NATIONAL INVENTORY
OF SOURCES
AND EMISSIONS:
COPPER - 1969
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Water Programs
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
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. Property Of
EPA Library
HTPNC 277t|
APTD-1129
NATIONAL INVENTORY
OF
SOURCES AND EMISSIONS:
COPPER - 1969
by
W. E. Davis § Associates
9726 Sagamore Road
Leawood, Kansas
Contract No. 68-02-0100
EPA Project Officer: C. V. Spangler
Prepared for
ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Water Programs
Office of Air Quality Planning and Standards
Research Triangle Park, N.C. 27711
April 1972
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The APTD (Air Pollution Technical Data) series of reports is issued by
the Office of Air Quality Planning and Standards, Office of Air and
Water Programs, Environmental Protection Agency, to report technical
data of interest to a limited number of readers. Copies of APTD reports
are available free of charge to Federal employees, current contractors
and grantees, and non-profit organizations - as supplies permit - from
the Air Pollution Technical Information Center, Environmental Protection
Agency, Research Triangle Park, North Carolina 27711 or may be obtained,
for a nominal cost, from the National Technical Information Service,
5285 Port Royal Road, Springfield, Virginia 22151.
This report was furnished to the Environmental Protection Agency
in fulfillment of Contract No. 68-02-0100. The contents of this report
are reproduced herein as received from the contractor. The opinions,
findings and conclusions expressed are those of the author and not
necessarily those of the Environmental Protection Agency. The report
contains some information such as estimates of emission factors and
emission inventories which by no means are representative of a high
degree of accuracy. References to this report should acknowledge the
fact that these values are estimates only.
Publication No. APTD-1129
11
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CONTENTS
PREFACE v
ACKNOWLEDGEMENTS vii
SUMMARY 1
Emissions by Source 2
Emissions by Regions 3
Emission Factors 4
MINERAL SOURCES OF COPPER 6
MATERIAL FLOW THROUGH THE ECONOMY. . . 8
Chart 9
USES AND EMISSIONS OF COPPER
Mining and Milling 10
Metallurgical Processing 15
Secondary Copper Production 26
Metal Fabrication 32
End Product Uses of Copper 34
Electrical Equipment 34
Construction 35
Industrial Machinery 37
Transportation 38
Ordnance 41
Miscellaneous 43
OTHER SOURCES OF COPPER EMISSIONS
Coal 50
Oil 54
Iron and Steel 56
Foundries 63
Incineration 64
UPDATING OF EMISSION ESTIMATES 66
111
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TABLES
Table I Emissions by Source 2
Table II Emissions by Regions 3
Table III Emission Factors 5
Table IV Typical Analysis of Copper Smelter
Dusts 23
Table V Copper Recovered from Scrap Processed
in the United States During 1969 .... 27
Table VI Copper Recovered from Copper-Base
Scrap Processed in the United States
During 1969 31
Table VII Average Minor Element Contents of
Coals from Various Regions of the
United States - ppm 53
Table VIII Residual Fuel Oil Data 55
Table IX Spectrographic Analysis of Particulate
Discharge from an Open-Hearth
Furnace 58
Table X Typical Emissions from an Electric
Arc Furnace «... 62
FIGURES
Figure I Material Flow Through the Economy . . 9
Figure II Typical Copper Smelter Material
Balance 24
Figure III Typical Copper Refinery Material
Balance » 25
IV
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PREFACE
This report was prepared by W. E. Davis & Associates pur-
suant to Contract No. 68-02-0100 with the Environmental
Protection Agency, Office of Air Programs.
The inventory of atmospheric emissions has been prepared
to provide reliable information regarding the nature, mag-
nitude, and extent of the emissions of copper in the United
States for the year 1969.
Background information concerning the basic characteristics
of the copper industry has been assembled and included.
Process descriptions are given, but they are brief, and are
limited to the areas that are closely related to existing or
potential atmospheric losses of the pollutant.
Due to the limitation of time and funds allotted for the study,
the plan was to personally contact all of the primary pro-
ducers and about twenty percent of the companies in each
major emission source group to obtain the required informa-
tion. It was known that published data concerning emissions
of the pollutant were virtually nonexistent, and contacts with
industry ascertained that atmospheric emissions were not a
matter of record. The copper emissions and emission
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factors that are presented are based on the summation of
data obtained from production and reprocessing companies.
Additional information was acquired during field trips to in-
spect the air pollution control equipment and observe pro-
cessing operations.
VI
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ACKNOWLEDGEMENTS
This was an industry oriented study and the authors express
their appreciation to the many companies and individuals in
the copper industry for their contributions.
We wish to express our gratitude for the assistance of the
various societies and associations, and to the many branches
of the Federal and State Governments.
Our express thanks to Mr. C. V. Spangler, Project Officer,
EPA, Office of Air Programs, Research Triangle Park,
N. C. , for his helpful guidance.
vn
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-1-
SUMMARY
The flow of copper in the United States has been traced and
charted for the year 1969. The consumption was 3,058,000
tons, while primary and secondary production totaled
3, 118,000 tons. Imports and exports were 131,000 tons
and 200, 000 tons, respectively.
Emissions to the atmosphere during the year were 13,680
tons. About 64 percent of the emissions resulted from the
metallurgical processing of primary copper, and about ZO
percent from the production of iron and steel. The combus-
tion of coal was the only other significant emission source.
Emission estimates for mining, production of primary and
secondary copper, and reprocessing operations are based
on data obtained by personal contact with processing and
reprocessing companies.
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TABLE I
Source Category
Mining and Milling
Metallurgical Processing
Secondary Production
Metal Fabrication
End Product Uses
Other Emission Sources
EMISSIONS BY SOURCE
1969
Source Group
Miscellaneous
Coal
Oil
Iron and Steel
Foundries
Incineration
Emissions - Tons
Emissions
1,
2,
190
8,700
210
N
230
230
4, 350
030
50
760
50
460
1. 4
63. 6
1. 5
1. 7
31. 8
i
ro
TOTAL
133 680
100. 0
N - Negligible
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-3-
TABLE II
EMISSIONS BY REGIONS
Tons
Region No. 1 8,730
Region No. 2 3- 157
Region No. 3 880
Region No. 4 913
TOTAL 13,680
Region No. 1
Arizona
California
Colorado
Idaho
Montana
Nevada
New Mexico
Oregon
Utah
Washington
Wyoming
Illinois
Indiana
Iowa
Kansas
Alabama
Arkansas
Delaware
Florida
Georgia
Kentucky
Connecticut
Maine
Massachusetts
Region No. Z
Michigan
Minnesota
Missouri
Nebraska
Region No. 3
Louisiana
Maryland
Mississippi
North Carolina
Oklahoma
South Carolina
Region No. 4
New Hampshire
New Jersey
New York
North Dakota
Ohio
South Dakota
Wisconsin
Tennessee
Texas
Virginia
West Virginia
District of
Columbia
Pennsylvania
Rhode Island
Vermont
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-4-
EMISSION FACTORS
The emission factors presented herein are the best currently
available. They were determined through a combination of
methods consisting of: (1) direct observation of emission
data and other related plant processing and engineering data;
(2) estimates based on information obtained from literature,
plant operators, and others knowledgeable in the field; (3)
calculations based on experience and personal knowledge of
metallurgical processing operations; and, (4) specific analy-
tical results where available.
The basic data used to calculate the emission factors are
contained in the files of the Contractor.
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TABLE III
EMISSION FACTORS
Mining and Milling
Metallurgical Processing
Secondary Production
Metal Fabrication
200 lb/1,000 tons of copper mined
10 Ib/ton of copper produced
300 lb/1, 000 tons of copper produced
1 lb/1, 000 tons of copper fabricated
Other Emission Sources
Coal
Oil
Bla.st Furnaces
Open-Hearth Furnaces
Basic Oxygen Furnaces
Electric Furnaces
Foundries
4 lb/1,000 tons of coal burned
160 Ib/million bbls of oil burned
22 lb/1, 000 tons of pig iron produced
51 lb/1,000 tons of steel produced
2 lb/1, 000 tons of steel produced
7 lb/1, 000 tons of steel produced
5 lb/1, 000 tons of gray iron
produced
NOTE - The emission factors shown above for mining and
milling, metallurgical processing, secondary pro-
duction, and metal fabrication are based on the
averages reported by industry. The degree of ac-
curacy is judged to be plus or minus 30 percent.
