MTR-6401
Volume II
SELECTED
CHARACTERISTICS
OF HAZARDOUS
POLLUTANT EMISSIONS
!MAY 1973 THE MITRE CORPORATION
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MTR-6401
Volume II
SELECTED CHARACTERISTICS
OF HAZARDOUS
NT EMISSIONS
L. j. DUNCAN
E. L. KEITZ
E. P. KRAJESKI
Contract No.: 68-01 -0438
Sponsor: Environmental Protection Agency
Project No,: 095A
MAY 1973
THEE
:r^is document was prepared for authorized distribution.
MITRE
approved for public release. WASMmfiTO*
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Department Approval:
R. f. Ouellette
MITRE Project Approval:
J. T, Stone
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ABSTRACT
This document is the final report for the Hazardous Pollutant
Study. Emissions data, including sources and quantity produced by
selected major industrial processes, are presented for 18 potentially
hazardous pollutants. In addition, applicable control devices are
reported. Specific gas and particulate emission characteristics and
process descriptions are included for those industrial processes
found to be the major emitters.
iii
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TABLE OF CONTENTS
Page
LIST OF ILLUSTRATIONS x
EXECUTIVE SUMMARY xvii
1.0 INTRODUCTION 1
1.1 Background 1
1.2 Purpose 4
2.0 SCOPE AND MAGNITUDE OF EMISSIONS 19
2.1 Hazardous Pollutant Sources 19
2.2 Material Flows Through the Economy 69
2.2.1 Arsenic 76
2.2.2 Asbestos 76
2.2.3 Barium 77
2.2.4 Beryllium 77
2.2.5 Boron 77
2.2.6 Cadmium 78
2.2.7 Chlorine 78
2.2.8 Chromium 79
2.2.9 Copper 79
2.2.10 Fluorides 80
2.2.11 Lead 80
2.2.12 Manganese 80
2.2.13 Mercury 81
2.2.14 Nickel 81
2.2.15 POM 81
2.2.16 Selenium 82
2.2.17 Tin 82
2.2.18 Vanadium 82
2.2.19 Zinc 83
3.0 PRESENT CONTROL TECHNOLOGY FOR SELECTED PROCESSES 85
4.0 THE PRIMARY NON-FERROUS SMELTING INDUSTRIES 111
4.1 Introduction 111
4.2 The Primary Copper Industry 112
4.3 The Primary Lead Industry 116
4.4 The Primary Zinc Industry 120
4.5 Copper Ore Roasting 124
4.5.1 Multiple Hearth Copper Ore Roasters 124
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TABLE OF CONTENTS (Continued)
124
4.5.1.1 Process Description
4.5.1.2 Chemical and Physical Properties of
Input Feed and Effluents
4.5.2 Fluid Bed Copper Ore Roasters
4i5.2.1 Process Description
4.5.2.2 Chemical and Physical Properties! of
Input Feed and Effluents
4*6 Lead Sintering
4.6.1 Process Description
4.6.2 Chemical and Physical Properties of Input Feed
and Effluents 156
4.7 2ine Ore Roasting 163
4.7.1 Process Description 163
4.7.1.1 Ropp Roaster 163
4.7.1.2 Multiple Hearth Roaster 164
4.7.1.3 Suspension/Flash Roasters 164
4.7.1.4 Fluid Bed and Fluid Column Roasters 166
4.8.1 Chemical and Physical Properties of Input Feed
and Effluents 168
4.8*1.1 Suspension/Flash Roaster 168
4.8.1.2 Fluid Bed Roaster 173
4.9 Interpretation of the Data 178
4.9.1 Polluting Gases 178
4.9.2 Particulates and Fine Particulates Not Containing
Hazardous Chemicals 178
4.9.3 Particulates and Fine Particulates Containing
Hazardous Chemicals 185
4.9.4 Summary of Recommendations 185
5.0 OVERVIEW OF OTHER SELECTED INDUSTRIAL PROCESSES 189
5.1 Copper Reverberatory Furnace 190
vi
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TABLE OF CONTENTS (Continued)
Page
5.1.1 Process Description 190
5.1.2 Chemical and Physical Properties of Input Feed
and Effluents 191
5.1.2.1 Data for Furnaces Using Unroasted
Concentrates 191
5.1.2.2 Data for Furnaces Using Roasted
Concentrates 204
5.2 Reduction of Zinc Oxide in Retorts 207
5.2.1 Zinc-Vertical Retort 207
5.2.1.1 Process Description 207
5.2.1.2 Chemical and Physical Properties of
Input Feed and Effluents 208
5.2.2 Zinc-Horizontal Retort 217
5.2.2.1 Process Description 217
5.2.2.2 Chemical and Physical Characteristics
of Input Feed and Effluents 219
5.3 Copper Converter 224
5.3.1 Process Description 224
5.3.2 Chemical and Physical Properties of Input Feed
and Effluents 226
5.3.2.1 Input Feed 226
5.3.2.2 Effluent Immediately After the Converter 235
5.3.2.3 Effluent After Converter Gases Join
Gases From Reverberatory Furnaces Using
Unroasted Ores 236
5.3.2.4 Effluent After Converter Gases Join
Gases From Reverberatory Furnaces Using
Roasted Ores 236
5.4 Lead Blast Furnace 237
5.4.1 Process Description 237
5.4.2 Chemical and Physical Properties of Input Feed
and Effluents 238
vii
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TABLE Of CONTENTS (Continued)
Page
5.5 Steelmaking Furnaces
5.5.1 Open Hearth Furnaces
244
'5.5.1.1 Process Description
5.5.1.1.1 With Oxygen Lance
5.5.1.1.2 Without Oxygen Lance
5.5.1.2 Chemical and Physical Charactreistics
of Input Feed and Effluents
5.5.1.2.1 With Oxygen Lancing 247
5.5.1.2.2 Without Oxygen Lancing 250
5.5.2 Basic Oxygen Steel-Making Furnace 251
5.5.2.1 Process Description 251
5.5.2.2 Chemical and Physical Characteristics
of Input Feed and Effluents 255
5.5.3 Electric-Arc Furnace 256
5.5.3.1 Process Description 258
5.5.3.2 Chemical and Physical Properties of the
Input Feed and Effluents 258
5.6 The Chlor-Alkali Industry 262
5;.6.1 Chlorine Manufacture in Mercury Cells 262
5.6>1.1 Process Description 262
5.6.1.2 Chemical and Physical Properties of the
Input Feed and Effluent 165
5.6.2 Chlorine Manufacture in Diaphragm Cells 268
5.6.2.1 Process Description 268
5.6.2.2 Chemical and Physical Properties of
Input Feed and Effluents 27°
5.6.3 Chlorine Liquefaction 272
viii
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TABLE OF CONTENTS (Continued)
Page
5.6.3.1 Process Description 272
5.6.3.2 Chemical and Physical Properties of
Input Feed and Effluent 272
5.6.4 Hydrochloric Acid Manufacture 276
5.6.4.1 Process Description 276
5.6.4.2 Chemical and Physical Properties of
Input Feed and Effluent 280
5.6.5 Chlorine Bleach Manufacture 284
5.6.6.1 Process Description 284
5.6.6.2 Chemical and Physical Properties of
Input Feed and Effluents 284
APPENDIX 287
BIBLIOGRAPHY 303
NON-BIBLIOGRAPHIC REFERENCES 329
DISTRIBUTION LIST 331
ix
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LIST OF ILLUSTRATIONS
Table
I MAGNITUDE OF HAZARDOUS POLLUTANT EMISSIONS FROM
SELECTED INDUSTRIAL SOURCES
II HAZARDOUS POLLUTANT SOURCES - ARSENIC
III HAZARDOUS POLLUTANT SOURCES - ASBESTOS
IV HAZARDOUS POLLUTANT SOURCES - BARIUM
V HAZARDOUS POLLUTANT SOURCES - BERYLLIUM
VI HAZARDOUS POLLUTANT SOURCES - BORON
VII HAZARDOUS POLLUTANT SOURCES - CADMIUM
VIII HAZARDOUS POLLUTANT SOURCES - CHLORINE
IX HAZARDOUS POLLUTANT SOURCES - CHROMIUM
X HAZARDOUS POLLUTANT SOURCES - COPPER
XI HAZARDOUS POLLUTANT SOURCES - FLUORIDES
XII HAZARDOUS POLLUTANT SOURCES - LEAD
XIII HAZARDOUS POLLUTANT SOURCES - MANGANESE
XIV HAZARDOUS POLLUTANT SOURCES - MERCURY
XV HAZARDOUS POLLUTANT SOURCES - NICKEL
XVI HAZARDOUS POLLUTANT SOURCES - POLYCYCLIC ORGANIC
MATERIAL (POM)
XVII HAZARDOUS POLLUTANT SOURCES - SELENIUM
XVIII HAZARDOUS POLLUTANT SOURCES - TIN
XIX HAZARDOUS POLLUTANT .SOURCES - VANADIUM
XX HAZARDOUS POLLUTANT SOURCES - ZINC
7
21
22
23
24
25
26
27
28
29
30
32
34
35
36
37
38
39
40
41
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LIST OF ILLUSTRATIONS
(Continued)
Table
XXI
XXII
XXIII
XXIV
XXV
XXVI
XXVII
XVIII
XXIX
XXX
XXXI
XXXII
XXXIII
XXXIV
SOURCE OF HAZARDOUS POLLUTANTS - ORDERING OF
EMITTERS - TOTAL TONNAGE OF ALL PRODUCTS
BY OPERATION
SOURCE OF HAZARDOUS POLLUTANTS - ORDERING OF
EMITTERS- TOTAL TONNAGE WITHIN GROUPS
NUMBER OF SOURCE LOCATIONS AND GENERAL EMISSION
CHARACTERISTICS FOR SELECTED OPERATIONS
NUMBER OF SOURCE LOCATIONS AND GENERAL EMISSION
CHARACTERISTICS FOR ADDITIONAL OPERATIONS
CONTRIBUTING ASBESTOS, BERYLLIUM OR MERCURY
PARTICLE SIZE DISTRIBUTION FOR EMISSIONS FROM
SELECTED PROCESSES WITHOUT CONTROL DEVICES
AND WITH TYPICAL CONTROL DEVICES
EMISSIONS OF PARTICULATES AND FINE PARTICULATES
AFTER 100% APPLICATION OF BEST CONTROL DEVICE
U.S. PRIMARY COPPER SMELTERS
U.S. PRIMARY LEAD SMELTERS
U.S. PRIMARY ZINC SMELTERS
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF
INPUT FEED AND EFFLUENTS-MULTIPLE HEARTH
COPPER ROASTERS
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF
INPUT FEED AND EFFLUENTS-FLUID BED
COPPER ROASTERS
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT
FEED AND EFFLUENTS - LEAD SINTERING MACHINE -
UPDRAFT TYPE
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF
INPUT FEED AND EFFLUENTS-FLASH TYPE ZINC ROASTER
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT
FEED AND EFFLUENTS-FLUID BED ZINC ROASTER
Page
43
46
70
74
86
96
117
119
126
129
146
157
169
174
xi
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LIST OF ILLUSTRATIONS
(Continued)
Table Page
XXXIVA SOLUBILITIES OF CHEMICALS FOUND IN SMELTER
EFFLUENTS 186
XXXV SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF
INPUT FEED AND EFFLUENTS-COPPER REVERBERATORY
FURNACE 193
XXXVI PARTICLE SIZE DISTRIBUTION OF ROASTER PRODUCTS
AT CQPPERHILL, TENNESSEE 206
XXXVII SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF
INPUT FEED AND EFFLUENTS-ZINC VERTICAL RETORT 210
XXXVIII SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF
INPUT FEED AND EFFLUENTS-ZINC HORIZONTAL RETORT 220
XXXIX SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF
INPUT FEED AND EFFLUENTS-COPPER CONVERTER 227
XL SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF
INPUT FEED AND EFFLUENTS-LEAD BLAST FURNACE 240
XLI SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF
INPUT FEED AND EFFLUENTS-OPEN HEARTH STEEL
FURNACE WITH OXYGEN LANCE 248
XLII SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF
INPUT FEED AND EFFLUENTS-OPEN HEARTH STEEL
FURNACE WITHOUT OXYGEN LANCE 252
XLIII SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF
INPUT FEED AND EFFLUENTS-BASIC OXYGEN STEEL
FURNACE 256
XLIV SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF
INPUT FEED AND EFFLUENTS-ELECTRIC-ARC STEEL
FURNACE 2:60
XLV SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF
INPUT FEED AND EFFLUENTS-MERCURY CELL CHLOR/
ALKALI MANUFACTURE 266
XLVI SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF
INPUT FEED AND EFFLUENTS-DIAPHRAGM CELL CHLOR/
ALKALI MANUFACTURE 273
xii
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LIST OF ILLUSTRATIONS
(Continued)
Table
XLVII
XLVIII
XL IX
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF
INPUT FEED AND EFFLUENT-CHLORINE LIQUEFACTION
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF
INPUT FEED AND EFFLUENTS-HYDROCHLORIC ACID
MANUFACTURE
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF
INPUT FEED AND EFFLUENTS-CHLORINE BLEACH
MANUFACTURE (COMMERCIAL 12-15% AVAILABLE Cl)
Page
274
281
285
Figure
1
3
4
10
MATERIAL FLOW THROUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES - ARSENIC
MATERIAL FLOW THROUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES - ASBESTOS
MATERIAL FLOW THROUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES - BARIUM
MATERIAL FLOW THROUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES - BERYLLIUM
MATERIAL FLOW THROUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES - BORON
MATERIAL FLOW THROUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES - CADMIUM
MATERIAL FLOW THROUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES - CHLORINE
MATERIAL FLOW THROUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES - CHROMIUM
MATERIAL FLOW THROUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES"- COPPER
MATERIAL FLOW THEOUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES - FLUORIDES
50
51
52
53
54
55
56
57
58
59
xiii
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LIST OF ILLUSTRATIONS
(Continued)
Figure IS8S.
11 MATERIAL FLOW THROUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES - LEAD
60
12 MATERIAL FLOW THROUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES - MANGANESE 61
13 MATERIAL FLOW THROUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES - MERCURY 62
14 MATERIAL FLOW THROUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES - NICKEL 63
15 MATERIAL FLOW THROUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES - POLYCYCLIC
ORGANIC MATERIAL 64
16 MATERIAL FLOW THROUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES - SELENIUM 65
17 MATERIAL FLOW THROUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES - TIN 66
1.8 MATERIAL FLOW THROUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES - VANADIUM 67
19 MATERIAL FLOW THROUGH THE ECONOMY SHOWING
PRIMARY EMISSION SOURCES - ZINC 68
20 FRACTIONAL EFFICIENCY DATA FOR ELECTROSTATIC
PRECIPITATORS 100
21 FRACTIONAL EFFICIENCY DATA FOR A FABRIC FILTER 101
22 FRACTIONAL EFFICIENCY DATA FOR CYCLONES 102
23 FRACTIONAL EFFICIENCY DATA FOR SCRUBBERS 1Q3
24 EXTRAPOLATED FRACTIONAL EFFICIENCY OF CONTROL
DEVICES 104
25 BASIC OPERATIONS - PRIMARY COPPER SMELTING
26 BASIC OPERATIONS - PRIMARY LEAD SMELTING 121
xiv
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LIST OF ILLUSTRATIONS
(Continued)
Figure
27 BASIC OPERATIONS - PRIMARY ZINC SMELTING
AND ZINC OXIDE MANUFACTURE 125
28 MULTIPLE HEARTH ROASTING FURNACE 127
29 BASIC FLUIDIZED BED SYSTEM 142
30 SCHYTIL'S PHASE DIAGRAM OF GAS-SOLID SUSPENSIONS 144
31 LEAD SINTERING MACHINE DOWNDRAFT TYPE 155
32 COMPARISON OF CONVERTED MULTIPLE HEARTH ROASTER
TO STUB COLUMN SUSPENSION ROASTER AT BUNKER
HILL CO. KELLOGG, IDAHO 165
33 TYPICAL ZINC FLUID BED ROASTER 167
34 COPPER REVERBERATORY FURNACE 192
35 ZINC VERTICAL RETORT REDUCTION FURNACE 209
36 ONE BANK OF A BELGIAN RETORT FURNACE 218
37 COPPER CONVERTER 225
38 LEAD BLAST FURNACE 239
39 BASIC OPERATIONS - IRON & STEEL INDUSTRY 245
40 OPEN HEARTH FURNACE WITH OXYGEN LANCING 246
41 BASIC-OXYGEN STEEL-MAKING FURNACE 254
42 ELECTRIC-ARC FURNACE 259
43 MERCURY CELL WITH HORIZONTAL DECOMPOSER 263
44 FLOW DIAGRAM OF MERCU&Y CELL CHLOR/ALKALI
MANUFACTURE 264
45 HOOKER DIAPHRAGM CELL 269
xv
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LIST OF ILLUSTRATIONS
(Continued)
Figure ,page-
46 BASIC OPERATIONS - DIAPHRAGM CELL CHLOR-ALKALI 271
47 DIAGRAM OF A KARBATE ALL-CARBON HYDROCHLORIC
ACID COOLER-ABSORBER (NATIONAL CARBON CO. MODEL) 278
48 BASIC OPERATIONS - HYDROCHLORIC ACID MANUFACTURE 279
49 BASIC OPERATIONS - IRON ORE PELLET PLANT 288
5.0 BASIC'OPERATIONS - FERRO-ALLOYS (INCL.
SILICOMANGANESE) 289
51 BASIC OPERATIONS - PRIMARY ALUMINUM 290
52 BASIC OPERATIONS - MANUFACTURE OF ALUMINA 291
53 BASIC OPERATIONS - NORMAL SUPERPHOSPHATE
MANUFACTURE
292
54 BASIC OPERATIONS - SULFITE PULPING PROCESS,
AMMONIA BASE 293
55 BASIC OPERATIONS - SULFITE PULPING PROCESS,
MAGNESIA BASE 294
56 BASIC OPERATIONS - RAW CERAMIC CLAY
MANUFACTURE 295
57 BASIC OPERATIONS - TYPICAL ASPHALT AIR-
BLOWING PROCESS 296
58 BASIC OPERATIONS - COMMERCIAL/RESIDENTIAL
COMBUSTION 297
59 BASIC OPERATIONS - INDUSTRIAL COMBUSTION 298
60 BASIC OPERATIONS - POWER PLANT COMBUSTION 293
61 BASIC OPERATIONS - TYPICAL APARTMENT HOUSE
TYPE INCINERATOR 300
62 BASIC OPERATIONS - TYPICAL MUNICIPAL INCINERATOR 301
xvi
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EXECUTIVE SUMMARY
This paper documents the study which The MITRE Corporation performed
in support of The Environmental Protection Agency (EPA), Office of Research,
Air Pollution Technology Branch. The objective of the study was to
identify hazardous pollutant sources, characteristics of those sources,
and available control technology.
EPA is currently attempting to define the specific hazards posed by
particulate and gaseous emissions other than the six major pollutant
categories of sulfur oxides, nitrogen oxides, carbon monoxide, oxidants,
hydrocarbons, and particulates. Many of these less prominant pollutants
have been designated as "hazardous" or "potentially hazardous" by EPA in
accordance with rules set forth in Section 112 of the Clean Air Act of
1970 as amended. In fact, emission standards for three hazardous pollutants,
namely, asbestos, beryllium and mercury were specified in the Federal
Register of April 6, 1973. Another 15 substances have been designated
by EPA as hazardous pollutant candidates for which control strategies are
to be determined by the end of FY 1974 and standards promulgated as soon
thereafter as possible.
Those pollutants chosen for this study were selected from the EPA
list of potentially hazardous pollutants. The initial list was as follows:
o Arsenic o Lead
p Asbestos o Manganese
q Barium o Mercury
o Beryllium o Nickel
xvii
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o Boron o Polycyclic organic material (POM)
o Cadmium o Selenium
o Chlorine o Tin
o Chromium o Vanadium
o Copper o Zinc
o Fluorides
In accordance with specific direction from EPA the significance of
toxicity for any specific pollutant was not taken into account. EPA
has funded a separate study of the toxicity factor in order to develop
data for selection of presumed safe ambient air quality levels.
The study was divided into four major phases which were:
1) The scope and magnitude of emissions;
2) Present control technology for selected processes;
3) The primary non-ferrous smelting industries;
4) Other selected industrial processes.
A brief description of the objectives of each of these parts follows, along
with a description of the study techniques used and a discussion of the
major results.
THE SCOPE AND MAGNITUDE OF EMISSIONS
This phase of the study had as its objective the determination of the
magnitude of the emissions of each pollutant and the characteristics of
the distribution of these emissions among the principal industrial sources.
Data were compiled by surveying the literature for emissions data, combining
data where appropriate to produce the desired emissions data and the use of
published emission factors. All of the emissions data which were found are
xviii
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presented (see Table I) along with information on control devices in use*
their application, and efficiency. The values in this table represent the
best information available from the sources cited. In many cases, these
values were estimates but, nevertheless, the results are adequate to
identify key sources of potentially hazardous pollutants and to establish
the relative importance of certain industries.
In order to better understand the nature of the data presented in
Table I, 19 additional tables are presented, one for each of the hazardous
pollutants. Each table shows the annual emissions in tons of the specific
pollutant emitted by each source and the percentage which the source
contributed to the total emissions of that pollutant. The purpose of
these tables is to provide a quick reference to emissions for each pollutant
The data were also compiled and presented in two other tables which
show which specific industrial operations (Table XXI) and which industries
(Table XXII) contribute the largest annual quantities of all hazardous
pollutants combined. The data show that the open burning of wastes
contributes two orders of magnitude more hazardous pollutants than the
highest industrial operation, open hearth furnaces (4.5 million tons
annually versus 68 thousand tons annually). Inspection of the data compiled
by "industry" shows the top five emitters to be,
Agricultural burning 2.1 million tons annually
Forest fires 1.4 million tons annually
Open burning 0.5 million tons annually
Conical burners 0.2 million tons annually
Coal refuse fires 0.2 million tons annually
six
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It is interesting to note that two of these "industries", namely,
forest fires and coal refuse fires, are not really industries at all
unplanned natural occurrences which have been included in this table.
In addition, the other three are all concerned with the disposal of waste
products in the nation's economy. It is obvious that development of better
techniques for disposal of agricultural, industrial and residential wastes
is a useful goal.
At this point, the decision was made to select some operations for
indepth study rather than to look at emissions resulting from specific
industries. Additional information was gathered on some of those operations
contributing the greatest quantity of hazardous pollutants. The information
presented includes the number of locations of each operation, the total
population in those cities closest to the source, and the basic nature of
the pollutants emitted in each case. No analysis of the data was performed.
The final part of this phase of the study consisted of the preparation
of a flow chart for each of the 19 pollutants in order to show primary
emission sources as the materials flow through the economy. The processes
which cause emissions have been divided into five sectors of the economy:
1) ore mining
2) concentrating and raw material preparation
3) product manufacture
4) consumptive uses
5) waste disposal
The estimated annual tons of emissions from each type of source are
shown in the flow diagrams and are summed for each of the five sectors of
xx
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the economy. Specific comments are presented for each of the 19 pollutants.
Unfortunately these comments are so individual and varied that a summary
here would be impossible.
PRESENT CONTROL TECHNOLOGY FOR SELECTED PROCESSES
The second phase of the study had as its objective the determination
of the present status of control technology for those industries which
ranked highest as emitters of the pollutants of interest. In this and
following phases of the study special attention was focused on the fine
particulate (less than 2fi size) fraction of the emissions. The extent to
which the hazardous pollutant problem is a fine particulate problem was
studied by gathering data which give a breakdown of the fraction by weight
of particulates in each particle size range emitted by the largest pollution
sources. These sources were selected from the top eighteen operations
presented in the first phase of the study with the exception of open burning
for which there are no control devices and chlorine liquefaction which
emits only gases. Also included were all major coal burning sources. In
addition to showing the particle size distribution in the absence of any
control device the table of data also shows the particle size distributions
after passage through control devices typical to the process.
The relative importance of the fine particulate problem is shown by
hypothetical computations based on the assumption that the best available
control devices are applied to all sources. Computations were made to
reflect this situation in order to determine the extent of the residual
emissions problem assuming that the best control technology was implemented
xxi
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everywhere. The results clearly show that although there is some reduction
in the total emissions, a large portion of the problem remains, especia y
in the fine particulate size ranges.
The processes that would be most greatly impacted by universal
application of the best control devices now in use are open hearth furnaces
in the iron and steel industry, blast furnaces used in the secondary lead,
secondary copper and non-ferroalloy industries, sintering operations for
primary metal smelting and incineration. In each of these cases, the
total emissions would be greatly reduced if the best control technology
was applied.
THE PRIMARY NON-FERROUS SMELTING INDUSTRIES
In the foregoing phase of the study the point was stressed that,
even if the best control technology were applied, fine particulates
would continue to be a significant problem in many processes. On the basis
of this fact, it was decided that a more detailed study should be made
of the roasting (sintering) process in the primary copper, lead, and zinc
industries. The primary purpose of these detailed studies was to determine
the characteristics of the gases and particulates being emitted at various
points in the process. These data are intended primarily for use in
control technology studies.
Tables were prepared to show both gaseous and particulate emission
characteristics. The gas characteristics include flow rate, temperature,
and chemical composition, while the particulate characteristics are grain
loadings, percent weight analysis of chemicals, size profiles, and chemical
composition. All data reported are for a typical industrial process and
xxii
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are not intended to represent any specific installation. In all cases
the data were prepared by using the best available of the following
sources,
o Measured data reported in the literature on the process being
studied
o Combination and analysis of data contained in the literature by
methods not previously applied
o Data reported for similar processes in other industries
o Theoretical (stoichiometric) calculations
o Materials balance calculations
o Engineering estimates
Analysis of the data substantiates statements made earlier that fine
particulates constitute a major problem in these processes. The multiple
hearth copper roasters show 40% by weight of the particulate to be less
than Wfi in size while for fluid bed copper roasters 94% of the particulate
is less than 10fi in size. These particulates result from two processes.
In most cases the particulate results from mechanical entrainment into
the airstream. However in copper roasting the arsenic and antimony compounds
in the ore are volatilized at low temperatures and solidify in the cooler
effluent stream as fine particulates of arsenic trioxide and antimony
trioxide. The other major chemicals in the copper roaster effluent are
copper oxides and sulfides, and iron oxides and sulfides.
In the lead sintering process the particulate which is less than lOfl
in size varies from 5 to 29%. The principal chemicals in the effluent are
lead oxides and sulfides, iron oxides and sulfides, silicon dioxide,
calcium oxide and arsenic trioxide. Both the flash and fluid bed type
xxiii
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zinc roasters show 31% of the particulate to be less than 10// in size.
However, zinc oxide, the principal chemical in the effluent, comprises
52% by weight for flash roasters and 55% by weight for fluid bed roasters.
This phase of the study also contains an interpretation of the data
in light of current control technology. The application of various generic
types of control techniques to the problem is discussed and recommendations
ave made for future research and development. The principal recommendations
are,
(1) Fabric filter technology
o Development of new or improved high temperature, acid
resistant fibers
o Further study of the use of synthetic fibers attached to
metal support screens
(2) Scrubber technology
o Further Research into the practical application of water
scrubbers in the non-ferrous industry
o Development of acid or alkali scrubbers for specific classes
of hazardous chemicals
(3) Electrostatic precipitation technology
o Studies to develop improved removal of dust collected on plates
o Studies of the resistivity of specific chemicals
o Studies to determine methods for improving the effective
migration velocity of sub-micron particles
(4) Other technologies
o Limited research studies of thermal precipitation, magnetic
precipitation, Brownian agglomeration, and sonic agglomeration.
xxiv
-------
OTHER SELECTED INDUSTRIAL PROCESSES
In phase four of the study short literature surveys and analyses were
performed for eleven selected industrial processes in order to compile
emission characteristics for those processes. The processes studied were,
1) Copper reverberatory furnaces
2) Zinc retort furnaces
3) Copper matte converters
4) Lead blast furnaces
5) Steel open hearth furnaces
6) Steel basic oxygen furnaces
7) Steel electric arc furnaces
8) Chlorine electrolysis
9) Chlorine liquefaction
10) Chlorine bleach manufacture
11) Hydrochloric acid manufacture
The objectives of these studies and the study methods used were basically
similar to those of the non-ferrous roasting and sintering studies. However
each of the eleven studies was made on a much more limited scale. The data
presented are similar to those for roasting and sintering but due to the
limitations in their development no interpretation was made and no
conclusions or recommendations appear in this report for these eleven
processes.
XXV
-------
1.0 INTRODUCTION
1.1 Background
"During the past few years, much research has been done on the
six major pollutants: sulfur dioxide, nitrogen oxides, carbon
monoxide, particulates, oxidants, and hydrocarbons. Primary and
secondary standards have been set for these pollutants and are included
in each state implementation plan. The Environmental Protection Agency
is now attempting to define the specific hazards posed by other
particulate and gaseous emissions. Thus far, three materials have
been designated hazardous in accordance with Section 112 of the Clean
Air Act of 1970 as amended. They are asbestos, beryllium, and mercury.
Emission standards were specified for them in the Federal Register
of April 6, 1973. Another 15 substances have been designated
hazardous pollutant candidates by the Administrator of EPA for which
control strategies are to be determined by the end of FY 1974 and
standards promulgated as soon thereafter as feasible.
"It is probable that a number of these pollutants are or may come
to be generally present in the atmosphere at sufficient levels to
constitute a serious hazard. The dangers associated with these
pollutants are compounded because a major fraction of these materials
is emitted in gaseous or fine particulate form which escape the
normally used'Collection devices, and which also penetrate the natural
filters of the respiratory tract to reach the air spaces of the lung.
Moreover, submicron particles are more heavily deposited in the lungs,
-------
the efficiency of deposition approaching 100 percent as participate
size decreases. Even those particles that have settled out of the
atmosphere remain of great concern because of their ability to
contaminate food and water.
"The difficulty of the control problem for hazardous pollutants
is compounded because the degree of toxicity is generally not
proportional to the mass of emissions. Quite possibly very small
amounts of some materials can have severe effects on human health,
not only because these substances are more potent but because
they persist in the atmosphere, are more easily respirable, and more
readily retained in the lungs. The total amount of emissions is
neither the sole nor necessarily the chief criterion to be used in
selecting problems for further attention. A prime consideration is
the toxicity of the material emitted in a typical location, which
depends not only on the number and sizes of the sources in a given
locality, but also the local topography and meteorological conditions
and the physical layout of the source.
"Fine particulates, often defined as <2.0 microns in diameter,
can modify weather patterns by acting as nuclei for condensation or
freezing. They absorb and scatter light and decrease visibility.
Visibility reduction is caused primarily by the 0.1 to 1.0(a radius
particles which appear in the atmosphere. Fine particles may also
interfere with solar radiation and can cause changes in the heat
balance of the earth-atmosphere system. Here too, small changes
-------
associated with increasing particle loads may well have disproportionate
long term meteorological effects.
"Considering these issues and the extent of documentation of the
toxic and otherwise injurious nature of most of these substances,
EPA must be as precise as possible in establishing quantitative
standards for ambient air quality and/or emission levels. However,
a number of prerequisites exist before this can be done. The first
requirement is to specify maximum safe ambient air concentration
for each pollutant and then compare the anticipated control measures
required to meet standards based on these data with control systems
in use or available. On the basis of this comparison, gaps can be
identified in technology necessary to control hazardous pollutants
and an R&D program prepared for this technology.
"The effort is now underway to generate the information upon which
to make the aforementioned comparisons. The first stage of this
activity is to determine the distribution and magnitude of emissions
from the chief pollutant sources, the extent of control in use and
the degree to which existing technology can be implemented to improve
the controls.
"The second step is to specify the degree to which certain emission
sources must be controlled. This requires the establishment of values
of ambient air quality to be regarded as probable goals of a control
strategy and that emission levels from each candidate source be
related to the target air quality level.
-------
"Then the third step is to state the specific technological
achievements necessary to devise a control system that will restr
emissions to the levels stipulated as maximal if the air quality
targets are to be reached."
1.2 Purpose
This paper documents study by The MITRE Corporation performed in
support of EPA's Office of Research, Air Pollution Technology Branch.
The objective of the study was to identify hazardous pollutant sources,
characteristics of those sources, available control technology, and assist
in developing a scheme to rank sources according to need for abatement.
The information and data used for this study were taken from current
literature. A complete listing of the information sources used appears
in the bibliography at the end of this report.
The EPA list of potentially hazardous pollutants was considered
by MITRE and EPA and revised according to interest and availability
of data. Those pollutants which were agreed upon for study were:
o Arsenic o Lead
o Asbestos o Manganese
o Barium o Mercury
o Beryllium o Nickel
o Boron o Polycyclic organic material (POM)
o Cadmium o Selenium
o Chlorine o Tin
o Chromium o Vanadium
o Copper o Zinc
o Fluoride
-------
Although the significance of toxicity in ranking the emission
sources is great, this factor was not taken into account. (Instead,
the sponsor funded a separate study to look into and provide
data for the development of presumed safe AAQ levels.)
Very little emissions data have been reported in the literature,
and frequently the information which has been published estimates
values rather than reports actual measurements. The emissions data
used in this report to rank sources are the best data presently
available, but should be used only with cognizance of their potential
inaccuracy.
For certain industries, such as the iron and steel industry,
much research and documentation has been done regarding the emission
characteristics and control technology. In other cases, data were
much more difficult to obtain, particularly if the industry was a
relatively small one. Data such as total annual production were often
not reported in order to protect privileged company records. Plants
which closed seemed more inclined than operating plants to publish
detailed data relating to their operating characteristics. These data
were assumed to be representative of data for plants in operation
and were consequently used when no other information was available.
The work began by compiling all hazardous emissions data by
source and by pollutant. The sources were ranked by the total amount
of the 19 pollutants being emitted. The data were organized in
several different ways in order to determine which sources would be
-------
the best candidates for more detailed study. These data are presented
and discussed in Section II, "Scope and Magnitude of Emissions."
The third section of the report describes the work performed to
determine the present control technology for industries which ranked
highest as emitters of the pollutants of interest. The point which
is stressed here is that even if the best control technology were
applied, fine particulates would continue to be a significant problem
in many cases. One such case is roasting in both the primary
copper and primary zinc industries. This fact plus data gathered on
the pollutants emitted, resulted in the sponsor and MITRE agreeing
that a more detailed study should be made of the roasting (sintering)
process in the primary copper, lead, and zinc industries. Section IV
describes briefly the various stages in the primary copper, lead, and
zinc industries, and then presents a more detailed look at the
roasting processes and the data gathered on the specific emission
characteristics.
Time did not permit studies of other major emitting processes
to be as detailed. Processes to be studied were selected from the
major emitters in Table I . Those studied are discussed in Section
V. Other sources which were candidates for additional study, but
had to be eliminated because of priority were:
o Pellet Plants
o Bleaching in the pulp and paper industry
o Superphosphate manufacture
-------
TABLE I. MAGNITUDE OF HAZARDOUS POLLUTANT EMISSIONS FROM SELECTED INDUSTRIAL SOURCES
(1)
INDUSTRY AND PROCESS
MINING AND RAW
MATERIAL PREPARATION
Copper
Ore Crushing
Raw Material Handling
Zinc
Ore Crushing
Raw Material Handling
Lead
Ore Crushing
Raw Material Handling
Iron Ore
Ore Crushing
Raw Material Handling
Pellet Plants
Coal
Mining and Handling
Coal Cleaning
M
Asbestos Mining
Crushing and Drying
Milling
Handling and All Other
Barium Mining
Ore Crushing
Raw Material Handling
CONTROL DEVICES
TYPE IN I'SE
None
Sone
Hood, Chambers, Cyclones, Bagnouse
None
tiood, Chambers, Cyclones, ESP, Baghouse
None
Hood, Chambers, Cyclones, ESP, Baghouse
•/.
APPLICATION
0
0
35
0
35
0
35
(Est. 75%
None
Cyclone Plus Wet Scrubber
Cyclone Only
Cyclones
Cyclones and Baghouse
None
None
Hood, Chambers, Cyclones, ESP, Baghouse
Mica, Feldspar, Mining (Beryllium)
Ore Crushing
Raw Material Handling
Borax Mining
Ore Crushing
Other Mining Operations
None
Hood, Chambers, Cyclones, ESP, Baghouse
Baghouse
Sone
Manganese Mining (98-99% Imported)
Tailing Wind Loss
Nickel Mining
Phosphate Rock
Grinding
Drying
Handling
Calcining
Rock
Mercury Mining
Ore Crushing and Grinding
Other Mining Operations
Vanadium Mining
Ore Crushing and Grinding
Other Mining Operations
Primary Aluminum
Calcining of Hydroxide
Reduction H.S. Soderberg
TI
Reduction V.S. Soderberg
Prebake
"
Raw Material Handling
None
Hood, Chambers, Cyclones, ESP, Baghouse
Cyclones, and/or Wee Scrubbers
,.
Hood, Cyclones, Wet Scrubbers
Hood, Cyclones, Wet Scrubbers
Hood, Chambers, Cyclones, ESP, Baghouse
Cyclones, ESP, Baghouse
Floating Bed Scrubber
Spray Scrubber
Multicyclone
Spray Scrubber
Multi-cyclone
Spray Scrubber After Multicyclone
Spray Scrubber After ESP
Cell Exhaust and Baghouse
Roof Monitor-ESP Plus Wet Filter
Cyclones or Baghouse
0
50
50
Est. 100
Est. 100
0
0
Est. 35
0
Est 100
Est 100
0
0
Est 35
100
100
25
100
Est 100
Est 35
Est 35
Est 35
net c
100
(3)
(3)
(3)
(10)
(10)
(6)
(6)
(M)
'4
EFFICIENCY
EFFICIENCY
OF FLUORIDE
COLLECTION
0 (43)
90 (
-*J>
0 (43)
90 (43)
ARSENIC
(«4) <2'
1
1190(1. 41) ( '
1
FLUORIDES
(J50)
18200(11.16)
1770(1.09)
5160(3.17)
2460(1.51)
8610(5.28)
LEAD
<*«)
See Lead
See Lead
345(3.84)
MANGANESE
(S6)
5(0.03)
MERCURY
«7)
2.6(.33)
NICKEL
(}2)
2(0.03)
POM
(*48)
1
1
1
Unk
SELENIUM
(012)
•
TIN
(»56)
VANADIUM
US)
Neg
ZINC
<«3)
72(0.05)
*
.
