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
+
+
-------
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
-------
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
-------
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
-------
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:
-------
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
-------
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.
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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.
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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.
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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.
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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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Environmental Protection Office of Air Quality Planning and Standards
Agency Research Triangle Park NC 27711
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