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MINERAL SOURCES OF COPPER
Copper (Cu) is widely distributed in nature and its concen-
tration in the earth's crust averages about 55 ppm. It melts
at 1, 083 C, its atomic weight is 63. 57, and its specific grav-
ity is 8. 94.
Copper ore deposits of commercial importance are found
throughout the world. The United States is the largest pro-
ducing country and the other principal producers, named in
order of importance, are the U. S. S. R. , Zambia, Chile,
Canada, the Congo, and Peru.
The minerals of importance as copper ore are azurite, born-
ite, chalcocite, chalcopyrite, chrysocolla, and malachite.
They range in color from yellow, brown, and red to blue,
green, gray, and black.
In the United States most of the copper ore is produced in
Arizona. Montana, Nevada, New Mexico, Utah, Michigan,
and Tennessee. About 98 percent of the domestic production
is from ores mined principally for their copper content with
the remainder from complex or base metal ores. In addi-
tion to the copper that is recovered there are important
quantities of arsenic, rhenium, selenium, tellurium,
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platinum, silver, gold, and molybdenum that are recovered
as by-products.
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COPPER
MATERIAL FLOW THROUGH THE ECONOMY - 1969
(Thousand Tons - Cu Content)
SOURCES
USES
1,469
PRIMARY PRODUCTION FROM
DOMESTIC ORES
274
PRIMARY PRODUCTION FROM
FOREIGN ORES
131
IMPORTS OF REFINED
?OQ
COPPED
EXPORTS
INDUSTRY STOCKS
1. 375
SECONDARY PRODUCTION
3.D58
1. 500
ELECTRICAL EQUIPMENT
480
CONSTRUCTION
300
INDUSTRIAL MACHINERY
365
TRANSPORTATION
185
ORDNANCE
228
MISCELLANEOUS
i
vO
CONSUMER
1,_375_
SCRAP
Figure I
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USES AND EMISSIONS OF COPPER
MINING AND MILLING
Underground and open-pit copper mining methods are both
used in the United Statds; however, the principal method
currently employed is open-pit. During 1969 about 88 per-
cent of the ore and 84 percent of the recoverable copper was
produced by the open-pit method.
Traditional open-pit operations commence with the stripping
of overburden followed by drilling, blasting, and ore handling.
The first drilling operation, known as "primary drilling",
consists of sinking holes in which to load explosives behind
the rock face. Following the blasting, secondary drilling
takes place to break boulders that are too large to be handled
by loading and hauling equipment. Typically, ore and waste
are loaded by large diesel or electric powered shovels and
hauling is done by rail for the long haul, or by trucks for a
shorter distance. The trend in recent years ha.s been toward
usage of la.rger loading and hauling units. At some locations
belt conveyors and skip-ways are used to transport the ore.
Regardless of the type of mine (underground or open-pit),
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most of the first steps ir:processing sulfide and non-sulfide
ores are basically the same: drilling, b'asting, ore handling,
ore removal, hauling, unloa.ding, stockpiling, rushing, and
grinding. The ore is dry or perhaps damp when removed
from the mine and while crushing, but is wet during the grind-
ing step.
A major development in open-pit mining has been the leach-
ing of waste dumps. The overburden, a major pa.rt of the
waste, is dumped into canyons and gulches to create roadbeds
as the mine develops. As these low-grade copper minerals
are exposed to slightly acid water, the soluble salts dissolve
and are carried to precipitation plants by natural drainage
routes. The dissolved copper precipitates ~n s^ra.p iron, is
washed into settling tanks, and is reclaimed as slurry or
pulp. This precipitated copper, referred to as "cement cop-
per", usual y a.ssa.ys 70 to 90 percent copper and is a. suita.ble
smelter fe -d.
Benefaction of copper ores ma.y be accomplished by flotation
or hydrometallurgy. Flotation is the principal method used
for concentrating copper sulfide ores, which comprise the
bulk of United States copper ore production. Hydrometallurgy
is the method employed for non-sulfide ores.
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The typical steps for processing sulfide ores are crushing,
grinding, classifications flotation, and dewatering. The ore
enters the mill by rail car or truck and is discharged over a
grizzly into a gyratory crusher. The grizzly, a ra.ther crude
sizing device, consists of bars or rails spaced equidistantly
over an area; this removes oversize materials. Most of the
crushing of the ores is done in 3 steps. The first gyratory
crusher reduces the ore to a 6 to 9 inch size. Following
screening, the oversized pieces are further crushed in gyra-
tory or cone-type crushers to yield a one to 2 inch product.
Water and lime are mixed with the ore and fine grinding is
accomplished in rod and/or ball mills. Primary and secon-
dary ball mills are in closed circuit and are equipped with
classifiers so that the coa.rse material circulates for re-
grinding, while the fine feed material is delivered for flo-
tation.
The finely ground pulp (-200 to -325 mesh) is then conditioned
to adjust its alkalinity before feeding to the flotation cells.
Air and a small amount of "frother", which might be pine oil
or a long chain alcohol, a.re added in the flotation cells to pro-
duce a froth. Small amounts of chemicals referred to as "col-
lectors" are also added, and this causes the copper sulfide
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particles to attach themselves to air bubbles an.d be removed
in the froth. The ga.ngue sinks to the eel] bottom and is re-
moved as a tailing. Very often. 2 or more sets of flotation
cells are employed. The bulk of the ore goes through the
"rougher" cells and then the concentrate is further upgraded
in "cleaner" cells. Following flotation the concentrate is
thickened, filtered, and shipped to a smelter. The copper
content of the concentrate resulting from these procedures
may analyze 15 to 38 percent and the overall copper recovery
should average a.bout 83 percent.
Emissions from Mining and MiJ.ling - During this study 9
of the 11 major copper mining companies in the United States
were contacted concerning the quantity of ore mined, its cop-
per content, an.d the emissions (hat occur during mining and
milling. Five companies provided some information about 9
mining opera.tions. Al.iJi.ough. no emission records were avail-
able, most of the mine operators agreed there are slight
emissions due to handling, crushing, and as a wind loss from
tailings.
During 1969 there were 223, 752, 000 tons of copper ore pro-
duced in the United States / containing approximately 1.9
1- Minerals Yearbook; Bureau of Mines; .1969.
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million tons of copper. The tailings totaled approximately
218. 5 million tons, and the copper content, was about 260, 000
tons. None of the copper mining companies provided esti-
mates of emissions to the atmosphere: therefore, emissions
were estimated by the Contractor at 200 pounds per 1, 000
tons of copper mined (Cu content), or 190 tons for the year
1969.
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METALLURGICAL PROCESSING
In the United States most of the primary copper is recovered
from low-grade sulfide ores using pyrometallurgical proced-
ures. Hydrometallurgy (leaching) can sometimes be used for
these ores; however, it is normally employed only for oxide
and mixed ores in which oxide minerals predominate. A small
quantity of copper is recovered by a by-product during the pro-
cessing of lead, zinc, and other ores.
There are 4 principal hydrometallurgical methods practiced:
(1) in-place leaching; (2) heap leaching; (3) dump leaching;
and3 (4) vat leaching. In all 4 methods the copper-containing
solids are leached with a dilute solution of sul.furic acid. In-
place leaching techniques are applicable to shattered, broken,
or porous ore bodies. Air and a leach solution a.re alternately
circulated through the fractured rock. The solution drains
through tunnels under the ore and is treated to recover the
copper.
Heap leaching is generally employed to dissolve copper from
an oxide ore. The mined ore is placed in heaps in areas pro-
vided with drainage ditches. Leaching and oxidation periods
a.re alternated until* the copper can be recovered from the
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solution by cementation on iron or by solvent extraction.
Dump leaching is used to recover copper from the low-grade
waste material resulting from open-pit copper mining opera-
tions. Vat leaching is more suitable for the extraction of
copper from crushed and sized oxide or mixed oxide-sulfide
ores that contain more than 0. 5 percent acid -soluble copper.
From the standpoint of air pollution, the emissions from
pyrometallurgical extraction processes are a far greater
problem than those from leaching. The major steps are
roasting, reverberatory smelting, and converting. The ob-
ject of roasting copper sulfide ores and concentrates is to
regulate the amount of sulfur so that the material can be ef-
ficiently melted and to remove certain volatile impurities
such as antimony, a.rsenic, and bismuth. However, in cur-
rent practice the concentrate produced from some sulfide
ores is sufficiently con'..rolled, at the concentrator to eliminaie
roa.sting prior to reverberatory smelting.