(1) Source: The MITRE Corporation
Preliminary Results
EPA Contract So. 68-01-0438
(2) Sources of information for tabulated data are indicated by numbers in parentheses which refer to Bibliography in Section VI.
(3) Underlined numbers in parentheses show percentage jf all emissions of that pollutant from that source.
-------
TABLE I. MAGNITUDE OF HAZARDOUS POLLUTANT EMISSIONS FROM SELECTED INDUSTRIAL SOURCES -(CONT'
INDUSTRY AND PROCESS
MINING AND RAW
MATERIAL PREPARATION
Secondary Al, All Cu, Pb, Zn)
Primary Mercury
Primary Copper
Roasting
Converters
Material Handling
Primary Manganese
Primary Zinc
Roasting
Fluid Bed
Ropp and Multihearth
Sintering
Distillation
Material Handling
Primary Nickel
Primary Lead
Sintering
Blast Furnace
Dross Reverberatory Furnace
Material Handling
Zinc Oxide
Secondary Aluminum
Sweating Furnace
Refining Furnace Hood
Chlorine Fluxing
Chlorine Fluxing
Scrap Preparation
Wire Burning
Sweating Furnaces
Blast Furnace
Smelting and Refining
Reverberatory
Rotary
Secondary Zinc
Sweating Furnaces
Distillation Furnaces
Secondary Lead
Sweating Furnaces
Blast
Reverberatory
Pot Refining
Barton Process (Lead Oxide)
Secondary Manganese
Each Pot and Total Plant
Vanadium Refining
Iron and Steel
Sintering
Metallurgical Coke
Blast Furnace
Open Hearth
Basic Oxygen Furnace
Chlorine Fluxing
Gray Iron Foundary
Cupola '
Coke and Limestone Handling
Sand Handling and Operations
CONTROL DEVICES
TYPE IN USE
ESP
Settling Plus Cyclones or ESP
Hood, Chamber, Cyclone, ESP or Baghouse
ESP Baghouse, 1 _s?
or Scrubber i
None (Intentional by Industry)
Hood, Chamber, Cyclone or Baghouse
Waste Heat Boiler Plus Baghouse or EST
Hood, Chamber, Cyclone, ESP or Baghouse
Hood Plus Settling Plus Baghouse
Afterburner Plus Baghouse
Hood Plus Baghouse
Slot Scrubber-Caustic Solution
None
None
Afterburner Plus Baghouse
Baghouse (Rarely Scrubber)
Hood plus Baghouse
Hood Plus Baghouse
None
Afterburner Plus Baghouse
Product-Collecting Exhaust Plus Baghouse
None
Baghouse or Baghouse Plus ESP
Baghouse or Baghouse Plus ESP
Hood Plus Baghouse
Ducting Plus Baghouse Plus Screw Conveyor
Assumed Same as Primary Copper
None
Cyclones
Cyclones and ESP
Baghouse
None
ESP
ESP
High Energy Venturi Scrubber
Baghouse (Ocnl. Scrubber or ESP)
Alkali Scrubbers
ESP
Cyclones
Baghouse
Wet Scrubber
Wet Cap
Hood and Cyclone'
Wet Scrubber (Ocnl. Cyclone or Baghouse)
7.
APPLICATION
100
Est 100
100
80-85
85
35
100
100
100
0
35
90
98 (4
Est 50-60
35
Est 100 (M)
Unk
Est 20
60
Unk
Unk
0
0
Est 20
75
71
80
0
Est 20
100
0
95-100
95-100
95
100
Est 100
0
80-100
45
36
19
0
100
41
61
39 10°
100
100
Negl.
: .
•ri
25
Est 25
%
EFFICIENCY
95-100 (<
85 «
95 «
95 (4
90 (4
85-95
98 (4
85 (4
95 (4
0 (4
90 (4
85-95 (H
95 (4
3) 85 (V
95 (4
90 (4
85-95 (4
94 «
95 (<
95 (i
50-60 «
80-90 (4
0 (4
0 «
95 ('
90 «
95 (4
95 ('
0 (4
95 «
95 (4
0 (4
95 (4
95 ('
95 .(«
95-99 (4
0 «
85-95 (I
90 (t
90 <4
90 (4
0
99 ('
97 (4
99 (4
99 «
95-100 (4
97 ('
75 (4
99 (4
90 (4
50 (i
80 (4
99 (4
EFFICIENCY
OF HCL
COLLECTION
4)
M)
3)
3)
3)
3)
M)
3)
3)
3)
3)
3)
)
3)
)
3)
3)
3)
3)
3)
3)
3) 95-99 (<
3) 50-60 (4
3)
3)
3)
3)
3)
3)
3)
3)
3)
3)
3)
3)
3)
3)
)
)
)
3)
3)
3)
3)
3)
3)
3)
3)
3)
3)
3)
3)
3)
3)
3)
ARSENIC
900(10.07)
400(4.48)
1150(12.87)
250(2.80)
1390(15.55)
Unk
285(3.19)
80(0.90)
11(0.12)
Unk
3)
3)
1
97U.09)
ASBESTOS
BARIUM
Unk
112(1.04)
38(0.35)
\20(0.19)
36(0.33)
150(0,46)
BERYLLIUM
'4(2.77)
BORON
}
CADMIUM
136(5.91)
56(2.44)
160(6.96)
36(1.96)
395(17.1
170(7.39
54(2.36
Neg
Neg
40(1.75
12J0.53
3(0.14
Neg
See Prima
Aluminum
70(3.04)
55(2.39)
1000(43.3
CHLORINE
100(0.13)
>)
)
;
•
ry(neg)
9)
1900(2.43)
CHROMIUM
COPPER
2900(21.54)
3729(27.70)
828(6.15)
5(0.04)
155(1.15)
15 (.11)
15(.ll)
15(01)
5(.Q4)
1070(7.95)
1550(11.51)
| 70 (.52)
70 (.52)
) 50(.37)
FLUORIDES
86(0.06)
257(0.16)
57(0.04)
127(0.08)
55(0.04)
18(0.02)
150(0.10)
40(0.03)
10(0.01)
18200(11.16)
2800(1.72)
25400(15.37)
LEAD
127(1.42)
54(0.60)
163(1.82)
36(0.40)
159(1.77)
68(0.76)
23(0.26)
-.85(5.39)
138(1.45)
65(0.73)
0
390(4.34)
42(0.47)
42(0.47)
42(0.47)
4(0.05)
Neg
1500(16.67)
500(5.56)
Neg
20(0.23)
150(1.67)
1
j
Il400(15.56)\
MANGANESE
325(1.71)
1000(5.27)
1660(8.74)
1060(5.58)
620(3.26)
2270(14.58
MERCURY
55(6.94)
11(1.39)
NICKEL
248 (3.98)
100(1.61)
1
179(1.27)
POM
Unk
Unk
| Unk
J
Unk
1 °"k
Unk
Unk
} -
) -
I Unk
I Unk
Unk
Unk
Unk
Unk
Unk
43380(0.90)
1 Unk
Unk
SELENIUM
«<12) (-J
17(1.99)
8(0.94)
22(2.57)
5(0.59)
27(3.16)
5(0.59)
2(0.23)
11(0.12)
includes
.11
smelters)
TIN
(S56)
Unk
260(73.03)
VANADIUM
(08)
<
81(0.43)
63(0.34)
166(0.88)
| 7(0.04)
Neg
> 1(0.01)
ZINC
(M3)
\31818
j (21.14)
"\13637 .
j(9.06)
4545(3.02)
8100(5.39)
ft
135(0.09)
14(0.01)
14(0.01)
14(0.01)
3(Seg>
2890(1.90)
950 (.64>
1070(0.71)
39000(25.91)
\ 900 (0.60)
7400(4.92)
8.700(1.13)
(1) Source: The MITRE Corporation
Preliminary Results
EPA Contract No. 68-01-0438!
(2) Sources of information for tabulated data are indicated by numbers in parentheses which refer to Bibliography in Section VI.
(j) Underlined numbers in parentheses show percentage of all emissions of that pollutant from that source.
9
-------
TABLE I. MAGNITUDE OF HAZARDOUS POLLUTANT EMISSIONS FROM SELECTED INDUSTRIAL SOURCES - (CONT'D)1
INDUSTRY AND PROCESS
MINING AND RAH
MATERIAL PREPARATION
Pulp and Paper
Kraft Pulp Mill
Lime Kiln
Dissolving Tank
Sulflte Pulp Mill
Digester Relief & Blow Tank
Pulping
Blow Tank
Absorption Tower
Flui-iized Bed Reactor
Phosphate Fertilizer
Pulverizing
Granulation
Material Handling
Cotton Ginning (Arsenic)
Asphalt
Paving Material
Roofing Material
Blowing
Saturation
Ferro Alloys
Blast Furnace
Material Handling
Non-Ferrous Alloys
Furnaces
Material Handling
Silicomanganese (Electric
Furnace)
Phosphoric Acid
Hydrofluoric Acid
Vents
Kilns
Chlorine
Manufacture
Liquification and Handling
Organic Chlorine Chemicals
Hydrochloric Acid Manufacture
Frit Production
Zinc Galvanizing
Misc. Arsenic Chemicals
Barium Milling and Handling
Barium Chemicals
Vanadium Chemicals
Boron Chemicals
Manganese Chemicals
Ceramic Coatings
CONTROL DEVICES
TYPE IX USE
ESP
Scrubber
Cyclonic Scrubber
Packed Tower
Orifice Scrubber
Mesh Pad
ESP
ESP
Xone
Cyclones
Cyclones
Cyclones and/or Wet Scrubbers
Mostly Cyclones
Chambers, Cyclones, Scrubbers, ESP
Hood, Cyclones, Scrubbers, ESP, Baghouse
liood, Chambers, Cyclones , ESP , Baghouse
Hood, ESP, Baghouse
g
Packed or Open Tower Scrubbers
High Energy Wire-Mesh Contactors
ESP
Scrubbers
Scrubbers
Wet Cyclone
None
Same as Primary Zinc
Various
:;oods , Cyclones , Chambers
Cyclones, ESP, Baghouse
Cyclones, ESP, Baghouse
riood, Cyclone, Scrubber , Baghouse
\PPLICATIOX
99
99
0
• 33
99
0
99
0
33
100
100
100
95
0
40
5 99
st 99 (43)
100
50
35
50
35
100
Est 100
Est 100
Est 100
Est 100
Est 100
Est 100
Est 100
Unk
0
tst 100
Unk
Est 100
Lst 100
Est 80-100
100 (1C
Est. Snail
100
EFFICIENCY
85-97 (43
60-95 (43
95 (43!
0 (43:
80 (43.
90 (43;
97 (43:
75 (43:
85-97 (43:
0 (43:
85-97 (43:
0 (43)
74-98 (43:
70 (43)
80 (43)
95 (43)
0 (43)
80 (4)
70 (43)
99 (43)
86 (43)
99 (43)
81 (43)
90 (43)
Esc 80-90(43
90 (43)
-80 (M)
99.9 (43
40-98 (43
99.9 (43
>99.9 (43
96-99.9 (43
Lst 90-95(50
ist 90-95(50
17 (50
95-100 (24
95-100 (24
95-100 (24
95-100 (24
I'nk
16
0
85-95 (M
unk
Est -99 (M
Est 96 (!•
Est 80-95(M
) Unk («
Est Neg (M
Unk (M
EFFICIENCY
OF FLUORIDE
COLLECTION
)
)
)
)
)
)
)
1
)
)
)
)
)
)
)
)
)
)
)
)
ARSENIC
1
345(3.73)
Neg
Neg
j-g
j
Unk
Neg
3.3(0.04)
\SBESTOS
15(0. 24P>
15
eg
BARIUM
40(0.37)
2700(24.94)
4400(40.64)
BERYLLIUM
See BE
Alloys
Meg
BORON
1000(10.55)
2400(25.32)
470(4.96)
2.5(0.0!
Neg
CHLORINE
18000(23.0S
)
4000(5.12
43000(54.9
8500(10.8
800(1.02
CHROMIUM
0.02(tieg)
1 Seg
)
)
9)
t
7)
T
)
COPPER
FLUORIDES
) 380(3. 91)
500(0.31)
200(0.13)
5800(3.56)
3320(2.04)
" 700(0.43)
LEAD
1ANCANESE
1113(5.86)
3669(19.32
60(0.32)
Beg
4164(21.92
300(1.58)
MERCURY
) Neg
70.2(8.86)
NICKEL
491(7.88)
98(1.58)
Neg
64(1.03)
Neg
POM
( Unk
800(0. On)
-3230(0.48)
Unk
Sunk
Wk
Unk
N Unk
SELENIUM
203(23.74)
TIN
ANADIUM
115(0.61)
29(0.16)
3(0.02)
Keg
4(0-02)
Neg
ZINC
%
500(1.66)
500(.34)
Neg
950(.64)
(1) Source: The MITRE Corporation
Preliminary Results
EPA Contract No. 68-01-0438
(2) Sources of information for tabulatjd data are indicated by numbers in parentheses which refer to Bibliography in Section VI.
(3) Underlined numbers in parentheses show percentage of all emissions of that pollutant from that source.
11
-------
MINING AND RAW
MATERIAL PREPARATION
-^TnTchemicals
Cadmium Paint Pigments
Cadmium- Barium Plastic
Stabilizers
primary Chromium
production
Handling
Petroleum Refining
Diamraonium Phosphate
Triple Superphosphate
Normal Superphosphate
Beryllium Alloys & Compounds
END PRODUCT PRODUCTION"
Cement Kilns
Wet and Dry
Chlorine Bleach Manufacture
Asbestos Products
Shingles & Siding Products
Arsenic Pesticides
Paint, Varnish, Enamel, Lacquer
Beryllium Metal £, Alloy
Fabrication
Cadmium-Nickel Batteries
Misc. Tin Products
structural Clay Products
Instrument Manufacture
electrical Apparatus
)ental Preparations
Products
felding Rods
CONSUMPTIVE USE
Fungicides
Well Drilling Mud
Fertilizer Application
Pharmaceuticals
TYPE IN USE
Cyclones, Wet ESP, Baghouse
Baghouses
Assumed Sir.ilar To Copper)
Hoods , Baghouses
c rubbers , Ocnl. Baghouse
lost Uncontrolled, Ocnl. Scrubbers
Ammonia Scrubber Plus Wet Scrubber
yclones
oods, Wet Scrubbers
y clone , Scrubber, Saghouse
Cyclone
Baghouse
None
Hood, Baghouse
None, Cyclones, Baghouses
Unk
Unk
Various
Various
Baghouse
Xone, Ocnl. Spray Scrubbers
Unk
Unk
Unk
"yclones , ESP , Baghouse
None
None (Emissions .01% of Consumption)
None
None
APPLICATION
Lst 95-1
100
100
Est 70-8
Esc 70-8
Esl 100
Unk
Xeg
Unk
Unk
) Unk
Unk
100
61
16
0
Est 100
Est 100
Est 100
Est 100
Esc 100
Est 55
100
Unk
Unk
Unk
Unk
Est 100
100
Xeg.
Unk
Unk
Unk
0
(tst.
0
0
0
0
00
(1)
00
(1)
0
0
00
(>1)
CM)
100
CM)
00 (M
00
89% N
EFFICIENCY
Est 85-95 (>
90-99 CM
1
90-99 (M
1st 90-95 (J5
1st 90-95(25
Unk
1st 88 (M)
Unk (M)
Unk
80 (43
32 (50
74 (50
80 (50
Est >99 (5
70 (43
>9<3 (43
99 (43
0 (43
99 (43
0 (43
Est 95-99 0
Est 95-99 (t
Esc 95-99(b
>99 (9
Near 100 (5
Unk
Unk
Unk
Unk
Unk
99 (2
80 (4
Unk
Unk
Unk
) 85-95 (
0 (
Unk (
ec ControlH
0 (
0 (
0 (
0 (
JF FLUORIDE
.M)
M)
24)
)
)
)
)
)
)
>)
3)
I)
I)
3)
i)
1)
1)
1)
0
0
ARSENIC
197(2.20)
Neg
Neg
ASBESTOS
205(3^27)
18(0.29)
61(0.97)
25(0.40)
BARIUM
30(0.28)
70(0.65)
BERYLLIUM
5.25(3.64)
39 Ibs(Neg)
BORON
13(0.14)
1800(18.99)
CADMIUM
0.5(0.48)
3(0. U)
400 IbsC
1128 IbsC
500 Ibs
(0.01)
910 Ib
(0.02)
CHLORINE
(3)
3.01)
1.02)
1000(1.28)
HROMIUM
200(34.98)
.5(Seg>
.3(Neg)
Neg
7.3(0.06)
• KSeg)
Neg
Neg
COPPER
2(0.02)
230(1.71)
FLUORIDES
300(3.25)
290(0.18)
3790(2.33)
980(3.06)
4090(2.51)
'270(0.17)
Neg
9720(5.96)
LEAD
1250(13.89)
810(9.00)
Hnk
2(0.02)
Neg
MANGANESE
90(0.47)
24(0.13)
MERCURY
1C. 13)
2.6(.33)
3C.38)
1.2(.15)
19 (2.40)
2.6033)
NICKEL
POM
Unk
Unk
2170(0.05)
Unk
Unk
Unk
Unk
Unk
link
Unk
Unk
SELENIUM
1(0.12)
TIN
Unk
VANADIUM
ZINC
*-
10(0.01)
(1) Source: The MITRE Corporation
Preliminary Results
EPA Contract No. 68-01-0438
(2) Sources of information for tabulated data are indicated by numbers in parentheses which refer to Bibliography in Section VI.
(3) Underlined numbers in parentheses show percentage of all emissions of that pollutant from that source.
13
-------
TABLE I. MAGNITUDE OF iAZARDOUS POLLUTANT EMISSIONS FROM SELECTED INDUSTRIAL SOURCES -(CONT'D)1
CONSUMPTIVE USE
(Continued)
-— ~rT~i~iboratory Use of
General i-»
Mercury
paint (Consumptive)
INCINERATION
Bdustrial/Large
Industrial/Small
pomestic (Apartments)
Domestic (Apartments)
Domestic (Homes)
pathological
Auto Body
Conical Burner
Open Burning
Agricultural Burning
Natural Fires (Urban)
Wigwam Burners
Municipal
Cotton Gin Waste (Arsenic)
Sewage and Sludge Burning
Coal Refuse Fire
COMBUSTION
Power Plants
Pulverized Coal Boilers
Stoker Fired Coal Boilers
Residual and Distillate Oil
Natural Gas & LNG
Industrial
Pulverized Coal Boilers
Residual and Distillate Oil
Natural Gas and LNG
Residential/Commercial
Coal
Oil
Gas
TOTAL (TONS)
TYPE IN USE
None
Multiple Chaaber Burning
None
Peabody Scrubber
Afterburner
None
None
None
None
None (Flue Settling Only)
Dry Expansion Chamber
Spray Chamber
Wetted Wall Chamber
Wetted, Close Spaced Baffles
Dry Cyclone
Medium Energy, Wet Scrubber
Est. None
Est. None
None
Cyclones
ESP
ESP Plus Cyclones
Settling Chambers
None
ESP
Cyclones
Cyclones Plus ESP
None
None or Cyclones (For Soot Blowing)
None
Multicyclones
ESP
Multicyclones
ESP
None
ESP
None
None or Cyclone or ESP (For Soot Blow)
None
None
None
2
1C
0
10
0
0
Ne
0
Un
Un
0
0
0
0
0
0
17
22
2
12
17
16
9
5
0
0
0
23.5
58.7
14.6
Neg.
3.1
4.5
82.6
12.9
13.3
57.3
29.4
Ur
C
65.9
29.6
4.5
52.6
9.1
38.3
40.7
49.8
9.5
U
!
)
;
t
k
]
i
uoo
100
100
100
k
100
100
100
D
0
0
0
2
0 (
0 (
Est Max 30
0 (
0 (
94 (
0 (
Unk
Unk
0 (
0 (
0 (
0 (
0 (
0 (
M
20 (43
20 (43
33 (43
,40 (43
35 (43
50 (43
70 (43
90 (43
0 (4)
o(G>
0 (M)
82.2 (4
96 (4
96 (<
Neg.(/
0 (4
80 (4
91 (4
Est 99 «
0 (4
84.7 (
84.7 <
| 82.4 (
Est 99 (
0 (
0 (
0 (
0 (
EFFICIENCY
OF FLUORIDE
COLLECTION
1)
1)
43)
1)
3)
<3)
t3)
I)
I)
1)
1}
1)
0
EFFICIENCIES
etals P.O.M
) 2 (43) 10
) 0 (43) 10
) 4 (43) 20
) 5 (43) 40
) 7 (43) 48
HO (43) 85
) 0 (43) 35
)80 (43) 95
3)
3)
3)
3)
3)
3)
3)
3)
3)
3)
3)
t3)
»3)
43)
43)
43)
43)
ARSENIC
Unk
Neg
Seg
Neg
Neg
Neg
Neg
Unk
Neg
Seg
Unk
(43)
43)
(43)
(43)!.Neg
(43)
(43)
(43)
(43)j
Unk
Neg
Unk
429(4.8)
49(.55)
15(.17)
19(.21)
67(.75)
9(.10)
Neg
6(.Q7)
9268
ASBESTOS
6261
BARIUM
12311(21.35)
1 266(2.46)
> 80(.74)
J
29(.27)
None
S 102(.94)
I 358(3.31)
\ 5K.47)
22(.20)
None
32 (.30)
49(.45)
10826
BERYLLIUM
\ 86(59.62)
"1 10(6.93)
\ 3(2.08)
2(1.39)
> 8(5.55)
/ ~
I 13(9.01)
\ 2(1.39)
2(1.39)
K.69)
8(5.55)
144
BORON
>
20(0.21)
)2655
(28.01)
~1 304(3.21)
\ 9K.96)
5(.06)
\ 118(1.25)
I 413(4.36)
59 (.62)
5(0.6)
37(.J9)
30(^32)
9520
CADMIUM
95(...l )
!
2305
CHLORINE
78200
CHROMIUM
i
>
15571
(46.40,
"> 640(5.33)
} 92(1. 60)
(M)
22G18)
H(3~
\ 247 (2.06)
1 (M)
864(7.20)
(M)
\ 123(1.02)
/ (M)
17 (.14)
J43
?^
38C.32!
12007
COPPER
460(3.42)
)535(4.35)
~\ 67 (.50)
I 20(.15)
15(.ll)
S 26 (.19)
I 9K.68)
\ 13 (.10)
1K.08)
8(.Q6)
25(.19)
13463
FLUORIDES
124698
(15.14)
~\ 2839
\ (!•»)
}852 0.53)
~
\ 1092(0. 67)
\ 3830(2.35)
V 547(0.34)
; ~~
342(0.21)
163140
LEAD
20(3.56)
J614(6.83)
} 71(0. 79)
/ 21(0.24)
7(0.08)
\ 27(0.30)
I 95(1.06)
\ 14(0.16)
5(.06)
9(.10)
12(.U)
9000
MANGANESE
>
175(0.92)
)1409
(7.42)
1 162(0. 85
) 49(0.26
2(0.01
\ 62(0.33
1218(1.15
\ 31(0.16
2(0.01
20(0.11
3(.02)
18993
MERCURY
51(6.44)
135(17.04
(includes
open burning)
11(1_.3J>)
I 150(18.94)
"> 17(2.15)
1 6(^76)
K.13)
S 6(.76)
I 23(2.90)
\ 3(.38)
K.13)
2(.25)
3(.38)
792
NICKEL
)
*
1 87(1.40)
'S 10(0.16)
} 3(0.05)
1441
(23.12)
\ 7(0.12)
\ 23(0. 37)
\ 3(0.05)
1139(18.28)
3(0.05)
2435(39.07)
6233
POM
Unk
\ 2228(0.05)
I 730(0.02)
Unk
14602(0.30)
212211(4.42)
526843(10.98)
2161142(45.05)
1433712(29.89)
6060(0.13)
Unk
682(0.01)
Unk
Unk
193500(4.03)
1 8980(.19)
~ll032(Q.02)
) 310(0. 01)
J ~
7675(0.16)
6151(0.13)
^1896 (0.04)
[6635 (0.14)
\948(0.02)
10001 (0.21)
20220(0.42)
66796(1.39)
33105(0.69)
10065(0.21)
4797104
SELENIUM
1(0.12)
Uincludes
^open-
burning)
1360(42.11)
"1 41(4.80)
) 12(1.40)
19(2.22)
I 16(1.87)
1 56(6.55)
I 8(0.94)
14(1.64)
5(0.59)
32(3.74)
855
TIN
168(19.10)
(M)
"1 8(2. 25) (M)
> 2(0. 56) (M)
0
I 3(0.84)
/ ^
^11(3.09)
) (M)
I 2(0.56)
? THT
0
K0.29XM)
1(0.29)
J43
356
VANADIUM
11013
(5.37)
~) 116(.62)
) 35(.J19)
4930
(26.13)
\45(.24)
1 158 (.8 4)
\23(^3)
3740
(19.82)
14 (.08)
8330
(44.14)
18,873
ZINC
%
27700
(18.37)
Uincludes
/ open-
burning)
1750(1.16)
/2457
(1.64)
1282(0.19)
/85 (^06)
130 (.09)
i!09COJ)
1 382 (.26)
155(^04)
99(.Q7)
34(^01)
22K.15)
150,516
M - MITRE Estimate G - Private Communication, Dr. Y. Gordoi
Potomac River Regional Commission
(1) Source: The MITRE Corporation
Preliminary Results
EPA Contract No. 68-01-0438
(2) Sources of information for tabulated Jata are indicated by numbers in parentheses which refer to Bibliography in Section VI.
(3) Underlined numbers in parentheses show percentage of all emissions of that pollutant from that source.
15
-------
o Phosphoric acid
o Hydrofluoric acid
o Alkylation
o Aluminum prebake
o Gray iron cupolas.
Because less time was allotted for the study of the emitters
discussed in Section V, the data presented for those sources could
not be checked as carefully as the data were for the roasting
processes. Nevertheless, the data do present a fairly complete
picture of the emission characteristics for typical plants using
these processes.
Throughout the study, the data presented on emissions, control
devices employed, types of plant processes employed, and material
flow through a plant, are meant to describe a typical plant. A
conscious effort has been made to avoid the description of the
operations or emissions of a specific plant. However, in some cases
only one plant exists for a particular study category, thus
necessitating specific data.
17
-------
2.0 SCOPE AND MAGNITUDE OF EMISSIONS
2.1 Hazardous Pollutant Sources
The first phase of analysis was to determine how much of each
pollutant was being emitted to the atmosphere and how these emissions
were distributed among the principal industrial sources. This was
accomplished by surveying the literature for emissions data and in a
few cases using emission factors to compute annual emissions. All
of the emissions data which were found are presented in Table I. The
coal and oil combustion figures were usually reported as total emissions
from all sectors and had to be broken down using historic fuel data.
Emissions from coking coals were not included in the combustion figures
shown. Information on control devices in use, their application, and
efficiency were also extracted from the literature and included in
this table. The reference numbers from the bibliography appear on
the table (in parenthesis and not underlined) at the tops of columns
or after entries to identify the source of each piece of information.
The numbers in this table represent the best information available
from the sources cited. In many cases, these numbers were estimates
prepared and included in the sources stated. As measuring techniques
improve and information reporting by industries becomes more complete,
revised data with greater reliability will become available. Never-
theless, the results are adequate to identify key sources of potentially
hazardous pollutants and to establish the relative importance of
certain industries.
19
-------
The emissions data presented in Table I have been divided up into
19 tables (see Tables II through XX), one for each of the hazardous
pollutants. Each table shows the amount in tons of the specific
pollutant emitted by each source and the percentage which the source
contributed to the total emissions of that pollutant. The purpose
of these tables was to provide a quick reference of emissions for
each pollutant.
Other interesting considerations are which industry and which
operation contributed the most tons of the 19 hazardous pollutants
under consideration in this study. The data presented in Table I
were used to prepare tables showing these two things. Table XXI
shows the industrial processes in order of the tons of hazardous
pollutants they emit. The actual number of tons emitted by each
process is also shown. Open burning heads the list contributing
almost 4.5 million tons more than the next process, open hearth
furnaces. In general, processes with the greatest emissions are
those within the ferrous and non-ferrous industries and boilers and
burners of all types. Table XXII presents the number of tons of all
hazardous pollutants emitted by each industry. In this case, the
"industry" which contributes the greatest number of tons is agricultural
burning, followed by forest fires and open burning. The nature and
characteristics of the emissions from these sources do not readily
lend themselves to the application of control devices and could not
be considered good candidates for additional study of emission
characteristics and control device requirements.
20
-------
TABLE II
HAZARDOUS POLLUTANT SOURCES
ARSENIC
Source Amount % This
in Tons Pollutant
Mining 2 0.03
Phosphate Rock NEC NEC
Primary Copper
Roasting 900 9.71
Reverberatory Furnaces 400 4.32
Converters 1,150 12.41
Material Handling 250 2.70
Primary Zinc
Roasting 1,390 15.00
Primary Lead
Sintering 285 3.08
Blast Furnace 80 .87
Reverberatory Furnace 11 0.12
Gray Iron Foundary 97 1.05
Cotton Ginning and Burning 345 3.73
Non-Ferrous Alloys NEC NEC
Phosphoric Acid NEC NEC
Glass Manufacture 638 6.89
Wood Preservatives NEC NEC
Miscellaneous Arsenic Chemicals 3 0.04
Arsenic Pesticide Production 196 2.12
Pesticide, Herbicide, Fungicide Use 2,925 31.56
Power Plant Boilers
Pulverized Coal 429 4.63
Stoker Coal 49 0.53
Cyclone Coal 15 0.17
Industrial Boilers
Pulverized Coal 19 0.21
Stoker Coal 67 0.73
Cyclone Coal 9 0.10
All Oil NEC NEC
Residential/Commercial Coal 6 0.07
Incineration 2 .03
TOTAL 9,268 100.10
21
-------
TABLE III
HAZARDOUS POLLUTANT SOURCES
ASBESTOS
Amount % This,
Source in Tons Pollutant
Asbestos Mining 5,610 89.6
Kraft Pulp Mill
Recovery Furnace 15 0.24
Sulfite Pulp Mill NEC NEC
Asbestos Products
Brake Lining Production 312 4.98
Shingle & Siding Production 205 3.27
Asbestos Textile Production 18 0.29
Installation of Asbestos Con-
struction Material 61 0.97
Spray on Steel Fire Proofing 15 0.24
Insulating Cement Application 25 0.40
TOTAL 6,261 99.99
22
-------
TABLE IV
HAZARDOUS POLLUTANT SOURCES
BARIUM
Amount % This
Source in tons Pollutant
Barium Mining 30 0.28
Blast Furnace 112 1,04
Open Hearth 38 0.35
Basic Oxygen Furnace 20 0.19
Electric Arc Furnace 36 0.33
Gray Iron Foundry
Cupola 50 0.46
Glass Manufacture 40 0.37
Barium Milling & Handling 2,700 24.94
Barium Chemicals 4,400 40.64
Paint, Varnish, etc.
