . AUTHOR(S)
  Radian Corporation
  3024 Pickett  Road. Durham, NC   27705
                                                            8. PERFORMING ORGANIZATION REPOI
9. PERFORMING ORGANIZATION NAME AND ADDRESS
                                                            10. PROGRAM ELEMENT NO.
                                                            11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
  Office Of Air Quality Planning  And Standards
  U. S. Environmental Protection  Agency
  MD 14
  Research  Triangle, NC  27711          	
                                                             13. TYPE OF REPORT AND PERIOD COVERED
              14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
  EPA Project Officer:  Thomas  F.  Lahre
16. ABSTRACT
            To assist groups  interested in  inventorying air emissions of various
       potentially toxic  substances, EPA is  preparing a series  of  documents such
       as this to compile available information on sources and  emissions of these
       substances.  This  document deals specifically with nickel.   Its intended
       audience includes  Federal, State and  local air pollution personnel and
       others interested  in locating potential emitters of nickel  and in making
       gross estimates of air emissions therefrom.

            This document presents information on 1) the types  of  sources that may
       emit nickel, 2) process variations and  release points  that  may be expected
       within these sources,  and 3) available  emissions information indicating the
       potential for nickel release into the air from each operation.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS  C.  COS AT I Held/Group
  Nickel
  Air  Emission Sources
  Locating Air Emission  Sources
  Toxic Substances
'18. DISTRIBUTION STATEMENT
                                               19. SECURITY CLASS (ThisReport!
                            21. NO. OF PAGES
                             185
                                               20. SECURITY CLASS (This page)
                                                                           22. PRICE
 EPA For.Ti 2220-1 (R«v. 4-77)   PREVIOUS EDITION is OBSOLETE

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