Various types of feed materials may be delivered to a smelter.
The largest portion consists of copper and iron sulfide concen-
trates usually containing 15 to 32 percent copper. Much, smal-
ler quantities of sulfide and oxide ores containing 4 to 6 percent
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copper also may be a part of the smelter feed, as well as
precipitates containing 70 to 85 percent copper.
Since concentrates and precipitates arrive at the smelter
containing some free moisture, predrying may be required.
Rotary or multiple-hearth dryers are used to drive off about
half of the moisture.
Roasting is deemed necessary when the feed material is low
in copper and high in iron and sulfur. The roaster removes
a part of the sulfur by converting it to sulfur dioxide, while
an equivalent portion of the iron is oxidized. Multiple-hearth
roasters are in general use although some plants have the
more modern fluid bed roaster facilities. The calcine from
the roaster is charged to the reverberatory furnace where
iron oxide combines with silica to make a slag while the
copper, iron, and the remaining sulfur are left in the prod-
uct material, known as matte. The molten matte is remov-
ed from any of several holes and conveyed to the converter
aisle. The immediate matte tapping area is enclosed and
fumes are exhausted to the atmosphere. The slag is remov-
ed through slag skimming holes, transported either molten
or granulated in water, and dumped outside the smelter
building. Collection and recovery of furnace gases is a
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major problem. A main dust, collector, usually an electro-
static precipitator, is used and may have an efficiency of 95
to 99 percent.
Next, it is the function of the converters to oxidize and sep-
arate the iron and sulfur from the matte. This is accom-
plished by blowing air into t;he liquid matte through openings
in the converter called "tuyeres". A silica flux is added to
combine with the iron oxide and form a sla.g to be skimmed
off and returned to the reverberatory furnace. As more matte
is added to the converter, the process is repeated until a
suitable charge of copper sulfide is accumulated. Then con-
tinued blowing eliminates the remaining sulfur resulting in
a blister copper more than 99 percent pure, which can then
be removed to holding furnaces for casting or further refine-
ment. The gases coming from a copper converter are heavily
laden with dusts, containing a Jarge quantity of copper. The
blister copper produced from the converter is the principal
product of a primary copper smelter.
The amount of dust in a smelter will depend on variables
such as the fineness of the charge, the amount, of agitation
in charging and working, the amount of volatile metals in the
ore, and the temperatures used. The value of dust recovery
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is considerable since the copper content of dusts from the
roaster may be 10 percent, from the reverberatory about 25
percent, and from the converter as much as 45 percent. The
lead content also is usually high. After the gases, fume, and
dusts leave the furnaces and enter the flues they are cooled
and lose velocity. The coarser dust and some fume settles
to the bottom to wait for removal. Fine dust and fume is col-
lected by electrostatic precipitators and recycled for direct
resmelting in the reverberatory furnace.
Fire refining and anode casting operations may be included
at copper smelters. Copper from the converter is either
pa.rtially fire-refined and cast into anodes for electrolytic
purification, or fire-refined to a practical limit to achieve
a commercially salable product; the latter is done when the
silver and gold contents are very low.
The fire refining is commonly done in either a small reverb-
eratory furnace or one of the tilting cylindrical type. A
charge of blister copper is oxidized by blowing air through
iron pipes into the cha.rge. The slag is skimmed several
limes and returned to the converter. After the oxidation pro-
cedure, the bath is covered with coke and logs are forced into
the metal. As the destructive distillation of the wood occurs,
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hydrogen, hydrocarbons, carbon monoxide, and water vapor
evolve. When the desired stage called "tough pitch" is
reached, charcoal is spread on top to maintain the desired
composition until the metal is cast.
Copper which is to be further purified is ca.st into anodes
and sent to an electrolytic refinery. The impure copper an-
odes are dissolved electrolytically in an electrolyte solution
of copper sulfate and sulfuric acid. The copper alone mi-
grates to and is deposited at the cathode. The impurities in
the anode either dissolve in the electrolyte or fall to the bot-
tom as slime. The purified copper is then melted and cast
into bars for shipment, and tJie slimes are treated further
for recovery of precious and rare metals.
Overall recovery of copper averages about 97 percent at cop-
per smelting and refining facilities, but at plants producing
primary lead and zinc the recovery of copper from such ores
and concentrates averages 85 percent.
Throughout processing from the ore to the final product
there are fumes, dusts, slags, and residues containing cop-
per that are discharged from dryers, roasters, furnaces,
converters, and other equipment. In most cases these
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materials are collected, retreated, and recycled. At one
smelting and refining complex where copper, lead, and zinc
ores are processed there are several locations where fume
is recycled. For example, fume from the copper roaster
enters an electrostatic precipitator and the dust collected is
returned to the roaster. The recycling is continuous, except
periodically the dust may be directed elsewhere for recovery
of certain materials that build up in the system. Fume from
the reverberatory furnace and converter also enters an elec-
trostatic precipitator; dusr collected is forwarded to a dust.
roaster and on to the lead processing circuit. Fume from
the lead blast furnace is directed to another electrostatic
precipitator and the resulting dust: is returned to the lead
circuit. Speiss from the lead blast furnace is directed to
the copper roaster.
These are only a few of the numerous recycles and inter-
changes between the copper, lead, and zinc circuits.
Emissions from Metallurgical Processing - During this
study 9 copper smelting and refining companies were re-
quested to provide data concerning the atmospheric emis-
sions at 16 smelters and 11 refineries. Six companies re-
sponded with some information about 10 smelters and 7
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refineries, while 3 companies either refused to cooperate
or ignored the request for information.
Table IV shows the analyses of paniculate matter discharged
from the stack of a copper smelter, while Figures II and III
give the material balance for a typical copper smelter and a
typical copper refinery.
The data obtained from 6 industrial sources regarding metal-
lurgical processing of copper-bearing ores and the production
of copper show tha.t emissions to the atmosphere during pro-
cessing range upward to more than 40 pounds of copper per
ton of primary copper produced, averaging about 10 pounds
per ton.
During 1969 copper emissions to the atmosphere in the United
States due to metallurgical processing totaled 8,700 tons.
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TABLE IV
TYPICAL ANALYSIS OF COPPER SMELTER DUSTS
From
Element n .
Roasters
Copper %
Iron %
Lead %
Sulfur %
(as SO2)
Zinc %
Arsenic %
Antimony %
Bismuth %
Cadmium %
Silver oz/ton
Gold oz/ton
5
6
7
5
1
43
5
0
7
0
.2
.6
.6
.8
.7
.0
. 3
.4
-
.6
.02
From
Reverberatory
Furnaces
2.
1.
30.
2.
8.
25.
3.
1.
0.
18.
0.
9
6
5
1
3
7
0
11
71
6
04
From
Converters
1.
1.
47.
8.
3.
9.
1.
1.
1.
10.
0.
12
2
1
2
2
6
6
64
15
9
02
From
Stack
1.
2.
23.
7.
6.
21.
4.
1.
0.
10.
0.
03
4
4
8
3
8
6
0
8
1
02
Source - Private communication.
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-24-
TYPICAL COPPER SMELTER MATERIAL BALANCE
(100 Tons - Cu Content)
439
ORES AND CONCENTRATES
74
RAW MATERIAL FROM STOCK
FLUXES AND CLEAN-UP
RETURNS FROM COPPER CIRCUIT
63
RETURNS FROM LEAD CIRCUIT
SMELTER
17
IEVERBERATORY SLAG
1
STACK TO ATMOSPHERE
MISCELLANEOUS LOSSES
(4)
UNDETERMINED GAIN
417
ANODES TO REFINERY
,37
BLISTER COPPER SHIPPED
8
COTTRELL DUST RECYCLE
MISCELLANEOUS RECYCLE
Figure II
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TYPICAL COPPER REFINERY MATERIAL BALANCE
(100 Tons - Cu Content)
419
ANODES
REFINERY
1
UNDETERMINED LOSS
INVENTORY ADJUSTMENT
403
REFINED COPPER
COPPER SULFATE
1
MOLDS
SCRAP AND CLEAN-UP
Figure III
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-26~.
SECONDARY COPPER PRODUCTION
In the United States the secondary copper industry is very
important. It accounts for a significant part of the total cop-
per supply and it is the largest of the nonfe.rrous secondary
metal industries. The production of secondary copper during
1969 was 1, 375,493 tons while primary production was
1,742,815 tons.