Manufacture 30 0.28
Well Drilling Mud 70 0.65
Power Plant Boilers
Pulverized Coal 2,311 21.35
Stoker Coal 266 2.46
Cyclone Coal 80 0.74
All Oil 29 0.27
Industrial Boilers
Pulverized Coal 102 0.94
Stoken Coal 358 3.31
Cyclone Coal 51 0.47
All Oil 22 0.20
Residential/Commercial Boilers
Coal 32 0.30
Oil 49 0.45
TOTAL 10,826 100.02
23
-------
TABLE V
HAZARDOUS POLLUTANT SOURCES
BERYLLIUM
Amount % This
Source in Ions Pollutant
Mica, Feldspar Mining NEC NEC
Gray Iron Foundry
Cupola 4 2.77
Ceramic Coatings NEC NEC
Beryllium Alloys & Compounds 5 3.64
Beryllium Fabrication NEC NEC
Power Plant Boilers
Pulverized Coal 86 59.62
Stoker Coal 10 6.93
Cyclone Coal 3 2.08
All Oil 2 1.39
Industrial Boilers
Pulverized Coal 8 5.55
Stoker Coal 13 9.01
Cyclone Coal 2 1.39
All Oil 2 1.39
Residential/Commercial Boilers
Coal 1 0.69
Oil 8 5.55
TOTAL 144 100.01
24
-------
TABLE VI
HAZARDOUS POLLUTANT SOURCES
BORON
Source Amount % This
in tons Pollutant
Borax Mining 100 1.05
Glass Manufacturing 1,000 10.51
Boron Chemicals 2,400 25.21
Ceramic Coatings 470 4.94
Soaps and Detergent Manufacturing 13 0.14
Use of Pesticides, Herbicides, and
Fungicides 1,800 18.91
Sewage and Sludge Incineration 20 0.21
Power Plant Boilers
Pulverized Coal 2,655 27.89
Stoker Coal 304 3.20
Cyclone Coal 91 0.96
All Oil 5 0.06
Industrial Boilers
Pulverized Coal 118 1.24
Stoker Coal 413 4.34
Cyclone Coal 59 0.62
All Oil 5 0.06
Residential/Commercial Boilers
Coal 37 0.39
Oil 30 0.32
TOTAL 9,520 100.05
25
-------
TABLE VII
HAZARDOUS POLLUTANT SOURCES
CADMIUM
Amount % This^
Source in Tons Pollutant
Copper Mining NEC NEC
Zinc Mining <1 0.01
Lead Mining NEC NEC
Primary Copper
Roasting 136 5.91
Reverberatory Furnace 56 2.44
Converters 160 6.96
Material Handling 36 1.58
Primary Zinc
Roasting 395 17.15
Sintering 170 7.39
Distillation 54 2.36
Material Handling NEC NEC
Primary Nickel NEC NEC
Primary Lead
Sintering 40 1.75
Blast Furnace 12 0.53
Reverberatory 3 0.14
Material Handling NEC NEC
Secondary Copper
Sweating Furnace 70 3.04
Blast Furnace 55 2.39
Iron & Steel
Blast Furnace 1,000 43.39
Non-Ferrous Alloys
Furnaces 3 0.13
Material Handling NEC NEC
Cadmium Paint Pigments 11 0.48
Cadmium-Barium Plastic Stabilizers 3 0.13
Cadmium-Nickel Batteries
-------
TABLE VIII
HAZARDOUS POLLUTANT SOURCES
CHLORINE
Amount % This
Source in Tons Pollutant
Chlorine Fluxing
Non-Ferrous Metals 100 0.13
Iron and Steel 1,900 2.43
Bleaching, Pulp and Paper 18,000 23.02
Chlorine Industry
Manufacture 4,000 5.12
Liquefaction and Handling 43,000 54.99
Organic Chlorine Chemicals 8,500 10.87
Hydrochloric Acid Manufacture 800 1.02
Bleach Manufacture 900 1.15
Miscellaneous Chlorine
Products 1,000 1.28
TOTAL 78,200 100.01
27
-------
TABLE IX
HAZARDOUS POLLUTANT SOURCES
CHROMIUM
Amount % This
Source in Tons Pollutant
Asbestos Mining 8 0.07
Kraft Pulp Mill
Recovery Furnace
Sulfite Pulp Mill
NEC
NEC
Primary Chromium Production 4200
Asbestos Products
Refractory Brick Production
Installation of Asbestos Material
Spray-on Fire Proofing
Use of Insulating Cement
Power Plant Boilers
Pulverized Coal 5
Stoker Coal
Cyclone Coal
All Oil
Industrial Boilers
Pulverized Coal
Stoker Coal
Cyclone Coal
All Oil
Residential/Commercial Boilers
Coal
Oil
NEC
7
NEC
NEC
NEC
,571
640
192
22
247
864
123
17
77
38
NEC
NEC
34.98
NEC
0.06
NEC
NEC
NEC
46.40
5.33
1.60
0.18
2.06
7.20
1.02
0.14
0.64
0.32
TOTAL 12,006 100.00
28
-------
TABLE X
HAZARDOUS POLLUTANT SOURCES
COPPER
Amount
in Tons
Source
Copper Mining 190
Primary Copper
Roasting 2,900
Reverberatory Furnace 1,243
Converters 3,729
Material Handling 828
Secondary Copper
Scrap Prepatation 5
Wire Burning 155
Sweating Furnace 15
Blast Furnace 15
Smelting, Reverberatory 15
Smelt ing, Ro tary 5
Iron and Steel
Blast Furnace 1,070
Open Hearth Furnace 1,550
Basic Oxygen Furnace 70
Electric Are Furnace 70
Gray Iron Foundry 50
Miscellaneous Copper Metals
and Alloys 2
Miscellaneous Copper Chemicals
and Prqducts 230
Incinerators 460
Power Plant Boilers
Pulverized Coal 585
Stoker Coal 67
Cyclone Coal 20
All Oil 15
Industrial Boilers
Pulverized Coal 26
Stoker Coal 91
Cyclone Coal 13
All Oil 11
Residential/Commercial Boilers
Coal 8
Oil 25
Total
13,463
% This
Pollutant
1.41
21.54
9.23
27.70
6.. 15
0.04
1.15
0.11
0.11
0.11
0.04
7.95
11.51
.52
.52
.37
0.02
1.71
3.42
4.35
0.50
0.15
0.11
0.19
0.68
0.10
0.11
0.06
0.19
100.05
29
-------
TABLE XI
HAZARDOUS POLLUTANT SOURCES
FLUORIDES
Amount % This
Source in Tons Pollutant
Iron Ore Pellet Plants 18,200 11.16
Defluorination of Phosphate
Rock 1,770 1-09
Primary Aluminum
Reduction, H.S. Soderberg
Reduction, V.S. Soderberg
Prebake
Primary Copper
Roasting
Reverberatory Furnaces
Converters
Material Handling
Primary Zinc
Roasting
Sintering
Distillation
Primary Lead
Sintering
Blast Furnace
Dross Reverberatory Furnace
5,160
2,460
8,610
200
86
257
57
127
55
18
150
40
10
Iron and Steel
Sintering 18,200
Blast Furnace 2,800
Open Hearth 25,400
Phosphoric Acid Production
Hydrofluoric Acid Production
Hydrofluoric Acid Alkylation
6,380
700
5,800
Glass Manufacture, Frit Production 700
Expanded Clay Aggregate
Preparation
Diammonium Phosphate Preparation
Triple Superphosphate
Preparation
Normal Superphosphate
Preparation
Electrothermal Phosphorous
Prenaration
5 , 300
290
3,790
4,980
4.090
3.17
1.51
5.28
0.13
0.06
0.16
0.04
0.08
0.04
0.02
0.10
0.03
0.01
11.16
1.72
3.91
3.91
0.43
3.56
0.43
3.25
0.18
2.33
3.06
2.51
30
-------
TABLE XI
HAZARDOUS POLLUTANT SOURCES
FLUORIDES (Continued)
Source Amount % This
in Tons Pollutant
Opal Glass Production 3,320 2.04
Cement Kilns 270 0.17
Structural Clay Products 9,720 5.96
Power Plant Boilers
Pulverized Coal 24,698 15.14
Stoker Coal 2,839 1.74
Cyclone Coal 852 0.53
Industrial Boilers
Pulverized Coal 1,092 0.67
Stoker Coal 3,830 2.35
Cyclone Coal 547 0.34
Residential/Commercial Boilers
Coal 342 0.21
TOTAL 163,140 100.14
31
-------
Source
TABLE XII
HAZARDOUS POLLUTANT SOURCES
LEAD
Amount
in Tons
Copper, Zinc, Lead Mining
Primary Copper
Roasting
Reverberatory Furnaces
Converters
Material Handling
Primary Zinc
Roasting
Sintering
Distillation
Primary Lead
Sintering
Blast Furnace
Dross Reverberatory Furnace
Secondary Copper
Wire Burning
Sweating Furnace
Blast Furnace
Smelting, Reverberatory
Smelting, Rotary
Secondary Lead
Scrap Preparation
Blast Furnace
Reverberatory Furnace
Pot Refining
Barton Process
Iron and Steel
Open Hearth
Gray Iron Foundry
Cupola
Petroleum Refining
Lead Alkyl Chemicals
Use of Pesticides, Herbicides,
Fungicides
Incinerators
345
150
1,400
1,250
810
NEC
320
% This
Pollutant
3.84
127
54
163
36
159
68
23
485
130
65
390
42
42
42
4
NEC
1,500
500
NEC
20
1.42
0.60
1.82
0.40
1.77
0.76
0.26
5.39
1.45
0.73
4.34
0.47
0.47
0.47
0.05
NEC
16.67
5.56
NEC
0.23
1.67
15.56
13.89
9.00
NEC
3.56
32
-------
TABLE XII
HAZARDOUS POLLUTANT SOURCES
LEAD (Continued)
Source Amount % This
in Tons Pollutant
Power Plant Boilers
Pulverized Coal 614 6.83
Stoker Coal 71 0.79
Cyclone Coal 21 0.24
All Oil 7 0.08
Industrial Boilers
Pulverized Coal 27 0.30
Stoker Coal 95 1.06
Cyclone Coal 14 0.16
All Oil 5 0.06
Residential/Commercial Boilers
Coal 9 0.10
Oil 12 0.14
TOTAL 9,000 99.96
33
-------
TABLE XIII
HAZARDOUS POLLUTANT SOURCES
MANGANESE
Amount % This
Source in Tons Pollutant
Manganese Mining 5 0.03
Primary Manganese Preparation 325 1.71
Iron and Steel
Blast Furnace 1,000 5.27
Open Hearth Furnace 1,660 8.74
Basic Oxygen Furnace 1,060 5.58
Electric Arc Furnace 620 3.26
Gray Iron Foundry
Cupola 2,770 14.58
Ferro-Alloy Preparation
Blast Furnace 1,113 5.86
Electric Furnace 3,669 19.32
Non-Ferrous Alloy Preparation
Furnaces 60 0.32
Material Handling NEC NEC
Silico Manganese Preparation
Electric Furnace 4,164 21.92
Manganese Chemical Preparation 300 1.58
Dry Storage Battery Production 90 0.47
Welding Rod Production 24 0.13
Sewage and Sludge Burning 175 0.92
Power Plant Boilers
Pulverized Coal 1,409 7.42
Stoker Coal 162 0.85
Cyclone Coal 49 0.26
All Oil 2 0.01
Industrial Boilers
Pulverized Coal 62 0.33
Stoker Coal 218 1.15
Cyclone Coal 31 0.16
All Oil 2 0.01
Residential/Commercial Boilers
Coal 20 0.11
Oil 3 0.02
TOTAL 18,993 100.10
34
-------
TABLE XIV
HAZARDOUS POLLUTANT SOURCES
MERCURY
Amount
Source in Tons
Mercury Mining
Chlorine Fluxing, Non-Ferrous
Metals
Secondary Mercury
Pulp and Paper Industry
Organic Chlorine Chemical
Preparation
Paint, Varnish, Lacquer Production
Instrument Manufacture
Electrical Apparatus Manufacture
Dental Preparations Manufacture
Use of Pesticides, Herbicides,
Fungicides
Use of Pharmaceuticals
Laboratory Use of Mercury
Consumption of Paint
Incinerators
Sewage and Sludge Burning
Power Plant Boilers
Pulverized Coal
Stoker Coal
Cyclone Coal
All Oil
Industrial Boilers
Pulverized Coal
Stoker Coal
Cyclone Coal
All Oil
Residential/Commercial Boilers
Coal
Oil
3
55
11
NEC
70
1
3
3
1
19
3
51
215
135
11
150
17
6
1
6
23
3
1
2
3
% This
Pollutant
0.33
6.94
1.39
NEC
8.86
0.13
0.33
0.38
0.15
2.40
0.33
6.44
27.15
17.04
1.39
18.94
2.15
0.76
0.13
0.76
2.90
0.38
0.13
0.25
0.38
TOTAL
793
100.04
35
-------
Source
Nickel Mining
Primary Nickel
Iron and Steel
Blast Furnace
Gray Iron Foundry
Cupola
Ferro-Alloys
Blast Furnace
Electric Furnace
Non-Ferrous Alloys
Furnaces
Material Handling
Power Plant Boilers
Pulverized Coal
Stoker Coal
Cyclone Coal
All Oil
Industrial Boilers
Pulverized Coal
Stoker Coal
Cyclone Coal
All-Oil
TABLE XV
HAZARDOUS POLLUTANT SOURCES
NICKEL
Amount
in Tons
2
248
100
79
491
98
64
NEC
87
10
3
1,441
7
23
3
1,139
Re s id ent ial/Commer ica1
Coal
Oil
TOTAL
3
2,435
6,233
% This
Pollutant
0.04
3'. 98
1.61
1.27
7.88
1.58
1.03
NEC
1.40
0.16
0.05
J3.12
0.12
0.37
0.05
L8.28
0.05
39.07
100.06
36
-------
TABLE XVI
HAZARDOUS POLLUTANT SOURCES
POLYCYCLIC ORGANIC MATERIAL (POM)
Amount % This
Source in Tons Pollutant
Iron and Steel
Metallurgical Coke 43,380 0.90
Asphalt Industry
Paving Material Preparation 2,800 0.06
Roofing Material Prepar-
ation 23,230 0.48
Petroleum Refining 2,170 0.05
Incineration
Industrial 2,228 0.05
Domestic 730 0,02
Auto Body 14,602 0.30
Conical Burner 212,211 4.42
Open Burning 526,843 10.98
Agricultural Burning 2,161,142 45.05
Natural Fires, Forest 1,433,712 29.89
Natural Fires, Urban 6,060 0.13
Municipal 682 0.01
Coal Refuse 193,500 4.03
Power Plant Boilers
Pulverized Coal 8,980 0.19
Stoker Coal 1,032 0.02
Cyclone Coal 310 0.01
All Oil 7,675 0.16
All Gas 6,151 0-13
Industrial Boilers
Pulverized Coal 1,896 0.04
Stoker Coal 6,635 0.14
Cyclone Coal 948 0.02
All Oil 10,001 0.21
All Gas 20,220 0.42
Residential/Commercial
Coal 66,796 1.39
Oil 33,105 0.69
Gas 10,065 0.21
TOTAL 4,797,104 100.00
37
-------
TABLE XVII
HAZARDOUS POLLUTANT SOURCES
SELENIUM.
Source in Tons
Primary Copper
Roasting 17 1.99,
Reverberatory Furnace 8 0,94
Converters 22 2,57
Material Handling 5 0.59
Primary Zinc
Roasting 27 3.16
Primary Lead
Sintering 5 0»59
Blast Furnace 2 0.23
Secondary Copper, Zinc, Lead 1 0.. 12
Glass Manufacture 203 23.74
Paint, Varnish, Lacquer Manufacture 1 0..12
Incineration 1 0.12.
Po^er Plant Boilers
Pulverized: Coal 360; 42.11
Stoker Coal 41 4,8®
Cyclone Coal 12 1,40
All Oil 19 2.22
Industrial Bailers.
Pulverized Coal 16 1.8,7:
Stoker Coal 56. 6.,55
Cyclone Coal & 0.94
All Oil 14 1.64
Residential/Gommercial Boilers
Coal 5: 0,59*
Oil 32, 3;. 74
TOTAL 855
-------
TABLE XVIII
HAZARDOUS POLLUTANT SOURCES
TIN
Source
Iron and Steel
Open Hearth
Power Plant Boilers
Pulverized Coal
Stoker Coal
Cyclone Coal
Industrial Boilers
Pulverized Coal
Stoker Coal
Cyclone Coal
Residential/Commercial
Coal
All Boilers, Oil
TOTAL
Amount
in Tons
260
63
8
2
3
11
2
1
1
356
% This
Pollutant
73.03
19.10
2.25
0.56
0.84
3.09
0.56
0.28
0.28
99.99
39
-------
TABLE XIX
HAZARDOUS POLLUTANT SOURCES
VANADIUM
Amount % This
Source in Tons Pollutaat
Vanadium Refining 81 0.43
Iron and Steel
Blast Furnace 63 0.34
Open Hearth Furnace 166 0.8,8
Basic Oxygen Furnace 7 0.04
Gray Iron Foundry
Cupola 1 0.01
Ferro-Alloys
Electric Furnace 115 0.61
Material Handling 29 0.16
Non-Ferrous Alloys
Furnaces 3 0.02
Vanadium Chemical Preparation 4 0.02
Ceramic Coating Preparation NEC NEC
Power Plant Boilers
Pulverized Coal 1,013 5.37
Stoker Coal 116 0.62
Cyclone Coal 35 0.19
All Oil 4,930 26.13
Industrial Boilers
Pulverized Coal 45 0.24
Stoker Coal 158 0.84
Cyclone Coal -23 0.13
All Oil 3,740 19.82
Residential/Commercial Boilers
Coal 14 0 i 08
Oil 8,330 44.14
TOTAL 18,873 99.94
40
-------
TABLE XX
HAZARDOUS POLLUTANT SOURCES
ZINC
Amount % This
Source in Tons Pollutant
Zinc Mining 72 0.05
Primary Zinc
Roasting 31,818 21.14
Sintering 13,637 9.06
Distillation 4,545 3.02
Zinc Oxide Production 8,100 5.39
Secondary Copper
Wire Burning 135 0.09
Sweating Furnace 14 0.01
Blast Furnace 14 0.01
Smelting, Reverberatory
Furnace 14 0.01
Smelting, Rotary Furnace 3 NEC
Secondary Zinc
Sweating Furnaces 2,850 1,90
Distillation Furnaces 950 0.64
Iron and Steel
Blast Furnace 1,070 0.71
Open Hearth Furnace 39,000 25.91
Basic Oxygen Furnace 900 0.60
Electric Arc Furnace 7,400 4.92
Gray Iron Foundry
Cupola 1,700 1.13
Ferro-Alloys
Blast Furnace 2,500 1.66
Electric Furnace 500 0.34
Material Handling NEC NEC
Zinc Galvanizing 950 0.64
Zinc Chemical Preparation 1,030 0.69
Paint,. Varnish, Lacquer
Manufacture 10 0.01
Incineration 29,450 19.57
Power Plant Boilers
Pulverized Coal 2,457 1.64
Stoker Coal 282 0.19
Cyclone Coal 85 0.06
All Oil 130 0.09
41
-------
TABLE XX
HAZARDOUS POLLUTANT SOURCES
ZINC (Continued)
Amount % This
Source in Tons Pollutant
Industrial Boilers
Pulverized Coal 109 0.08
Stoker Coal 382 0.26
Cyclone Coal 55 0.04
All Oil 99 0.07
Residential/Commercial Boilers
Coal 34 0.03
Oil 221 0.15
TOTAL 150,516 100.12
42
-------
TABLE XXI
SOURCE OF HAZARDOUS POLLUTANTS.
ORDERING OF EMITTERS
TOTAL TONNAGE OF ALL PRODUCTS
BY OPERATION
SOURCE
1, Open Burning
2. Open Hearth Furnaces
3. Pulverized Coal Boiler, Power Plant
4, Oil Burners, Residential
5, Metallurgical Coke
6, Chlorine Liquefaction
7, Roasting, Non-Ferrous Metals
8. Incineration
9. Sintering, Non-Ferrous Metals
10. Ore Mining and Handling
11. Asphalt Roofing Materials
12. Gas Burners, Industrial
13. Pellet Plants, Iron Ore Preparation
14. Bleaching,Pulp and Paper
15. Oil Burners, Power Plants
16. Oil Burners, Industrial
17. Blast Furnace
18. Stoker Coal Boiler, Industrial
19. Electric Furnace
20. Gas Burners, Residential/Commercial
21. Structural Clay Products
22. Superphosphate Manufacture
23. Prebake, Aluminum Ore Reduction
24. Organic Chemicals
2.5. Zinc Oxide Manufacture
26. Reduction, Aluminum
27, Phosphoric Acid, Wet & Thermal Processes
28. Gas Burner, Power Plant
29. Cupola, Gray Iron Foundry
30. Stoker Coal Boiler, Power Plant
31. Hydrofluoric Acid Alkylation
TONS
4,548,070
68,227
51,471
44,063
43,380
43,000
38,560
34,307
33,620
26,855
23,330
20,220
18,200
18,000
14,273
14,053
13,352
13,237
12,508
10,065
9,720
8,980
8,610
8,570
8,100
7,620
6,830
6,151
6,151
5,994
5,800
43
-------
TABLE XXI
(Continued)
32. Distillation, Primary Zinc 5,626
33. Converters, Primary Copper 5,591
34. Expanded Clay Aggregate 5,300
35. Use of Pesticides, Herbicides, Fungicides 4,744
36. Barium Chemicals 4,400
37- Primary Chromium 4,200
38. Electrothermal Phosphorous 4,080
39. Chlorine Manufacture 4,000
40. Pulverized Coal Boiler, Industrial 3,783
41. Petroleum Refining 3,420
42. Sweating Furnace, Secondary Non-Ferrous Metals 3,031
43. Asphalt Paving Material 2,800
44. Barium Milling & Handling 2,700
45. Reverberatory Furnace 2,548
46. Boron Chemicals 2,400
47. Basic Oxygen Furnace 2,057
48. Fluxing Chlorine 2,000
49. Cyclone Coal Boiler, Industrial 1,891
50. Glass Manufacture 1,881
51. Cyclone Coal Boiler, Power Plant 1,776
52. Defluorination of Phosphate Rock 1,760
53. Material Handling, Manufacture 1,264
54. Zinc Chemicals 1,130
55. Miscellaneous Chlorine Products 1,000
56. Zinc Galvanizing 950
57. Chlorine Bleach Manufacture 900
58. Lead Alkyl Chemicals 810
59. Hydrochloric Acid Manufacture 800
60. Frit Production, Glass Manufacturing 700
61. Wire Burning, Secondary Copper 681
62. Residential/Commercial Coal Boilers 657
63. Hydrofluoric Acid Vents 500
64. Manganese Chemicals 470
65. Ceramic Coatings 470
66. Primary Manganese 325
67- Brake Lining Manufacture 312
68. Cement Kilns 270
69. Primary Nickel 246
70. Miscellaneous Copper Products Manufacture 230
71. Application of Paint 215
72. Shingle & Siding Manufacture 205
73. Hydrofluoric Acid Kilns 200
74. Pesticide Manufacture 197
75. Dry Storage Batteries 90
76. Vanadium Refining 81
77. Well Drilling Mud 70
78. Installation of Asbestos Materials 61
44
-------
TABLE XXI
(Concluded)
79. Primary Mercury 55
80. Laboratory Use of Mercury 51
81. Paint Manufacture 42
82. Use of Insulating Cement 25
83. Welding Rods Consumption 23
84. Barton Process, Secondary Lead 20
85. Cotton Ginning 19
86. Asbestos Textiles 18
87. Recovery Furnace, Pulp and Paper 15
88. Spray-on Fire Proofing 15
89. Soap & Detergent Manufacture 13
90. Rotary Furnace 12
91. Secondary Mercury H
92. Cadmium Paint Pigments H
93. Refractory Bricks 7
94. Scrap Metal Preparation - Secondary Non-Ferrous Metal 5
95. Beryllium Alloys and Compounds 5
96. Vanadium Chemicals 4
97. Cadmium-Barium Stabilizers 3
98. Miscellaneous Arsenic Chemicals 3
99. Electrical Apparatus Manufacture 3
100. Miscellaneous Copper Metals & Alloys 2
-101. Instrument Manufacture 2
102. Pharmaceuticals 2
103. Dental Apparatus 1
104. Cadmium-Nickel Batteries NEC
105, Miscellaneous Cadmium Products NEC
106. Fertilizer Application NEC
45
-------
TABLE XXII
SOURCE OF HAZARDOUS POLLUTANTS
ORDERING OF EMITTERS
TOTAL TONNAGE WITHIN GROUPS
BY INDUSTRY
SOURCE
1. Agricultural Burning
2. Forest Fire
3. Open Burning
4. Conical Burners
5. Coal Refuse Fires
6. Iron and Steel
7- Power Plants
8. Chlorine Manufacture
9. Residential Fuels
10. Industrial Fuels
11. Primary Zinc
12. Incinerators
13. Asphalt Blowing
14. Pellet Plants
15. Pulp and Paper
16. Primary Aluminum
17. Burning of Auto Bodies
18. Primary Copper
19. Structural Clay Products
20. Superphosphate Manufacture
21. Ferro-Alloys
22. Zinc Oxide Manufacture
23. Phosphoric Acid
24. Gray Iron Foundry
25. Hydrofluoric Acid Alkylation
26. Asbestos Mining
27. Expanded Clay Aggregate
28. Use of Pesticides, Herbicides, etc.
46
TONS
2,161,142
1,433,712
526,843
212,211
193,500
149,102
79,665
56,370
54,785
53,184
52,907
34,307
23,330
18,200
18,015
16,230
14,:602
13,084
9,720
8,980
8,515
8,100
6,830
6,151
5,800
5,618
5,300
4,744
-------
TABLE XXII
(Continued)
29. Barium Chemicals 4,400
30. Primary Chromium 4,200
31. Silicomanganese 4,164
32. Electro Thermal Phosphorous 4,080
33.. Secondary Zinc 3,840
34. Petroleum Refining 3,420
35. Asphalt Paving Materials 2,800
36. Barium Milling and Handling 2,700
37. Boron Chemicals 2,400
38, Secondary Lead 2,020
39. Glass Manufacture 1,881
40. Defluorination of Phosphate Rock 1,760
41. Primary Lead 1,395
42. Zinc Chemicals 1,130
43. Secondary Copper 1,036
44. Miscellaneous Chlorine Products 1,000
45. Zinc Galvanizing 950
46. Chlorine Bleach Manufacture 900
47. Lead Alkyl Chemicals 810
48. Hydrofluoric Acid 700
49. Frit Production 700
50. Zinc Mining 602
51. Asbestos Products 535
52. Ceramic Coatings 470
53. Lead Mining 365
54. Primary Manganese 325
55, Manganese Chemicals 300:
56. Cement Kilns 270
57. Primary Nickel 246
58. Misc. Copper Chemicals and Products 230
59. Consumption of Paint 215
47
-------
TABLE XXII
(Continued)
60. Arsenic Pesticide Manufacture 197
61. Copper Mining 190
62. Non Ferrous Alloys 130
63. Borax Mining 100
64. Chlorine Fluxing 100
65. Dry Storage Battery Manufacture 90
66. Vanadium Refining 81
67. Use of Well Drilling Mud 70
68. Installation of Asbestos Materials 61
69. Primary Mercury 55
70. Laboratory Use of Mercury 51
71. Paint Manufacture 42
72. Barium Mining 30
73. Use of Asbestos Cement 25
74. Welding Rod Manufacture 24
75. Cotton Ginning 19
76. Spray-on Fireproofing 15
77. Soaps and Detergents 13
78. Secondary Mercury 11
79. Cadmium Paint Pigments 11
80. Refractory Bricks 7
81. Manganese Mining 5
82. Beryllium Alloys and Compounds 5
83. Vanadium Chemicals 4
84. Mercury Mining 3
85. Miscellaneous Arsenic Chemicals 3
86. Cadmium-Barium Stabilizers 3
87. Electrical Apparatus 3
88. Nickel Mining 2
89. Misc. Copper Metals and Alloys 2
90. Instrument Manufacture 2
48
-------
TABLE XXII
(Concluded)
91. Pharmaceuticals
92. Dental Preparations
93. Beryllium Mining
94. Vanadium Mining
95. Secondary Aluminum
96. Beryllium Metals and Alloys
97. Cadmium-Nickel Batteries
98. Miscellaneous Cadmium Products
99. Fertilizer Application
100, Wood Preservatives
101. Phosphate Rock Mining
102. Coal Mining
103* Lead Storage Batteries
2
1
Negligible
Negligible
Negligible
Negligible
Negligible
Negligible
Negligible
Negligible
Negligible
Unknown
Unknown
49
-------
Ul
o
"NATIONAL INVENTORY OF SOURCES AND EMISSIONS
- ARSENIC," W. E! DAVIS AND ASSOCIATES, MAY 1971
I I
2"PRELIMINARY_AIS. POLLUTION SURVEY OP ARSENIC AND
ITS COMPOUNDS," LITTON SYSTEMS, INC., OCTOBER 1969.
TOTAL
EMISSIONS
2 TONS
4466 TONS
934 TONS
3519 TONS
(TONS)
9268
FIGURE 1
MATERIAL FLOW THROUGH THE ECONOMY SHOWING PRIMARY EMISSION SOURCES
-ARSENIC-
-------
MINING & MILLING
(56io TONS)1
IMPORTED
ASBESTOS3
(NONE)
TEXTILE! (ig TONS)
MANUFACTURE
PAPER1 (15 TONS)
MANUFACTURE
BRAKE LINING1
(312 TONS)
EMISSIONS ARE
NOT INCLUDED
MANUFACTURE OF
ASBESTOS CEMENT
PRODUCTS (205 TONS)'
MANUFACTURE OF
OTHER ASBESTOS3
BLD MATERIALS
(UNKNOWN)
CONSTRUCTION
OF BUILDINGS
(61 TONS)1
5610
TONS
MANUFACTURE OF
(UNKNOWN)3
MANUFACTURE AND
APPLICATION OF
INSULATING CEMENT
(UNKNOWN)
550 TONS
APPLICATION OF
(15 TONS)1
WEARING AWAY
CEMENT (25 TONS)1
101 TONS
UNKNOWN
EMISSIONS
(TONS)
6261
INCINERATION &
DESTRUCTION BY
FIRE (UNKNOWN)3
•"•"NATIONAL INVENTORY OF SOURCES AND EMISSIONS - ASBESTOS," W. E. DAVIS
AND ASSOCIATES, FEBRUARY 1970.
PRELIMINARY AIR POLLUTION SURVEY OF ASBESTOS, LITTON SYSTEMS, INC.,
OCTOBER 1969.
3MITRE
FIGURE 2
MATERIAL FLOW THROUGH THE ECONOMY SHOWING PRIMARY EMISSION SOURCES
-ASBESTOS-
-------
Ol
ra
(30 TONS)
30 TONS
(2700 TONS)
IMPORTED
BARIUM
(NONE)
2700 TONS
-
-
-
-
MANUFACTURE
METALLIC BARIUM1
PRODUCTION (NEC)
BARIUM CHEMICALS
PRODUCTION (4400
TONS)1
RUBBER PRODUCTS
PRODUCTION (NEC)
IRON FOUNDRIES
(50 TONS)
STEEL PRODUCTION
(206 TONS)1
4796 TONS
—
COAL (3200 TONS)1
COMBUSTION
OIL1 (100 TONS)
COMBUSTION
3300 TONS
—
-
INCINERATION3
(UNKNOWN)
UNKNOWN
TOTAL
EMISSIONS
(TONS)
10,826
I I
"NATIONAL INVENTORY OF SOURCES AND EMISSIONS - BARIUM," W. E. DAVIS
AND ASSOCIATES, MAY 1972. I
PRELIMINARY AIR POLLUTION SURVEY OF BARIUM AND ITS COMPOUNDS, LITTON
SYSTEMS, INC., OCTOBER 1969. I
3MITRE . I
FIGURES
MATERIAL FLOW THROUGH THE ECONOMY SHOWING PRIMARY EMISSION SOURCES
-BARIUM-
-------
MINING
(NEC)1
IMPORTED
BERYL ORE
(NONE)3
MANUFACTURE OF
BERYLLIUM METAL,
ALLOYS & COMPOUNDS
(5 TONS)1
BERYLLIA CERAMICS
MANUFACTURE
(NEC)1
BERYLLIUM & ALLOYS
FABRICATION
(NEC)1
IRON FOUNDRIES
(4 TONS)1
cn
01
COAL (123 TONS)-1
COMBUSTION
OIL (12 TONS)
COMBUSTION
INCINERATION
(NEG)1
TOTAL
EMISSIONS
(TONS)
5 TONS
4 TONS
135 TONS
NEG
144
^'NATIONAL INVENTORY OF SOURCES AND EMISSIONS - BERYLLIUM," W. E. DAVIS
AND ASSOCIATES, SEPTEMBER 1971.
2"PRELIMINARY AIR POLLUTION SURVEY OF BERYLLIUM ABE ITS COMPOUNDS,"
LITTON SYSTEMS, INC., OCTOBER 1969.
FIGURE 4
MATERIAL FLOW THROUGH THE ECONOMY SHOWING PRIMARY EMISSION SOURCES
-BERYLLIUM-
-------
MINING1
(100 TONS)
REFINING AND
PRODUCING
COMPOUNDS
(2400 TONS)1
IMPORTED
BORON
(NONE)3
Ol
-£»
100 TONS
2400 TONS
GLASS1 (1000 TONS)
MANUFACTURE
CERAMIC1
COATINGS (470 TONS)
IRON FOUNDRIES
(UNKNOWN)2
MANUFACTURE OF
FERTILIZER &
PESTICIDE
(UNKNOWN) 3
MANUFACTURE OF
(13 TONS)1
NONFERROUS3
METAL OPERATIONS
INCL. REFINING
(UNKNOWN)
FERTILIZER AND
PESTICIDE
APPLICATION1
(1800 TONS)
USE OF
(NEC)3
COAL1 (3677 TONS)
COMBUSTION
OIL3 (40 TONS)
-
INCINERATION OF
SEWAGE & SLUDGE
(20 TONS)
1483 TONS
COMBUSTION
5517 TONS
20 TONS
TOTAL
EMISSIONS
(TONS)
9,520
"NATIONAL INVENTORY OF SOURCES AND EMISSIONS - BORON, W. E. DAVIS
AND ASSOCIATES, JUNE 1972.
^"PRELIMINARY AIR POLLUTION SURVEY OF BORON AND ITS COMPOUNDS, LITTON
SYSTEMS, INC., OCTOBER 1969.
3MITRE.
FIGURES
MATERIAL FLOW THROUGH THE ECONOMY SHOWING PRIMARY EMISSION SOURCES
-BORON-
-------
MANUFACTURE OF
ZINC MINING
(NEG)l
IMPORTED
ORES
(NONE) 3
•Ol
O1
Gu, Pb, Zn
(1050 TONS)
SECONDARY Cu
(FROM AUTOMOBILE
RADIATORS) (125 TONS)
OTHER
REPROCESSING
(17 TONS)
IMPORTED
CADMIUM
(NONE)3
;
-
FUNGICIDES &
FERTILIZERS (NEG)3
PIGMENT
MANUFACTURE
(11 TONS)1
MANUFACTURE OF
(3 TONS)1
CADMIUM ALLOY
(3 TONS)!-
MANUFACTURE OF
NICKEL- CADMIUM
BATTERIES (NEG)1
ELECTROPLATING
(NEG)1
STEEL PRODUCTION
USING SCRAP
APPLICATION OF
FUNGICIDES &_
FERTILIZERS(1 TON)1
INCINERATION
(95 TONS)1
- -
NEG
1192 TONS
-
STEEL PRODUCTION
USING SCRAP
(1000 TONS)1.
1017 TONS
-
1 TON
95 TONS
TOTAL
EMISSIONS
(TONS)
2305
""""NATIONAL INVENTORY OF SOURCES AND EMISSIONS - CADMIUM, W. E. DAVIS AND
ASSOCIATES," FEBRUARY 1970.
2"PRELIMINAHY AIR POLLUTION SURVEY OF CADMIUM AND ITS COMPOUNDS," LITTON
SYSTEMS, ISC-, OCTOBER 1969.
3MITRE
FIGURE 6
MATERIAL FLOW THROUGH THE ECONOMY SHOWING PRIMARY EMISSION SOURCES
-CADMIUM-
-------
CHLORIDE
COMPOUNDS
(NONE)2
*
NONE
-
HYDROCHLORIC
ACID MANUFACTURE
(800 TONS)1
ELECTROLYTIC
MANUFACTURE OF
CHLORINE .
(4000 TONS)
4800 TONS
-
'—
-
-
ORGANIC
CHLORINATIONS
(8500 TONS)1
PULP
BLEACHING
(18,000 TONS)1
CHLORINE
(2000 TONS)1
BLEACH
MANOTACTURING
(900 TONS)1
QTHEE CHLORINE
PRODUCT
MANUFACTURING
(1000 TONS)1
CHLORINE
LIQUEFACTION &
HANDLING
(43,000 TONS)1
73,400 TONS
™
!-
-
f
NONE
i 'NONE
TOTAL
EMISSIONS
(TONS)
78,200
111 CONTROL TECHNIQUES FOR CHLORINE 4 HYUSOGEN CHLORINE EMISSIONS," EPA.
2"FRELIMINARY AIR POLLUTION SURVEY OF CHLORINE GAS," LITTON SYSTEMS,
INC. , OCTOBER 1969.
\ITRE
FIGURE?
MATERIAL FLOW THROUGH THE ECONOMY SHOWING PRIMARY EMISSION SOURCES
-------
IMPORTED
CHR0MITE ORE
(NQNE)^
METALLURGICAL
PROCESSING
(4200 TONS)1
ASBESTOS
MINING
(8 TONS)3
MANUFACTURE OF
(7 TONS)1
MANUFACTURE OF
OTHER CHEMICALS :
(UNKNOWN)2
CHROME
PLATING
(UNKNOWN)2
^™
APPLICATION Of
PRIMER PAINTS &
DIPS (UNKNOWN)2
APPLICATION AS
FUNGICIDES & WOOD
PRESERVATIVES
COAL (7715 TONS)
COMBUSTION3
OIL (77 TONS)
!-
INCINERATION
(UNKNOWN)3
8 TONS
4200 TONS
7 TONS
I
OIL (77 TONS)
COMBUSTION3
7792 TONS
UNKNOWN
TOTAL
EMISSIONS
(TONS)
12007
lnCONTROL TECHNIQUES FOR EMISSIONS CONTAINING CHROMIUM, MANGANESE; NICKEL, AND
VANADIUM," BATTELLE.
PRELIMINARY AIR POLLUTION SURVEY OF CHROMIUM AND ITS COMPOUNDS, LITTON:
SYSTEMS, INC., OCTOBER 1969.
3MITRE
FIGURE 8
MATERIAL FLOW THROUGH THE ECONOMY SHOWING PRIMARY EMISSION SOURCES
-CHROMIUM-
-------
MINING
(190 TONS)1
SMELTING AND
(8700 TONS)
CJI
oo
SECONDARY
COPPER (210 TONS)1
PRODUCTION
IMPORTED
COPPER
(NONE)2
-
-
-
-
-
-
COPPER METAL
FABRICATION
(2 TONS)1
MISC USES OF
COPPER
(230 TONS)1
CONSTRUCTION OF
(SEE MISC)1
USED IN INDUSTRIAL
MACHINERY PARTS
& ELECTRICAL EQUIP.
(SEE MISC)1
USED FOR SEED'
TREATMENT 6,
FUNGICIDE
(SEE MISC)
ELECTROPLATING
(SEE MISC)
GLASS
MANUFACTURE
(SEE MISC)1
IRON & STEEL
PRODUCTION
(2760 TONS)
IRON
FOUNDRIES
(50 TONS)
COAL (810 TONS)1
COMBUSTION
OIL (51 TONS)a
COMBUSTION
INCINERATION OF
SEWAGE, SLUDGE, &
REFUSE (460 TONS)
TOTAL
EMISSIONS
(TONS)
190 TONS
8910 TONS
3042 TONS
861 TONS
460 TONS
13,463
"NATIONAL INVENTORY OF SOURCES AND EMISSIONS - COPPER, W.E. DAVIS, APRIL 1972.
FIGURE 9
MATERIAL FLOW THROUGH THE ECONOMY SHOWING PRIMARY EMISSION SOURCES
-COPPER-
-------
FLUORSPAR
MINING
(UNKNOWN)1
IMPORTED
FLUORSPAR
(NONE)1
Ol
to
HYDROFLUROIC2
ACID PRODUCTION
& ALKYLATION
(6500 TONS)
MILLING &
FLOTATION
(UNKNOWN)1
Cu, Pb, Zn
SMELTING &
REFINING
(1000 TONS)2
PHOSPHATE
ROCK MINING
(UNKNOWN)1
1
1
PROCESSING OF
PHOSPHATE ROCK
(21,300 TONS)2
IRON & STEEL
PRODUCTION
(64,600 TONS)2
PRIMARY ALUMINUM
PRODUCTION
(16,230 TONS)2
STRUCTURAL
CLAY PRODUCTION
(9720 TONS)2
EXPANDED CLAY
AGGREGATE PRODUCTION
(5300 TONS)2
OPAL GLASS
PRODUCTION
(3320 TONS)2
ENAMEL PRIT
PRODUCTION
(700 TONS)2
CEMENT
H MANUFACTURE
(270 TONS)2
COAL (34,200 TONS)
COMBUSTION2
INCINERATION
(UNKNOWN) 3
TOTAL
EMISSIONS
(TONS)
UNKNOWN
28,800 TONS
100,140 TONS
34,200 TONS
163,140
IMIHERAL FACTS AND PROBLEMS. BOM.
2ENG:
ilNEERING AND COST EFFECTIVENESS STUDY OF FLUORIDE EMISSIONS CONTROL.
FIGURE 10
MATERIAL FLOW THROUGH THE ECONOMY SHOWING PRIMARY EMISSION SOURCES
-FLUORIDES-
-------
ORE •CRUSHING
(345 Ttfe)1
345 TONS
J
i
-.
PRIMARY LEAD
(680 TONS)1
SECONDARY LEAD
(2000 'TONS)1
IMPORTEb
(NONE)3 '.
LEAH 'OXIDE
(20 TONS)1
PRIMARY ZINC
(250 TONS)1
PRIMARY COPPER
SMELTING
(380 TONS)1
333.0. TONS
:
i
;*~1
;
IRON & STEEL
PRODUCTION.
(150 TONS)1 :
IRON FOUNDRIES '•••
(1400 TONS)1
BRONZE & ERASS ;
(520 TONS)1
PETROLEUM
(1250 TONS)2
MaSUFACT»RE OF j
(UNKNOWN) !
LEAD ALKYL
MANUFACTURE
(810 TONS)1
4130 TONS
-1
'
EMISSIONS «RE
FROM "MOBILE
SOURCES NOT
INCLUDED3
EMISSIONS ARE
FROM MOBILE
SOURCE NOT
INCLUDED3
COAL (850 TONS)1
COMBUSTION
OIL (24 TONS)1 .
COMBUSTION
874 TONS
_
:!
1.
-
MUNICIPAL
(320 TONS)1
320 TONS
TOTAL
EMISSIONS
(TONS)
8989
""""CONTROL TEfCHglOTJES FOR LEAD EMISSIONS," EPA.
MINERAL'jatCtg 'AND PROBLEMS, -'iffM.
MG PRIMARY EM ISSION SOU RCES
-------
MINING
(5 TONS)1
MANGANESE
ORE IMPORTED
(NONE) 3
1
-
FERROMAHGANESE
PRODUCTION
(4782 TONS)1
PRIMARY MANGANESE
(325 TONS)1
SILICOMANGANESE
PRODUCTION
(4164 TONS)1
-
•^
HM
™
IRON 5. § JEEL
PRODUCTION
(4340 IONS)1
IRON FOUNDRIES
(2770 TONS)1
WELDING ROD
(24 TONS)1
NONFERROUS ALLOY.
MANUFACTURE
(60 TONS)1
MANUFACTUHE OF
DRY CELL BATTERIES
(90 TONS)1
MANGANESE CHEM-
ICAL PRODUCTION
(300 TONS)1
COAL (1950 TONS)1
COMBUSTION
OIL (7 TONS)1
COMBUSTION
SLUDGE &
SEWAGE BURNING
(175 TONS)1
TOTAL
EMISSIONS
5 TOHS
; 9271 TONS
7584 TONS
1957 TONS
175 TONS
(TONS)
18,992
\l. E. DAVIS - "NATIONAL INVENTORY OF SOURCES AND EMISSIONS - MANGANESE,"
W. E. DAVIS AND ASSOCIATES,, AUGUST 1971.
2LITTON - "•PRELIMINARY AIR POLLUTION SURVEY OF MANGANESE AND ITS COMPOUNDS,"
LITTOM SYSTEMS, INC.,. OCTOBER 1969.
3MITRE.
FIGURE 12
MATERIAL FLOW THROUGH THE ECONOMY SHOWING PRIMARY EMISSION SOURCES
^MANGANESE-
-------
MINING
(3 TONS)1
PRIMARY MERCURY
PRODUCTION
(55 TONS)1
SECONDARY MERCURY
PRODUCTION
(11 TONS)1
IMPORTED
MERCURY
(NONE)3
-------
MINING
(SEE PRIM.