The industry includes several thousand scrap dealers, sev-
eral hundred foundries, the brass mills, the secondary
smelters, and the primary smelters. It employs many pro-
cesses unique to the industry as -well as many currently used
by the producers of pr.ima.ry copper.
Secondary copper is produced in both alloyed and unalloyed
forms from new and old sc:rap, as shown in Table V. The
new scrap is that resulting from fabrication, and manufactur-
ing operations while old scrap is defined as i'ems discarded
after serving a useful purpose.
When dealing with scrap metal various problems are involved
th.a.t are different than those encountered when dealing with
ores and concentrates. There are many types of scrap. Some
are relatively pure and others are alloys containing various
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...27.
TABLE V
COPPER RECOVERED FROM SCRAP PROCESSED IN THE
UNITED STATES DURING 1969 }J
(Short Tons)
Kind of Scrap
New Scrap:
Copper --base
Aluminum -base
Other
TOTAL
Old Sc rap:
Copper-base
Aluminum-base
Ot he r
TOTAL
787,72?
12,595
281_
800,603
568,769
4,973
J..J.48
574,890
Form of Recoxerv
As Unalloyed Copper:
At Primary Plants
At Other Plants
TOTAL
In Brass and Bronze
In. Alloy I'on and Steel
In Aluminum Alloys
In Other Alloys
In Chemical Compounds
TOTAL
4.12, 843
514, 593
820, 945
2, 570
32, 826
735
___ 3, 824
860,900
1- Minerals Yearbook; Bureau of Mines; 1969.
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-28-
amounts of copper. Even though scrap metal may be pure
copper, it is often intimately associated with non-metallic
materials such as chemicals, dirt, g.rea.se, insulation, mois-
ture, oil, paint, plastics, rubber, and many others.
Raw material preparation is an important operation in the
secondary copper industry. The dealer must first identify
and sort the scrap. Small dealers may rely principally on
visual inspection and experience. Larger dealers can just-
ify the use of more precise methods such as examination of
metal color and structure, filing and drilling, chemical spot
testing, and rapid chemical analysis. When the scrap is re-
ceived at smelters, brass mills, and other processing fa.cil-
ities, it must be inspected further and materials sorted to
assure proper product quality control.. These additional
tests may include sampling and melting for spect.rographic.
analysis.
After sortingjSome scrap material is pre -treated mechn.icallv
and some requires a preliminary furnace treatment. Insula-
tion and lead sheathing are removed from wire and cable by
hand or by machine stripping. Drillings, clippings, and turn-
ings are usually passed o\ er a magnetic separator to remove
tramp iron. Bulky and sponge-like materials are often
-------
crushed and compacted for ea.sie.r handling, while l.a.rge solid
items are cut or broken to reduce the size.
The preliminary furnace treatment prior to smelting is us-
ually at a rather low temperature and various types of furn-
aces are employed. A muffle furnace or kiln, may be used to
drive off moisture, oil, and other organic impurities. For
the removal of solder, babbitt, and lead from radiators,
bearings, and similar articles, a sweating operation is re--
quired. The simplest sweating furnace is the sloping-hearth
type: however, many others are used for this purpose, in-
cluding rotary kilns, reverberatories, pots, and tunnel
furnaces.
After the raw material has been prepa.red the remaining pro-
cedures fo.r melting and refining are principally material
handling a.nd py .rometaJ.J.Vi rgical operations utilizing blast
furnaces, .reverberator ies, rotary furnaces, converters,
cupolas, and crucible furnaces. There is no basic differ-
ence in the melting and refining actions ir ?bese furnaces,
but there are differences in the types of alloys handled, 'he
furnace capacities, the condition of charge materials, and
l-h.e methods for heading.
During 1969 the brass mills were the largest users of scrap
-------
-.30-
materials (see Table VI). Principally they used new mater-
ials while the primary producers consumed about an equaJ
amount of old and new. The secondary smelters ranked third
in consumption of raw material using mostly old scrap. The
primary smelters produced about 80 percent of the refined
copper while brass and bronze ingots we.re the principal prod-
ucts of the seconda.ry smelters.
Emissions from Secondary Copper Production - Data ob-
tained from industry during this study shows that copper
emissions to the atmosphere in 1969 averaged 300 pounds
per 1, 000 tons of secondary copper produced. Published in-
formation agrees with the above data. Particulat.e emissions
from refining furnaces in the brass and bronze ingot industry
average 60 to 80 pounds per ton of ingots produced and the
ra.nge of copper content is from 0. 05 to .1. 0 percent /.
During 1969 copper emissions to the •atmosphere due to the
production of seconda.ry copper totaled 210 tons.
1- "Air Pollution Aspects of Brass and Bronze Smelting and
Refining .Industry"; National Air Pollution Control Ad-
ministration Publication No. AP-58; Nov., 1969.
-------
-3.1
TABLE VI
COPPER RECOVERED FROM COPPER-BASE SCRAP
PROCESSED IN THE UNITED STATES DURING 1969 _|/
(Short Tons)
From From
Recovery Plant New Scrap Old Scrap Total
Brass Mills 480,093 38,541 518,634
Primary Producers 215,561 197,282 412,843
Secondary Smelters 72,515 277,240 349,755
Foundries and Manufacturers I8:,68? 52,856 71,543
Chemical Plants 8_7J_ 2; 850 3/721^
TOTAL 787.-727 568,769 .1,356,496
!•• Minerals Yearbook; Burea.u of Mines; 1969.
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-32-
METAL, FABRICATION
I.n the metals industry the term fabrication usually refers to
the shaping and finishing of metals a.nd metal alloys into the
standard sizes, finishes, and shapes that are needed by the
construction industries and the manufacturers of finished
products. In the copper and copper alloy field, fabricators
are concerned with producing tubes, rods, sheet, and wire,
all in varying sizes.
The metals are generally received as cathodes, ingots,
slabs, cakes, or bars in large quantity shipments from the
refineries. The fabrication phase begins with hea.ting and
melting, and the melHng furnaces generally used by fabri-
cators in the copper industry are electric induction furnaces.
These furnaces are cha.rged with a layer of scrap and then
rhe high-melting consti'uent s. When rhe charge is melted,
the furnace is skimmed of impurities and dross through a
door and t.he surface of the me'al i? covered with charcoal to
pre-.en1 further oxidation. About 60 percent of this molten
metal is then poured from the furnace into casting molds and
recharging continues.
Following '.he casting of the metal into appropriate shapes,
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-33
the metal may be hea.ted for hot working, for reworking, for
stress relief, or to obtain final temper. The hea.ting prepara-
tory to hot working usually requires a higher temperature than
the annealing for cold working. Materials for hot working may
be rolled, conveyed, or pushed through a furnace and then
sent to the rolling mill. Materials for annealing are placed
in batch or continuous type furnaces and then enter a separate
cooling chamber before exposure to the air.
Emissions from Metal Fabrication - Information obtained
during this study regarding rolling, extrusion, cold-drawing,
pointing, pickling, and annealing operations has been used to
estimate copper emissions due to metal, fabrication. The
range of atmospheric emissions reported varied from less
than 0.5 to as much as 20 pounds per thousand tons of copper
processed. The average wa.s one pound per 'housand tons.
During 1969 the copper emissions TO the atmosphere due to
metal fabrication lota.led 2 tons.
-------
-34-
END PRODUCT USES OF COPPER
In the United States about 40 percent of the primary and sec-
ondary copper is used in the commercially pure fojfm, prin-
cipally because of its excellent properties as a conductor of
electricity. Approximately 50 percent, is consumed as an al-
loying element in the production of bra.ss, bronze, nickel-
silver, cupronickel, and numerous special alloys.
The largest application of copper during 1969 was in the elec-
trical industry. Nearly 50 percent was consumed in. the man-
ufacture of electrical equipment and supplies while the con-
struction, transportation, industrial machinery, and ordnance
industries used 5 to 1 5 percent each.
Manufacturers in all industries were conta.cted during this
study concerning materials handling, manufacturing opera-
tions, pollution control equipment, and atmospheric emissions
as related to their use of copper. Information from them indi-
cates that copper emissions to the atmosphere are negligible
except for certain.miscellaneous uses described herein.
Electrical Equipment - Tough-pitch copper is the predomi-
nant: type used by the electrical industry. It has good mechan-
ical properties and high electrical conductivity at minimum
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-35-
cost. Although used principally in the form of wire and ca.ble,
there are many brass and bronze products, including castings,
that enter into the manufacture of electric motors, power gen-
erators, motor-generator sets, dyn.amotors, fans, blowers,
controls, switchgea.r, transformers, and related apparatus.