SMELTING)1
PRIMARY NICKEL
(248 TONS*)1
SECONDARY1
(dEE PRIM. SMELTING)
IMPORTED
NICKEL,
(NONE)
STAINLESS & BEST
RESISTING STEEL
PRODUCTION
(442 TONS)1
ALLOY STEEL
(147 TONS)1
ELECTROPLATING
(NEG)1
MANUFACTURE OF
BATTERIES (2 TONS)1
IRON FOUNDRIES
(79 TONS)1
MANUFACTURE OF
OTHER STEEL
(100 TONS)1
MANUFACTURE OF
OTHER ALLOYS
(64 TONS)1
: MANUFACTURE OF
CATALYSTS
(NEG)1
1 ' I
"NATIONAL INVENTORY OF SOURCES AND EMISSIONS - NICKEL," W. E. DAVIS AND
ASSOCIATES, FEBRUARY 1970. * INCLUDES EMISSIONS FROM MINING & SECONDARY
SMELTING. " I
2 ' •
"PRELIMINARY AIR POLLUTION SURVEY OF NICKEL AND ITS COMPOUNDS," LITTON
SYSTEMS, INC., OCTOBER 1969. I
^MITRE. I I
COAL (136 TONS)1
COMBUSTION
OIL (5015)1
COMBUSTION
INCINERATION
(UNKNOWN)3
TOTAL
EMISSIONS
(TONS)
UNKNOWN
248" TONS
834 TONS
5151 TONS
UNKNOWN
6233
FIGURE 14
MATERIAL FLOW THROUGH THE ECONOMY SHOWING PRIMARY EMISSION SOURCES
-NICKEL-
-------
PETROLEUM
REFINING1
COKE
MANUFACTURE
METAL
REFINING!
MANUFACTURE OF
PRODUCTS1
MANUFACTURE
PRODUCTS1
PULP 6, PAPER
PRODUCTION1
CHEMICAL
PRODUCTION1
FOOD
PROCESSING1
MANUFACTURE
PRODUCTS !
MANUFACTURE
PRODUCTS1
.
OIL
COAL & COKE
COMBUSTION1
GAS
COMBUSTION1
WOOD
COMBUSTION1
—
INCINERATION
SEWAGE &
SLUDGE
BURNING1
CONTROL TECHNIQUES FOR POLYCYCLIC ORGANIC MATTER EMISSION, EPA.
FIGURE 15
MATERIAL FLOW THROUGH THE ECONOMY SHOWING PRIMARY EMISSION SOURCES '
POLYCYCLIC ORGANIC MATERIAL
-------
0>
Ol
COPPER
(NEG)
NEG
- -
SMELTING AND
(85 TONS)1
SECONDARY
(1 TON)1
IMPORTED
SELENIUM
(NONE)3
86 TONS
-
-
-
GLASS (203 TONS)1
MANUFACTURING
MANUFACTURE OF
ELECTRONIC
EQUIPMENT
(NEG)1
MANUFACTURE OF
DUPLICATING
MACHINES (NEG)1
MANUFACTURE OF
PIGMENTS (1 TON)1
IRON & STEEL
PRODUCTION
(1 TON)1
205 TONS
-
COAL (498 TONS)1
COMBUSTION
OIL (65 TONS)1
COMBUSTION
563 TONS
-
INCINERATION
OF REFUSE
(NEG)1
NEG
TOTAL
EMISSIONS
(TONS)
855
•"""NATIONAL INVENTORY OF SOURCES AND EMISSIONS - SELENIUM," W. E. DAVIS
AND ASSOCIATES; APRIL 1972.
2"PRELIMINARY AIR POLLUTION SURVEY OF SELENIUM AND ITS COMPOUNDS,"
LITTON SYSTEMS, INC,., OCTOBER 1969.
MITRE.
FIGURE 16
MATERIAL FLOW THROUGH THE ECONOMY SHOWING PRIMARY EMISSION SOURCES
-SELENIUM-
-------
IMPORTED TIN
(NONE)2
PRIMARY TIN
(UNKNOWN)1
BRASS & BRONZE
PRODUCTION
(UNKNOWN)1
NONE
SECONDARY
TIN SMELTING
(UNKNOWN )x
IMPORTED
TIN
(NONE)2
UNKNOWN
-
l-
1
-
-
TIN PLATING
(UNKNOWN)1
IRON FOUNDRIES
(UNKNOWN) !
IRON & STEEL
PRODUCTION
(260 TONS)1
260 TONS
-
-
-
COAL1 (95 TONS)
COMBUSTION
OIL (1 TON)1
COMBUSTION
96 TONS
-
-
INCINERATION
(UNKNOWN) 1
UNKNOWN
TOTAL
EMISSIONS
(TONS)
356
"SlITRE
FACTS AND PROBLEMS, BOM
FIGURE 17
MATERIAL FLOW THROUGH THE ECONOMY SHOWING PRIMARY EMISSION SOURCES
-TIN-
-------
MINING AND
MILLING
(81 TONS)1
IMPORTED
VANADIUM ORE
(NONE)3
FEKROVANADIUM
PRODUCTION
(144
. IMPORTED
VANADIUM
(NONE)3
IRON * STEEL
PRODUCTION
(236 TONS)1
IRON-FOUNDRIES
(1 TON)1
MANUFACTURE
Of CATALYTSTS
(4 TONS)1
GLASS & CERAMICS
MANUFACTURE
(NEG)i
VANADIUM CHEMICALS
MANUFACTURE
(UNKNOWN)2
NONFERROUS ALLOYS
MANUFACTURE
(3 TONS)1
COAL (1404 TONS)
COMBUSTION1
OIL (17,000 TONS)1
COMBUSTION
INCINERATION
(UNKNOWN)3
TOTAL
EMISSIONS
(TONS)
8J1 TONS
144 TONS
244 TONS
18,404 TONS
UNKNOWN
18,873
""•"NATIONAL INVENTORY OF SOURCES AND EMISSIONS - VANADIUM," W. E. DAVIS
AND ASSOCIATES, JUNE 1971.
2"PRELIMINARY AIR POLLUTION SURVEY OF VANADIUM AND ITS COMPOUNDS,"
LITTON SYSTEMS, INC., OCTOBER 1969.
FIGURE 18
MATERIAL FLOW THROUGH THE ECONOMY SHOWING PRIMARY EMISSION SOURCES
-VANADIUM-
-------
00
MINING
(72 TONS)
72 TONS
ZINC
(50,000 TONS)1
SECONDARY ZINC
(3800 TONS)1
IMPORTED
ZINC SLAB
(NONE)3
'ZINC OXIDE
PRODUCTION-PART OF
RUBBER MANUFACTURE
PROCESS (8100 TONS)1
61,900 TONS
-
"
-
-
-
-
-
DIE CASTING
(3000 TONS)1
ZINC
GALVANIZING
(950 TONS)1
SHERARDIZING &
DISPOSITION (NEG)1
PROCESSING OF BRASS
FINISHING) (180 TONS)!
MANUFACTURE OF
ZINC SULFATE
(30 TONS)1
ROLLED ZINC AND
ITS PRODUCTS
(NEG)1
IRON & STEEL
PRODUCTION
(48,370 TONS)1
IRON FOUNDRIES
(1700 TONS)1
MANUFACTURE OF GLASS
CERAMICS, FLOOR COVERING
ETC. (1000 TONS)1
WEAR OF RUBBER TIRES
SOURCES-NOT INCLUDED
PAINT
(10 TONS)1
PHOTOCOPYING
(NEG)3
55,240 TONS
-
-
-
-
-
-
-Ti
-
COAL (3404 TONS)1
COMBUSTION
OIL (450 TONS)1
COMBUSTION
3854 TONS
1
u
J
-
-
INCINERATION OF
SEWAGE & SLUDGE
(1750 TONS)1
INCINERATION OF
REFUSE
(26,200 TONS)1
INCINERATION
(1500 TONS)1
29,450 TONS
TOTAL
EMISSIONS
(TONS)
ISO. 516
IMNATIONAL INVENTORY OF SOURCES AND EMISSIONS - ZINC," w. E. DAVIS AND
ASSOCIATES, MAY 1972.
2"PRELIMINARY AIR POLLUTION SURVEY OF ZINC AND ITS COMPOUNDS," LITTON
SYSTEMS, INC., OCTOBER 1969.
FIGURE 19
MATERIAL FLOW THROUGH THE ECONOMY SHOWING PRIMARY EMISSION SOURCES
-ZINC-
-------
At this point, the decision was made to select some operations
for indepth study rather than to look at emissions resulting from
specific industries. Additional information was gathered on some of
those operations contributing the greatest number of tons of hazardous
pollutants. This information is shown in Table XXIII and includes
the number of locations of each operation, the total population in
those cities closest to the source, and the basic nature of the
pollutants emitted in each case. In a few instances, the source
locations and/or the surrounding populations were not available and
estimates could not be determined with any degree of reliability.
The last two columns of this table show that many of the sources emit
a variety of pollutants in several forms.
Because emission standards have been prepared for three of the
hazardous pollutants, asbestos, beryllium, and mercury, operations
emitting these pollutants are of particular interest. Thus the
same type of table was prepared for those operations not included in
Table XXIII, but which emit one or more of these three pollutants.
(see Table XXIV).
2.2 Material Flows Through the Economy
A flow chart was prepared for each of the 19 pollutants in order
to show primary emission sources as the materials flow through the
economy. These charts appear as Figures 1-19. The processes which
cause emissions have been divided into five sectors of the economy:
69
-------
TABLE XXIII
NUMBER OF SOURCE LOCATIONS AND GENERAL EMISSION CHARACTERISTICS
FOR SELECTED OPERATIONS
OPERATION
INDUSTRY
NO. OF
LOCATIONS
ADJACENT
POPULATION
(MILLION)*1'
POLLUTANT PROPERTIES
PHYSICAL(2) CHEMICAL
Pulverized Coal Boilers
Power Plants
Power Plants
325
Open Hearth Furnace
Blast Furnace
Roas:ting
Iron & Steel
(no oxygen
lance)
(with oxygen
lance)
Iron & Steel
F.erro-Alloys
Secondary Pb
Primary Pb
Secondary Cu
Primary Cu
Primary Zn
Small Boilers, Oil
(Residential, Commercial) Resident Fuel
(1) Data show total population of large
cities near to known sources.
604
140
53
64
10
20
19
17
44000
3.2
47.8
0.3
19.3
0.6
0.5
Gas
p
"F
Gas
Gas
P,PF, Gas
P,PF
P.Pp.Gas
P.Pp, Gas
P,PF, Gas
P,PF,Gas
(2) P - Particulates
P_ - Fine Particulates
r
Inorganic/metal oxides
Fluorides, Polyorganics
As, Ba, Be, B, Cr, Cu,
Pb, Mn, Hg, Ni, Se, Sn,
V, Zn
Fluorides
Ba, Pb, Mn, Hg, Sn, V,
Zn oxides, Fluorides,
POM
Fluorides, HF
Ba, Pb, Mn, Mg, Sn, V,
Zn oxides, POM
Fluorides, HF
As, Cd, Mn, Hg, Ni, V,
Zn oxides, Fluorides,
POM
Mn, Ni, Zn oxides, POM
As, Pb oxides, POM,
Fluorides
As, Cd, Pb oxides, POM
Fluorides
As, Cd, Zn
Cu., POM, As, Cd,
Fluorides, Pb, Se
Cd, Fluorides, Pb, POM
: Se, Zn
Ba, Be, Cr, Cu, Pb, Mn,
Hg, Ni, POM, Se, Sn, V,
Zn
-------
TABLE XXIII
NUMBER OF SOURCE LOCATIONS AND GENERAL EMISSION CHARACTERISTICS
FOR SELECTED OPERATIONS
(Continued)
OPERATION INDUSTRY "HO. OF ADJACENT (1)
LOCATIONS POPULATION
(MILLION)
Ore Mining and Handling Asbestos Mining
Lead Mining
Copper Mining
Borax Mining
Barium Mining
Open Burning Agri Burning
Forest Fires
Open Burning
Conical Burner
Coal Refuse
^J Converters Primary Cu
Large Boilers, Oil
Power Plants Power Plants
Liquefaction Chlorine MFC
Electric Furnace Iron & Steel
Ferro-Alloys
S i 11 comang anes e
9 Neg
25
25
4
43
19 0.6
115
39
379
53 3.2
POLLUTANT PROPERTIES
PHTS ICAL ( 2 ) CHEMICAL
P
P
P
P
P
P,P Gas
P,P 'Gas
P.PlJGas
P ,Gas
P'PF
P
PF
Gas
P«PF
Asbestos, Cr
As, Cd, Pb
As , Cd , Cu , Pb
B
Ba
As, POM
As, POM
As, POM
POM
As, B, POM
As, Cd, Cu, Fluoride,
Pb, POM, Se
Inorganic/Metal Oxides,
Polyorganics
Ba, Be, Cr, Cu, Pb,
Mn, Hg, Ni, Se, V
Cl^POM
Ba, Mn, Hg, Zn,
Mn, Ni, POM, V, Zn
Mn, POM
Pesticides, Herbicides,
Fungicides, Consumption
Pesticides,
etc., Use
(1) Data show total Population of Large Cities
near to known sources
(2) P - Particulates
P - Fine Particulates
' F
As, B, Cd, Hg, Pb,
Inorganic & Organic
Compounds, Polyorganics
-------
TABLE XXIII
NUMBER OF SOURCE LOCATIONS AND GENERAL EMISSION CHARACTERISTICS
FOR SELECTED OPERATIONS
(Continued)
OPERATION INDUSTRY NO. OF ADJACENT (1)
LOCATIONS POPULATION
(MILLION)
Stoker Coal Boiler, Industrial 124,000
Industrial Fuel
Sintering Iron & Steel
Primary Zn 17 0.5
Primary Pb 10 0.3
N Glass Manufacture Glass 249
10 Manufacture
Barium Chemicals Barium
Chemicals 11 1.1
Intermediate Boilers, Industrial 152,000
Oil, Industrial Fuel
•
Cupola Grey Iron 1,680
Foundry
POLLUTANT PROPERTIES
PHYSICAL(2) CHEMICAL
P P
F
P,Gas
P.Gas
P.Gas
P'PF
No
Hazardous
Except when
Fining ,
Oxidizing,
Color Agents
Added
P'PF
P
P,PF,Gas
As, Ba, Be, B, Cr,
Cu , Fluorides , Pb ,
Mn, Hg, Ni, POM, Se,
Sn, V, Zn
Fluorides, Metal
Oxides, Alkalis
Zn, Pb, Cd, As,
Fluorides
As, Cd, Fluorides,
Pb, Se
As, Ba, B, Se, Zn, Pb
Oxides, Fluorides
Fe2, 03 possible, POM
Ba, POM
As, Ba, Be, Cr, Cu,
Pb, Mn, Hg, Ni, POM,
Se, V, Zn
As, Ba, Be, Pb, Mn,
Hg, Ni, V, Zn oxides,
POM, Fluorides
(1) Date show total Population of Large Cities
near to known sources
(2) P - Particulates
PF - Fine Particulates
-------
TABLE XXSII '
WMBIR OF SOURCE LOCATIONS AND GENERAL EMISSION CHARACTERISTICS
FOR SELECTED OPERATIONS
(Concluded)
OPERWSiN INDUSTRY NO. OF ADJACENT £•)'
LOCATIONS POPULATION
(MILLION)
incin-erators
Sfeoker- Coal
Boiler ., Power Plants
Reverbatory Furnace
N
to
B6roa Chemicals
Barium Hilling
and Handling
Bleaching,
All Processes
Pulverized Coal
Boiler, Industrial
Materials, Handling,
MFG
Petroleum Refining
Incinerators
Power Plants
Primary Cu
Secondary Pb
Primary Pb
Secondary Cu
Boron Chemicals
Barium Milling
and Handling
Bleaching ,
Pulp Mills
Industrial
Fuel.
Primary Cu
Primary Zn
Ferro-Alloys
146
75
19 0, 6
64 47.8
10 0.3
20 19.3
54
7 0.8
35
35,600
19 0.6
17 0.5
53 3.2
263
POLLUTANT PROPERTIES
PHYSICAL(2) CHEMICAL
P, PF. Gas
P P
• IP
i?
P.Pp.Gas
p P
' F
P,PF,6as
P'PF
P
P
Gas
P.Pp.Gas
P
P
P
Pp.Gas
As* Cd, Cu, Pb, fig,
POM, Se, Zn
As, Ba, Be, B, Cr,
Cu, Fluorides, Pb,
Mn, Hg, Ni, POM,
Se, Sn, V, Zn
Cu, Zn, POM, Se, As,
Fluorides, Sb
As, Pb, POM
As, Cd, Fluorides, Pb,
POM, Se
As, Cu, Pb, POM, Se,
Sn, Zn
B
Ba
Cl
As, Ba, Be, B, Cr,
Cu, Fluorides, Pb,
Mn, Hg, Ni, POM,
Se, Sn, V, Zn
As, Cd, Cu, Fluorides,
Pb, POM, Se
Ni, V, Zn
Pb, POM
(1) Data-show total Population of Large Cities
near to known sources
P - Fine Particulates
-------
TABLE XXIV
NUMBER OF SOURCE LOCATIONS AND GENERAL EMISSION CHARACTERISTICS FOR
ADDITIONAL OPERATIONS CONTRIBUTING ASBESTOS, BERYLLIUM OR MERCURY
OPERATION
Organic Chemicals
Cyclone Coal Burners ,
PP
Basic Oxygen Furnace
Cyclojje Coal
Bu;T,ners > jc
Paint Cpnsumption
Residential/
Commercial Cpal
Brake Lining
Production
Beryllium Alloys
and Chemicals
Shingles,
Sidings , Mamuf ap,ture
Primary Mar ou,ry
Lab Hse, Mercury
Ashes tps Hater ial,
Secondary Mercury
AsfcesliQS Textiles
INDUSTRY NO. OF ADJACENT
LOCATIONS POPULATION
(MILLION)
Chlprine MFG 39
Power Plants 8
Iron & Steel 54
Indus trial 1 7 , 800
Fuel
Paint
Cpnsumption
Residential 92 , 000
Fuel
Asbestos 30 20.1
Prpducts
Be Alloys 2 .031
& Chemicals
Asbe,stp,s Prpducts
PTimgry Hg 24
Lab F As, Ba, B,e, B, Cr, Cu,
Fluoride , Pb , Mn, Hg ,
Ni, POM, Se, Sn, V, Zn
Gas Hg, P0M
P,PF,, Gas As, Ba, Be, B, Cr, Cu,
Fliioride, Pb, Mn, Hg,
Ni, POM, Se, Sn, V, Zn
P Asbestos , Cr
P.Pp Be, fQM
P Asbestos, Cr
Gas Hg
Gas Hg
P Aabes tps , Cr
PF, Gas Hg, POM
P Asbesstos, Cr
-------
Ol
TA£LE XXIV
NUMBER Of SOURCE LOCATIONS AMD GENERAL EMISSION CHARACTERISTICS FOR
ADDITIONAL OPERATIONS CONTRIBUTING ASBESTOS, BERYLLIUM OR MERCURY
(Concluded)
OPERATION
Paint, Varnish,
etc. , MFG
= Insu lating Ceinen t ,
lastallation
Recovery Furnace
Fire Proofing
Installation
Beryllium Fabrication
Instrument Manufacture
Electrical Apparatus
Dental Preparations s
INDUSTRY NO. OF ADJACENT POLLUTANT CHARACTERISTICS
LOCATIONS POPULATION PHYSICAL CHEMICAL
(MILLION)
Paint, MFG
Insulating
Cement
Kraft Pulp 35
Milling
Fire Proofing
Be Fabrication
Instrument MFG
Electrical AP
Dental Prep
, P.Pp.Gas
. P
P,Pp,Gas
P
P
Gas
Gas
Gas
Ba, Hg, POM, Se,
Asbestos, Cr
Asbestos, Cr, Hg
Asbestos, Cr
Be
Hg
Hg
Hg
Zn
, POM
Cons
Pharmaceuticals Use
Pharmaceuticals
Gas
Hg
-------
(1) ore mining
(2) concentrating and raw material preparation
(3) product manufacture
(4) consumptive uses
(5) waste disposal
The estimated annual tons of emissions from each type of source are
shown in the flow diagrams and are summed for each of the five
sectors of the economy. In the ease of POM, emissions result from
a large number of processes in every sector except ore mining. In
order to show the flow concisely for POM, large emission source
categories were used such as manufacture of metal products. Emissions
could not readily be computed for these categories and consequently
are not shown.
The information sources used for the tons of emissions are
footnoted on each chart. Below, specific comments have been made for
each of the 19 pollutants.
2.2.1 Arsenic
Figure 1 shows the arsenic flow through the economy noting primary
emission sources. Emissions from copper, zinc, and lead smelters
account for nearly 50% of the total. The other major source of emissions
in the application of arsenic containing insecticides, fungicides,
and desiccants.
2.2.2 Asbestos
The emission figure given by the Davis report for asbestos
emissions from ore mining also included the tons of emissions from
76
-------
milling. Together these two processes account for almost 90% of the
total asbestos emissions. Unlike most of the other hazardous
pollutants, asbestos is not emitted by the combustion of coal and
oil.
2.2.3 Barium
The largest source of barium emissions is from the production
of barium chemicals. Barite is used to manufacture barium sulfide
(BaS) which is then used to produce barium carbonate (BaCO ),
barium chloride (Bad ), blanc fixe (BaSO.) and others. The barium
carbonate is used to make barium oxide (BaO), barium hydroxide
(Ba(OH)2), and barium nitrate (Ba(NO-) ). In the future, the use of
barium in plastic stabilizers may result in a significant amount of
barium emissions if the expansion of the plastics industries
continues.
2.2.4 Beryllium
Approximately 94% of the total annual beryllium emissions are
from the combustion of coal. But the total amount of beryllium
emitted is only 164 tons. This is the smallest amount emitted for
any of the hazardous pollutants, but these emissions are nevertheless
important because of extremely toxic nature of beryllium.
2,2.5 Boron
The four major sources of boron emissions are coal combustion,
glass manufacturei fertilizer and pesticide application, and the
refining and producing of various boron compounds. Based on emission
77
-------
data from the Davis report, "National Inventory of Sources and
Emissions-Boron," mining emissions contribute only about 10% to the
total boron emissions in the United States. It is interesting to
correlate this with the fact that the U.S. mines approximately 70%
of the world's supply of boron.
2.2.6 Cadmium
Cadmium is not emitted by either coal or oil combustion. No ore
is mined solely for the cadmium content, but rather it is a by-product
of zinc-bearing ores. It is the smelting (roasting and sintering) of
this type of ore which accounts for a large proportion of the total
cadmium emissions. Because cadmium is present in scrap steel, it is
released to the atmosphere in the production of steel using scrap as
an input.
2.2.7 Chlorine
The majority of chlorine emissions to the atmosphere are produced
during the liquefaction and handling of chlorine. No emission result
from consumptive uses of chlorine nor from the disposal of chlorine
end products. Based on the control devices used during the electrolytic
manufacture of chlorine, their efficiency, and their widespread use,
it is possible that the emissions from electrolytic manufacture of
chlorine are less than 4000 tons indicated in the table. However, when
leaks in the system,malfunctions and accidents are taken into account,
it is very possible that this emission figure is correct.
78
-------
2.2.8 Chromium
Figure 8 shows coal combustion and metallurgical processing to
be the major contributors of chromium emissions. The number of tons
emitted by coal combustion is a MITRE estimate based on the assumption
that the chromium content in coal ash is equivalent to 0.01% of the
coal consumed. Having this number it is then possible to use the
Davis procedure for computing emissions from coal combustion. This
method assumes:
65% of total is fly ash
85% efficiency of control
90% application of control
and uses the fact that 516,084,000 tons of bituminous and anthracite
coal were consumed in the United States in 1969. It should also be
noted that while Battelle calculates 4200 tons of chromium emission
resulting from metallurgical processing, Bureau of Mines data show
60,000 tons of chromium were lost between 1969 and 1970. This implies
that roughly 56,000 tons were lost in slag. Additional verification
of these numbers should be sought.
2.2.9 Copper
Over half of the copper emissions result from the smelting and
refining of copper-bearing ores. This estimate is based on data from
six industrial sources who reported emissions of up to 40 pounds of
copper/ton of primary copper produced. The average was 10 Ibs/ton.
Two other major emission sources were iron and steel production and
coal combustion.
79
-------
2.2.10 Fluorides
Of the 18 hazardous pollutants for which emissions are shown
on these material flow diagrams, fluorides is the one which has the
greatest number of tons emitted. Most of the fluoride emissions
result from processing of phosphate rock, iron and steel production,
primary aluminum production, and coal combustion. MITRE assumed
that wastes include fluoride containing materials which would cause
fluoride emissions when incinerated. No attempt was made at
estimating the number of tons emitted annually from incineration.
2.2.11 Lead
At first glance, the total lead emissions shown in Figure 11
may seem low, but it pointed out to the reader that emissions from
mobile sourceswere not included in this study. The emissions
shown for petroleum refining are a result of the computation of the
mean value based on a range given in "Control Techniques for Lead
Emissions." The largest single source of lead emissions is the
secondary lead smelting process, followed by iron foundries,
petroleum refiners, coal combustion, and lead alkyl manufacture.
2.2.12 Manganese
The main use of manganese ore is in the production of manganese
metal, ferromanganese, and silicomanganese. This production causes
9271 tons of manganese to be emitted. The products are used by the
iron and steel industry which emits another 4340 tons of manganese.
Emissions from other sources account for the remaining 28% of the
total.
80
-------
2.2.13 Mercury
Although the total annual emissions of mercury are estimated to
be only 841 tons, this is considered significant because of the
apparent high toxicity of mercury. The two processes which emit the
most mercury are application of paint and coal combustion. Disposal
of mercury containing items (not by municipal incineration) also emits
a fairly significant amount of mercury, approximately 15% of the
\
total annual emissions.
2.2.14 Nickel
Approximately 82% of the total annual nickel emissions are
from the combustion of oil. Some emissions also result from the
manufacture of all kinds of steel and alloys. "National Inventory
of Sources and Emissions - Nickel," combines emissions from mining
and primary and secondary smelting. This made it impossible to show
the emission breakdown between the first two sectors of the economy
shown in the material flow.
2.2.15 POM *
This pollutant is not emitted from ore mining, but it is emitted
in large quantities by numerous processes in the other four sectors
of the economy. This fact would have made it difficult to provide
the same level of detail as that shown on the other material flow
diagrams. Consequently, the quantities of POM emitted have not been
shown on the diagram and generalized emission source categories were
used.
-------
2.2.16 Selenium
Slight amounts of selenium are emitted from several manuf act tiring
processes, but the bulk of the selenium emissions result from coal
combustion. The amount of selenium emitted from the combustion of
coal was computed by using the average selenium content of coal as
reported by a 1971 EPA study. Almost all selenium is produced as a
by-product of copper refining but this accounts for only 9% of the
total selenium emissions.
2.2.17 Tin
Tin is not mined in the United States, so there are no emissions
from the ore mining sector of the economy. Little information was
found regarding tin emissions, but some estimates were made. Emissions
from coal combustion were computed in the same way that they were
computed for chromium. The average tin content of coal was assumed
to be 1.5 ppm. Davis states that 1% of open hearth particulate
emissions are tin and this fact was used to compute the tin emissions
from iron and steel production.
2.2.18 Vanadium
Vanadium is present in both crude and residual fuel oils, being
as high as 280 ppm in residual oil imported from South America. This
combined with the fact that controls are not commonly used on oil
burning devises, results in an estimate of 17,000 tons being emitted
from oil combustion. This accounts for 88% of the total vanadium
emissions.
82
-------
2.2.19 Zinc
The three major zinc emitting processes are zinc smelting
(about 31% of tbtal), iron and steel production (about 30%), and
incineration of refuse (about 18%). Many other processes emit zinc
tp result in a total of 151,422 tons emitted per year which is the
second largest amount emitted for any of the 18 hazardous pollutants
for which emissions have been shown.
83
-------
3.0 PRESENT CONTROL TECHNOLOGY FOR SELECTED PROCESSES
The extent to which the hazardous pollutant problem is a fine
participate problem can be seen from Table XXV which gives a
breakdown of the fraction by weight of particulates in each particle
size range emitted by the largest pollution sources. These sources
were selected from the top eighteen listed in Table XXI with the
exception of open burning for which there are no control devices
and chlorine liquefaction which emits only gaseous pollutants. Also
included were all major coal burning sources. A point to be noted
here is that these measured particle size distributions will differ
from the in situ particle distribution. The difference depends on
the history of the pollutant stream between measurement and release
and on the measurement technique, both of which may promote agglomeration
resulting in changes in size distribution. Even so, in many cases
the fine particulates are a major mass fraction of the materials
which have escaped collection.
The data in Table XXVI shows the particle size distribution for
each process in the absence of any control device plus the particle
size distributions after passage through typical control devices for
that process. References for all data shown are given in the right
hand column along with the technique used to obtain the size analysis
when known. The references for typical control devices were selected
85
-------
PARTICLE SIZE DISTRIBUTION FOR EMISSIONS FROM SELECTED PROCESSES
WITHOUT CONTROL DEVICES AND WITH TYPICAL CONTROL DEVICES
PROCESS DESCRIPTION
Open Hearth Furnace
No Oxygen Lance
(composite run)
Open Hearth Furnace
Oxygen Lance
(Lime Boil)
Open Hearth Furnace
Oxygen Lance
(composite run)
INDUSTRY
Iron and Steel
Iron and Steel
Iron and Steel
CONTROL DEVICE
Uncontrolled
Typical Electrostatic
Precipitator
Uncontrolled
Typical Electrostatic
Frecipitator
Uncontrolled
Precipitator
PARTICLE SIZE
DISTRIBUTION
% WEIGHT
64.7% <5p
6.797. 5-10ii
11.9% 10-20u
8.96% 20-44p
7.65% >44p
58% <5p
34% 5-10p
2% 10-20p
1% 20-44p
5% >44p
45% <2p
30% 2-5p
17% 5-10p
8% >10p
72% <2y
18% 2-5p
6% 5-10y
4% >10p
20% <2p
25% 2-5p
24% 5-10p
31% >10p
55% <2p
26% 2-5p
16% 5-10y
3% >10y
REFERENCES
999-AP-40 A. P. Engineering Manual
Table 67 (Electron Microscope)
Allen et al, 1952: BuMines Inf. Circular 7627
MRI Volume II Figure 8
also
Englebrecht: Proceedings 28th American Power
Conference, April 1966
MRI Handbook - Table 9-3 (Electron Microscope)
Lownie, H. W. and J. Varga, "A System Analysis
Study of the Integrated Iron and Steel
Industry," Battelle, Contract No. PM-22-68-65,
May 1969
McCrone, W. C. et al: "The Particle Atlas"
Ann Arbor Science Publishers, 1967
MRI Volume II Figure 8
also
Englebrecht: op. cit.
MRI Handbook - Table 9-3 (Electron Microscope)
Lownie, H. W. : op. cit.
McCrone, W.C.: op. cit.
MRI Volume II Figure 8
also
Englebrecht: op. cit.
oo
o
-------
TABLE,-XXV
PARTICLE SIZE DISTRIBUTION FOR EMISSIONS FROM SELECTED PROCESSES
WITHOUT CONTROL DEVICES AND WITH TYPICAL CONTROL DEVICES
(Continued)
PROCESS DESCRIPTION
Pulverized Coal Boiler
Oil Burners
Metallurgical Coke
INDUSTRY
Power Plant
Residential/Commercial
Iron and Steel
CONTROL DEVICE
Uncontrolled.
Electrostatic
Precipitator
Cyclone - .6 in. dia.
High Efficiency
Cyclone - 6 in. dia.
High Efficiency
Followed By
Electrostatic
Precipitator
Uncontrolled
Uncontrolled
'PARTICLE SIZE ,
DISTRIBUTION
% HEIGHT
15% <3v
10% 3-5 y
17% 5-10 M
23% 10-20 V
16% 20-40 u
19% >40.y.
38% <3,ji
14% 3-5 v
15% 5-10 v
7% 10-20 y
2% 20-40(1
24% >40y
61% <3y
20% 3-5 y
13% 5-10 u
5% 10-20 y
1% 20-40 v
Neg >40 y
83% <3y
11% 3-5 w
5% 5-10 y
1% 10-20 u
Neg 20-40 u
Neg >40 M
Est 90% 47u
REFERENCES
MKI Handbook: BAHCO Analysis
MRI Volume II
Figure 8
also
Engelbrecht, Heinz L. : Proceedings 28th
American Power Conference, April 1966
MRI Volume II
Figure 13
also
Burdock: Proceedings 62nd APCA Meeting,
June 1969
Same as above for cyclone and ESP
Reference: MITRE Estimate Based On
Industrial and Power Plant Oil Burners
Reference: MRI Handbook: Private Communi-
cations with Several Steel Companies
GO
SJ
-------
TABLE XXV
PARTICLE SIZE DISTRIBUTION FOR EMISSIONS FROH SELECTED PROCESSES
WITHOUT CONTROL DEVICES AND WITH TYPICAL CONTROL DEVICES
(Continued)
PROCESS DESCRIPTION
Roasters
Incineration
INDUSTRY
Primary Copper
Primary Zinc
Municipal
CONTROL DEVICE
Uncontrolled
Spray Tower
Plus Wet ESP
Uncontrolled
Cyclone Plus Wet
Electrostatic
Precipitator
Uncontrolled
Medium Energy
Wet Scrubber
Dry Expansion Chamber
Wet Bottom Expansion
Chamber
PARTICLE SIZE
DISTRIBUTION
% WEIGHT
15% <10y
85% >10u
54% <10p
46% >10p
57. <5p
26% 5-10p
39% 10-12p
30% >20p
37% <5p
63% 5-10y
Neg 10-20p
Neg >20.p
17% <2p
12% 2-10p
7% 10-20 p
4% 20-30 p
60% >30p
72% <2p
28% 2-10p
Neg 10-20 p
Neg 20-30^
Neg >30u
'Unknown
Unknown
REFERENCES
MRI Handbook
Stairmahd, C. J. : Journal of the Institute
of Fuel, 58-81, Feb. 1956
Watkins and Darby: The Application of
Electrostatic Precipitation to the Control
of Fume in the Steel Industry. Scrap Iron
and Steel Institute pp. 24-37
MRI Handbook: BAHCO Analysis
MRI: op. cit.
Burdock: ap. cit.
Ehglebrecht: op. cit.
MRI Handbook: BAHCO Analysis i
Kalika, P. W. : How Water Reeirculation .and
Steam Plumes Influence Scrubber Design.
Chem. Eng. , 133-138 July 1969
A. P. Engineering .Manual: "Simple Settling
Chambers Collect Particles 40p or Greater"
09
03
-------
TAStE XXV
PARTICLE SIZE DISTRIBUTION FOR EMISSIONS FROM SELECTED PROCESSES
WITHOUT CONTROL -DEVICES AND WITH OTICAL CONTROL DEVICES
(Continued)
PROCESS DESCRIPTION
Incineration (continued)
Sintering
INDUSTRY
Municipal (continued)
Domestic
Iron and Steel
\
CONTROL DEVICE
1 Spray Chamber
Wetted Wall Chamber
Wetted Wall
Close Spaced
•Baffles
Dry Cyclone
Uncontrolled
Peabody Scrubber
Uncontrolled
Fabric Filter
Dry Cyclone
PARTICLE SIZE
DISTRIBUTION
% WEIGHT
62% <2y
22% 2-lOu
3% 10-2011
2% 20-30y
11% >30y
Unknown
Unknown
52% <2U
29% 2-10y
8% 10-20M
2% 20-30 v
9% >30y
Unknown
Unknown
1% <2y
4% 2-10y
15% 10-30 y
5% 30-50y
75% >50y
43% <2 y
57% 2-10y
0% lOy
9% <2y
28% 2-10M
46% 10-30y
3% 30-50'y
14% >50,y
REFERENCES
Stairmandi op. cit.
A. P. Engineering Manual: op. cit.
A. P. Engineering Manual: op. cit.
A. P. Engineering Manual: op. cit.
MRI: op. cit.
A. P. Engineering Manual: op. cit.
Southern Research Institute: The Applica-
tion of Electrostatic Precipitators in
the Iron and Steel Industry. Final Report
NAPCA Contract CPA-22-69-73, June 1970.
.(Size Analysis: BAHCO Plus Seive)
Sommerlad, R. S. : Fabric Filtration State
of the Art. Foster Wheeler Corp.
March 1967.
A. P. Engineering Manual: op. cit.
00
-------
TABLE XXV
PARTICLE SIZE DISTRIBUTION FOR EMISSIONS FROM SELECTED PROCESSES
WITHOUT CONTROL DEVICES AND WITH TYPICAL CONTROL DEVICES
(Continued)
PROCESS DESCRIPTION
Sintering (continued)
Ore Mining and Handling
INDUSTRY
Iron and Steel (continued)
Primary Zinc
Primary Lead
Asbestos
CONTROL DEVICE
Dry Cyclone Plus ESP
Uncontrolled
Fabric Filter Plus
Wet ESP
ESP Plus Wet ESP
Scrubber Plus Wet
Wet ESP
Uncontrolled
Cyclone Plus
Fabric Filter
Cyclone Plus ESP
Uncontrolled
Cyelone Plus
Fabric Filter
PARTICLE SIZE
DISTRIBUTION
% WEIGHT
13% <2V
177. 2-10jj
27% 10-30y
3% 30-50vj
40% >50p
100% <10y
100% <10p
100% <10p
100% <10p
15% <10y
85% >10p
100% <10u
0% >10u
81% <10p
19% >10y
100% <40«
Est. 100% <40w
REFERENCE
A. P. Engineering Manual: op. cit.
Watkins and Darby: op. cit.
Verein Deutscher Ingenieure, VE1, p. 2285
Sept. 1961 (Size Analysis: Unspecified)
Sommerlad, R. S.: op. cit.
Watkins and Darby: op. cit.
Watkins and Darby: op. cit.
Kalika, P. W. : op. cit.
Watkins and Darby: op. cit.
MRI Handbook says similar to copper
roasting
Air Engineering: 28-38, Sept. 1964
Sommerlad, R. S. : op. cit.
Air Engineering: op. cit.
Watkins and Darby: op. cit.
Davis, W. E. & Associates: National Inventory
of Sources and Emissions Cadmium, Nickel,
and Asbestos
Air Engineering: 28-38, Sept. 1964
Sonnnerl-ad, R. S.: op. cit.