In the home the use of copper is equally important. It is found
in household refrigerators, freezers, laundry equipment,
dishwashers, disposals, vacuum cleaners, air conditioners,
television sets, radios, telephones, toys, record players,
tape recorders, lighting fixtures, and power tools.
Copper in electrical equipment manufacturing is used prin-
cipally in a series of mechanical, operations. Wire received
from metal fabricators ma.y be insulated and wound into coils
for generators, motors, transformers, and solenoids. Ba.rs,
sheet, and strip may be sa.wed, stamped, sheared, drilled,
formed, and machined in various ways as required for equip-
ment components.
Construction - Copper, due to its high resistance to corro-
sion, has found extensive and varied uses in the construction
of buildings. The roof is one of the most important compo-
nents of a structure and when properly erected, copper roofs
resist indefinitely the penetration of rain, snow,, and sleet.
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-36-
There are 3 types of roofs: batten seam, standing seam,
and flat seam. All are normally constructed of cola-rolled
sheet copper; however, corrugated copper sheets may be
used.
Because its ductility assures easy fabrication, copper is
ideally suited as a flashing material to insure against leaks
at surface intersections whether vertical, horizontal, curved,
or sloped. Flashings ma.y be found on roofs, doors, windows,
skylights, ventilators, and expansion joints.
Copper's resistance to corrosion has long made it a sought
after material for tubing to carry water. The development
of the copper water tube wifh soldered fittings has made this
material available to the small home owner for plumbing,
heating, air conditioning, a.nd sprinkler systems. Radiant
heating systems use large quantities of copper tubing hidden
in floors, walls, and ceilings. Radiant heating can also be
used for snow removal by embedding tubing in concrete walks
and driveways.
Copper has many other uses in construction. Gutters and
leaders to convey rain water a.way to designated areas are
best constructed with cold-rolled copper. A 16-ounce sheet
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-37-
of copper may be placed over the top of a masonry foundation
to form a termite barrier. Sheet copper and copper rod are
employed in the construction of louvers, ventilators, lighten-
ing rods, and fasteners. Domestic furnaces, kitchen stoves,
and hot water heaters are often supplied with oil or gas through
copper tubes because of its stability and ease of installation.
Brass and bronze a.re popular ha.rdwa.re materials used in
Jocks, doorknobs, handles, letter slots, mail boxes, house
numbers, door knockers, hinges, door holders, door closers,
push and kick plates, window latches, railings, curtain rods,
name plates, elevator doors, window fra.mes, fireplace hoods,
light fixtures, andirons, and many other household decora-
tive items.
From the standpoint of copper emissions to the a.tmosphe re,
the manufacturing and installation operations used in connec-
tion with copper construction materials are simila.r in many
respects to those used in the manufacture of elect.ric.al equip-
ment.
Industrial Machinery - Large quantities of bronze castings
are employed in the machine too] industry as gears, bear-
ings, and special purpose pa rrs such as shifter forks a.nd
-------
-38-
feed nuts. In all machinery parts the copper alloys are used
to prevent seizure or scuffing with the mating steel part.
In mechanical power transmission and linkage systems, the
use of copper alloy parts is common where scuffing and gall-
ing are to be avoided. For instance, a bronze bearing is
used in earthmoving equipment in the hitch between the power
unit and the conveyor truck. In high pressure hydraulic sys-
tems, bronze parts are often employed to prevent seizing.
The textile industry finds many uses for bronze in intricate
machinery parts. Bronze is used beca.use of its corrosion
resistance, high strength, and castability.
Numerous miscellaneous applications involving slides and
clutches indicate the usefulness of the copper-base alloys
for combinations of castability, strength, wear, corrosion
resistance, and machinability.
Transportation - Copper and its alloys possess combinations
of properties which make them useful for a variety of func-
tions in the transportation industry. High thermal and elec-
trical conductivity, good corrosion resista.nce, good bearing
properties, softness, and ease of fabrication are some of
the most important properties. High heat conductivity is
-------
-39-
needed in radiators, heater cores, and oil coolers. The
starting, lighting, and ignition circuits require high electri-
cal conductivity. Copper's corrosion resistance makes cop-
per and its alloys useful in fabricating radiators exposed to
air, lubricants, and coolants. By utilizing copper these
parts can be made without protective films. Where an air-
tight seal is required, gaskets and washers are often fabri-
cated of copper because of its softness. The ductility of cop-
per is valuable in the manufa.cturing of pa.rts where deep
drawing and forming operations are involved. Copper can
also be easily soldered a.nd brazed for various assemblies.
Many automotive parts are prepared from copper sheet,
strip, and plate. The parts are generally formed by some
combination of drawing, sta.mpi.ng, riveting, soldering, a.nd
brazing. A partial list of these parts includes ga.skets,
washers, spa.cers, thrust bearings, retainers, gears, springs,
housings, thermostats, carburetor floats, fue] and oil ga.ges,
oil coolers, dials, and electrical contacts. The largest single
use of copper and copper-ba.se alloys is in radiators and heat-
ers. The radiator contains top and bottom tanks, filler neck,
overflow tube, drain cock, core, and mounting shell. All
these pa.rts are fabricated from copper or copper-base alloys.
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-40-
Bars and rods of copper, brass, and bronze may be machined
and cold formed to produce parts. These may include nuts,
screws, bolts, elbows, tees, connectors, adapters, studs,
rivets, buttons, knobs, gears, dowels, valve guides, spacers,
jets, and needles.
Copper tubing is used in oil, fuel, brake, and coolant lines
because it resists corrosion. This same property is import-
ant for tubing in instrument assemblies, oil coolers, and
heaters.
Copper wire is required for many parts including generators,
starter motors, windshield wiper motors, coils, relays,
switches, instrument wiring, lighting, and ignition systems.
Metal powders also find some use in vehicles for self-lubri-
cated bearings where the sintered parts are impregnated
with liquid or solid lubricants. These bearings are used in
transmissions, water pumps, distributors, starter motors,
generators, windshield wipers, and heater fans.
In the area of transportation the railroad, marine, and air-
~raft industries should have special mention. In general,
the excellent resistance of copper-base alloys to salt water
pitting, ^avitation, and corrosion along with their other
-------
-.41-
processing characteristics leads to widesprea.d use in marine
applications. Copper and copper alloys a.re useful both struc-
turally and in electrical applications. Structurally* copper
may be in the hull, deck, funnel, superstructure, and rudder.
It may be a part of the distillation plant, boiler, turbines,
propeller shaft and bea.rin.gs, propeller, speed reducer, and
bull gear. Also copper, brass, and bronze are utilized ex-
tensively for hardware and decoration.
In the aircraft industry most of the copper is found in the wir-
ing and electrical components. Some large planes use as
much as 3,000 pounds in the electrical systems.
Ordnance - Malleability and work ha rdenability are the two
outstanding characteristics which permit the development of
the various properties required in ordnance items such as
rotating bands, bullet jackets, bearings, springs, detonators,
fuse parts, primer cups, and cartridge c^ses.
The largest consumption in ordnance has been in cartridge
brass for ammunition. This brass alloy of 70 percent, cop-
per and 30 percent zinc is well suited for cartridge cases,
which are made normally by a cup-and-draw process using
strip brass. The blanking and cupping operations are
-------
frequently combined through the use of a double-acting press.
Annealing operations are used to condition the metal for sub-
sequent deep-drawing operations in which the sinking and
ironing result in as much as a 60 percent reduction in the
side-wall volume. Other steps include bumping and head-
turning. A final trim to control the overall length of the
case is followed by a venting operation and a mouth anneal,
which softens the neck of the case so it will function satis-
factorily when a bullet is assembled in it.
The second largest use of copper in ordnance has been the
projectile rotating bands, which are usually ma.de of pure
copper. The properties required in a rotating band are good
bearing, engraving, and shear properties, along with low re-
silience, since the band must engrave rea.dily, spin the pro-
jectile, and not wea.r the barrel of the rifle when the project-
ile is fired.
The uses of copper-base metals in mobile mounts, jeeps,
trucks, and tanks are similar to those discussed in the trans-
portation applications; usage in field telephones, walkie-
'aJkies, power generators, distribution systems, radios,
and radar is like tha.t in electrical applications.
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-43-
Miscellaneous - Although most of the copper is used in
alloys or as commercially pure metal, there is about one
percent in the various compounds used in pharmaceuticals,
pyrotechnics, pigments, paints, wood preservatives, fuel
additives, glass, catalysts, ceramics, textiles, dyes, rub-
ber, plastics, photography, electroplating, and products for
various agricultural applications.
Copper sulfate is the most common compound of copper and
is often used for producing other compounds. It is usually
prepared by the action of hot sulfuric acid and air on copper
shot. This produces a copper sulfate solution. Copper car-
bonate can be precipitated chemically as a green powder by
adding a copper sulfate mixture to a solution of soda ash.
Bordeaux Mixture for agricultural use is a solution of copper
su]fa.te a.dded to a lime suspension. Cuprous cyanide is pre-
pa.red by adding potassium cyanide to a copper sulfate solu-
tion. This produces a precipitate of cup.ric cyanide, which
decomposes during boiling or drying to yield cuprous cyanide.
Other important copper compounds are made in a variety of
ways. Cuprous oxide is prepared in. a commercially pure
form by furnace reductions of mixtures of copper oxides
with copper brought to a high tempera.ture (above 1, 900 F)
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-44-
and quickly cooled. Cupric oxide occurs when copper is oxi-
dized at a temperature above 550 F. It can be manufactured
by furnace oxidation or by indirect oxidation of copper in the
ammonia leaching process for the recovery of copper from
ores. Chlorine is passed into molten cuprous chloride con-
taining excess copper metal to produce the solid salt of cup-
rous chloride. The molten mixture is cast, cooled, and
sometimes ground to a powder. A cupric chloride crystal
can be made by reacting chlorine with copper in a cupric
chloride bath. The cupric chloride solution occurs after
chlorine is pa.ssed up a tower packed with scrap or shot cop-
per. A solution of copper nitrate is prepared by dissolving
cupric oxide, hydroxide, or carbonate, or copper metal, in
nitric acid. Basic cupric acetate is obtained by the action
of acetic acid and air on copper scrap.
Agricultural - A wide variety of copper compounds and mix-
tures are valuable as fungicides. Copper sulfate was used
extensively in the past, but now orher compounds have be-
come the principal means of protecting plants from disease.
Bordeaux Mixture is a common fungicide that is low in cost.
Burgundy Mixture is similar to Bordeaux., although a little
more expensive. Copper acetate, copper ox.ychloride, and
-------
copper-ammonium compounds all serve as fungicides for
various plants.
Some copper compounds are utilized as insecticides. Paris
Green, a mixture of white arsenic, basic copper ca.rbonate,
and acetic acid, is one of the most well known. It can be
used as a spray or mixed with Hour and lime for dusting.
The copper salts may be given directly to sheep to control
worms. Microscopic organisms in water can be eliminated
by using copper sulfate powder for dusting the surface. Cop-
per oxide has been used for seed treatment for many years
a.nd has yielded excellent results. Even though copper com-
pounds and mixtures are used in agriculture, there is no re-
liable information regarding the quantity actually consumed
for that purpose during 1969.
Electroplating - Copper is employed extensively in the elec-
troplating industry, sometimes as a final finish, but more
often as a coating on steel before other deposits are made.
It is also universally used for plating on zinc--base die castings.
Ma.n.y types of copper-plating baths are available because of
t.h.e wide variety of uses of copper in industry. The cyanide
bath is generally for "copper••striking" steel and for the
-------
-46-
initia.l plate on zinc-base die castings. Rochelle baths are
similar to cyanide baths except the Rochelle salt addition per-
mits higher operating current densities. Copper sulfa.te ba.ths
are inexpensive, fast, and easily controlled. They are very
popular but cannot be used directly on steel.
Paints and Pigments - Inorganic compounds of copper have
been used in paint pigments, but the current use in paints is
usually because of some desirable property other than, color.
They are used in marine anti fouling paints and in poisonous
paints to protect timber from certain insec's a.nd fungi.
Verte antique or copper green is a fine pigment for imitating
a copper finish. It gi-'es a corroded copper effect that is
superior fo other pigments. Copper compounds may also be
used in preparing azo dyes, in dyeing polyacrylic fibers, and
in treating textiles fo improve lightfa sfness.
Glass - In the glass indusi ry copper is most often used in
'he form of copper oxide as an additive to impart, flex, and
abrasion resistance to glass fibers and as a polishing agent
for optical glasses. It may also be added to the glass batch
as a pigment.
Even though glass mixing procedures vary from small manual
-------
-47-
operations to full automations the mixing and charging are
done with the materials dry or nearly dry, and there is a
loss due to dusting. The furnace itself ma.y be a small cov-
ered or uncovered clay pot or a large "continuous tank"
furnace. Following the melting, the glass may be formed
by blowing, pressing, casting, rolling, or drawing. Final.
operations include finishing and secondary forming.
Fuel Additives - Numerous compounds that contain heavy
metals are marketed as additives for fuel oil. Some are
used to modify the physical characteristics of the fuel, while
others are intended to improve combustion. These additives,
when used as recommended by the manufacturers, increase
the copper content of the fuel an average of about 2 ppm.
During this study more than 200 additives were examined
and 16 were found that contained copper /: however, re-
J.ia.ble information was not available concerning the actua.l
amount: of copper used in additives.
Catalysts - The copper-chromium oxide catalyst is useful
1 - "EffecT.s of Fuel Additives on Air Pollutant Emissions
from Distillate-Oil-Fired Furnaces": Environmental
Protection Agency: Office of Air Programs Publica-
tion No. AP-87; June, 1971.
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-48-
fo.r the hydrogenation of aldehydes and ketones to alcohols,
of esters to alcohols, and of amides to amines. It is pre-
pared by the thermal decomposition of copper ammonium
ch.roma.te formed by the reaction of copper nitrate with am-
monium dichromate in an ammonium hydroxide, ammonium
ca.rbonate solution.
Cupric sulfate may be used for some catalytic oxidation pro-
cedures, and cupric oxide has been an intermediate reactant
i.n converting barium compounds.
Pharmaceuticals - Copper is an essential element in both
plant and animal metabolism, and trace amounts of copper
compounds must be available for proper functioning of liv-
ing organisms /. However, copper in excess of require-
ments is tox.ic io both plants and animals.
Copper compounds may be found in intestinal an'iseptics,
vitamin prepa rations, astringents, ba ctericides, and emet-
ics for certain poisons.
1 Vikmn, A. A. "Production and Use of Trace Salts in
Fertilizers", in Chemistry and Technology of Fertili-
lizers; Reinhold Publishing Corp. . New York, N. Y. ;
T9607
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-49-
Emissions Due to Miscellaneous Uses of Copper - Although
more than 100 industrial companies were contacted during
this study concerning processing of copper and copper com-
pounds, there was only a relatively small amount of informa-
tion available regarding emissions and the quantity of copper
consumed.
The Contractor's estimate for copper emissions to the atmos-
phere resulting from the miscellaneous uses of copper com-
pounds and mixtures totaled 230 tons for the year 1969. In-
formation obtained from 10 companies was used as a basis
for the estimate. Even though they did not report emissions,
the information furnished about operating procedures and
methods of ha.ndling copper-bearing materials was some help.
In most instances the emissions were judged to be due princi-
pally to mechanical operations, including unloading and
handling.
-------
OTHER SOURCES OF COPPER EMISSIONS
COAL
A search has been conducted and information has been ob-
tained regarding the copper content of coal, ash of coal, and
fly ash emissions.
With respect to fly ash, there is a study of emissions from
coal fired power plants which shows the analysis of several
fly ash samples. Six power boilers were tested, each a dif-
ferent type, and each value reported was the average of at
least 2 tests. Two of the boilers were fired with Illinois
coal; 2 burned Pennsylvania coal; one used some coal from
Ohio and some from West Virginia; one burned part Ken-
tucky and part West Virginia coal. The coal burned during
the tests represented only a small portion of the coal mined
in the various regions of the United States.
Copper concentrations in the fly ash samples taken before
fly ash collection ranged from 1. 9 to 25. 0 x 10"^ grains per
scf /. The average was 10. 5 x 10 grains per scf.
1- Cuffe, Stanley T. and Gerstle, Richard W. ; "Emissions
from Coal Fired Power Plants"; Public Health Service
Publication No. 999-AP-35; 1967.