•o
o
-------
TABLE XXV
PARTICLE SIZE DISTRIBUTION FOR EMISSIONS FROM SELECTED PROCESS
WITHOUT CONTROL DEVICES AND WITH TYPICAL CONTROL DEVICES
(Continued)
PROCESS DESCRIPTION
Asphalt Blowing
Natural Gas Combustion
: Pellet Plants
INDUSTRY
Roofing Material
; Industrial
Iron Ore
CONTROL DEVICE
uncontrolled
Wet Scrubber and
: Afterburner
Uncpn trolled
Uncontrolled
Fabric Filter
Dry Cyclone
Dry Cyclone Plus ESP
PARTICLE SIZE
DISTRIBUTION
% WEIGHT
18% <5y
22% 5-10y
28% - 10-20y
17% 20-SOp
15% >50y
92% <5y
5% 5-10y
i 3% 10-20 y,
Neg 20»50u
Neg >50y
100% <5u
1% <2y
4% 2-10y
15% 10-30y
5% 30-50,1
7'5% ." >50y
43% <2U
57% 2-10y
0%, >10,u ,
9% <2y
28% 2-10y
46% 10-30,y
3% 30-50y
14% >50y
13% <2y
17% 2-10y
27% 10-30y
3% 30-50y
40% >50y
REFERENCES
A. P. Engineering Manual
(Size Analysis: Unspecified)
Schell, T. W. : Cyclone/Scrubber .System
Quickly Eliminates Dust Problem. Rock ,
Products 66-68, July 1968 . 1
MRI Handbook (Size Analysis: MRI Estimate)
TRW: Engineering and Cost Effectiveness
Study of Fluoride Emissions Control.
Jan. 1972
Southern Research Institute: op. cit.
(Size Analysis: BAHCO plus SEIVE)
Sommerlad, R. S. : op. cit.
A. P. Engineering Manual: 'op, cit.
A. P. Engineering Manual: op. cit.
Watkins and Darby: op\ cit.
-------
TABLE XXV
PARTICLE SIZE DISTRIBUTION FOR EMISSION'S FROM SELECTED PROCESSES
WITHOUT CONTROL DEVICES AND WITH TYPICAL CONTROL DEVICES
(Continued)
PROCESS DESCRIPTION
^Bleaching
Oil Burners
Blast .Furnace
INDUSTRY
.Pulp and Paper
•Power Plants
Industrial
Primary lp
90% ly
JQ%* <74U
5058* >74y
size highly variable
Efficiencies are
highly variable
depending on cham-
ber parameters.
Limit on collec-
tion size i-s
usually 40p or
greater .
80% <74y
2-0% >74u
93. <74y
20% >7.4y
29Z <74y
,7-lX >74y
-REFERENCE
E.P.A. : Draft, Control Techniques for
Chlorine and Hydrogen Chloride Emissions.
March 1971
.MRI Handbook: (Size Analysis: Unknown)
MRI Handbook: (Size Analysis: Unknown)
HRI Handbook: (Size Technique: Unknown)
A.,P. Engineering Manual: op. cit.
Turner, -B.: Grit Emissions Bay Area APCD
Library Accession 9775
Watkins and Darby: pp. ,cit.
-Turner, B.,: op. cit.
Wa-tkins and Darby: op. cit.
to
-------
TABLE XXV
PARTICLE SIZE DISTRIBUTION FOR HUSSIONS FROM SELECTED PROCESS
WITHOUT CONTROL DEVICES AND WITH TYPICAL CONTROL DEVICES
(Continued)
PROCESS- DESCRIPTION
Blast Furnace (continued)
IWUST8X
Primary Lead
Secondary Lead
Secondary Copper
Ferroalloys
CONTROL DEVICE
Uncontrolled
High Efficiency
Cyclone
High Efficiency
ESP
Fabric Filter
Uncontrolled
High Efficiency
ESP
Fabric Filter
High Efficiency ESP
Plus Fabric Filter
Uncontrolled
Fabric Filter
Uncontrolled
Medium Energy Wet
Scrubber
Typical Electrostatic
Precifitator
High Efficiency
Cyclone
PARTICLE SIZE
DISTRIBUTION
7. WEIGHT
100% <.3y
96% Penetra*
tion at <.3,p
7% " "
5%
100% *.4y
,,.„ Penetra-
tion at < . 4y
SZ
.25% "
100% < . 5u
Penetra-
tion at <.5)j
80%
-------
TABLE X3W
PARTICLE SIZE DISTRIBUTION FOR EMISSIONS FROM SELECTED PROCESSES
WITHOUT CONTROL DEVICES AND WITH TYPICAL CONTROL DEVICES
(Continued)
PROCESS DESCRIPTION
Blast Furnace (continued)
Stoker Coal Boiler
Gas Burners
Pulverized Coal Boiler
INDUSTRY
Ferroalloys (continued)
Non-Ferrous Alloys
Industrial or Ppwer
Plant
Residential, Commercial
or Industrial
Industrial
PARTICLE SIZE
CONTROL DEVICE DISTRIBUTION
% WEIGHT
v Fabric Filter
Uncontrolled
High Efficiency ESP
Fabric Filter
High Efficiency
Cyclone
Uncontrolled
Cyclone - 6 in.
High Efficiency
Typical Electro-
static
Precipitator
Uncontrolled
High Efficiency ESP
Same as Pot
99% 44u
68% < 10- (i
. 6% 10-20 (i
19% 20-44 n
7% >44u
2% <10|i
neg . 10-20 (i
3% 20-44 (j.
95% > 44 (i
100% <5fi
Avg.5% Penetration
in 0—5 u Range
er Plant Data
REFERENCES
MRI Volume II
A. P. Engineering Manual: op. cit.
Allen, G. L., et al.: op. cit. (Size
Analysis: Electron Microscope)
MRI Volume II - Figure 17
"
•
MRI Handbook: op. cit. (average of
spreader stoker & underfed stoker)
Burdock: op . cit .
Englebrecht : op . cit .
MRI Handbook : op . ci.t .
MRI Volume II - Figure 17
MRI Handbook: op. cit.
-------
TABLE, XXV
P&RTICLE SIZE DISTRIBUTION FOR EMISSIONS MOM SELECTED PROCESSES
WITHOUT GQNTR®! DEVICES AMP WITH TYPICAL COMrROL -DEVICES
(Concluded)
PROCESS DESCRIPTION •
1 Cyclone Coal Boiler--
INDUSTRY
Industrial
o-r
Power Plant
CONTROL DEVICE j
Uncontrolled
Cyclone -6 in.daa. '
High Efficiency
Typical Electro-
static
Precipitatpr
PARTICLE SIZE
BISTRIBHTaON'
% HEIGHT
' 40X < 5f
25% 5-10 (i
16% 10-20 |i
lljt 20-40 H
8% >40)JL
83% < 5 K-
14% 5-lD,|i
2% 10-20 |i
1% 20-40 p.
neg,. > 40',jjL
67% <5;|» :
19% 5-10 p.
5% 10-20. (i
1% 20-40 ji
8% > 40 pi
REFERENCES
MRI Handbook: op. cii.
{BAMCO Analysis)
Burdock op . cit .,
Englebrecht, op. cit.
p>
-------
TABLE XXVI
EMISSIONS Of PARTICULATES AND FINE PAETICULATES AFTER 100% APPLICATION OF BEST CONTROL DEVICE
PROCESS
Open Burning
Open Hearth Furnace
No Oxygen Lance
(composite run)
Oxygen Lance
(composite run)
Pulverized Coal Boiler
Oil Burners
Metallurgical Coke
Chlorine Liquefaction
Roasting
Incineration
INDUSTRY
Agricultural
Forest Fires
Refuse Open Burning
Conical Burners
Coal Refuse
Iron & Steel
Iron & Steel
Power Plant
Residential/
Commercial
Iron & Steel
Chlorine &
Alkalis
Primary Copper
Primary Zinc
Municipal
Domestic
BEST DEVICE
IN USE
None
None
None
None
None
Electrostatic
Precipitator
Electrostatic
Precipitator
Cyclone plus ESP
None
None
Return Vents &
Alkali Scrubber
Settling, Water
Spray plus ESP
Waste Heat Boiler
plus Cyclone plus
ESP
Medium Energy
Wet Scrubber
Peabody Scrubber
7, BY WEIGHT
FINE PARTICULATE
FOR BEST DEVICE
Unknown
Unknown
Unknown
Unknown
Unknown
58% <5ti
55% <2^
83% <3/^
Unknown
4% <47//
0% All gas
54% <10ft
37% <5fl
72% <2fi
Unknown
%
APPLICATION
OF CONTROL
0
0
0
0
0
41%
41%
97%*
0
0
100%
100%
100%
100%*
Neg.
PRESENT
EMISSIONS
TONS
2,161,142
1,433,712
526,843
212,211
193,500
68,227
51,471
44,063
43,380
43,000
4,373
34,187
29,393
730
EMISSIONS WITH
100% USE OF BEST
CONTROL AVAILABLE
TONS
No controls
Available
"
3,445
20,164
No controls
Available
43,380
43,000
4,373
34,187
4,741
730
FINE PARTICULATE
EMISSIONS WITH 100%
BEST CONTROL - TONS
Unknown
Unknown
Unknown
Unknown
Unknown
1,895 <2fl
16,736 <3fi
Unknown
Unknown
None
2,361 <10^
12,649 <5/l
3,414 <2/i
Unknown
-o
o
*Best Control Device Not Universally Used.
** Applying High Efficiency ESP as Best Device.
-------
TAME XXVI
EMISSIONS OF PARTICULATES AND FINE PARTICULATES AFTER 100% APPLICATION OF BEST CONTROL DEVICE
(Continued)
PROCESS
Sintering
Ore -Mining & .
Handling-
Asphalt Blowing
Natural Gas Combustion
Pellet Plants
Bleaching
Oil Burners
Oil Burners
Blast Furnace
INDUSTRY
Iron & Steel
Primary Zinc
Primary Lead
Asbestos
Mica (Beryllium)
Borax
Manganese
Copper, Zinc, Lead
Barium, Nickel,
Mercury , Vanadium
Roofing Material
Industrial
Iron Ore
Pulp & Paper
Power Plants
Industrial
Iron & Stee-l
BEST DEVICE
IN USE
Baghouse
Baghouse Plus
Wet ESP
Cyclone Plus
Baghouse
Cyclone Plus
Baghous e
Cyclone Plus
Baghouse
Baghouse
Baghouse
Baghouse
Scrubber &
Afterburner
None
Baghouse
Alkali Scrubber
None (Except Soot
Blow)
None (Except Soot
Blow)
Cyclone Plus ESP
. % BY WEIGHT
FINE P ARTICULATE
FOR BEST DEVICE
43% <2/J
100'% <10/J
100% <10/i
100% <40#
Unknown
Unknown
Unknown
Unknown
92% <5rl
100%
-------
TABLE XXVI
EMISSIONS OF PARTICIPATES AND FINE PARTICULATES AFTER 100% APPLICATION OF BEST CONTROL DEVICE
(Concluded;
PROCESS
Blast Furnace
(cont'd)
Stoker Coal Boiler
Gas Burners
Gas Burners
Stoker Coal Boiler
Pulverized Coal
Burner
lyclone Coal Boiler
lyclone Coal Boiler
loal Boilers
INDUSTRY
Primary Lead
Secondary Lead
Secondary Copper
Ferroalloys
Non- Ferroalloys
Industrial
Residential
Commercial
Power Plant
Power Plant
Industrial
Industrial
Power Plant
Residential
Commercial
BEST DEVICE
IN USE
Cyclone Plus
Baghouse
High Eff ESP
Plus Baghouse
Baghous e
High Eff ESP
High Eff ESP or
Baghouse
High Eff. ESP
None
None
None
High Eff. ESP
High Eff. ESP
High Eff. ESP
High Eff. ESP
None
None
% BY WEIGHT
FINE PARTI CULATE
FOR BEST DEVICE
100% <.3n
100% <.4p
100% <.5/J
80%
-------
from available literature as representative and the fractional
efficiencies used should not be interpreted as precise final data.
They merely serve to show a plausible distribution for each control
device shown. The fractional efficiency curves which were used are
reproduced in Figures 20 through 24. Extrapolation of these
Curves to submicron size particles was made by using estimates given
in reference 42. Figure 25 taken from that reference shows these
estimates. In some cases other minor extrapolated estimates were
made by the authors as appropriate. The basic method for computing
the particle size distribution after the effluent passes through
a typical control device is to multiply the uncontrolled percent by
weight for each size range by the grain loading per standard cubic
foot to yield the weight per standard cubic foot for each size* This
weight is then multiplied by the fractional penetration for that
size range read from the appropriate fractional efficiency curve to
yield the weight per standard cubic foot of particles in that size
range which are not collected by the control device. The weights
for all the size ranges are then converted into percentages.
It should be reemphasized at this point that the hazards posed
by toxic trace materials in fine particulate form can be
disproportionate to the mass involved. As mentioned at the outset
the persistence of fine particulates in the atmosphere, their effect
on visibility and meteorology, their ability to penetrate the natural
barriers of the respiratory system to enter deep into the lungs and -
$9
-------
o
o
99.99
99.9
99.8
99.0
95.0
90.0
a
o
w
PM
50.0
20.0
10.0
5.0
2.0
1.0
0.5
0.2
0.1
0.05
0.01
0.01
IIIITT I I 111
ELECTROSTATIC PRECIPITATORS
1. TYPICAL ESP, REFERENCE 298.
2. WET ESP, REFERENCE 300.
0.1
1.0
PARTICLE DIAMETER - MICRONS
10.0
0.01
0.05
0.1
0.2
0.5
1.0
2.0
5.0
10.0 ^
20.0 g
50.0 !
g
90.0
95.0
99.0
99.8
99.9
99.99
100.0
FIGURE 20
FRACTIONAL EFFICIENCY DATA FOR ELECTROSTATIC PRECIPITATORS
-------
99.99
99.9 -
99.8 -
99.0 -
95.0 -
90.0
§
M
a
50.0
20.0
10*0
5.0
2.0
1.0
0.5
0.2
0.1
0.05
0.01
0.01
Till
FABRIC FILTER
1. TYPICAL FABRIC FILTER, REFERENCE 302.
0.1
1.0
.PARTICLE DIAMETER - MICRONS
10.0
0.01
0.05
0.1
0.2
0.5
1.0
2.0
5.0
10.0
20.0
H
O
50.0
90.0
95.0
99.0
99.8
99.9
99.99
§
M
H
U
H
»J
o
100.0
FIGURE 21
FRACTIONAL EFFICIENCY DATA FOR A FABRIC FILTER
-------
99.99
99.9
99.8
99.0
95.0
90.0
53
o
K3
50.0
20.0
10.0
5.0
2.0
1.0
0.5
0.2
0.1
0.05
0.01
0.01
i i i i T
i i i i i i f
CYCLONES
1. HIGH EFFICIENCY CYCLONE, 6 IN. DIAMETER, 2.5 IN. ^0 PRESSURE DROP,
REFERENCE 299.
2. TYPICAL HIGH CAPACITY CYCLONE, REFERENCE 304
0.1
1.0
PARTICLE DIAMETER - MICRONS
10.0
0.01
5.0
0.1
0.2
0.5
1.0
2.0
10.0
20.0
o
23
50.0 H
w
D.O |
95.0 u
s
99.0
99.8
99.9
99.99
100.0
FIGURE 22
FRACTIONAL EFFICIENCY DATA FOR CYCLONES
-------
O
CJ
g
M
y? • y? .
99.9
99.8:
99.0
95.0
90.0
50.0
20.0
10.0
5.0
2.0
1.0
0.5
0.2
0.1
0.05
n.m
i i i i i i i i
i i i i i i i i
i i i i i i i i
1 1 1 1 1 1 I
SCRUBBERS
1. GRAVITY SPRAY TOWER, LESS THAN 1" H20 PRESSURE DROP, REFERENCE 180.
—
2. MEDIUM ENERGY WET SCRUBBER, 4-6" H20 PRESSURE DROP, 3.3 gpm/ 1,000 cfm,
" REFERENCE 301.
3. ASPHALT PLANT, WET SCRUBBER, LOW PRESSURE DROP, REFERENCE 303.
-
-
-
-
-
_
-
-
,
(
<
i i i i i i i i
. 1 ] 1 1 1 1 1 1
_
-
.-
1
2%
"*
-
-
i i i i i t i
U. UJ.
0.05
0.1
0.2
0.5
1.0
2.0
5.0
10.0
20.0
50.0
90. 0
95.0
99.0
99.8
99.9
99 . 99
0.01 0.1 1.0 10.0 100.0
w
Pn
&
§
H
E-i
O
PARTICLE DIAMETER - MICRONS
FIGURE 23
FRACTIONAL EFFICIENCY DATA FOR SCRUBBERS
-------
99.99
0.01
0.01
0.01
0.1
PARTICLE DIAMETER - MICRONS
FROM REFERENCE 42
1.0
9.99
FIGURE 24
EXTRAPOLATED FRACTIONAL EFFICIENCY OF CONTROL DEVICES
104
-------
their rate of retentivity all contribute to the hazardous character
of fine particulates.
The relative importance of the fine particulate fraction
increases if one considers the hypothetical situation in which the
best available controls are applied to all sources. A computation
was made to reflect this situation in order to determine the extent of
the residual emissions problem assuming that the best control
technology were implemented everywhere. The results of this computation
are shown in Table XXVI. One can see that although there is. some
reduction in the total emissions, a large portion of the problem
remains, following 100% application of the.best known control
technology. For example, estimated emissions of about 50,000 tons/
year from pulverized coal boilers would be reduced to 20,000 tons/
year if best available technology were universally applied.
It should be remarked, however, that the values presented are
based on the assumption that the device which now gives the best
results, i.e., lowest emissions, can be applied with equal effectiveness
to all sources. While this is generally not the case because sources.
may vary considerably, nevertheless, the numbers generated in
this way offer some insight into the approximate level of control
achievable. Thus, if no reduction in the level of emissions can
be made, this is indicated in Table XXVI, in a column showing the
mass emissions expected assuming that the best available controls
are used. In these cases where some best control technique can be
105
-------
identified, and where a reduction in the mass of emissions is
indicated the bulk of the improvement is in the large particulate
fraction.
To calculate the estimated emissions for fine particulates
shown in Table XXVI , it was assumed that the percent of fine
particulate emissions represented in the fourth column remains
unchanged. It should be noted that the principal purpose served
here is to highlight the key problems rather than to assign immutable
numbers to a situation.
The processes that would be most greatly impacted by universal
application of the best control devices now in use are open hearth
furnaces in the iron and steel industry, blast furnaces used in the
secondary lead, secondary copper and non-ferroalloy industries,
sintering operations for primary metals and incineration. In each
of these cases, the total emissions would be very greatly reduced if
the best control technology were applied.
Inspection of the data shows that the major emitters of
hazardous pollutants can be grouped in various ways. One such
grouping which is useful in further identification of the nature
of the problem is as follox^s.
1. Processes whose mass emissions could be somewhat reduced
if the best control devices are universally used, but
for which a residual fine particulate problem would remain.
Open hearth furnaces - steelmaking
106
-------
municipal incinerators
sintering furnaces - iron ore and zinc ore
iron ore pellet plants
blast furnaces - secondary lead, secondary copper,
non-ferroalloys
2. Processes whose residual emissions, after application of
the best conventional technology, are principally fine
particulates. (In this case arbitrarily specified as more
than 75% less than 5 micron size).
pulverized coal boilers
sintering - zinc ores and lead ores
asphalt blowing
natural gas combustion
oil burners - power plant and industrial
blast furnace - primary lead, ferroalloys, secondary
lead and copper
3. Processes whose emissions .are not principally fine
- i ' "'•(•"•';
particulates but which still have significant emissions
in spite of 100% application of best control.
roasting - primary copper, primary zinc
iirto •. , . . • •.',." .:••••
asbestos ore mining and handling
blast furnaces - steelmaking
ore mining and handling - general
4. Particulate emitting processes which are not controlled.
1:07
-------
open burning
residential and commercial oil burners
metallurgical coke
oil burners - power plant and industrial
5. Processes whose particulate emission distribution is
unknown.
open burning
ore mining and handling
oil burner operation
domestic incineration
6. Processes with primarily gaseous emissions
chlorine liquefaction
chlor-alkali industry
bleaching - pulp and paper
These groupings indicate different situations requiring different
R&D approaches if abatement of the emissions is to be achieved. The
need for further control technology studies of the generalized fine
particulate problem is clear. It will be necessary to further
identify and overcome those technological obstacles which interfere
with the compatibility of existing processes and existing best
technology. In some cases, best available control is not adequate
even excluding the problems associated with collecting fine particulates,
and in others no controls at all are in use either because of
economic or technological reasons. In still others, the problems
are undefinable because data are absent.
108
-------
In subsequent sections of this report the physical characteristics
of the emissions from selected sources x^ill be examined in more
detail. The primary purpose of these examinations is to provide
appropriate information pertaining to the development of new or
improved control devices.
109
-------
4.0 THE PRIMARY NON-FERROUS SMELTING INDUSTRIES'
4.1 Introduction
Preliminary inspection of the various types of emission and
control technology data reported in the foregoing sections indicated
that a more detailed study of ore roasting or sintering in the
copper, lead, and zinc industries should be made. The primary
purpose of these detailed studies was to determine the characteristics
of the gases and particulates being emitted at various points in the
process. It was specified that emissions from materials handling
not be considered in the study.
Copper roasting, zinc roasting, and lead sintering were
investigated separately and the results are presented in the next
three sections. Tables were prepared to show both gaseous and
particulate emission characteristics. The gas characteristics
include flow rate, temperature, and chemical composition, while the
particulate characteristics are grain loadings, % weight analysis of
chemicals, size profile, and chemical composition. Numbers appearing
in parentheses at the top of columns or after data entries, refer to
the numbers of the bibliography entries from which the data were
taken.
Pollutants can be emitted from more than one point during'any
of these processes and the pollutant characteristics will vary at
the different points, thus the emission characteristics were computed
111
-------
and reported on separate tables for the selected possible control
points. In most cases, no gases were emitted at the point where
the raw materials were charged into the process, so blanks appear
in the gas flow columns of the "input feed" entries. Data which
were not reported and for which MITRE estimates could not be made
were represented by "NR" (not reported).
In many cases % weight and % volume were reported as specific
numbers rather than as ranges. These should be considered as
typical values rather than as specific data. There is certain to
be some variation in these numbers not only from facility to facility,
but also at different time points within any operation.
Usually data from every plant in operation were not available
in the literature, and therefore all plants could not be considered
when the averages and ranges were prepared. Enough data were
available though, so that additional data would most likely not
cause the ranges in the tables to be significantly altered.
4.2 The Primary Copper Industry
Throughout the world copper is found in three main types -
native, oxide, and sulfide. Native copper is the pure metal mixed
with gangue and in some cases other valuable minerals or ores. It
is not a principal source of concentrate for the primary copper
industry. Copper oxides exist in significant quantities throughout
the world and provide a small fraction of the concentrates used in
112
-------
smelters. However, most of the world copper production comes from
low-grade sulfide ores from which the sulfide copper minerals are
concentrated by flotation. The usual composition of the concentrate
is copper sulfides, iron sulfides and residual gangue. The purpose
of smelting is to separate the copper from the iron, sulfur and
gangue. The thermodynamic relationships between these, principal
ingredients form the basis for the three major steps: roasting to
remove excess sulfur, smelting in a reverberatory furnace to remove
gangue and to form a copper-iron^sulfur mixture called matte, and
oxidation of the matte in a converter to form a separable iron
slag and to burn the sulfur away from the copper. Each of these
steps generates varying amounts 6f sulfur oxides and hazardous
pollutants. The basic steps in primary copper smelting are shown
in Figure 25.
Two types of equipment are used for roasting - multiple hearth
and fluosolids roasters. Operation of the fluosolids roaster
generally is autogenous in that no fuel is required other than that
needed for preheating of the roaster prior to start-up-. Operation
of multiple-hearth roasters, on the other hand, may or may not be
autogenous, depending primarily on the ratio of copper to sulfur
composition of cpncentrates and other copper-bearing materials
treated at primary copper smelters in the United States, the sulfur
dioxide content of roaster gases may range from as low as 1 percent
when it is necessary to" burn auxiliary fuel to as high as 12 percent
in autogenous fluosolids roasting.
113
-------
REVERBERATORY
FURNACE
ATMOSPHERE
**
•Jf MINOR EMISSION POINT
MAJOR EMISSION POINT
SOURCE: MRI
FIGURE 25
BASIC OPERATIONS-PRIMARY COPPER SMELTING
-------
In addition to removal of excess sulfur the roasting operation
serves other purposes as listed below.
o Drying the ore concentrate
o Volatilizing some impurities such as arsenic and antimony
o Oxidizing some of the iron to permit slagging with silica
o Preheating the ore for the reverberatory furnace
o Creation of a favorable balance of copper, iron and sulfur.
Calcined concentrates, if roasting is practiced, or unroas.t;ed
concentrates (green feed) are smelted in a reverberatory furnace
fired with oil, gas, or pulverized coal. The magnitude of the sulfur
oxide and hazardous pollutant emission problem varies widely with
the characteristics of the feed and fuel. The large volume of .
gas generated by the burners produces an off gas containing only
a dilute concentration of sulfur oxides and varying concentration
of total particulates based on the fuel used. The sulfur dioxide
content of the furnace gas generally ranges from 0.25 to 1 percent
when smelting calcines or low-sulfur feed, When concentrates rich
in sulfur are fed directly to the furnace, the sulfur dioxide content
of the gas may be as high as 2.5 percent.
The process of removing iron and sulfur from copper in a converter
is a controllable operation, but unlike the roasting and smelting
steps, it is a batch process. The sulfur dioxide content of the off
gas may range from 3 to 12 percent during the converting cycle. When
multiple converters are in use, the cycles can be staged to hold the
115
-------
strength of the combined off gases within a range of 4 to 6 percent,
which is suitable for sulfuric acid manufacture.
The sulfur dioxide and total particulate emissions problem for
primary copper, lead, and zinc smelters in the United States has been
studied in great detail and is reported in references 162, 163, and
164.
Table XXVII gives a listing of all primary copper smelters
operating in the United States during 1972. Also shown are the
general types of roasters used, if any.
4.3 The Primary Lead Industry
The most abundant lead mineral which has been exploited in the
United States is galena. Minerals commonly associated with galena
include zinc, silver, gold, and iron. Galena and other types of
lead ore usually must be concentrated by gravity or flotation methods
before being feed to the main smelting processes. Lead is mined
in several different states, but in 1970 Missouri mines supplied
74% of the total domestic mine production. In the mid-1950's, new
mining efforts began in southeastern Missouri. This area is known
as the "New Lead Belt" and more than tripled Missouri's lead
production in the period 1965-1970.
Most of the U.S. lead smelter operations date back to the turn
of the century, but in the late 1960's two new smelters began
operation in Missouri. In addition, the old plant located in
Herculaneum, Missouri was expanded and extensively modified. It is
116
-------
TABLE XXVII
U.S. PRIMARY COPPER SMELTERS
NAME AND LOCATION
Asarco, Hayden, Arizona
Inspiration Consolidated, Miami, Ariz.
Kenneeott, Hayden, Arizona
Phelps Dodge, Douglas, Arizona (253)
Phelps Dodge, Morenci, Arizona (253)
Phelps Dodge, AJO, Arizona (253)
Magma, San Manuel, Arizona
Copper Range, White Pine, Michigan
Anaconda, Anaconda, Montana
Kenneeott, MeGill, Nevada
Kenneeott, Hurley, New Mexico
Cities Service, Copperhill, Tenii.
Asarco, El Paso, Texas
Kenneeott, Garfield, Utah
Asarco, Tacoma, Washington
MAJOR ORE
TYPES (203)*
Sulfide, oxide
Sulfide
Sulfide, oxide, lake
Sulfide
Sulfide
Sulfide
Sulfide
Sulfide, Lake
Sulfide, oxide
Sulfide
Sulfide
Sulfide
Sulfide
Sulfide
Sulfide
HEARTH
ROASTERS
(N6)
1
(_(
H
0
0
0
0
17
0
0
0
0
0
0
0
0
4
0
5
>•<
:S
w
0
0
0
7
0
0
0
0
0
0
0
0
3
0
5
FLUID
OR
- FLASH
ROASTERS
(N6)
i
H
H
1
7
0
1
0
1
0
0
0
0
0
0
1(216)
0
0
0
>H
s
H
en
5
0
0
0
0
0
0
0
0
0
0
0
0
0
0
REVERBERATORY
FURNACES
-<
1
H
co
0
0
0
0
0
0
0
1
1
1
0
0
0
0
1
CONVERTERS
(196, N6)
4
g
H
1
ta
§>
4
3
2
3
8
2
5
1
6
3
3
1
3
7
3
^
§
g
s
CO
1
1
1
2
0
0
0
1
0
1
1
0
0
2
1
*Nu™bers in parentheses are references.
-------
now the largest primary lead smelter in the United States and the
second largest in the world. Three other operations make up the rest
of the United States lead smelting industry. See Table XXVIII for the
complete listing.
Primary lead smelting is comprised of three basic steps,
sintering, blast furnacing and refining. In the United States, all
primary lead smelters use sintering as the first principle step.
Sintering removes about 85% of the sulfur from the feed by roasting
and also produces a calcine that is a strong and porous mass suitable
for reduction in a blast furnace. The principal chemical reaction
is the oxidation of lead sulfide to lead oxide.
The smelting of lead ores is usually done in blast furnaces
which reduce lead oxide to metallic lead. Two minor reactions also
take place. These are a double decomposition reaction between lead
sulfide and lead sulfate or oxide which forms lead and sulfur dioxide;
and the decomposition of lead sulfide by metallic iron. All three
reactions noted above are endothermic.
Refining methods are used whenever the lead bullion produced
contains appreciable amounts of precious metals. There are two
refining methods used, electrolytic and pyrometallurgical. In the
electrolytic process, the refined lead is recovered from the cathode
and the impurities are recovered from the cell as slimes.
Pyrometallurgical refining consists of dressing, desilverizing,
and dezincing. The dressing involves heating to carefully controlled
118
-------
TABLE XXVIII
U.S. PRIMARY LEAD SMELTERS
NAME AND LOCATION
Bunker Hill Company
Kellogg, Idaho
ASARCO
East Helena, Montana
ASARCO
Glover, Missouri
ASARCO
El Paso, Texas
Missouri Lead Operating Company
Boss, Missouri
St. Joseph Lead Company
Herculaneum, Missouri
SINTERING MACHINES
OPERATIONAL
1
1
1
6
1
1
STANDBY
0
0
0
0
0
0
TYPE
Updraft
Updraft
Updraft
Downdraft
Updraft
Updraft
BLAST
FURNACES
OPERATIONAL
1
1
1
2
1
2
STANDBY
1
1
0
1
1
1
-------
temperatures and skimming off the various impurities which oxidize
at different temperatures. In the desilverizing kettles, zinc is
added to form a crust of the precious metals. Finally, in the
dezincing kettles the residual zinc in the bullion is distilled under
a vacuum. The refining drosses, skimmings, and crust are sent to
separate retorts for further treatment.
A flow diagram showing the various steps in the lead smelting
process is presented in Figure 26. A more detailed description of
the sintering process flows appears later in this section and an
additional discussion of the blast furnace appears in Section V.
4.4 The Primary Zinc Industry
Zinc rarely, if ever, occurs free in nature. The principal
zinc ores are:
Sphalerite (zinc blend) ZnS
Wurtzite ZnS
Zincite ZnO
Smithsonite ZnCO
Gaslaute ZnSO '7H 0
Willemite Zn.SiO.
2 4
Calamine Zn.SiO -H 0
Franklinite (Fe, Zn, Mn) 0-(Fe, Mn) 0
Hydrozincite ZnC03'2Zn(OH)
Nearly all deposits of zinc ore contain sphalerite or are the
oxidation products of sphalerite ores. Sphalerite, associated with
120
-------
(O
*MINOR EMISSION POINT
**MAJOR EMISSION POINT
SOURCE: LEAD AND ZINC vll
ATMOSPHERE
**
**
BY-PRODUCT
FURNACE
FIGURE 26
BASIC OPERATIONS-PRIMARY LEAD SMELTING
-------
galena (lead sulfide), occurs in the Joplin region of Missouri, Kansas,
and Oklahoma. According to reference 313 there are four principal
types of deposits which yield zinc ore. These four types accounted
for 97% of the zinc produced in the U.S. in 1970. The four types
and their percentage contribution are listed below:
Zinc ores 50%
Lead ores 10%
Zinc-lead ores 29%
Copper-zinc, copper-lead,
and copper-zinc-lead 8%
Total from these sources 97%
Tennessee is the leading state in zinc ore production. In 1970 it
produced ores which provided 22% of the total U.S. primary zinc
output. Other leading producers were New York (11%), Colorado (11%)
and the Missouri-Kansas-Oklahoma belt (10%).
Many ores of zinc have to be concentrated by the oil flotation
process before it is profitable to smelt them. Concentration of
sphalerite in the Joplin area produces a product of nearly 100% zinc
sulfide, while in some places the concentrate contains only about one
third this percentage.
The conversion of zinc sulfide into metallic zinc is done by
either a pyrometallurgical or a combination pyrometallurgical-
electrolytic process. The three major steps in the first process
are:
122
-------
1. Roasting of the zinc sulfide to form impure zinc oxide calcine
2. Sintering, of the impure zinc oxide
3. Pyrometallurgical reduction of zinc oxide into zinc
In the electrolytic process sintering is not required resulting
in two major steps:
1. Roasting of zinc sulfide to impure zinc oxide calcine
2. Electrolytic extraction of leached calcine
Existing zinc smelters utilize one or a combination of several' types
of roasters, including the almost obsolete Ropp roasters, multiple
hearth roasters, or modern flash and fluid-bed roasters. The basic
purposes and techniques of roasting zinc ores are the same as
described in the copper section with one major exception. .. In the
zinc industry the roast from zinc sulfide to zinc oxide is carried
to completion (dead roast) as opposed to the partial roast in the
copper industry.
Sintering machines used in the primary zinc industry are
similar to those used for lead. (See lead sintering section fo-r a
more complete description). Four of the eight zinc smelters currently
in operation in the U.S. use sintering machines and one other has
a combination roasting/sintering operation.
The;pyrometallurgical extraction of zinc from zinc sinter is
conventionally done in either horizontal retort, vertical retort, or
electric furnaces..j-fhe basic operation involves the reduction of
zinc oxide to zinc in the presence of carbon (usually coke) in a
123
-------
closed furnace. Since the operation is endothermic the addition of
heat is required. During the reaction the carbon is converted to
carbon monoxide and is either disposed of by burning or used as a
part of the input fuel.
The production of zinc from zinc calcine by the electrolytic
process is essentially air pollution free, since this is a wet
operation producing no exhaust gases. A basic flow diagram of the
zinc smelting industry is shown in Figure 27.
At the present time there are eight primary zinc smelters in
operation in the U.S. The locations of these and an indication of
the basic types of equipment used are given in Table XXIX.
4.5 Copper Ore Roasting
4.5.1 Multiple Hearth Copper Ore Roasters
4.5.1.1 Process Description. At present most copper ore
roasters are of the multiple hearth type. This type of roaster has
been in use in the industry for many decades while the fluids-bed type
roasters, described later, are a more modern type. A sketch of a
typical multiple hearth roaster is shown in Figure 28. Most multiple
hearth roasters are of the conventional MacDougall or Nichols-
Herreshoff type. They contain from 8 to 12 arched hearths or layers.
A central shaft drives rabble arms over the hearth to move the charge
through the roaster. The concentrate is fed to the outer edge of
the upper hearth where the temperature is approximately 400°F and is
124
-------
to
in
ATMOSPHERE
i
#*
I
L
1
r
DUST
COLLECTION
1
r
**
ROASTER
CADMIUM P'LANf .
k-
PURIFIER
-*
BRIQUET
*
1
r 1
*
REFINER
CAST
*
k
*
k
rKUJjUUTS
REFINED
ZINC
PRODUCTS
CADMIUM^
OXIDE
UNREFINED
ZINC
* MINOR EMISSION POINT
*"3fr MAJOR EMISSION POINT
SOURCE: MRI
L
J
FIGURE 27
BASIC OPERATIONS-PRIMARY ZINC SMELTING AND ZINC OXIDE MANUFACTURE
-------
TABLE XXIX
U.S. PRIMARY ZINC SMELTERS
10
o
NAME AND LOCATION (171)*
ASARCO, Corpus Christi, Texas
ASARCO, Amarillo, Texas
New Jersey Zinc, Palmerton,
Pennsylvania
Anaconda, Great Falls, Montana
Blackwell Zinc Company,
Blackwell, Oklahoma
National Zinc, Bartlesville,
Oklahoma
Bunker Hill Company, Kellogg,
Idaho
St. Joseph Minerals, Josephtbwn,
Pennsylvania
ROASTERS WINTERING
MACHINES
5!
M
§
w
CM
O
1
6
2
1
0
2
4
9
i
tH
PQ
O
H
H ' M
2 !S
w
PH
O
0
3
1
0
0
1
0
10
5!
H
CO
0
0
0
0
0
0
0
0
ROASTER
SINTERING
COMBINATION
0
0
0
0
!
0
0
0
REDUCTION
PROCESS
(171)
Electrolytic
Horizontal
Retort
Vertical
Retort
Electrolytic
Horizontal
Retort
Horizontal
Retort
Electrolytic
Electro thermic
*Numbers in parentheses are references.
-------
CHARGING
ROASTING FURNACE
OFF GAS & POLLUTANTS
TRANSPORTATION
CONTAINER
APPROXIMATE BASIC DIMENSIONS OF ROASTER:
OUTSIDE DIAMETER: 22 FEET
OUTSIDE HEIGHT:' 45 TO 65 FEET, DEPENDING ON NUMBER OF HEARTHS
CAPACITY: 100 TO 200 TONS/DAY CONTINUOUS OPERATION
FIGURE 28
MULTIPLE HEARTH ROASTING FURNACE
127
-------
slowly raked to the center where it discharges through a port to
the next hearth. The angle of the rakes on the next hearth is such
that the concentrate moves outward and then drops to the next
hearth and so on consecutively through all hearths to the, bottom.
The hot calcine is discharged into a car or conveyor below the
bottom hearth. The temperature is 1400°F on the Ipwest levels.
Except for autogeneous roasting, gas or oil is usually used for
heat. Hearth roasters operate continuously and have capacities in
the 100 to 200 tons per day range.