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-51-
Calculations have been made based on:
(a) 516, 084, 000 tons of bituminous and anthracite coal
consumed in the United States during 1969 /;
(b) 160 scf of flue gas per pound of coal;
(c) 10. 5 x 10 grains per scf copper concentration;
(d) 85 percent efficiency of control; and
(e) 90 percent application of control.
The copper emissions calculated in this manner totaled
2, 910 tons.
During the combustion of coal, copper is discharged with the
ash; part with the bottom ash and part with the fly ash. The
fly ash averages about 65 percent of the total ash.
Many samples of coal have been analyzed and the copper con-
tent reported as shown in Table VII. Calculations have been
made based on:
(a) 516, 084, 000 tons of bituminous and anthra.cite coal
consumed in the United States during 1969 /;
1- Minerals Yearbook; Bureau of Mines; 1969.
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-52-
(b) 13 ppm average copper concentration in coal;
(c) fly ash 65 percent of total ash;
(d) 85 percent efficiency of control; and
(e) 90 percent application of control.
The copper emissions calculated ill this manner totaled
1, 030 tons.
516, 084, 000 x 13 x 10"6 x 0. 65 fl - (0. 85 x 0. 90)1 = 1,
030
In this report, the figure of 1, 030 tons is used as the copper
emissions to the atmosphere during 1969 due to the combus-
tion of coal.
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-53-
TABLE VII
AVERAGE MINOR ELEMENT CONTENTS OF COALS
FROM VARIOUS REGIONS OF THE UNITED STATES - PPM
Region
Northern Great Plains
Eastern Interior
Appalachian
Ash Content
of Coal - %
13.42
6. 16
6. 11
Cu Content
of Goal - ppm
15
11
15
Western and Southwestern NR* 11
Average Copper Content in Coal 13
*Not reported.
NOTE - The above table based on Geological Survey Bulle-
tins 1117-C and 1117-D; 1966 and 1967.
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-54-
OI..L
In order to estimate the copper emissions to the atmosphere
due to the combustion of fuel oil, it was necessary to deter-
mine the copper content and the quantity of oil received from
numerous foreign and domestic sources. Some data, were ob-
tained from publications and some from major oil companies.
The copper content in crude was shown in more than 100
samples of foreign and domestic oils; however, the situa-
tion wa.s somewhat different with respect to the metal content
of residua] oils. The only reliable information available
seemed to be that regarding nickel and vanadium. Analyses
showing the copper content were virtually nonexistent, ex-
cept for 6 samples of imported oil analyzed for the Environ-
mental Protection Agency, Office of Air Programs, during
1971. The average copper content of the 6 samples was
0. 47 ppm.
The residual oil used in the United States during 1969, ex-
clusive of use in vessels, was 639 million barrels /. This
I- "Sales of Fuel Oil and Kerosine in 1970"; Mineral Indus-
try Surveys; U. S. Department of the Interior; Bureau
of Mines; Oct. 1, 1971.
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-55-
oil containing copper at 0.47 pprn (average) was used by in-
dustrials, electric utility companies, railroads, oil com-
panies, and the military, as well as for heating (Table VIII).
TABLE VIII
RESIDUAL FUEL OIL DATA
Residual Fuel Oil Burned - 1969 (bbls) 639,048, 000
Pounds per Barrel 340
Copper Content of Oil (ppm) 0.47
Based on the data in Table VIII, the copper emissions to the
atmosphere due to the combustion of residual, oil totaled 50
tons during 1969.
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-56-
IRON AND STEEL
Steel mills are important sources of copper emissions to
the atmosphere. Even though very little copper is used in
the production of steel, trace quantities enter the process
in the ra.w materials. In the blast furnace, where iron ore
is reduced to pig iron, there is a partial removal of impur-
ities. In the open-hearth, basic oxygen., and electric furn-
aces, further purification takes place as pig iron and scrap
are converted to steel.
Blast Furnace - As the gas leaves the blast furnace, it con-
tains large quantities of particulates averaging about 150
pounds per ton of pig iron _/; however, it is subsequently
cleaned and used as fuel. The gas cleaning is accomplished
in 2 or 3 stages and the annua] overall efficiency is estimated
by Ihe Contractor at 97 percen'..
During 1969: the pig iron produced in the United States totaled
95,472,000 tons /. The copper content of the particulate
1- "Air Pollutant Emission Factors"; Environmental Protec-
tion Agency; Preliminary Document: Apr., 1971.
2-- Minerals Yearbook; Bureau of Mines; 1969.
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emissions was not available, but it was assumed to 0. 5 per-
cent, the same as shown in Table IX for open-hearth furnaces.
Copper emissions to the atmosphere from blast furna.ree
totaled 1, 070 tons.
95,472,000 x 150 x 0.005 (1 - 0.97) n_n
270001>07°
Open-Hearth Furnace - The overall operating cycle of the
open-hearth furnace is about 10 hours. Even though fumes
are discharged continuously at varying rates, average emis-
sion factors have been established for operation both with
and without oxygen lancing. With oxygen lancing, the factor
for uncontrolled emissions is 21 pounds of particulate per
ton of steel. Without lancing, the factor is 8 pounds per ton.
The degree of emission control is estimated at 40 percent,
and the average emission factor (controlled) for all open-
hearth furnace operations is 10.2 pounds of particulate per
ton of steel produced /.
The mean particle size of the dust is generally considered
to be 0. 5 micron _/ and a typical chemical analysis is
I- "Emissions, Effluents and Control Practices"; Environ-
mental Protection Agency; Study in Progress (unpublished);
1970.
\
2- Aberlow, E. B. ; "Modification to the Fonta.na Open-
Hearth Precipitators": JAPCA; 7: May, 1957.
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TABLE IX
SPECTROGRAPHIC ANALYSIS OF PARTICULATE
DISCHARGE FROM AN OPEN-HEARTH FURNACE V
Element
Fe
Zn
Na
K
Al
Ca
Cr
Ni
Pb
Si
Sn
Cu
Mn
Mg
Li
Ba
Sr
Ag
Mo
Ti
V
Approximate Amount*
Percent
Remaining Amount
10 to 15
1 to 2
1 to 2
5
5
2
2
5
5
1
0. 5
0. 5
0. 1
Trace
Trace
Trace
0. 05
Trace
Trace
0.05
*These data are qualitative and require supplementary
quantitative analysis for actual amounts.
1- "Air Pollution Engineering Manual": Public Health Service
Publication No. 999-AP-40; p. 243; 1968.
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shown in Table IX.
During 1969 the steel produced in open-hearth furnaces was
60, 894, 000 tons _/, and the copper content of the particulate
matter emitted was about 0. 5 percent. Copper emissions to
the atmosphere totaled 1, 550 tons.
60,894,000 x 5. 1 x 0.005 _
Z, 000 " '
Basic Oxygen Furnace - During the one-hour operating cycle
of the basic oxygen furnace, large quantities of gas and par-
ticulate are discharged to the atmosphere. The emission fac-
tor for this type of furnace has been estimated at 46 pounds
of particulate per ton of steel (uncontrolled) _/, and the de-
gree of emission control at 90 percent.
During 1969 the steel produced in basic oxygen furna.ces was
60, 236, 000 tons _/, and the estimated copper content of the
particulate emissions wa.s 0.05 percent /. Copper emis-
sions to the atmosphere totaled 70 tons.
1- Minerals Yearbook; Bureau of Mines; 1969.
2-- "Air Pollutant Emission Factors"; Environmental Protec-
tion Agency; Preliminary Document; Apr., 1971.
3- Private communication.
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60,236,000 x 46 x 0.0005
jTooo V - °-9) ' 70
Electric Furnace - Electric arc furnaces are well suited
to the production of alloy steels and are used extensively for
that purpose. Emissions generated during operation consist
of fume and dust emitted throughout the charging and refining
operations. While charging, the top is open to receive the
cold metal and the exposure of the cold charge to the high
temperature inside the furnace results in the generation of
large quantities of fume.
Particulate emissions from electric arc furnaces have been
estimated with and without ox.ygen lancing at 11 pounds and
7 pounds per ton of steel, respectively /. The degree of
control is estimated by the Contractor at 77 percent, and the
average emission factor (uncontrolled) is 20 pounds of pa.r-
ticulate per ton of steel produced _/.
During 1969 the steel produced in electric arc furnaces was
20, 132, 000 tons /. The copper content of the particulate
.1 - "Air Pollutant Emission Factors"; Environmental Pro-
tection Agency: Preliminary Document; Apr., 1971.
2- Private communication.
3- Minerals Yearbook: Bureau of Mines; 1969.
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is estimated at 0. 16 percent (0. 2 percent CuO as shown in
Table X). Copper emissions to the atmosphere totaled 70
tons.
20, 132,OOP x 20 x 0. 0016 /j . 0 77) : 70
2,000
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TABLE X
TYPICAL EMISSIONS FROM AN
ELECTRIC ARC FURNACE l/
Component Weight %
Zinc Oxide (ZnO) 37
Iron Oxides 25
Lime (CaO) 6
Manganese Oxide (MnO) 4
Alumina (A12O3) 3
Sulfur Trioxide (SO,) 3
Silica (SiO2) 2
Magnesium Oxide (MgO) 2
Copper Oxide (CuO) 0. 2
Phosphorus Pentoxide (P2O5) 0. 2
1- Coulter, R. S. ; "Smoke, Dust, Fumes Closely Controlled
in Electrode Furnaces"; Iron Age; 173; Jan. 14, 1954.
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FOUNDRIES
During this study spectrographic analyses of dust samples
from foundries have been examined; they all indicate cop-
per and numerous other elements are contained in the dust
emitted to the atmosphere.
The cupola is the most used method for producing cast iron.
The rate of particulate emissions from gray iron cupolas
has been reported as 4 to 26 pounds per ton of process weight
not including emissions from handling, charging, or other
non-melting operations.
Based on information obtained from industry, the particulate
emission factor is estimated at 22 pounds per ton of process
weight, including melting and non-melting operations. The
copper content of the particulate is about 0. 03 percent / and
the degree of emission control approximately 25 percent.
During 1969 the pig iron and scrap used by iron foundries
totaled 18, 594,000 tons /. Copper emissions to the atmos-
phere due to the production of cast iron were about 50 tons.
1- Private communication with industrial sources.
2- Minerals Yearbook; Bureau of Mines; 1969.
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INCINERATION
Numerous studies and tests have been conducted to deter-
mine the quantity of solid waste burned in incinerators and
the particulate emissions that result. Reports from 3 sources
contain information regarding copper emissions. One source
shows that copper emissions are 4. 2 x 10 pounds per ton of
charge when burning refuse alone, and 5. 7 x 10"^ pounds per
ton of charge when burning a combination of refuse and sew-
age sludge _/. The ratio of refuse to sludge during the tests
was approximately 3. 5 to 1.
Another source reports that household, commercial, and
municipal wastes are over 250 million tons per year, and
that approximately 8 percent of all municipal solid waste is
burned in municipal incinerators /.
The third source indicates that the burning of sewage and
1- Cross, F. L. Jr., Drago, R. J. , and Francis, H. E. ;
"Metal and-Particulate Emissions from Incincerators Burn-
ing Sewage Sludge and Mixed Refuse"; Proceedings of the
National Incinerator Conference; Cincinnati, Ohio; 1970.
2- Black, R. J. , Muhich, A. T. , Klee, A. J. , Hickman, H.
L. Jr. , and Vaughn, R. D. ; "The National Solid Wastes
Survey, an Interim Report". (Presented at the 1968 An-
nual Meeting of the Institute of Solid Wastes of the Ameri-
can Public Works Association, Miami Beach, Florida;
Oct. 24, 1968.)
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sludge in the United.States is at the rate of about 700, 000
tons per year _/.
If we assume that all sewage sludge was burned with refuse
at the ratio of 3. 5 to 1, then 2. 5 million tons of refuse were
required for that purpose and 17. 5 million tons were burned
alone. The data reported indicate that copper emissions in
the United States due to the burning of refuse and sewage
sludge in municipal incinerators are nearly 460 tons per year.
17,500,000 x 4.2 x IP'2 (2. 500. OOP + 700, OOP) 5. 7 x. IP'2 .
2,000 2,000
- Private communication with the Federal Water Pollution
Control Authority,
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UPDATING OF EMISSION ESTIMATES
The emissions and emission factors presented in this report
are the result of calculations ba.sed principally on informa-
tion obtained from industrial sources. They are specifically
for the year 1969, but may be updated at any time when addi-
tional information is available. Either of the 2 methods de-
scribed herein may be used for updating; however, the longer
procedure, referred to as Method A, will yield results that
are much more reliable.
The procedures to be followed with Method A are essentially
the same as those used during the original study, which are
described briefly as follows. More than 170 inquiries were
sent to processing and reprocessing companies by mail or de-
livered during persona.], visits to plant sites. There was no
reply from 52 companies and the answers from 39 others con-
tained very little of the data requested. Some refused, but
most of them claimed the information was not readily avail-
able. There are 79 companies that furnished all or a substan-
tial part of the information requested, and this was the basis
for emissions and emission factors set forth in this report.
All of the smelting and refining companies that produce
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primary copper were requested to provide the essential data
required for the study. Information was obtained concern-
ing 9 of the 16 smelters and 7 of the 13 refineries. Ba.sed on
the data obtained, emission factors were calculated and re-
ported.
With respect to secondary copper, about 20 percent of the
processing companies were contacted and data was obtained
concerning nearly 25 percent of the production capacity. The
reprocessing companies that provided information represented
about 10 percent of the industry capacity.
Regardless of the method selected, the first step to be taken
when updating the emission estimates is to obtain the latest
issue of the Bureau of Mines Minerals Yearbook, Volume I-II,
which is normally available within 16 or 18 months after the
end of the calendar year (preprints of individual sections are
usually available sooner). This publication shows the quan-
tity of ore mined and the copper produced in the United States,
as well as the quantities imported and exported. It also shows
the amount of secondary copper produced and consumed, and
the various forms in which it was used. This one publication
contains all of the information that is required to update the
material flow chart for copper.
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When using Method A, the emission factors must be revised
by contacting industry to determine the improvements in air
pollution collection equipment efficiency and other process-
ing changes affecting copper emissions. The revised emis-
sion factors may then be used with the production quantities
obtained from the Minerals Yearbook or other referenced
sources.
Method B is considerably shorter than Method A and less re-
liable. The only requirement is to revise the material flow
chart according to the most recent published data and apply
the emission factors shown in this report. In reality, this
method is only a partial updating. There is no determination
regarding improvements in air pollution control, a shift in
production to more efficient plants, or any other considera-
tions affecting emission factors. The advantage is the report
can be updated within a very short length of time.
To update copper emissions from metallurgical processing
and the iron and steel industry, it is preferable to use Method
A. The remaining emissions shown in this report may be up-
dated by Method B without introducing an appreciable error
into the results.
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BIBLIOGRAPHIC DATA
SHEET
1. Report No.
APTD-1129
3. Recipient's Accession No.
4. Title and Subtitle
5. Report Date
National Inventory of Sources and Emissions: Copper - 1969
April 1972
6.
7. Author(s)
W. E. Davis
8' Performing Organization Kept.
No.
9. Performing Organization Name and Address
W. E. Davis & Associates
9726 Sagamore Road
Leawood, Kansas
10. Project/Task/Worlc Unit No.
II. Contract /Grant No.
68-02-0100
12. Sponsoring Organization Name and Address
ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Water Programs
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
13. Type of Report & Period
Covered
14.
15. Supplementary Notes
16. Abstracts
Information is provided regarding the nature, magnitude, and extent of the emissions o
copper in the United States for the year 1969. Background information concerning the
basic characteristics of the copper industry has been assembled and included. Brief
process descriptions are given; they are limited to the areas that are closely related
to existing or potential atmospheric losses of the pollutant. The copper emissions
and emission factors are based on data obtained from production and reprocessing com-
panies. Additional information was acquired during field trips to inspect the air'pol
lution control equipment and observe processing operations. Emissions to the atmos-
phere during the year were 13,680 tons. About 64 percent of the emissions resulted
from the metallurgical processing of primary copper, and about 20 percent from the
production of iron and steel. The combustion of coal was the only other significant
emission source.
17. Key Words and Document Analysis. 17o. Descriptors
Air pollution
Copper inorganic compounds
Inventories
Exhaust emissions
Industrial wastes
Metal industry
Iron
Steels
Coal
17b, Identifiers/Open-Ended Terms
17e. COSATI Field/Group
13B
18. Availability Statement
Unlimited
19. Security Class (This
Report)
UNC1.ASSIFIF
ffc
20. Security Class (
UNCLASSIFIED
21. No. of Pages
75
22. Price
FORM NTIS*SB
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