4.5.1.2 Chemical and Physical Properties of Input Feed and Effluents
Selected chemical and physical properties for input feed and
effluent for a multiple-hearth copper ore roaster are shown in
Table XXX. The data shown represent typical values since ore
feeds and roaster characteristics vary greatly for each installation.
As stated in the introduction, the types of data presented have been
selected to provide insight into the design and/or development of
possible new control devices.
The input grain loadings have been expressed in the equivalent
load per standard cubic foot of flow since the solids input and the
air input to the roaster are separate. Typical input grain loadings
were calculated as follows. Reference 163 reports the percentages
by weight for the major components of a typical roaster feed to be
as shown in the "percent weight analysis" column. This reference
also gives the tons of sulfur per day in the input feed for several
128
-------
TABLE XXX
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-MULTIPLE HEARTH COPPER ROASTERS
Numbers in parenthesis are references
Flow Rate Gas Temperature Chemical Composition
Control Point 1000 SCFM F of Gas
Avg Range Avg Range Chemical %Volume
Input Feed -
-------
TABLE XXX
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-MULTIPLE HEARTH COPPER ROASTERS
fContinued)
Numbers in parenthesis are references
GO
O
% Weight Analysis
Grain Loadings of Chemicals
Control Point A n „, . - „ rT . ,
Avg Range Chemical % Weight
Input Feed 1600 Tons/Day 829-2366 Cu
(163, N4) Tons/Day Fe
S
equivalent 2480 gr/SCF As
181 gr/SCF of , Sb
Roaster Gas 166^SCF Pb
Flow (N4) ^ ' Zn
Sn
Cd
Ni
Mn
Se
SiO,
CaC03
Inerts
27.5 (163)
24.5 (163)
31.5 (163)
tr - 3.0 (260,
tr - 1.5 (260,
tr (163, 245)
tr (163, 245)
tr (163, 245)
tr (163, 245)
tr (163, 245)
tr (163, 245)
tr (173, 255)
nn fifi^}
. U I. ID J J
1.0 (N5)
Typical Size
Profile
Size % Weight
>2000 y
1410-2000 y
840-1410 y
245) 638-840 y
245) 500-638 y
318-500 y
230-318 y
149-230 y
100-149 y
74-100 y
44-74 y
28-44 y
20-28 y
10-20 y
< 10 y
(259
2
2
3
3
2
2
13
9
7
8
10
11
6
7
9
,
.1
.9
.1
.4 (Cu,
.6
.2
.7
.0
.9
.3
.6
.5
.1
.2
.4
246)
Chemical
Composition
CuFeS2
Cu2S
Cu20
Fe)12As4S13
CuCo2S,
FeS2
FeS
Fe304
FeSAs
FeNiS
ZnS
CdS
PbS
SeS
Sb2S3
4Cu2S Sb2S.,
Si02
CaC03
Inerts
(259)
(256)
(256)
(236)
(56)
(259)
(259)
(259)
(173,
(173,
(259)
(173,
(173,
(173,
(173,
(256)
(163)
(163)
255)
255)
255)
255)
255)
255)
-------
TABLE XXX
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-MULTIPLE HEARTH COPPER ROASTERS
(Continued)
Numbers in parenthesis are references
Control Point
Flow Rate
1000 S'CFM
Avg Range
Gas Temperature
°F
Avg
Range
Chemical Composition
of Gas
Chemical % Volume
Control Point No. 1
(After roaster, ^ cageg 32 (
before joining other 139! 0(163) 1350(163) 1300-1400
gases) (163)
After leaving
Electrostatic
Precipitator 1 case 354.0* 600°F
(Mechanically (163,206)
entrained
particles)
After leaving
Electrostatic ^ case 354 0* 600°F
Precipitator ' (163,206)
(Sublimed
Particles)
so2
°2
Others
SO
£.
H 0
2
°2
Others
SO
L
°2
Others
4.3 (163)
N.R. (163)
neg.(163)
N.R. (163)
1.7 (N4)
N.R.
12 (N4)
N.R.
1.7 (N4)
N..R.
12 (N4)
N.R.
*Includes 196,000 SCFM dilution air at 70 F for
temperature reduction to 600 F.
-------
TABLE XXX
SELECTED CHEMICAL AMD PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-MULTIPLE HEARTH COPPER ROASTERS
Numbers in parenthesis are references
(Continued)
CO
JO
... % Weight Analysis
Grain Loadings ^ ° . .,
of Chemicals
Control Point Avg Range Chemical % Weight
Control Point No. 1 .59gr(SCF) Only Cu
(After roaster, before (163, 260) data Fe
joining other gases) Mechanically from S
Entrained one As
Particles plant Sb
reported Pb
Zn
Sn
Cd
Ni
Mn
Se
Si02
CaO
CaSO,
02 (as oxides)
Inerts
.25gr/SCF As90,
(163, 260) Sb203
Sublimed Inerts
23. 8-34. 5 (N4)
21.2-30.7 (N4)
1.7- 2.5 (N4)
tr (260, 245)
tr (260, 245)
tr (163, 245)
tr (163, 245)
tr (163, 245)
tr (163, 245)
tr (163, 245)
tr (163, 245
tr (173, 255)
10-15 (163, N4)
13-19 (N4)
0.8
tr-17 (260, 245)
tr-13 (260, 245)
tr (235)
Typical Size
Profile
Size % Weight
230-218y
149-230y
100-149y
74-100y
44-74 y
28-44 v
20-28 v
10-20 v
< 10 y
.5-10 p.
(4)
4.6
4.0
5.3
7.4
10.6
12.8
6.8
8.0
10.5
(258)
30.0
(4)
Chemical
Composition
CuO
CuSO,
CuS
Fe203
FeS2
FeS
Fe,0,
ZnS
ZnO
CdS
CdO
PbS
PbO
SeS
SeO
NiS
NiO
Sn02
Mn02
CaO
CaSO
Si02
Inerts
As 03
Sb203
Inerts
(199)
(199)
(199)
(199)
(259)
(259)
(259)
(259)
(199)
(259)
(199)
(173,
(199)
(173,
(12)
(173)
(199)
(255)
(255,
(163)
(209)
(163)
(260)
(260)
255)
255)
56)
Particles
-------
CO
CO
TABLE XXX
.SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-MULTIPLE HEARTH COPPER ROASTERS
(Continued)
Numbers in parenthesis are references
Control Point
After leaving
Electrostatic
Precipitator
(Mechanically
entrained
particles)
™
After leaving
Electrostatic
Precipitator
(Sublimed
Particles)
Grain Loadings
Avg Range
.024 gr/SCF
(305, 42, N5)
Mechanically
Entrained
Particles
.010 gr/SCF
(42, 206, N4)
Sublimed
Particles
Only data
from one
plant
reported
(163)
Only data
from one
plant
reported
(163)
% Weight Analysis
of Chemicals
Chemical % Weight
Same as
above for
entrained
particles
Same as
above for
entrained
particles
Same as
above for
entrained
particles
Same as
above for
entrained
particles
Typical Size
Profile
Size % Weight
230-218
149-230
100-149
74-100
44-74
28-44
20-28
10-20
< 10 u
.5-10 |JL
U
V1
V
u
VI
u
u
t-
22.
15.
10.
7.
5.
2.
1.
1.
3.
(305,
30%
(42
7
8
3
3
5
4
2
5
3
42, N5)
, 206,
N4)
Chemical
Composition
Same as above
for entrained
particles
Same as above
for entrained
particles
-------
TABLE XXX
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-MULTIPLE HEARTH COPPER ROASTERS
(Continued)
Numbers in parenthesis are references
Control Point
Flow Rate
1000 SCFM (163)
Avg Range
Gas Temperature
°F (163)
Avg
Range
Chemical Composition
of Gas (163)
Chemical % Volume
Control Point No. 2
(after roaster and „ ,.
, 2 cases 66
reverberatory ,--.
gases are joined,
before stack)
2 cases 510 SO,
390
HO
z
°2
Others
1.8
N.R.
9.8(N4)*
N.R.
After Electrostatic
Precipitator
66
437
2 cases
510
390
so2
H2°
°2
Others
1.8
N.R.
9.8(N4)*
N.R.
* From dilution air
-------
Numbers in parenthesis are references
TABLE XXX
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-MULTIPLE HEARTH COPPER ROASTERS
(Continued)
Control Point
Grain Loadings
Avg ___ Range
% Weight Analysis
of Chemicals
Chemical % Weight
Typical Size
Profile
Size % Weight
Chemical
Composition
Control Point No. 2
(after roaster and
reverberatory
gases are joined,
before stack)
U
Ol
0.68gr/SCF only data Cu
(N4) from one Fe
plant S
available
As
Sb
Pb
Zn
Sn
Cd
Ni
Mn
Se
(as sulfides
21 (N4)
16 (N4)
9 /M/. "\
and sulfates) ' ^"'
Si02
CaO
Ca
0
SOt
(as oxides)
Others
5 (N4)
4 (N4)
tr (N4)
5 (N4)
tr (N4)
tr (N4)
tr (N4)
tr (N4)
tr (N4)
47 (N4)
40 26 . 4
20-40 17.0
10-20 10.0
10 46 . 6
(N4)
CuO
CuSO^
CuS
Fe,O3
FeS2
FeS
Fe,04
ZnS
ZnO
CdS
CdO
PbS
PbO
SeS
SeO
NiS
NiO
Sn02
Mn02
CaO •-
CaSO,
Si02
As203
Sb203
Inerts
(199)
(199)
(199)
(199)
(259)
(259)
(259)
(259)
(199)
(259)
(199)
(173, 255)
(199)
(173, 255)
(12)
(173)
(199)
(255)
(255, 56)
(163)
(209)
(163)
(260)
(260)
After electrostatic
Precipitator
0.07 gr/SCF
(N4, 242)
same as
above
same a
above
Same as above
-------
TABLE XXX
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-MULTIPLE HEARTH COPPER ROASTERS
(Continued)
Numbers in parentheses are references
Control Point
Flow Rate
1000 SCFM
Gas Temperature
Chemical Composition
of Gas
CO
0
Avg Range
Control Point No. 3 1 case 177
(After roaster, only
reverberatory,
and converter gases
are joined before
stack)
Avg Range Chemical
1 case 350° S02
only H20
02
Others
% Volume
2.4
NR
NR
NR
After Electrostatic Same as Same as Same as Same as Same as
Precipitator above above above above above
Same as
above
-------
TABLE XXX
SELECTED CHEMICAL Alffl PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-MULTIPLE HEARTH COPPER ROASTERS
, (Concluded1) [
Numbers in parentheses are references
CO
M4 Grain Loadings
Control Po,.in-t . &.vg Range
Control Point No. 3 2.7 gr/SCF 1 case
(After roaster, (N4) only
reverberatory, and
converter gases are
joined before stack)
After Electrostatic
Precipitator .05 gr/SCF
(N4, 42)
% Weight Analysis
of Chemicals
Chemical % Weight
Cu
Fe
S
As
Sb
Pb
Zn
Sn
Cd
Ni
Mn
Se
Inerts
same as
above
3
1
9
tr
tr
, tr
17
tr
tr
tr
tr
tr
70
si
(N4)
(•N4)
(N4)
(N4)
(N4)
(N4)
(N4)
(N4)
(N4)
(N4)
(N4)
(N4)
(N4)
ime as
above
Typical Size
Profile Chemical
Size % Weight Composition
>40 p 2 (N4) CuO
20-40 ; 1 (N4) CuSO,
10-20 n 2 (N4) CuS
5-10 u 3 (N4) Fe2°3
2-5 n 4 (N4) FeS2
1-2 y 6 (N4) FeS
<1 u 82 (H4) Fe304
ZnS
ZnO
CdS
CdO
PbS
PbO
SeS
SeO
NiS
NiO
Sn02
Mn02
CaO
CaSO,
SM>2
As203
Sb203
Other-s
same as
above
(199)
(199)
(199)
(199)
(259)
(259)
(259)
(259)
(199)
(259)
(199)
(173,255)
(199)
(173,255)
(12)
(173)
(199)
(255)
(255,56)
(163)
(209)
(163)
(260)
(260)
above
-------
specific hearth roaster complexes. Thus the total input feed per
day can be calculated and converted into equivalent grains per
standard cubic foot of the roaster gas flow. The typical size
profile shown is a combination of data from two sources. Reference
246 gives a size/weight analysis of particles in the larger size
range but it does not give a detailed breakdown of sizes less than
44 microns. Hence, data from reference 259 which gives this breakdown
were used.
None of the three smelters in the United States which use
multiple hearth roasters exhaust the effluent directly to the
atmosphere. In one case the exhaust gases are combined with
reverberatory furnace exhausts before entering particle control
devices and the stack. In the second case the roaster and reverberatory
gases are combined before entering particle control devices but
are joined with converter gases before entering the stack. The
converter gases have separate particle control devices and the
converter gas has already passed through an acid plant for SCL
removal. In the third case the roasters, reverberatory furnaces,
and converters have three separate particle control devices. Then,
all three gas streams are joined before entering the stack. In the
tables physical and chemical characteristics of the effluent stream
are shown for three cases,
1. Immediately after the roasters
2. After roaster and reverberatory gases are joined
3. After roaster, reverberatory and converter gases are joined.
138
-------
In calculating the grain loadings and particle size profiles for
the roaster effluent it was assumed that approximately 100% of the
arsenic and antimony in the roaster feed is volatilized during the
roasting and that the volatilized metals oxidize and sublime as the
airstream temperature cools. This sublimation results in very fine
particulate as shown in the table. This assumption is based principally
on discussions contained in reference 260, The remainder of the
particles found in the effluent are considered to have been mechanically
entrained into the airstream. In order to estimate the average air
flow inside a hearth roaster, airflow data from reference 163 was
used. It was assumed that the roaster had a diameter of twenty
feet across the beds and an area of approximately 300 square feet.
Thus the upward velocity through the roaster is approximately .5
feet per second. Estimates of the percent of particles entrained
were made by using the .5 fps curve of Schytil's phase diagram.
(See Fluid Bed Roasting Section for discussion of the diagram).
The estimates used were as follows:
Particle Size Type of Movement Entrainment Estimate
300 absolutely fixed 0%
200 movable 30%
100 in motion 70%
50 pneumatic transport 100%
By applying these entrainment estimates to the size profile
data for the input feed the size profile of the mechanically entrained
particles in the effluent was calculated.
139
-------
The percent weight analysis of the solid effluents was calculated
based on the assumption that all sizes of particle mechanically
entrained contain the same ratios of chemical constituents. This
assumption is supported by data contained in reference 259 which
gives the chemical analysis for various particle sizes of copper
concentrate. The variation between the maximum and minimum value
was 4%. Thus, if no chemical reactions occurred the effluent would
have the same chemical composition as the input feed regardless of
particle size. However, during the roasting much of the sulfide ore
is converted to oxides by replacing the sulfur atoms with oxygen
atoms from the airstream. For simplicity it was assumed that every
mole of sulfur in the effluent gas was replaced in the ore by a
mole of oxygen. This assumption ignores the fact that the ores contain
some elemental sulfur but it does give a working estimate of the
situation which is the goal of this analysis. In addition it was
assumed that the loss of CO from the calcium carbonate flux is
approximately balanced by the sulfur gain in forming calcium sulfate.
By using these assumptions and data on the SO content in roaster
exhaust gas given in reference 163 calculations of the chemical
analysis of the entrained particulate emissions were made. These data
were then combined with the data for sublimed particles to yield the
total analysis. Data for the gas composition, temperature and flow
rates was taken directly from reference 163.
140
-------
The roaster effluent stream was then assumed to pass through a
typical medium efficiency electrostatic precipitator. The fractional
collection efficiency for each particle size was used to calculate the
grain loadings and weight analysis of the effluent stream leaving the
precipitator. Fractional efficiencies for particles above 10 microns
were based on data from reference 300, while efficiencies for particles
less than 10 microns in diameter were based on references 42 and
206.
The chemical and physical properties of the effluent streams
after combination with reverberatory furnace gases and/or converter
gases were calculated by making a pro rata combination of the roaster
effluent properties and the properties of the reverberatory furnace
and converter. The basic properties of the reverberatory furnace
effluent and the converter effluent are given in later sections of
this report.
4.5.2 Fluid Bed Copper Ore Roasters
4.5.2.1 Process Description. The use of fluid bed roasting
of sulfide ores began about twenty five years ago making it a
relatively new practice in metallurgy. A great number of iron
sulfide fluid bed roasters are in operation throughout the world
and also a significant number of fluid bed roasters are used in the
primary copper, cobalt and nickel industries.
Figure 29,schematically illustrates the essential elements of
this type of roaster as it is applied to sulfide ores or concentrates.
141
-------
SULFIDE
FEED.
HEAT
REMOVAL
AIR
CYCLONE
SEPARATOR
BASIC DIMENSIONS OF ROASTER:
INSIDE DIAMETER 12 ft.
INSIDE HEIGHT 16 ft.
CAPACITY: 250 TONS/DAY CONTINUOUS OPERATION
FIGURE 29
BASIC FLUIDIZED BED SYSTEM
142
-------
Basic to the system is a layer or bed of solids in the lower part of
a reaction vessel through which the reacting gas, usually air, is
forced under a positive pressure. Immediately below this bed means
are provided to distribute the air over the area of the roaster.
Roasted product or calcine is continuously discharged either from the
fluidized solids layer itself or from dust collectors such as
cyclones and/or electrostatic precipitators in the gas stream. Since
nearly all sulfide concentrates are "self-roasting" in air with the
fluid bed system, it is usually necessary and desirable to cool the
fluidized layer of solids by one means or another. Therefore
removal of heat from the bed is a usual characteristic of this roaster,
and greatly influences its design and operation. The capacity of
this roasting system per unit of area is high and is dependent on
the gas velocity through the reacting vessel. Gas velocity, in turn,
is dependent on the particle size of the roasted product.
The conditions under which fluid beds are obtained and the
detailed behavior of the solids and gas in a fluidized suspension
depend on a complex interrelationship of factors, the most important
of which are particle diameter and superficial gas velocity and these
may vary over a wide range of values. As applied to sulfide roasting,
the operational parameters may be reduced to the two mentioned, and
their interrelation is shown on the ditnensionless plot shown in
Figure 30. This plot was first shown by Schytil and is discussed in
reference 312. The plot constitutes a phase diagram in that it
143
-------
00
p
-------
delineates the boundaries between fluidized beds (the liquid phase)
and pneumatic transport (gas phase) on one side, and fixed beds
(solid phase) on the other. The basic plot is Froude number versus
Reynolds number, while superimposed on it is a grid of particle
diameter versus superficial gas velocity at 900°C.
The upper limit of the diagram, the boundary between pneumatic
transport and dense phase fluidization applies for isolated particles.
All particles in a mixture which are smaller than the diameter indicated
on the boundary line would eventually be blown out, but in practice
a small amount of even very fine particles remain in the voids of
the bed and the situation is not as clear cut as the diagram would
indicate. Similarly, all particles which are larger than the diameter
indicated by the lower boundary line are essentially immobile and remain
in the roaster bed. The particles whose diameters lie between
these upper and lower values tend to remain in fluid suspension
above the roaster bed.
4.5.2.2 Chemical and Physical Properties of Input Feed and Effluents.
Selected physical and chemical properties for input feed and
effluent for a fluid bed copper ore roaster are shown in Table XXXI.
The data shown represent typical values and should not be considered
to be immutable. As with the multiple hearth case the input grain
loadings have been expressed in the equivalent load per standard cubic
foot of flow since the solids and the air enter the roaster at
different points.
145
-------
TABLE XXXI
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-FLUID BED COPPER ROASTERS
Numbers in parenthesis are references
Flow Rate Gas Temperature Chemical Composition
Control Point 1000 SCFM °F of Gas
Avg Range Avg Range Chemical % Volume
Input feed -
-------
TABLE XXXI
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AHD EFFLUENTS-FLUID BED COPPER ROASTERS
(Continued)
Numbers In parenthesis are references
Grain Loadings-
Control Point Avg Range
Input Feed 980 Tons /Day
(163, N4)
equivalent
628 gr/SCF
of roaster
g
814-1146
Tons /day
(163, N4)
389-833
gr/SCF
% Weight Analysis
of Chemicals
Chemical % Weight
Cu
Fe
S
As
Sb
Pb
Zn
Sn
Cd
Ni
Mn
Se
SiO ]
CaC03
Inerts
27.5 (163)
24.5 (163)
31.5 (163)
tr-3.0 (260, 245)
tr-1.5 (260, 245)
tr (163, 245)
tr (163, 245)
tr (163, 245)
tr (163, 245)
tr (163, 245)
tr (163, 245)
tr (173, 255)
11.0 (163)
1.0 (N5)
Typical Size
Profile
Size % Weight
> 104 |i
74-104 (J-
52-74 fi
40-52|i
28-40p.
20-28 H
10-20 n
<10n
2.3
5.4
17.2
15.6
16.7
11.5
13.6
17.7
(259)
Chemical
Composition
CuFeS
ZnS .
FeS
FeS
Fe3°4
CdS
PbS
SeS
FeSAs
Sb.S-
FeNiS ,
CaC03
sio2
(259)
(259)
(259)
(259)
(259)
(173, 255)
(173, 255)
(173, 255)
(173, 255)
(173, 255)
(173, 255)
(163, 209)
(163)
-------
TABLE XXXI
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-FLUID BED COPPER ROASTERS
(Continued)
Numbers in parenthesis are references
Flow Rate Gas Temperature Chemical Composision
Control Point 1000 SCFM (163) °F (163) of Gas (163)
Avg Range Avg Range Chemical % Volume
Control Point No. 1
(after roaster and
dilution 17.0* 9.5-24.6* 1200
Air, before joining 1 case •- 35.7** 1 case
other gases)
Dilution air case 35.7 - 393
After leaving
Electrostatic Precipi- 35 _ 393**
tator (dilution air
case)
1150-1250* SO
393** HO
°2
Others
so2
H^O
o
Others
SO
n2
0
Otfiers
13.0
NR
NR
NR
7.0
N.R.
10.6
N.R.
7.0
N.R.
10.6
N.R.
*Before dilution air
**After dilution air
-------
TABLE XXXI
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-FLUID BFD COPPER ROASTERS
(Continued)
Numbers in parenthesis are references
Control Point
Control Point No. 1
(After roaster and
dilution air,
before joining
other gases)
Dilution air
Case
% Weight Analysis Typical Size
Grain Loadings of Chemicals Profile
Avg Range Chemical % Weight Size I Weight
4.1gr/SFC*** only data Cu
(163, N4) from one Fe
(before plant S
dilution reported As
air) Sb
Pb
Zn
1.9gr/SFC Sn
(after Cd
dilution Ni
air) Mn
(N4) Se
cjfi
CaO2
CaSO ,
Oz (as
14-20 (216) >52,|J
26-38 (216) 40-52|J.
11-16 (216) 28-40 (i
tr-17 (260, 245) 20-28^
tr-13 (260, 245) 10-20|i
tr (163, 245) <10
2-3 (216)
tr (163, 245)
tr (163, 245)
tr (163, 245)
tr (163, 245)
tr (163, 245)
3-4 (216)
oxides) 13-19 (N4, N5)
neg
.3
.7
.9
4.3
93.8
(299)
Inerts tr (N5)
After leaving
Electrostatic
Precipitator
(dilution air case)
.14gr/sfc only data Same
(305, 42) from one as
plant above
reported
Same 40-52 ji
as 28-40 ;jl
above 20-28 u
10-20 [i
< 10 |JL
.1
.2
.2
1.1
98.4
(305, 42)
Chemical
Composition
CuO
CuS04
Fe203
ZnS
ZnO
FeS,
FeS
Fe30,
CdS
CdO
PbS
PbO
CuS
SeS
SeO
HIS
NiO
As203
Sb20o
Si02
CaO
CaS04
Same as
(199)
(199)
(199)
(259)
(199)
(259)
(259)
(259)
(259)
(199)
(173, 255)
(199)
(199)
(173, 255)
(12)
(173)
(199)
(260)
(260)
(163)
(209)
(209)
above
*** Primary cyclone collectors are considered to be part of the roaster (not control devices).
Data shown is after cyclones.
-------
TABLE XXXI
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-FLUID BED COPPER ROASTERS
(Continued)
Numbers in parenthesis are references
Ul
o
Flow Rate Gas Temperature -
Control Point 1000 SCFM (163) °F (163)
Avg Range Avg Range
Control Point No. 2 1 case 250.0 1 case 250.0
(after roaster and
reverberatory gases
are joined, before
stack)
After electrostatic
Precipitator 1 case 250.0 1 case 250.0
Chemical Composition
of Gas (163)
Chemical %Volume
SO
£-
Hr\
9
°2
Others
so2
H20
°2
Others
0.7 (7)
ND
• XX *
17 (N4)*
N.R.
0.7 (7)
N.R.
17 (N4)*
N.R.
*From dilution air
-------
TABLE XXXI
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-FLUID BED COPPER .ROASTERS
(Concluded)
Numbers in parenthesis are references
UI
1 Weight Analysis
Grain Loadings of Chemicals
:.' Control Point : Avg Range Chemical % Weight
"^ -
Control Point No. 2 1.02gr/SCF Cu
(After roaster and (N 4) Fe
9 (N4)
8 (N4)
revefberatory gases S (as sulf ides 6 (N4)
are joined, before and sulfates)
stack) As
Sb
Pb
Zn
Sn
Cd
Ni
Mn .
Se
Si02
CaO
CaS04
0 (oxides)
Others
.
3 (N4)
2 (N4)
tr (N4)
11 (N4)
tr (N4)
tr (N4)
tr (N4)
tr (N4)
tr (N4-)
61 (N4)
Typical Size
Profile Chemical
Size % Weight Composition
>40 2.5 CuO
20-40 3.7 CuS04
10-20 8.5 CuS
<10 85.2 (N4) Fe2°q
FeS2
FeS
FegO^
ZnS
ZnO
CdS
CdO
PbS
PbO
SeS
Se£>
NiS
NiO
Sn02
Mn02
CaO
CaS04
S2°2
As2U3
sb2o3
Inert s
(199)
(199)
(199)
(199)
(259)
(259)
(259)
(259)
(199)
(259)
(199)
(173,
(199)
(173,
(12)
(173)
(199)
(255)
(255
(163)
(209)
(163)
(260)
(260)
255)
255)
56)
After Electrostatic
Precipitator
.Igr/SCF
(N4, 242)
Same
as
above
Same
above
Same as above
-------
Typical input grain loadings were calculated as follows.
Reference 163 gives the percentages by Weight for the major
components of a typical western copper ore used in a fluid bed
roaster. This reference also gives the tons of sulfur per day in
the input feed for several specific smelters with fluid bed roasters.
Thus the total input feed of ore concentrate can be calculated.
Adjustments for the input of flux material to these roasters must
also be made. Reference 216 states that the flux averages 16 percent
by weight of the ore concentrate. Addition of this amount to the
ore input and conversion to grains per standard cubis foot of flow
yields the average and ranges shown in the table. These values are
reinforced by data given in Reference 216 which shows that the feed
to the fluid bed roaster at the Copperhill, Tennessee smelter is
250 tons per day. Since the reference also gives a typical roaster
flow as 6000 SCFM and the bed diameter as twelve feet, a calculation
of the grain loading yields 405 gr/SCF. This is well within the
range shown in the table.
Currently four smelters in the U.S. use fluid bed copper ore
roasters and the exhaust gas is handled differently at each smelter
as shown below.
1. Roaster off gas goes directly to an acid plant,
2. Roaster and reverberatory off gases are combined before
entering control devices.
3. Roaster gases pass through control devices and then join
50% of the converter gases before entering acid plant.
152
-------
A. The Copperhill, Tennessee smelter uses a complex combination
of roaster gas plus gases from the iron ore operation at
the site. All the gases flow through an acid plant.
Since each of these eases in reality would require individualized
study two standard situations were assumed for the data contained in
the table. The first case studies the point in the process immediately
after the roaster gases and dilution air have joined but before other
process gases enter the stream. The second case studies the point
where the roaster and reverberatory gases are joined and emitted
through one stack.
Data for the gas flow characteristics of the first control point
shown in the table gives values for both before and after addition
of the dilution air. The basic weight analysis of the chemicals was
taken from data in Reference 216 with additional inputs from the
sources indicated. As in the multiple hearth case the arsenic and
antimony are volatilized and oxidized in the presence of the airflow
to form fine particulates of these compounds. The other chemical
particulates shown enter the air stream through mechanical
entrainment. The arsenic and antimony compounds account for 65.9%
by weight of the particulate and they are all in the less than ten
micron size. This figure has been combined with the entrainment data
to yield the 93.8% figure shown for less than 10 micron size particles.
As was the case in the multiple hearth roaster study the effluent
was assumed to pass through a medium efficiency electrostatic
precipitator resulting in the data shown in the table.
153
-------
The data shown for the case where roaster and reverberatory gases
are joined were calculated by making a pro rata combination of the
roaster effluent properties and the properties of the reverberatory
furnace contained in a later section of this report.
4.6 Lead Sintering
4.6.1 Process Description
There are two types of lead sintering machines: downdraft, the
older type (see Figure 31) and updraft, the newer type. The
configuration of these two machines is very similar with the major
difference being the direction in which the combustion air follows
through the charge. In both cases a thin layer of charge material is
spread over pallets traveling along a continuously moving conveyer
where the ore is ignited. Lead concentrates, lead ores, return
sinter, slag, and limestone are blended to provide the typical
charge to lead sintering machines. The feed materials are ignited
by passing under an ignition hood fired by oil or gas. The next
section of the sintering machines is different in the updraft machines
than in the downdraft machines, so separate discussions appear
below.
Downdraft - In the downdraft arrangement the sectionalized
windbox is located below the pallets and draws the air down through
the charge. The windboxes control the burning rate of the ore as
the pallets carry it along the conveyor system. When the pallets
reach the end of the conveyor, they turn over, dumping off the
154
-------
CONVEYOR
LEAD
DOWNDRAFT
BASIC DIMENSIONS OF GRATE:
LENGTH: 24 FEET
WIDTH: 42 INCHES
CAPACITY: 100 TONS/HOUR FEED, CONTINUOUS OPERATION
FIGURE 31
LEAD SINTERING MACHINE DOWNDRAFT TYPE
155
-------
concentrate. Forty to sixty percent of this sinter is ground and
recycled as feed to adjust the sulfur content of the inlet charge.
Updraft - This type of sintering machine has both updraft and
downdraft sections. First, the charge travels over a downdraft
windbox where it is ignited. This windbox is below the pallets and
the combustion air is sucked through the charge. Next the pallets
move along to the updraft section where the windboxes are again
below the pallets, but the air is blown up through the bottom of the
pallets and the charge. The concentrate is dumped off the pallets
and recycled in the same way as in the downdraft machine.
There are three main advantages to the updraft machines:
1) reduced fan power and more efficient combustion resulting from
the action of upward air flow in preventing bed packing;
2) relative ease of designing machines to reduce ambient air
infiltration which would decrease SO concentrations in exhaust gas;
3) prevention of lead deposits in windboxes.
Because of these advantages, switch-overs have been made from
downdraft to updraft machines. Of the six primary lead smelters in
the United States, only the operation in El Paso, Texas, still
operates a downdraft sintering machines.
4.6.2 Chemical and Physical Properties of Input Feed and Effluents
Because downdraft machines are being replaced by the more efficient
updraft machines, emissions characteristics have been presented
here for only the updraft type machines. Table XXXII shows these
156
-------
TABLE XXXII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED AND EFFLUENTS-
LEAD SINTERING MACHINE, UPDRAFT TYPE
Numbers in parenthesis are references
Flow Rate Gas Temperature Chemical Composition
Control Point 1000 SCFM °F of Gas
. . Avg Range Avg Range Chemical % Volume
Input feed -
-------
TABLE XXXII
Numbers in parenthesis are references
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED AN1J EFFLUENTS-
LEAD SINTERING MACHINE, UPDRAFT TYPE
(continued)
cn
oo
Grain Loadings
Cpntrol Point Avg Range
Input Feed 2400 Tons/ data from
Day one plant
(247) only
equivalent
933 gr/SCF
of sinter
gas flow
% Weight Analysis
of Chemicals
Chemical 7. Weight
Si02
Fe
CaO
MgO
Zn
S
Pb
Cu
As
Cd
Se
Inert s
10
12
9
1
5
6
46
tr
tr-2
tr
tr
9-11
(247)
(247)
(247)
(247)
(247)
(247)
(247)
(247)
(260)
(174)
(174)
(Nl)
Typical Size
Profile
Size % Weight
>2.5
1.9-2.5
.94-1.9
.64-. 94
cm
cm
cm
cm
3360-6400 u
1
5
9
17
1410-3360 v
500-1410 p
<500 v
22
11
.5
.5
.5
12
.5
20
.5
.5
(248)
Chemical
Composition
PbS
FeS
CaO
Si02
MgO
ZnS
CuS
FeSAs
CdS
SeS
Inerts
(174,
(174,
(174,
(247)
(247)
(174,
(174,
(174,
(174,
(174,
255)
255)
255)
255)
255)
255)
255)
255)
-------
TABLE XXXII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES Of INPUT FEED AND EFFLUENTS-
LEAD SINTERING MACHINE, UPDRAFT TYPE
(Continued)
Numbers in Parentheses are references
PI
Control Point
Flow Rate
1000 SCFM (163)
Avg Range
Gas Temperature
°F (163)
Avg
Range
Chemical Composition
of Gas (163)
Chemical % Volume
Control Point No. 1
(After sintering
machine, before
joining other
gases)
After leaving
Fabric Filters
34 (V)1 32. 4-35. 5 (V) 350 (V)2 300-400 (V) S02
HO
£,
°2
Others
32.4 - 350 - S02
H00
2
°2
Others
4.3
19.1
10.5
66.1
4.3
19.1
10.5
66.1
(V) Plus ventilation air
In one ease, ventilation flow known - flow before control device was 105.7-1000 SCFM
In one case, ventilation flow known - temperature before control device was 184°F.
-------
TABLE XXXII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED AND EFFLUENTS-
LKAT) SINTERING MACHINE, DPDRAFT TYPE
(Concluded)
Numbers in parenthesis are references
O)
Grain Loadings
Control Point Avs Range
Control Point No. 1 6.6 gr/SCF only one
(after sintering (163) plant
machine, before used
joining other
gases)
After leaving .07 gr/SCF Only one
Fabric Filters (242) plant
used
% Weight Analysis Typical Size
of Chemicals Profile
Chemical 7, Weight Size % Weight
Sid2
Fe
CaO
MgO
Zn
S
Pb
Cu
As
Cd
Se
Inert s
same as above
8-11
9-13
7-10
.7-1
4-6
.7-1
35-50
tr
tr-30
tr
tr
6-8
same
(247) 20-40 y 15-45
(247) 10-20 u 9-30
(247) 5-10 u 4-19
(247) <5 v 1-10
(247, (43)
(247)
(247)
(247)
(260)
(174)
(174)
(247)
as above <6 (j. loo
(302)
Chemical
Composition
PbS
PbO
FeS
FeO
CaO
S102
MgO
ZnS
ZnO
CuS
CuO
As20 -
CdS J
CdO
SeS
SeO
Inerts
same as
(174,
(199)
(174,
(199)
(174,
(247)
(247)
(174,
(199)
(174,
(199)
(260)
(174,
(199)
(174,
(199)
above
255)
255)
255)
255)
255)
255)
255)
-------
characteristics at the point of input feed for updraft machines.
These characteristics are the same for downdraft machines with neither
the updraft nor the downdraft contributing any gaseous pollutants to
the atmosphere.
Grain loadings at the point of input feed were not usually
reported, so data were found for only one plant. Reference 247
reported the feed to be 100 tons per hour, or 2400 tons per day.
This was converted to 933 grains per standard cubic feet by using the
given flow rate of 708 cubic meters per minute and 14 x 10 grains
per ton as the conversion factor.
A partial percent weight analysis of the chemicals was also
given in reference 247. Other references were used to complete the
missing parts of this analysis. Reference 248 gave a typical size
profile of the emissions at the input feed. At the lower end of
the size scale, USS-ASTM standard sieve sizes were given. The
standard conversion was used to express these size ranges in microns.
Because the particulate emissions range in size from 2.5 centimeters
to less than 500 microns, they are easier to control than the fine
particulates released by many of the industrial processes studied.
The chemical composition of the emissions was compiled from
several different references and is representative of the type of
chemicals found in emission's from lead sintering input feed.
Control point number one is defined as being after the sintering
machine but before the sintering emissions join the gases from other
l&l
-------
smelting processes. The emission characteristics for this point
are shown in Table XXXII. The gas flow rate and temperature are
shown before ventilation air was added to the emission stream. The
ventilation air will decrease the temperature of the emission gases
and increase the flow rate. Traveling through the fabric filter does
not significantly change these parameters. The gas temperature and
flow data and the chemical composition of the gas emissions before
and after the fabric filter were all found in reference 163. The
percent volumes of SO , HO, and 0 are averages of values given for a
few of the lead sintering plants. These are weighted averages
computed by multiplying the gas flow rate by the percent volume of
the chemical and then divided by the total gas flow of all the plants
included in the average. The remainder of the gas (66.1%) is
composed primarily of nitrogen.
The grain loadings reported for one plant were 22 tons per day.
This was converted to 6.6 grains per standard cubic feet based on
3
a flow rate of 32.4 x 10 standard cubic feet per minute. Based on a
99 percent efficiency for the fabric filter, the grain loading after
leaving the filter is 0.07 grains per standard cubic ffet. The
percent weight analyses shown in the various references indicated
ranges of values rather than specific qualities. Nevertheless, it is
clear which chemicals comprise the largest percentages of the total
particulates emitted. The fabric filter does not effect the chemical
composition of the emissions nor their percent weight analysis.
162
-------
Reference 43 provided a typical size profile which indicated
that between one and ten percent of the total particulate weight was
comprised of particles less than five microns. It was shown in
reference 302 that fabric filters are 100 percent efficient in
controlling particles larger than six microns. The typical size
profile after leaving the fab'ric filter is thus shown as 100 percent
of the weight made up of particles less than six microns in size.
4.7 Zinc Ore Roasting
4.7.1 Process Description
As stated in a previous section zinc ores are usually roasted
to convert the sulfide to zinc oxide calcine. As opposed to copper
ore roasting which is stopped short of completion, the roasting of
zinc ores is carried close to completion (93 to 97% removal of sulfur,
according to reference 162). This process is called dead roasting.
There are four principal types of roasters used by zinc smelters
today:
o Ropp
o, Multiple Hearth
o Flash (Suspension)
o Fluid-Bed (Suspension)
4.7.1.1 Ropp Roaster. The Ropp roaster is the oldest type
still in use. It is basically a reverberatory type furnace divided
into two parallel hearths. The ore is mechanically rabbled as it
moves through the roaster. Operating temperatures are generally
163
-------
around 1200°F (Reference 162). Since this type of roaster is rapidly
being phased out of the industry a detailed study of particulate
emissions for this roaster were not made.
4.7.1.2 Multiple Hearth Roaster. Multiple-hearth roasters are
the next oldest type currently in use in zinc smelting. This type of
roaster is very similar to the copper ore multiple hearth roaster.
(See Figure 28). Operating temperatures are in 1200-1350°F range.
The chemical and physical characteristics of this type of roaster
were not studied for the same reason as stated for the Ropp roaster,
that is the rapid phase out of this operation. Reference 249 describes
the use of suspension/flash roasters at the Bunker Hill smelter in
Kellogg, Idaho which were converted from multiple-hearth units. It
is probable that other companies using hearth roasters will either
convert or replace them in the next several years.
4.7.1.3 Suspension/Flash Roasters. Suspension or flash roasting
evolved concurrently with the increasing availability of finely
ground concentrates from zinc flotation plants. Sketches of two types
of flash roasters in use at Bunker Hill, Kellogg, Idaho are shown in
Figure 32 taken from Reference 249. Each of the converted roasters
consists of a cylindrical steel shell lined with firebrick and covered
with insulation. It has a large combustion chamber, four brick hearths,
and a revolving center column which has been retained from the
multiple hearth operation. The center column supports alloy steel
164
-------
SUSPENSION ROASTER
FEED TO
COMBUSTION
CHAMBER
CONVERTED FLASH ROASTERS
DYRING
HEARTHS
COLLECTING
HEARTHS
FEED TO DRYING
HEARTHS
FEED TO
COMBUSTION
CHAMBER
FEED TO
DRYING
HEARTHS
DISCHARGE
FROM DRYING
HEARTHS
CALCINE
DISCHARGE
APPROXIMATE BASIC DIMENSIONS
DISCHARGE
FROM
DRYING
HEARTHS
CALCINE
DISCHARGE
CONVERTED HEARTH: OUTSIDE DIAMETER 22 FEET; HEIGHT 45 FEET
"NOMINAL CAPACITY: 110 TONS/DAY CONTINUOUS OPERATION
STUB COLUMN: OUTSIDE DIAMETER 22 FEET; HEIGHT 100 FEET
NOMINAL CAPACITY: 350 TONS/DAY CONTINUOUS OPERATION
FROM REFERENCE 249
FIGURE 32
COMPARISON OF CONVERTED MULTIPLE HEARTH ROASTER TO STUB COLUMN
SUSPENSION ROASTER AT BUNKER HILL CO. KELLOGG, IDAHO
165
-------
arms carrying rabbles that rake the material across the hearths.
Since the concentrate feed has a moisture content of 3-4% the
upper two hearths are used for material drying and are operated
separately from the main portion of the roaster. The dry concentrate
is discharged from the upper hearths and ground to a fine particle
size in a ball mill circuit. The ground concentrate is blown or
injected into the combustion chamber along with the combustion air.
Autogenous roasting occurs at a temperature of about 2300°F.
According to reference 162 conventional flash roasters operate in the
1800°F range. In the Bunker Hill roasters the two lower hearths are
utilized to collect the calcine from the combustion chamber and
provide additional time for more complete elimination of sulfide
sulfur. The calcine is discharged from the lower hearth and moved
to storage.
4.7.1.4 Fluid Bed and Fluid Column Roasters. Fluid Bed and
Fluid Column roasters for zinc sulfide are new to the industry. The
principal of fluid roasting is the same as for copper sulfide ore
with the basic exception that the zinc sulfide is roasted completely
to the oxide. According to reference 162, several variations of
fluid bed roasters are now in use, the chief difference being in the
method used to charge the concentrates. The Dorr-Oliver type uses
a slurry feed which is sprayed into the lower part of the reaction
chamber, while other feeders convey moist feed or dry solid feed
into the reactor. A schematic of a typical zinc fluid-bed roaster
is shown in Figure 33.
166
-------
A-Gas Outlet
8 - Oil Burner Nozzle
C-Bed Overflow Discharge
D-Underflow Discharge
E - Bed Grate
F - Vyind Box
DIMENSIONS SHOWN ARE IN METERS.
G-Wind Box Discharge
H-Air Inlet
I - Bed Coils
J - Slinger Belt
K-Charging Port
L - Safety Valve
CAPACITY: 240 TONS/DAY CONCENTRATE FEED, CONTINUOUS OPERATION.
• FROM REFERENCE' 25b
FIGURE 33
TYPICAL ZINC FLUID BED ROASTER
167
-------
The fluid-column roaster is a newer development than the fluid-
bed but the operating principal is the same. The horizontal cross
section of the fluid-bed area is a long rectangle and above it is a
large chamber. The charge is supported on a perforated false bottom
allowing air to penetrate from below. Additional air enters from
the sides. A typical unit has a capacity of 225 tons/day of feed.
4.8.1 Chemical and Physical Properties of Input Feed and Effluents
4.8.1.1 Suspension/Flash Roaster. Selected chemical and physical
properties for input feed and effluent for the suspension/flash type
zinc ore roaster are shown in Table XXXIII. Input grain loadings were
calculated from data published in reference 163 and the % weight
analysis for the input feed was estimated by combining data from the
six references shown. Particle size profile was taken directly from
reference 259 which gives the size analysis of a typical zinc concentrate
prepared at the Cities Service ore mill at Copperhill, Tennessee.
As indicated previously in Table XXIX, there are eight flash
type roasters in operation or on standly in the U.S. today. The
output gas characteristics shown were based on data in reference 163
while the output grain loadings were based on data given in reference
250. The weight analysis of the major output products was taken from
reference 249 with modifications made based on information contained
in the other references shown. Size profile and chemical composition
were taken directly from the references indicated. Data are also
given for effluent characteristics after passing through a typical
168
-------
TABLE XXXIII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-FLASH TYPE ZINC ROASTER
Numbers in parenthesis are references
Control Point
Flow Rate
1000 SCFM
Avg Range
Gas Temperature
°F
Avg Range
Chemical Composition
of Gas
Chemical % Volume
Input feed
-------
TABLE XXXIII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-FLASH TYPE ZINC ROASTER
(Continued)
Numbers in parenthesis are references
-4
O
Grain Loadings
Control Point Avg Range
Input Feed 1008 Tons/
Day
Equivalent
166 gr/SCF
of roaster
flow
(163, N4)
580-1435
Tons /Day
Equivalent
148-237
gr/SCF
of roaster
flow
(163, N4)
% Weight Analysis
of Chemicals
Chemical 7. Weight
Zn
Pb
Fe
S
As
Se
Cd
F
Average Analysis
Zn
Pb
Fe
S
As
Se
Cd
F
Others
52-60
2.5
4-11
30-33
tr-2
tr
tr
tr
55
2.
7
32
1
tr
tr
tr
2.
(163)
(249)
(163)
(163)
(260)
(175)
(175,
(50)
'5 I
I
.5
Typical Size
Profile
Size % Weight
>147 y
104-147 V
74-104 t
52-74 y
40-52 v
28-40 y
163) 20-28 y
10-20 y
<10 y
(259,175,163
260,50,249)
2.2
4.2
4.9
19.2
10.7
11.5
10.3
13.8
23.2
(259)
(259)
(259)
(259)
(259)
(259)
(259)
(259)
(259)
Chemical
Composition
ZnS (175, 255)
PbS (175, 255)
FeS (175, 255)
FeSAs (175, 255)
SeS (175, 255)
CdS (175, 255)
Others
-------
TABLE XXXlII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-FLASH TYPE ZINC ROASTER
(Continued)
Numbers in; parenthesis are references
Control Point
Control Point No. 1
(after roaster and
before acid plant
or stack)
After cyclone
Collectors
After
Electrostatic
Precipitator
Flow Rate Gas Temperature Chemical Composition
1000 SCFM (163) °F of Gas (163)
Avg Range Avg Range Chemical % Volume
59.2 23.8-94.5 17001 1600- 18001 SO,
(163) (163) *
fif.\J
°2
Others
59.2 23.8-94.5 575 540-600 SO
(252) (252) -.
-2
°2
Others
59.2 23.8-94.5 600 570-630 SO
(N5) (N5) H J
^
V
Others
7.6
4.02
10.0 2
78.4
7.6
4,02
2
10.0
78.4
7.6
4.02
2
10.0
78.4
Gases will go to a waste heat boiler before entering control device
2
Based on data from only one plant
-------
TABLE XXXIII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-FLASH TYPE ZINC ROASTER
(Concluded)
Numbers in parenthesis are references
Control Point
Control Point No. 1
(After roaster and
before acid plant
or stack)
After Cyclone
Collectors
After Electrostatic
Precipitator
Grain Loadings
Avg Range
45 gr/SCF
(250)
4.5 gr/SCF
(304)
.5 gr/SCF
(242)
40-64 gr/
SCF
(250)
4-6.4 gr/
SCF
(304)
.4-. 6 gr/
SCF
(242)
% Weight Analysis
of Chemicals
Chemical 7, Weight
Zn
Pb
Fe
S
As
Se
Cd
F
Others
same as above
same as above
52
5
7
tr
2
tr
tr
tr
34
(N4,
(N4,
(N4,
(N4,
(260
(N5)
(N5)
(N5)
(Nl)
same as
same as
249)
249)
249)
249)
, N4)
above
above
Typical Size
Profile Chemical
Size % Weight Composition
ZnO
>20 v 30 (43) PbO
10-20 v 39 (43) FeO
5-10 u 17 (43) FeS04
<5 p 14 (43) As-0.,
Se6
SeS
CdO
CdS
Others
Same as
Same as
(175)
(175)
(175)
(175)
(175, 260)
(175)
(175)
(175)
(175)
above
above
-------
cyclone collector or a medium efficiency electrostatic precipitator.
4.8.1.2 Fluid-Bed Roaster. Table XXXIV displays the chemical
and physical properties of emissions from input feed and effluent for
zinc fluid-bed roasters. The input grain loadings were given as tons
per day in reference 163 and converted to grains per standard cubic
feet. No single reference gave a complete percent weight analysis,
so data were compiled from the various references shown. In addition,
an average analysis was compiled from the same information sources
and presented along with the ranges. The typical size profile was
taken from reference 250 and 259 and shows that 83% of the particulate
weight is composed of particles greater than ten microns in size.
The chemical composition reported showns that all the compounds are
sulfides.
Data are given in Table XXXIV for effluent characteristics both
before and after control devices. The drop in the gas temperature
after control is not caused by the control device. Rather, the gas
temperature is lowered (usually by a waste heat boiler) before
reaching the cyclones or electrostatic precipitators for more efficient
heat utilization and to attain acceptable input temperatures to the
control devices. For the particulate characteristics, reference 197
was used to obtain the grain loadings, and reference 43 gave a typical
size profile. The percent weight analysis indicated in reference 251
required a couple of additions as shown and the chemical composition
was taken directly from the references shown in parentheses on the
table.
173
-------
TABLE XXXIV
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-FLUID BED ZINC ROASTER
Numbers in parenthesis are references
„!_-,„. Flow Rate Gas Temperature Chemical Composition
Control Poznt op of
_ Avg _ Range _ Avg _ Range _ Chemical _ % Volume
Input feed - - - -
-------
Numbers in parenthesis are references
TABLE XXXIV
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-FLUID BED ZINC ROASTER
(Continued)
Ul
Control Point
Input Feed
Grain
.. Avg
615 Tons/
Day
Equivalent
415 gr/SCF
of roaster
flow
(163, N4)
Loadings
Range
254-975
Tons /Day
260-491
gr/SCF
% Weight Analysis
of Chemicals
Chemical % Weight
Zn
Pb
Fe
S
As
Se
Cd
F
52-60
2.5
4-11
30-33
tr-2
tr
tr
tr
(163)
(249)
(163)
(163)
(260)
(175)
(175, 163)
(50)
Typical Size
Profile
Size % Weight
>150 y
75-150 y
40-75 y
20-40 y
10-20 y
<10 y
11
26
21
15
10
17
(250)
(250)
(259,
(259,
(259,
(259,
Chemical
Composition
ZnS
PbS
25 0) FeS
250)FeSAs
250) SeS
250) CdS
Others
(175,
(175,
(175,
(175,
(175,
(175,
255)
255)
255)
255)
255)
255)
Average Analysis
Zn
Pb
Fe
S
As
Se
Cd
F
Others
55
2.
7
32
tr
tr
tr
2.
5
(259,
260,
5
175, 163,
50, 249)
-------
TABLE XXXIV
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-FLUID BED ZINC ROASTER
(Continued)
Numbers in parenthesis are references
O
Control Point
Control Point No. 1
(after roaster,
before acid plant
or stack)
After cyclone
Collectors
After Electrostatic
Precipitator
Flow Rate Gas Temperature
1000 SCFM °F
Avg Range Avg Range
14. 4 (D)
(163)
14. 4 (D)
(163)
14. 4 (D)
(163)
9.5-19.3(0) 1470 (D)
(163) (163)
9.5-19.3(0) 575
(163) (252)
9.5-19.3(0) 600 (N5)
(163)
1200-1600(0)
(163)
540-600
(252)
570-630
(N5)
Chemical Composition
of Gas (163)
Chemical % Volume
S°2
2
H2°
°2
Others
Same as
above
Same as
above
10.7
Neg1
1
61
83.3
Same as
above
Same as
above
(D) Plus dilution air
Based on data from only 1 plant
-------
TABLE XXXIV
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-FLUID BED ZINC ROASTER
(Concluded)
Numbers in parenthesis are references
Control Point ... .
..' Control Point No. 1
(After roaster,
before acid .plant
or stack)
After Cyclone
Collectors
After Electrostatic
Precipitator
Grain loadings
;Av£ . Range
62 gr/SCF
(197)
•6.2 gr/SCF
,(304)
.6 gr/SCF
(242)
39-74 gr7
SCF
(197)
4-7.4 gr/
SCF
(304)
.4-. 7 gr/
SCF
(242)
% Weight Analysis
O'f Chemicals
Chemical % Volume
Zn
.' Pb
Fe
S
As.
Se
Cd
F
Others
55
1.5
8.5
3
tr-13
tr
tr
tr
19-32
(251)
(251)
(251)
(251)
(N4)
(175)
(251)
(251)
(Nl)
Typical Size
Profile Chemical
Size % Weight Composition
>20 n 30 (43) ZnO
10-20 u 39 (43) PbO
5-10 u 17 (43) FeO
<5 u ' 14 (43) FeS04
As20
SeO 3
SeS
CdO
CdS
Others
(175)
(175)
(175)
<175)
(175, 260)
(175)
(175)
(175)
(175)
-------
4.9 Interpretation of the Data
Analysis of the effluents from the copper, lead and zinc roasting and
sintering operations shows that these effluent may be divided into six
different types for further discussion.
o gases considered to be pollutants
o non-polluting gases
o particulates containing hazardous chemicals
o particulates containing only chemicals classes as non-hazardous
o fine particulates containing hazardous chemicals
o fine particulates containing only chemicals classes as non-hazardous.
Except for small contributions^ to heat pollution and the possibility
of a water cloud effluent the non-polluting gases may be ignored. However,
the other types of effluents are all significant contributors to the primary
non-ferrous smelter pollution problem.
4.9.1 Polluting Gases
In all three industries the only significant polluting gas in the
effluent is sulfur dioxide. Since the study of sulfur dioxide is not
within the scope of this hazardous pollutant study no further discussion of
its control will be made here. However, sulfur dioxide influences the
development of hazardous pollutant control devices since it is a corrosive
gas and its derivative, sulfuric acid, is highly corrosive. These factors
play an important role in choice of control methods and materials.
4.9.2 Particulates and Fine Particulates Not Containing Hazardous
Chemicals
The control technology which must be developed for this type of smelter
effluent is basically the same as for any non-specific particulate. All
178
-------
discussion in this section will pertain to particulates in general rather
than the non-ferrous smelting industry.
The removal of gaseous contaminants in an effluent stream is generally
accomplished by one of three methods, chemical reaction, absorption or
adsorption. Usually only one of these is applicable to a particular process.
Thus a straight forward engineering analysis of the problem is possible.
However the removal of small particles and droplets is a much more
complex mechanism and frequently several removal techniques must be used
in combination. The basic techniques which are generally considered in
particulate removal are,
o gravity separation
o centrifugal separation
o inertial impaction
o direct interception
o Brownian diffusion
o eddy diffusion
o electrostatic precipitation
o thermal precipitation
o magnetic precipitation
o Brownian agglomeration
o Sonic agglomeration
Gravity Separation - The use of gravity in removing particles is
generally restricted to large particle sizes unless the flow rate of the
gas is very low. Most control devices using the gravity separation technique
are variations of settling chambers. Such devices generally have a lower
179
-------
limit of applicability in the 75 micron particle diameter range. The use
of gravity separators in the non-ferrous smelting industry would be
restricted to only the simplest of initial gas cleaning devices.
Centrifugal Separation - The use of centrifugal force in the separation
of particles from a gas stream is widely practiced throughout industry.
The generic name "Cyclone" is applied to these devices. Theoretical and
practical studies of this process are numerous and new breakthroughs in
the use of centrifugal separation are not foreseeable. Present methdos
are generally applicable only to large and medium size particles with a
lower limit of 10 micron diameter. These devices are used in some smelters
for initial removal of large particles from roasters or sintering machines
but it appears that there is very little likelihood of improvement over
present performance.
Aerodynamic Capture - Four of the techniques listed above may be
classified as techniques employing aerodynamic capture. Each of the four
techniques in reality uses one of three basic mechanisms,
1. Inertial impaction
2. Interception
3. Diffusion
All of the fibrous filter and liquid scrubbing control devices use
aerodynamic capture techniques. In general, practice inertial impaction
and interception predominate for the capture of particles in the micron
size range while diffusion is of importance for sub-micron sized particles.
The theory of the three mechanisms of aerodynamic capture has been well
180
-------
developed in recent years and will not be repeated here. An excellent
discussion is contained in reference 307. The following paragraphs
will discuss the practical application of that theory in the non-ferrous
industry.
In all three of the non-ferrous roasting or sintering processes
studied there are several factors in common which serve as general design
guides for any control equipment design studies. They are,
large amounts of fine particulate up to 95% by weight
high flow rates 10k to 350k SCFM
high temperatures 250° to 630°F at typical
control points
corrosive gas stream 1% to 13% SO by volume
These criteria should form the basis of any design study for fine
particulates from non-ferrous smelters.
In recent years significant advances have been made in the technology
of particulate control with fabric filters. These advances are principally
the result of the development of synthetic fibers which can withstand high
temperatures, have excellent tensile strength and exhibit reasonable
resistance to acids and alkalis. Reference 307 reports on the useful
working temperatures of several synthetic fibers as follows.
Fiber Typical Trade Name Useful Temperature
Polyester Dacron 250 F
Polyamide Nylon >200°F
Polyaerylonitrite Orion 275°F
Polytetrafluorethrylene Teflon 450 F
181
-------
The same reference also reports on some typical case histories
of synthetic fiber usage at relatively high temperatures,
o Waste gas from a grey iron cupola was filtered successfully
at 275°F.
o Zinc oxide fumes containing some sulfur dioxide were successfully
filtered at 275°F.
o Non-ferrous oxide fumes were filtered from furnace gases with
some sulfur dioxide at 284°F.
Riley (reference 308) reports the successful filtration of particulates
at 400°C (750°F) by winding fiberglass on to a metal former screen.
Silverman at the Harvard University Air Cleaning Laboratory for open
hearth furnace fumes, fly ash, acid gases and mists reports on the use of
a fiber blanket supported on a steel mesh which is continuously replaced
according to the rate of particulate deposition (references 309, 310, 311
and 312). Studies were made with temperatures ranging from 610 to 1200°F
and results of up to 98 percent efficiency were achieved in the laboratory.
However, extension of the work to pilot plant scale met with engineering
difficulties and the studies were disbanded.
In another study of fly ash collection Kane (reference 313) successfully
collected fly ash at a temperature of 1800°F using an aluminum silicate fiber
In contrast to gravity and centrifugal separation there appears to
be a distinct possibility for development of new filtration fabrics
or techniques and this area of study deserves strong support from funding
agencies.
182
-------
As is the case with the filtration methods already discussed, particle
collection by liquid scrubbing can be made by a variety of methods. The
device which has been used frequently in industry for small diameter
particles is the venturi scrubber. A very successful adaptation of the
venturi scrubber is the well known Pease-Anthony design. Data presented in
reference 307 indicate that this control device shows high efficiencies
down to a lower limit of 0.05 microns in some cases. Some typical data for
the non-ferrous metals industry is shown below,
Source Particle Size Range Average Efficiency
Lead Blast Furnace 0.1-1 99
Reverberatory Lead Furnace 0.1-0.8 91
Magnesium Alloy Furnace 0.1-0.9 95
Zinc sintering 0.1-1 98
Reverberatory Brass Furnace 0.05-0.5 95
These scrubbers have the additional advantage of removing sulfuric
acid mist when water is used as the scrubbing liquor. It is recommended
that this type of control device be studied further for use in the primary
non-ferrous smelting industry.
Electrostatic Precipitation - Theoretically it is possible to construct
an electrostatic precipitator which would collect all particles entering
the device. Obviously, this is not true in practice. Three factors are
dominant in the practical efficiency limit of precipitators.
(1) The first of these is reentrainment of particles when collected
dust is removed from the plates. Present removal methods, whether
183
-------
they involve rapping or washing, are imperfect. This area
of precipitator technology should receive additional practical
research.
(2) The second factor of importance is the resistivity of the
incoming dust particles. Precipitators operate most efficiently
4 10
when the dust resistivity lies in the range from 10 to 10
ohm«cm. Many important dusts have resistivities outside this
range. Studies are needed to define more thoroughly restivities
of the various particles of interest in the non-ferrous industry
and also to examine the possibility of altering undesirable
particle resistivities.
(3) The factor which plays a large role in limiting the lower size
limit for precipitator collection is the effective migration
velocity (emv). Studies have shown that for particles less
than 5 microns the emv falls off rapidly toward zero. This is a
dominant factor in the relative inefficiency of precipitators
in the sub-micron particle size range. Additional study of the
emo problem is indicated especially in order to increase the
emv for sub-micron size particles.
Other Methods - The other four techniques originally mentioned, namely,
thermal precipitation, magnetic precipitation, Brownian agglomeration and
sonic agglomeration are still principally theoretical in nature. Only
laboratory study or very limited field use has been attempted. However,
each of the methods has sufficient theoretical merit to warrant some additional
study.
184
-------
4.9.3 Particulates and Fine Particulates Containing Hazardous
Chemicals
Obviously, all of the methods mentioned in the previous section
for collection of non-specific particulates may, in general, be used
on particulates containing hazardous chemicals. This section will
discuss the removal of specific chemicals found in non-ferrous smelting
effluents.
Inspection of the chemical composition of the particulates emitted
from copper and zinc roasters and lead sintering machines shows that the
hazardous chemicals are generally either oxides, sulfides or sulfates
of the various metals. In addition the majority of these effluents are
soluble in varying degrees in either water, acids or alkalis. Table XXXIVA
summarizes the chemicals of interest and indicates their solubility
classes. It is recommended that consideration be given to the development
of specific scrubbers for the non-ferrous smelting industry using an
acid solution as the scrubbing medium. The availability of sulfuric
acid produced from smelter effluents makes this a particularly attractive
option.
4.9.4 Summary of Recommendations
The principal recommendations discussed in foregoing sections are
summarized here.
(1) Fabric filters
o Development of new or improved high temperature, acid
resistant fibers.
o Further study of the use of synthetic fibers attached to
metal support screens.
185
-------
TABLE XXXIVA
SOLUBILITIES OF CHEMICALS FOUND IN SMELTER EFFLUENTS
oo
o>
Arsenic Trioxide
Antimony Trioxide
Calcium Oxide
Calcium Sulfate
Cadmium Oxide
Cadmium Sulfide
Copper Oxide
Copper Sulfide
Copper Sulfate
Ferrous Oxide (FeO)
Ferrosoferric Oxide ^6304)
Ferric Oxide (Fe203)
Ferrous Sulfide (FeS)
Ferric Bisulfide (FeS2>
Ferrous Sulfate (FeS04>
Lead Oxide
Lead Sulfide
Magnesium Oxide
Manganese Dioxide
Nickel Oxide
Nickel Sulfide
Selenium Dioxide
Selenium Sulfide
Silicon Dioxide
Tin Dioxide
Zinc Oxide
Zinc Sulfide
PRESENT IN EFFLUENT FROM
COPPER
ROASTING
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
LEAD
SINTERING
ZINC
ROASTING
X X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X X
CHEMICAL IS SOLUBLE IN
WATER
X
X
X
X
XX
ACID ! ALKALI
(
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
x slight
X X
X
I
-------
(2) Scrubbers
o Further research into the practical application of water
scrubbers in the non-ferrous industry.
o Development of acid or alkali scrubbers for specific
classes of hazardous chemicals.
(3) Electrostatic Precipitation
o Studies to develop improved removal of dust collected
on the plates.
o Studies of the resistivity of specific chemicals.
o Studies to determine methods for improving the effective
migration velocity of sub micron particles.
(4) Other Methods
o Limited research studies of thermal precipitation, magnetic
precipitation, Brownian agglomeration, and sonic agglomeration.
187
-------
SECTION V
OVERVIEW OF OTHER SELECTED INDUSTRIAL PROCESSES
5.0 INTRODUCTION
Short literature surveys were performed for several industrial
processes in order to compile emission characteristics for those
processes. Tables were prepared for the following 11 processes:
1) Copper Reverberatory Furnaces
2) Zinc Retorting
3) Copper Converting
4) Lead Blast Furnaces
5) Steel Open Hearth Furnaces
6) Steel Basic Oxygen Furnaces
7) Steel Electric Furnaces
8) Chlorine Electrolysis
9) Chlorine Liquefaction
10) Chlorine Bleach Manufacture
11) Hydrochloric Acid Manufacture
These emission characteristic tables appear in this section and
are in the same format as those which are in Section IV. Again the
numbers in parenthesis appearing after the data refer to the references
in the bibliography. Separate emission tables.were prepared for
each control point of the process. The reader is reminded that the
data shown in these tables are the best data available in the
references cited or MITRE's best estimate when specific data were not
189
-------
available. In both cases the information is not meant to represent
values for any specific plant. The averages and ranges included in
these tables are a composite of all data found in the literature for
presently operating, plants. It is possible that plant data not
published in the literature may lie outside the ranges shown.
A summary description of each of these 11 processes accompanies
the tables. In addition, a brief explanation of each table has been
included in this section. The first four processes are part of the
non-ferrous smelting industries discussed earlier. For flow diagrams
of these industries, the reader is referred to Section IV. The other
processes listed above are in the steel industry and the chlorine
industry. Flows of the basic operational processes in each of the
industries are included in this section.
At the beginning of the study, industrial flow diagrams were
prepared for several industries that were later dropped from the list
of those to be given additional study. These flow diagrams appear in
the Appendix, but emission characteristics have not been prepared for
the processes appearing on these diagrams.
5.1 Copper Reverberatory Furnace
5.1.1 Process Description
All United States copper smelters except one use fossil-fuel
fired reverberatory furnaces. The furnace operates the same regardless
of whether or not the charge has undergone prior roasting. The charge
of copper ore and concentrates is fed into the furnace through openings
190
-------
in the roof or on top of the side wall. Fluxes are usually added to
obtain a suitable slag. The fuel is burned above the concentrates.
Heating of the charge is accomplished by radiation from the roof and
side walls. Figure 34 shows a sketch of a typical reverberatory
furnace.
The principle chemical reactions take place between the charge
materials to form a matte and a slag. The molten copper sulfides
and iron sulfides settle to the bottom to form matte, and the iron
oxides combine with fluxes to form a slag which floats on top of the
furnace matte. The entire operation is continuous with the slag
periodically being extracted from the upper end of the furnace. The
matte is also topped periodically from the furnace and charged into
a converter.
5.1.2 Chemical and Physical Properties of Input Feed and Effluents
Table XXXV shows the chemical and physical properties of the input
feed and effluents for copper reverberatory furnaces operating with
two different input feeds. In the first case the furnace uses unroasted
ore (green feed) while the second case was roasted ore. All data
shown were taken directly from the references cited except as discussed
below.
5.1.2.1 Data for Furnaces Using Unroasted Concentrates. The
percent by weight analysis of the input feed for furnaces using green
ore was calculated a$ follows. Reference 173 gives the basic constituents
of reverberatory furnace feed at the Ray smelter in Arizona as,
191
-------
VO
ro
CALCINE
FUEL
CONVERTER
SLAG
AIR AND
OXYGEN
FETTLING DRAG
CONVEYOR
BURNERS
SLAG
MATTE.
FETTLING PIPES
J ^OFF-GAS
SLAG
MATTE
BASIC DIMENSIONS OF REVERBERATORY FURNACE
WIDTH
LENGTH
22 TO 38 ft.
96 TO 125 ft.
TYPICAL CAPACITY: 230 TONS/DAY
FIGURE 34
COPPER REVERBERATORY FURNACE
-------
TABLE XXXV
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-COPPER REVERBERATOR! FURNACE
Numbers in parenthesis are references
Control Point
Flow Rate
1000 SCFM (163)
Avg _ Range
Gas Temperature
°F (163)
Avg _ Range
Chemical Composition
of Gas (163)
Chemical _ %5 Volume
Input feed
when reverberatory
furnace follows a
roaster
28.4-128
100-700
>o
CJ
* Not calculated because of the variety of temperature control techniques employed.
If air preheater or waste heat boiler used, temperature will be approximately 700 F,
if not, temperature will be approximately 100 F.
-------
TABLE XXXV
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-COPPER REVERBERATORY FURNACE
(Continued)
Numbers in parenthesis are references
to
% Weight Analysis
Grain Loadings of Chemicals
Control Point Avg Range Chemical % Weight
Input feed 1826 Tons/ J.270-2883 Cu
when Reverberatory Day Tons /Day Fe
Furnace follows a (173,163,216) (173,163,216) S
Roaster _ . , As
Equivalent „,
331 gr/SCF 243-408 £?
of reverb. gr/SCF
flow gas (163, N4) f1
(163, N4) j£
Ni
Mn
Se
CaCO,
Si02
Others
14.0
35.4
13.7
tr
tr
tr
2.1
tr
tr
tr
tr
tr
6.0
13-7
17.1
(216,
(216,
(216,
(163,
(163,
(163,
(216,
(163,
(163,
(163,
(163,
(163,
(216,
(216,
(Nl)
Typical Size
Profile
Size % Weight
203) > 230 V 13.5
203) 149-230 u 2.5
203) 100-149 u 2.5
245) 74-100 u 11.5
245) 53-74 u' 46.5
245) 44-53 y 16.0
203) < 44 v 7.5
245) (N4, 216)
245)
245)
245)
245)
203)
203)
Chemical
Composition
CuO
CuSO,
CuS
Fe20
FeS2
FeS
Fe3°4
ZnS
ZnO
CdS
CdO
PbS
PbO
SeS
SeO
NiS
NiO
CUnO
Sn02
Mn02
•FeSAs
SboS.o,
CU2S
CaC03
(199)
(199)
(199)
(199)
(259)
(259)
(259)
(259)
(199)
(259)
(199)
(173,
(199)
(173,
(12)
(173)
(199)
(256)
(255)
(255,
(173,
(173,,
(256)
U63)
/•i cnA
255)
255)
36)
255)
255)
-------
TABLE XXXV
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-COPPER REVERBERATORY FURNACE
(Continued)
Numbers In parenthesis are references
Control Point
Flow Rate
1000 SCFM(163)
Ayg Range
Gas Temperature
°F (163)
Ayg Range
Chemical Composition
of Gas (J63)
Chemical % Volume
«o
On
Control Point No, 1
(after reverberatory
that has roaster,
after waste heat
boiler, and before
joining other gases)
63.5(D) 27.0-155(0)
704 (D)
600-820(0)
so
2
Others
1.7
10.01
3.32
85.0
After leaving
Electrostatic
Precipitator
63.5 (D) 27.0-155(0)
600°F
(163, 206)
S°
0
2
Others
1.7
10.01
3.32
85.0
(D) Plus dilution air
T)ata for 1 plant only
9
One other plant reported negligible
-------
TABLE XXXV
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-COPPER REVERBERATOR? FURNACE
(Continued)
Numbers In parenthesis are references
Control Point
Control Point No. 1
(After reverberatory
that has roaster,
after waste heat
boiler, and before
j oining other gases)
After leaving
Electrostatic
Precipitator
Grain Loadings
Avg Range
.4 gr/SCF only data
(163, N4) from one
plant
reported
2-5 gr/SCF
(163)
1-6 gr/SCF
(43)
.04 gr/SCF only data
(163,N4,242) from one
plant
reported
.1-.6 gr/SCF
(43,163,242)
% Weight Analysis
of Chemicals
Chemical 7, Weight
Cu
Fe
S
As
Sb
Pb
Zn
Sn
Cd
Ni
Mn
Se
CaC03
Si02
Others
same as
above
6.2
tr
3.0
tr
tr
tr
13.0
tr
tr
tr
tr
tr
77.8
same
(43)
(N5)
(163)
(43)
(43)
(N5)
(43)
(N5)
(N5)
(N5)
(N5)
(MS)
(Nl)
as
above
Typical Size
Profile
Size % Weight
>40 v
20-40 u
10-20 v
5-10 V
2-5 p
<2 p**
40 v
20-40 ;
10-20 v
5-10 ).
2-5 u
7
8
17
22
26
20
8
1
6
26
31
28
(239)
(239)
(239)
(239)
(239)
(239)
A12
(42,298)
(42,298)
(42,298)
(42,298)
142,298)
.(42,298)
Chemical
Composition
CuO
CuS04
Fe304
Sb203
PbO
ZnO
SnOo
CdO
NiO
MnO,
SeO
5i2(S04)?
Others
Same as
(43)
(N5)
(N5)
(43)
(43)
(N5)
(43)
(H5)
(N5)
(N5)
(N5)
(N5)
(43)
above
** Reference N9 says that most particles (in number) are less than 0.1 micron in diameter
-------
TABLE XXXV
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-COPPER REVERBERATORY FURNACE
(Continued)
Numbers in parenthesis are references
Flow Rate Gas Temperature Chemical Composition
Control Point 1000 SCFM (163) °F (163) of Gas (163)
. . Avg Range Avg Range Chemical % Volume
Input feed 45.3 34.4-69.9 100° 100° Air 90 or 100
without prior 4.5 3.4-7 100° 100° Natural Gas* 10 or 0
roast
*Two plants use coal instead of natural gas (not taken into account in above data)
-------
TABLE XXXV
SELECTED CHEMICAL AMD PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-COPPER REVERBERATORY FURNACE
(Continued)
Numbers in parenthesis are references
CO
00
% Weight Analysis
Grain Loadings of Chemicals
Control Point Avg Range Chemical % Weight
Input feed 1638 Tons/
Without prior Day
Roast (173, 163, N4)
Equivalent
325 gr/SCF
of furnace
gas and air
feed
530-2740 . Cu
Tons/day Fe
(173, 163, N4) S
Equivalent As
136-545
gr/SCF Sb
Pb
Zn
Sn
Cd
Hi
Mn
Se
CaC02
Si02
Others
21
30
23
tr
tr
tr
tr
tr
tr
tr
tr
tr
6
8
9
(173
(173
(173
- 2
- 1
(163
(163
(163
(163
(163
(163
(173
(173
(173
(173
, 163) >
, 163)
, 163)
(173, 245,
260)
(173, 245,
260)
, 245)
, 245)
, 245)
, 245)
, 245)
, 245)
, 255)
, 203)
, 203)
, 203)
Typical Size
Profile
Size 7,
2000 ji
1410-2000u
840-1410y
638-840
500-638
318-500
230-318
149-230
100-149
74-100
44-74 v
28-44 \
20-28 \
10-20 \
< 10 u
V
V
V
V
y
u
u
i
2.
2.
3.
3.
2.
2.
13.
9.
7.
8.
10.
11.
6.
7.
9.
(259
Chemical
Weight Composition
1
9
1
4 (Cu.Fe).
6
2
7
0
9
3
6
5
1
2
4
, 246) 4Cu,
CuFeS,,
Cu2S
Cu20
L2^S4^13
CuCo2S,
FeS2
FeS
Fe30,
FeSAs
FeNiS
ZnS
CdS
PbS
SeS
Sb2S3
S-SboS,
Si02
CaC03
Others
(259)
(256)
(256)
(236)
(56)
(259)
(259)
(259)
(173,
(173,
(259)
(173,
(173,
(173,
(173,
(256)
(163)
(163)
255)
255)
255)
255)
255)
255)
-------
TABLE XXXV
SELECTED -CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-COPPER REVERBERATORY FURNACE
(Continued)
Numbers in parenthesis are references
Control Point
Control Point No. 1
(After reverberatory
that does not have
prior roast,
after waste heat
boiler, and before
joining other gases)
After leaving
Electrostatic
Precipltator
Flow Rate Gas Temperature Chemical Composition
1000 SCFM (163) °F (163) of Gas (163)
Avg Range Ayg Range Chemical % Volume
55 (D) 26.2-79.4 739 (D) 600-800(0) S02
(D) one case at
1100° (D) H20
n
U2
Others
(~i
55 (D) 26.2-79.4 600 F - SO
(D) (163,206) R *
°2
Others
2.0
19.8
i 7*
-L • /
76.5
2.0
19.8
1.7*
76.5
(D) Plus dilution air
* Two additional plants reported negligible
-------
TABLE XXXV
10
o
o
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-COPPER REVERBERATORY FURNACE
(Concluded)
Numbers in parenthesis are references
% Weight Analysis Typical Size
Grain Loadings of Chemicals Profile Chemical
Control Point Avg Range Chemical % Weight Size 7, Weight Composition
Control Point No. 1 3 gr/SCF 1-6 gr/SCF Cu
(After reverberatory (43, 163) (43, 163) Fe
that does not have S
prior roast, after As
waste heat boiler, Sb
and before joining Pb
other gases) Zn
Sn
Cd
Ni
Mn
Se
CaCO,
Si02
Others
After leaving .3 gr/SCF .1-.6 gr/ Same as
Electrostatic (163, N4, 242) SCF above
Precipitator (43, 163, 242)
6.2 (43) > 40y 2 CuO
tr (N5) 20-40y 2 CuSO,
13.6 (43) 10-20vi 4 Fe3o7
50 (260, N4) 5-10u 29 As20,
25 (260, N4) 2-5 u 35 Sb20,
tr < 2 u** 28 PbO
tr (4, N4, 239) ZnO
tr Sn02
tr CdO
tr NiO
tr Mn02
tr SeO
Al2Si (SO,),
5.2 (N4) Others
^
Same as > 40[i 2 Same as
above 20-40|j. neg .
10-20(1 1
5-10(1 29
2-5 fi 35
< 2 h 33
(42,298)
(43)
(N5)
(N5)
(43,
(43)
(N5)
(43)
(N5)
(N5)
(N5)
(N5)
(N5)
(43)
260)
above
** Reference N9 says that most particles (in number) are below 0.1 micron in diameter
-------
Material
Copper Concentrates
Copper Sulfate
Calcium Carbonate
Silicon dioxide
Flue dust
Recycled converter slag
Percent by Weight
65
2
6
1
1
25
By combining data contained in references 163, 245, and 260 the
percent by weight composition of a typical unroasted copper concentrate
was estimated as,
Percent by Weight
Material
Copper
Iron
Sulfur
Arsenic
Antimony
Lead
Zinc
Tin
Cadmium
Nickel
Manganese
Inerts
31
27
35
3
2
t race
trace
trace
trace
trace
trace
1
201
-------
Reference 203 gives the composition of a typical converter slag
as,
Material Percent by Weight
Copper 3.25
Silicon dioxide 26.3
Iron 47.7
Others 22.75
A simple combination of the above three lists yields the analysis
reported in the table.
The input grain loadings were calculated from data given in
references 163 and 173. The input feed to the furnaces at the Ray
smelter is given as 1426 tons per day and the gaseous flow as 35,200
SCFM plus 4100 SCFM of natural gas. Thus the equivalent input grain
loading would be,
9725.26 (1426 tons/day) . . ,
39 3QO SCFM =352 grains/SCF (for the Ray smelter)
where 9725.26 is the conversion factor from tons/day to grains/minute.
Reference 163 gives the number of tons of sulfur per day in
reverberatory furnace green feeds for various smelters. Since the
sulfur content of the feed is shown to be 23% in the percent weight
analysis, straightforward calculations show the average feed to be
1638 tons/day with a range of 530 to 2740 tons/day. By using the
flow rates reported in reference 163 the equivalent grain loadings
were calculated to have an average of 325 grains/SCF and a range of
136 to 545 grains/SCF.
202
-------
The particle size distribution for the particulates in the
furnace exhaust was estimated by using the following assumptions,
information and calculations,
o Almost all of the arsenic and antimony in the feed are
volatilized and solidify in the exhaust stream as fine
particulates of arsenic trioxide and antimony trioxide.
o Reference 4 states that 100% of the particulates of arsenic
and antimony are less than 10p. in size.
o The arsenic and antimony compounds constitute 75% by weight
of the particulates; the other materials 25%.
o The particle size distribution for the non-volatile materials
was assumed to be similar to that of an open hearth steel
furnace. The size distribution given in reference 239 was
used.
o The particle sizes for the arsenic and antimony compounds
were distributed among the,5 to 10}i, 2 to Sfj. and <2|j. size
ranges in the same proportions as reference 239 shows for
open hearth furnaces.
The above information when combined with the particle size
distribution given in reference 239 yields the data shown in the
table. The grain loadings shown for the flow after the electrostatic
precipitator were based on an overall ESP efficiency of 90% as shown
in reference 242.
203
-------
5.1.2.2 Data for Furnaces Using Roasted Concentrates. The percent
by weight analysis of the input feed for furnaces using roasted ores
was calculated in a manner similar to that for unroasted ores. The
basic constituents of the furnace feed are assumed to be the same as
for unroasted ores, namely,
Material Percent by Weight
Copper Concentrates 65
Copper Sulfate 2
Calcium Carbonate 6
V
Silicon dioxide 1
Flue dust 1
Recycled converter slag 25
A typical percent by weight analysis for roasted copper concentrates
at the Copperhill, Tennessee smelter is given in Reference 216 as,
Material
Copper
Iron
Sulfur
Arsenic
Antimony
Lead
Zinc
Tin
Cadmium
Percent by Weight
19.4
36.2
20.6
trace
trace
trace
3.2
trace
trace
204
-------
Material Percent by Weight
Nickel trace
Manganese trace
Silicon dioxide 6.3
Inerts 14.3
The composition of a typical converter slag was taken to be the
same as for the unroasted ore feed shown previously. Combination
of all the data cited above yields the analysis reported in the
table.
The input grain loadings were calculated from data given in
References 163, 173, and 216 in the same manner as shown for the
unroasted ore feed.
The particle size distribution was calculated from data given
in Reference 216 for Copperhill, Tennessee. The copper concentrate
from the fluid-bed roaster is collected from the following sources,
Location Percent by Weight
Primary Cyclone 80
Secondary Cyclone 5
Roaster bed overflow 15
The above reference gives the size distribution for each of these
types of roaster product as shown in Table XXXVI.
Combination of the three sets of particle sizes in proportion
to their occurrence in the total product yields the data reported for
particle size in Table XXXV.
205
-------
TABLE XXXVI
PARTICLE SIZE DISTRIBUTION OF ROASTER PRODUCTS AT COPPERHILL, TENNESSEE
Size
>230|j.
149-230 p.
100-149 |i
74-100 |i
53-74[jL
44-53 n
<44
Primary Cyclone
1.3
2.9
2.7
14.3
51.3
19.4
9.0
Secondary Cyclone
.2
.2
.5
1.8
91.9
3.7
1.7
Bed Overflow
82.9
6.5
1.5
1.3
4.2
1.3
2.3
206
-------
The grain loading for the effluent from the furnace was based on
data reported for copper smelter number 5 in Reference 163. This
smelter is shown to have a flow of 83,200 SCFM after the reverberatory
furnaces with a dust load of 3.3 tons/day. The standard conversion
factor of 9725.26 yields the value shown in the table.
5.2 Reduction of Zinc Oxide in Retorts
5.2.1 Zinc-Vertical Retort
5.2.1.1 Process Description. The vertical retorting process is
a much newer and more efficient process than horizontal retorting.
Reference 264 gives a thorough description of the vertical retort
smelter at Depue, Illinois. This plant has since closed, but the
vertical retort smelter at Palmerton, Pennsylvania, which is operated
by the same company (New Jersey Zinc), is very similar in operation.
The advantages of the vertical retort process derive from the mechanical
handling of materials into and from a large, continuously operated
retort producing zinc and reaction products of uniform-'composition
at constant rates with high thermal efficiency and recovery. A
fundamental requirement of the process is that the smelting charge
be supplied to the retort in a form conducive to the rapid and
efficient transmission and utilization of heat developed by combustion
of gas in firing chambers adjacent to the high conductivity, refractory
sidewalls of the retort. The required form of the charge is a large,
. - ,--• ~~' { L , , .
loaf shape (2 1/2" x 4" x 3") produced by roll-briquetting a
specially prepared mix.
207
-------
A sketch of a typical vertical retort furnace is shown in Figure
35. The briquets are lifted to the retort charge floor in buckets
and emptied into the retort on a time schedule corresponding to the
removal of reduced briquets from the bottom. During downward passage
through the vertical retort with retention time correlated with the
reduction reaction, the reduction heat is supplied by its transmission
through the high-conductivity sidewalls from the combustion chamber.
The zinc vapor and reaction gases produced flow upwardly through the
retort and the dezinced briquets are extracted at the bottom. The
vapor and gases escape via a duct leading from an upper extension of
the retort and are drawn into a zinc vapor condenser from which
the liquid zinc is withdrawn for casting and refining. The permanent
gases escaping the condenser are cooled and cleaned and piped to the
retort firing chambers for supplementary fuel.
The Palmerton plant of New Jersey Zinc has a larger capacity
than the Depue plant having 43 vertical retorts presently in operation.
It is currently the only primary zinc smelter in the U.S. using
vertical retorts.
5.2.1.2 Chemical and Physical Properties of Input Feed and Effluents.
Selected chemical and physical properties for zinc vertical retorts
are given in Table XXXVII. The basic characteristics of the vertical
retort were taken from the description of the New Jersey Zinc Company
smelter at Depue, Illinois (Reference 264). Since this plant is now
closed all computations were adjusted proportionally to the size and
208
-------
GAS
SCRUBBER
CONVEYOR BRIQUET
RESIDUE
WASTE
TRUCK
(NOT TO
SCALE)
'£&l'0:'K°^—^^^'-?V&'DEWATERING SCREW W/A'.?(>'o^&hv/=^i?^«^O»oW"r/)?S'OX:'
..:?$&gaSg#£k^
APPROXIMATE DIMENSIONS OF RETORT SECTION
INTERNAL RECTANGULAR CROSS SECTION: 1 Ft. x 6 TO 8 Ft.
INTERNAL HEIGHT: 33 TO 37 FEET
CAPACITY: 6 TO 9 TONS/DAY ZINC PER RETORT (DEPENDING ON SIZE)
FIGURE 35
ZINC VERTICAL RETORT REDUCTION FURNACE
209
-------
TABLE XXXVII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-ZINC VERTICAL RETORT
Numbers in parentheses are references
Control Point
Flow Rate
1000 SCFM
Avg Range
Gas Temperature
°F
Ayg Range
Chemical Composition
of Gas
Chemical % Volume
Input Feed
27.4
(N4)
Only one
plant
1025
(264)
Only one
plant
10
o
so2
H20
°2
CO
CH/.
0
neg,
11
14
33
42
(N4)
* Gas data given for furnace flow since retort exhaust
Is cycled through furnace.
-------
TABLE XXXVII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-ZINC VERTICAL RETORT
(Continued)
Control Point
Grain Loadings
Aye Range
7, Weight Analysis
of Chemicals
Chemical %.Weight
Typical Size
Profile
Size . % Weight
Chemical
Composition
Input Feed*
Does not apply
Calcine
Se
Zn
Pb
Fe
Cd
S102
S
*• Other
Soft Coal
Hard Coal
Clay
Sulfite
Liquor
tr (N5)
33.3 (264,
0.2 (264,
4.7 (264,
tr (264,
5.6 (264,
0.1 (264,
16.1 (264,
25.0 (264)
5.0 (264)
10.0 (264)
1.0 (264)
265)
265)
265)
265)
265)
265)
265)
Large Briquets
100% (264)
ZnO
PbO
FeO
CdO
SeO
Si02
C
(175)
(175)
(175)
(175)
(N5)
(265)
(264)
* Data shown in this table are for the actual input feed material.
Emissions from material handling, during input are not addressed.
-------
TABLE XXXVII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS^ZINC VERTICAL RETORT
(Continued)
Numbers in Parentheses are references
Control Point
Flow Rate
1000 SCFM
Avg Range
Gas Temperature
Avg
Range
Chemical Composition
of Gas
Chemical % Volume
10
Control Point No. 1 25.5 Only one 1605 Only one
(After retort and furnace, (N4) plant (264) plant
before stack)
SO
°2
co2
0,
11
neg
20
69
(N4)
No control devices
used on furnace stack
Gas data given for furnace flow since retort exhaust
is cycled through furnace.
-------
Numbers in parentheses are- references
TABLE XXXVII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUEHTS-ZINC VERTICAL RETORT
(Concluded)
Control Point
Control Point So. 1
(After retort and
furnace, before
stack)
- % Weight Analysis
Grain Loadings of Chemicals
Avg Range Chemical % Weight
.94 gr/S>CF
(N4)
only one Zn
plant ZnO
Pb
Cd
Se
50-70 (43)
,0-3 (43)
tr (N5)
tr (N5)
Typical Size
Profile
Size % Weight
<1 u 100 (43)
Chemical
Composition
ZnO (175)
PbO (175)
CdO (N5)
SeO (N5)
No control devices
used on furnace stack
N)
-------
capacity of the New Jersey Zinc vertical retort smelter at Palmerton,
PennsyIvan ia.
As stated previously the solid input to the retort consists of
large briquets containing all the ingredients necessary for the
reduction of zinc oxide to zinc. The briquets are intentionally
manufactured to have excellent structural integrity which results
in almost complete absence of pa'rticulate emissions during charging
of the retort.
Since the vertical retort itself is a closed system, there is no
input air or gas. The zinc vapor and carbon monoxide gas which are
the principal products are cycled through a sealed system to a
condenser for the zinc vapor. The carbon monoxide, trace amounts of
metallic impurities and residual zinc fume (about 3 to 4% of the zinc
fume produced) pass through a scrubber and the carbon monoxide is
recycled to the furnace chamber as supplemental fuel. The flow rates
shown in the table for input and exist gases are based on the furnace
flow since this is the only way the retort exhaust reaches the atmosphere.
The flow rate for the Depue smelter was calculated from the
following data given in Reference 264:
Zinc production 182 tons/day
Natural gas used 1666 cu. ft./min.
Carbon monoxide recycled 2218 cu. ft./min.
Thermal efficiency of retorts 45%
214
-------
The reference states that the carbon monoxide contributes 30% of
the BTU used in the furnace. Reference 244 gives the BTU content
of carbon monoxide as 322 per cubic foot and of natural gas as 1000
per cubic foot. For the purpose of stoichiometric calculations
natural gas was assumed to be methane. Conversion of these values
for use at the Palmerton smelter was made by using the ratio of zinc
produced at Palmerton to zinc produced at Depue, which is 1.7
(Reference 317). The conversion is made by assuming that Palmerton
uses 1.7 times the BTU used at Depue after adjustments for thermal
efficiency. Thus the BTU balance sheet would show:
BTU input at Depue 2,380,048 per minute
Thermal efficiency at Depue 45%
BTU delivered to retorts at Depue 1,071,022 per minute
Conversion factor 1.7
BTU delivered to retorts at
Palmerton 1,820,737 per minute
Thermal efficiency at Palmerton 70%
BTU input at Palmerton 2,601,053 per minute
Carbon monoxide at Palmerton
(1.7 times Depue) 3771 cubic feet per minute
Based on the total BTU required at Palmerton and the carbon monoxide
recycled as fuel the natural gas requirement was calculated as 1387
cubic feet per minute. Assuming zero excess air would result in the
following fuel/air balance at Palmerton
215
-------
Carbon Monoxide
Methane
Air for carbon monoxide
Air for methane
3771 cubic feet per minute
1387 cubic feet per minute
8975 cubic feet per minute
13218 cubic feet per minute
Total gaseous input 27351 cubic feet per minute
Calculation of the exhaust gas flow is made by a stoichiometric
balance of the two following equations:
2CO + Nn + CL -
N2 + 2C°2
air
N
C°2 + 2H2°
air
Using gas densities as shown in Reference 244 gives the following
theoretical composition of the exhaust gas at Palmerton:
Carbon dioxide 5158 cubic feet per minute (20% Volume)
Water vapor 2774 cubic feet per minute (11% Volume)
Nitrogen 17533 cubic feet per minute (69% Volume)
Total 25465 cubic feet per minute
The particulate grain loading was based on an initial metallic fume
emission of 3 to 4% of production. For Palmerton this would yield
.00856 tons per minute. Based on data in Reference 42, the average
penetration of a high efficiency wet scrubber for submicron particles
was taken as 20%. This would yield a grain loading of .94 per standard
cubic foot for a 25,500 cubic feet per minute flow.
216
-------
5.2.2 Zinc-Horizontal Retort
5.2.2.1 Process Description. The chemical reaction taking
place in the zinc horizontal retort furnace is the same as in the
vertical retort, namely, the reduction of zinc oxide to zinc in the
presence of heat and carbon. The major differences are the smaller
size of each horizontal retort and the batch rather than continuous
operation. A sketch of a typical horizontal (Belgian) retort is
shown in Figure 36. According to Reference 263 a typical retort is
approximately 9 inches in diameter and 5 feet deep. A complete cycle
of operation takes 48 hours. Approximately 4 hours are used for
unloading, cleaning and recharging each retort with the remaining
44 hours used for the chemical reduction.
The charging operation consists of two basic steps. First a
carefully measured quantity of the zinc oxide, coke, flux and other
minor constituents are loaded into the retort. The second operation
consists of sealing the front of the condenser section with a porous
loam mix which allows the carbon monoxide to escape but retains the
molten zinc. The* carbon monoxide is burned immediately outside the
retort mouth without recovering its heat value, or in some cases CO
recycled to the furnaces. In a typical Sine smelter the various
banks of retorts are unloaded and recharged on a schedule which allows
the most efficient use of manpower and results in a relatively steady
flow of furnace exhaust gases for the entire smelter.
217
-------
FRONT WALL
OF FURNACE
N>
H>
00
GROUT JOINT
CONDENSED METAL
VAPORS
FLAM'E FROM
COMBUSTIBLE GASES
METALLIC OXIDE CHARGE
WITH REDUCING MATERIALS
BURNER PORT
TYPICAL RETORT DIMENSIONS:
INSIDE DIAMETER: APPROXIMATELY 9 INCHES
DEPTH: APPROXIMATELY 5 FEET
AVERAGE CHARGE PER RETORT: 150 POUNDS OF CHARGE MIXTURE
PER 48 HOUR CYCLE.
NUMBER OF RETORTS PER SMELTER: 5,800 TO 10,400
FROM "REFERENCE "57
FIGURE 36
ONE BANK OF A BELGIAN RETORT FURNACE
-------
There are three zinc smelters using the horizontal retort process
in the U.S. today (See Table XXIX). The number of retorts in operation
at these smelters is 5824, 6400, and 10,400. None of the smelters
has emission control equipment on the retorts.
5.2.2.2 Chemical and Physical Characteristics of Input Feed
and Effluents. The chemical and physical characteristics of the
input feed and effluents from a typical horizontal retort smelter
I
are shown in Table XXXVIII. The data shown in the tables were taken
directly from the references cited. Control point number 1 is
assumed to be in the exhaust ductwork where all the exhaust gases
plus extraneous air converge. It is also assumed that all CO is
burned to C0_ at the mouth of each retort.
The theoretical flow rate for the carbon monoxide from a single
typical retort was computed based on data contained in Reference 263.
The retort used has a volume of 2.394 cubic feet and is charged with
materials averaging 148.2 Ibs. This charge has a zinc content of
69.6 Ibs. The reaction taking place in the retort is,
ZnO + C - CO + Zn
Since the reduction is a straight replacement of one atom of carbon
for one atom of zinc every mole (65.38 grams) of zinc produced requires
one mole (12 grams) of carbon. This is a carbon to zinc ratio of
0.1835. Thus for each retort charge containing 69.6 Ibs. of zinc,
12.76 Ibs. of carbon are required. When combined with oxygen this
amount of carbon will produce 29.72 Ibs. of carbon monoxide,
219
-------
(0
NJ
a
TABLE XXXVIII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-ZINC HORIZONTAL RETORT
Numbers in parentheses are references
Control Point
Flow Rate
1000 SCFM
Avg Range
Gas Temperature
Avg
Range
Chemical Composition
of Gas
Chemical % Volume
Input Feed
-------
TABLE XXXVIII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-ZINC HORIZONTAL RETORT
(Continued)
Numbers in parentheses are references
NJ
tsj
% Weight Analysis Typical Size
. Grain Loadings of Chemicals Profile Chemical
on ro oint Avg Range Chemical % Weight Size % Weight Composition
A
Input Feed does not apply , Zn
Pb
Sinter Cu
and • Fe
Returns Cd
,Se
^Others
Coke
Coal
NaCl
CaF2
0
0
0
2
47
.5
.5
4
.5
tr
29
15
.5
1
tr
(263) <4760
(263) 3360-4760
(263) 2000-3360
(263) 840-2000
(263) 500-840 y
(263) 230-500 y
(263) >230 (.
(263)
(263)
(263)
(263)
M 7
V 1
y 19
P 22
17
10
13
.6 ZnO
.9
.9
.8
.0
.9
PbO
CuO
(263) FeO
CdO
SeO
.9 C
NaCl
CaF2
(175)
(175)
(N5)
(175)
(175)
(N5)
(263)
(263)
(263)
Data shown in this table are for the actual input feed material.
Emissions from material handling during input are not addressed.
-------
TABLE XXXVIII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-ZINC HORIZONTAL RETORT
(Continued)
Numbers in parentheses are references
Control Point
Flow Rate
1000 SCFM
Avg Range
Gas Temperature
°F
AVE
Range
Chemical Composition
of Gas
Chemical % Volume
Control Point No. 1 4.25 3.4-5.1
(after retort - in (43) (43)
duct work)
900
(57)
780-1020
(57)
to
Is]
SO,
H,5
C02**
Other
neg (N5)
NR
NR
NR
NR
* Condenser Outlet Temperature
** Flow of Carbon Monoxide is 68.1 SCFM for a Furnace containing
448 retorts based on References 244, 263 and MITRE calculations.
No Control Devices used, but Some Plants Recycle the CO to the Furnaces.
-------
Numbers in parentheses are references
TABLE XXXVIII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-ZINC HORIZONTAL RETORT
(Concluded)
% Weight Analysis
Grain Loadings
Control Point
Control Point No. 1
(After re tort- in
duct work)
Avg
.09 gr/SCF
(43)
Range
0.04-0.13
(43)
of Chemicals
Chemical
Zn
Pb
Cd
Se
F
% Weight
50-70 (43)
0-3 (43)
tr (N5)
tr (N5)
tr (N5)
Typical
Size
Profile Chemical
Size
Micron to
Submlcron
7. Weight Composition
100 ZnO (175)
PbO (175)
CdO (N5)
SeO (N5)
ro
isi
CJ
-------
Reference 244 states that 1 Ib. of carbon monoxide occupies
13.506 cubic feet at standard conditions. Thus a single run of one
retort produces 401.4 standard cubic feet of carbon monoxide.
If a firing cycle of 44 hours is used for a standard furnace of
448 retorts, the carbon monoxide flow becomes 68.1 SCFM.
5.3 Copper Converter
5.3.1 Process Description
The copper converting process has two stages. First the converter
is charged with molten matte. Air is blown up through the charge
from the tuyeres at the bottom of the converter. This causes the
rapid oxidation of the iron sulfide in the matte to iron oxide and
releases sulfur dioxide. Silica is added to form an iron silicate
slag which at the end of the first stage is poured off leaving
behind molten copper sulfide (white metal). The converter slag is
usually returned to the reverberatory furnace. Thin streams of air
are blown through the molten metal during the second stage in order
to oxidize the sulfur of the white metal and leave metallic copper.
The converter is then tilted to pour the copper metal into ladles.
A sketch showing a converter and its various positions appears in
Figure 37. The entire batch operation takes about 8 to 10 hours.
The copper converting process is autogenous, so no fuel is
required to maintain the converter bath in a molten state. In fact,
during the first stage excess heat is generated which can be used to
smelt fresh concentrates in the converter. Thus, for low grade
224
-------
REFRACTORY
LINING^
TRUNDLES -
to
M
Ol
EXHAUST HOOD
TUYERES
MOLTEN METAL
CHARGING
BLOWING
SKIMMING
BASIC DIMENSIONS OF CONVERTER:
DIAMETER 13 Ft.
LENGTH 30 Ft.
CAPACITY: 35 TONS/BATCH
FIGURES?
COPPER CONVERTER
-------
matte, copper scrap and copper concentrates can be charged directly
to the converter in significant proportions.
5.3.2 Chemical and Physical Properties of Input Feed and Effluents
The chemical and physical properties of the converter input
feed are shown in Table XXXIX. The table also shows the properties
of the effluent for three logical control points. The first is
immediately after the converter. The other two control points are for
cases where converter and reverberatory furnace exhaust gases are
joined before entering the exhaust stack. In one of these cases the
reverberatory furnace feed uses unroasted ore and in the other one
roasted ore. These cases were selected since Reference 163 identifies
copper smelter number 6 as combining converter gases with reverberatory
furnace gases in a smelter using roasted ore. The same report also
indicates that smelters number 4, 7, 8 and 20 join converter gases
and reverberatory furnace gases but these smelters use unroasted
ores .
5.3.2.1 Input Feed. The percent weight analysis of input feed
to copper converters was estimated by combining the following
information. Reference 203 gives the basic analysis of copper matte
for 4 smelters as,
Material Percent by Weight Range
Copper 36.8 27.2 - 45.0
Iron 30.2 22.0 - 40.7
Sulfur 24.5 24.0 - 25.0
226
-------
TABLE XXXIX
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-COPPER CONVERTER
Numbers in parentheses are references
Control Point
Flow Rate*
1000 SCFM
Avg Range
Gas Temperature
°F
Avg Range
Chemical Composition
of Gas
Chemical % Volume
K3
NJ
Input Feed
13.04
(163)
5.7-26.7
(163)
100 (163)
100 (163)
Air
100%
All flow rates for converters are variable depending on
stage of the flow.
-------
TABLE XXXIX
Numbers in parentheses are references
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-COPPER CONVERTER
(Continued)
10
ro
oo
7, Weight Analysis Typical Size
Grain Loadings of Chemicals Profile
Control Point Avg Range Chemical % Weight Size % Weight
A
Input Feed Input is molten Cu
matte and silica
Fe
S
As
Sb
Pb
Ni
Se
Sn
Zn
Cd
Mn
21-59 Input is molten
Avg 36 (203) matte and silica
22-41
Avg 30 (203)
24-25 (203)
tr-.5 (173,203,N5)
tr-.3 (173, 203, N5)
tr-.2 (173, 203, N5)
tr-.5 (173, 203, N5)
tr-.4 (173, 203, N5)
tr (203)
tr (203>
tr (163, 245)
tr (163, 245)
Si02 variable (238)
Inerts variable (N5)
Chemical
Composition
CuS
CuO
CuSO^
Fe203
FeS2
FeS
Fe304
ZnS
ZnO
CdS
CdO
PbS
PbO
SeS
SeO
NiS
NiO
Sn02
As203
Sb203
Si02
(199)
(199)
(199)
(199)
(259)
(259)
(259)
(259)
(199)
(259)
(199)
(173,255)
(199)
(173,255)
(12)
(173)
(199)
(255)
(260)
(260)
(238)
Data shown in this table are for the actual input feed material.
Emissions from material handling during input are not addressed.
-------
TABLE XXXIX
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-COPPER CONVERTER
(Continued)
Numbers in parentheses are references
Control Point
Control Point No. 1
(After converter,
before joining other
gases)
After Electrostatic
Precipitator
Flow Rate
1000 SCFM (163)
Avg Range
36 (D) 6.2-66.1 (D)
111
1 case after
dilution air 111
same as same as
above above
Gas Temperature Chemical Composition
°F (163) of Gas
Avg Range Chemical % Volume
2230 (D) 2150-2300 (D) S02
H20
260 02
Others
1 case after
dilution air 260
600 260-700 same as
(N3.N5) above
17.2
neg
0.9
81.9
same as
above
(D) Before dilution air
-------
TABLE XXXIX
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-COPPER CONVERTER
(Continued)
Numbers in parentheses are references
K3
co
o
Grain Loadings
Control Point Avg Range
Control Point No. 1 5.2 gr/SCF Not
(After converter, (238) Reported
before joining other
gases)
After Electrostatic
Precipitator 1.22 gr/SCF Not
(42, 29«, N4) Exported
% Weight Analysis
of Chemicals
Chemical 7. Weight
Cu
Zn
S (as sulfide
and sulfate)
As (203)
Sb (203)
Pb (203)
Inerts
Same as
above
1.2
18
10
tr
tr
tr
70.8
Same
(238)
(238)
(238)
(N5)
(N5)
(N5)
(N5)
as
above
Typical Size
Profile Chemical
Size % Weight Composition
<1 u 90% CuO
>1 p 10% CuS
(43) ZnO
As203
Sb20,
PbO
Inert
Sulfides
and
Sulfates
(203)
(N5)
(203)
(203)
(203)
(203)
(203)
<1 v 95.7% Same as above
>1 u 4.3%
(42, 298, N4)
-------
TABLE XXXIX
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-COPPER CONVERTER
(Continued)
Numbers j.n parentheses are references
Flow Rate Gas Temperature Chemical Composition
Control Point 1000 SCFM °F . of Gas
ro
Co
Control Point No, 2A
(After reverberatory
and converter gases
are joined,
before stack)
For smelters that
do not roast ore
Avg
91.3 (D)
(163)
Range Avg
3.19-144.6 (D) 338 (163)
(163)
Range
300-350
(163)
Chemical
SO 2
H2°
°2
Others
% Volume
1.4
NR
NR
NR
* *
After electrostatic 268 226-323 same as same as same as same as
Precipitator (163) (163) above above above above
(D) Before dilution air
Includes dilution air
-------
TABLE XXXIX
10
CO
10
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-COPPER CONVERTER
(Continued)
Numbers in parentheses are references
Control Point
Control Point Ho. 2A
(After reverberatory and
converter gases are
joined, before the
stack)
For smelters that do
not roast ore
After Electrostatic
Precipitator
7. Weight Analysis
Grain Loadings of Chemicals
Avg Range Chemical % Weight
1.3 gr/SCF .9-1.9 gr/SCF Cu
(N4) (N4) Fe
S
As
Sb
Pb
Zn
Sn
Cd
Ni
Mn
Se
Inerts
0.5 gr/SCF .005-. 10 same as
(163, N4) gr/SCF above
(163, N4)
3 (N4)
tr (N4)
12 (N4)
23 (N4)
12 (N4)
tr (N4)
10 (N4)
tr (N4)
tr (N4)
tr (N4)
tr (N4)
tr (N4)
40 (N4)
same as
above
Typical Size
Profile
Size % Weight
>40 v
20-40 11
10-20 y
5-10 u
2-5 u
1-2 p
<1 p
>40 p
20-40 p
10-20 u
5-10 p
2-5 p
1-2 v
<1 v.
1
1
2
14
18
16
48
(N4)
1
neg
neg
8
11
10
70
(42, 298, N4)
Chemical
Composition
CuO
CuS
CuS04
Fe304
Sb20o
PbO
ZnO
SnO,
CdO
NiO
MnO,
SeO
Others
same as
(203)
(N5)
(N5)
(N5)
(203)
(203)
(203)
(203)
(N5)
(N5)
(N5)
(N5)
(N5)
above
-------
TABLE XXXIX
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-COPPER CONVERTER
(Continued)
Numbers in parentheses are references
„ . ... i T, . „
Control Point
Avg
Flow Rate
1000 SCFM
Range
Gas Temperature
°F
Avg Range
Chemical Composition
of Gas
Chemical % Volume
Control Point No, 2B
(After revefberatory
and converter gases
are joined before
the stack)
368
(163)
only one
plant
350
(N4)
only one
plant
SO 2
H20
°2
Others
2.0
NR
NR
NR
(163)
KJ
w
&J
For smelter using
roasted ore
After Electrostatic same as
Precipltator above
same as
above
same as
above
same as
above
same as
above
same as
above
-------
IO
TABLE XXXIX
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-COPPER CONVERTER
(Concluded)
Numbers in parentheses are references
Control Point
Control Point No. 2B
(After reverberatory
and converter gases
are joined
before stack)
For smelter using
roasted ore
After Electrostatic
Precipitator.
% Weight Analysis
Grain Loadings of Chemicals
Avg Range Chemical % Weight
3.2 gr/SCF only one Cu
(H4) plant Fe
S
As
Sb
Pb
Zn
Sn
Cd
Ni
Mn
.Se
Inerts
.13 gr/SCF only one same as
(163, N4) plant above
2 (N4)
tr (N4)
9 (N4)
tr (N4)
tr (N4)
tr (N4)
18 (N4)
tr (N4)
tr (N4)
tr (N4)
tr (N4)
tr (N4)
71 (N4)
same as
above
Typical Size
Profile
Size 7. Weight
>40 y
20-40 y
10-20 y
5-10 y
2-5 y
1-2 y
<1 i
>40 y
20-40 y
10-20 y
5-10 y
2-5 y
1-2 y
<1 I
.5 (N4)
.5 (N4)
1 (S4)
3 (N4)
4 (N4)
6 (N4)
85 014)
neg
neg
neg
1
2
3
94
Chemical
Composition
CuO
CuS
CuS04
Fe3°4
As 20,
Sb20,
PbO
ZnO
Sn02
CdO
NiO
Mn02
SeO
Others
same as
(203)
(N5)
(N5)
(N5)
(203)
(203)
(203)
(203)
(N5)
(N5)
(N5)
(N5)
(N5)
above
(42, 298, N4)
-------
The same report also indicates the copper content of the matte used
in five unspecified U.S. smelters has a range of 21.5 to 59% by weight
with an average of 36%. These data were combined to yield the values
for the three major materials shown in the table.
References 173 and 203 each give percent by weight analyses of
the trace elements in blister copper, the basic product of the converter.
It is obvious that the input material to the converter must have
contained trace elements at least in the amounts shown for the converter
product. Data from the two references were averaged and then increased
slightly as an estimate of input content of the trace materials.
Reference 238 states that the amount of silica added as flux is quite
variable, depending on the composition of the matte and the product
desired.
5.3.2.2 Effluent Immediately After the Converter. Data on the
flow rates, temperatures and gas composition for converter exhaust
gases were taken from Reference 163, while the basic data on the
particulate grain loading was taken from Reference 238. Particle
sizes were assumed to be similar to that of a typical metal fume as
shown in Reference 43 for the basic oxygen furnace. Particle sizes
arid grain loading after the electrostatic precipitator were computed
from information contained in References 42 and 298. The penetration
for particles less than Ijj. in size was estimated to be 25% and for
particles greater than I|JL in size 10%.
235
-------
5 ,3.2.3 Effluent After Converter Gases__ie>sfa Gase§ fKOjOt
Reverberatory Furnaces Using Uriroasted Ores, Coattfol p0int number;
described in Table XXXIX shows the properties for the case where
converter gases are joined with reverberatory furnace gases in
m
using unroasted ore concentrates. The flow rates and temperaturei
shown are based on data in reference 163 for four shelters usingi tlis;i
process. Converter flow was prorated for the number of hours> for
slag and finish blows and the number of converters operational at the
smelter.
Grain loadings were computed by a proportional combination of
grain loadings for the converter effluent and reverberatory @ffItieMt <
with the dilution air included. In like manner the percent ,t(feigh%
i<
analysis and the size profile are proportional combinations of the
two input feeds.
Grain loadings after passage through the electrostatic
precipitator were based on stack effluent data given in Reference 163,
for the four smelters. Computations of the particle size distribution
were based on collection efficiencies given in References; 42 and 29$.
5,3.2.4 Effluent After Converter Gases Jojn Gas es^ from
Reverberatory Furnaces Using Roasted Oreg> Control point number 2B
shown in Table XXXIX shows the properties for:the case wfcere
«
gases are^joined with reverberatory furnace gases in sm;e;lter,s
«fe- •
roasted ore concentrates* The flow rate shown is taken 4ifectly><
Reference 163 for the one U.S. smelter using this procedure. The gas
236
-------
temperature was calculated by a proportional combination of the
reverberator/ gases, the converter gases and the dilution air at
ambient temperature. Grain loadings, particle size distribution
and weight analysis were computed in the same way as above for
control point 2A.
Data shown for the effluent after the electrostatic precipitator
were computed from data shown in the same references as for control
point 2A.
5 .4 Lead Blast Furnace
5.4.1 Process Description
The blast furnace is used to reduce the lead oxide in sinter
to metallic lead. The charge to the furnace contains coke and
coarsely crushed sinter. Some flux may also be added. When the
desired proportions of the feed materials have been weighed, they
are simultaneously fed into the furnaces in batches at whatever rate
is necessary to keep the furnace full of charge.
The tuyeres positioned on the sides of the furnaces, blow air
upward through the charge. The coke is converted to CO which acts
as the reducing agent for the sinter. Slag and matte are produced
and collected on the hearth or crucible which is at the bottom of
the furnace, These liquids are allowed to flow continuously from
the furnace. From here they pass into a settler, external to the
furnace, where they are separated and siphoned off. The dust and
fume§ produced are collected at the top of the furnace and exhausted
237
-------
to gas cleaning devices. Figure 38 shows a sketch of a typical lead
blast furnace.
5.4.2 Chemical and Physical Properties of Input Feed and Effluents
Emission characteristics at two control points have been compiled
for blast furnaces used for lead smelting. One of these control points
is when the charge is fed into the furance and the other is when the
finished metal is leaving the furance. Table XL presents the
emission data.
Virtually all of the emissions resulting from charging the furnace,
are large pieces of sinter greater than 5 centimeters in size. No
gases are emitted and only a trace of particles smaller than 5
centimeters has been found. Other dust emissions do occur from
handling the feed materials, but investigation of these emissions
was not included in the scope of this study. The chemical composition
reported for emission resulting from charging the blast furnace
included oxides of arsenic, cadmium, and selenium. Although, other
references do not show these chemicals in the % weight analysis of
the emissions, MITRE included traces of these three chemicals as
well as fluorine in the % weight analysis.
A chemical weight analysis was not available for emissions
resulting from the discharging of the finished lead, but the chemical
composition of the emissions is known and is very similar to the
composition from the feed input emissions. Only FeS and Pb»0. have
been added to the list. All the particulates released are less than
238
-------
CHARGE
., OFF SAS
SLAG
METALLIC LEAD
SETTLER TANK
TUYERES
BASIC DIMENSIONS OF BLAST FURNACE
OUTSIDE WIDTH
LENGTH
HEIGHT
10.5 ft.
28 ft.
18 ft.
CAPACITY 755 TONS/DAY CONTINUOUS OPERATION
FIGURE 38
LEAD BLAST FURNACE
-------
TABLE XL
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-LEAD BLAST FURNACE
Numbers in parentheses are references
Control Point
Flow Rate
1000 SCFM
Avg Range
Input Feed
Gas Temperature
OF
Ayg Range
Chemical Composition
of Gas
Chemical % Volume
Air
100
ro
ji.
o
-------
Numbers in parentheses are references
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-LEAD BLAST FURNACE
(Continued)
IO
*>.
T. Grain Loadings
Control Point , _B
AVE Range
Input Feed 755 Tons/ date from
day one plant
equivalent only
to
660 gr/SCF
of furnace
air flow
(247)
% Weight Analysis
of Chemicals
Chemical 7. Weight
Coke
SiO,
Fe Z
CaO
MgO
Zn
S
Pb
Cu
As
Cd
F
Se
Others
10
10
12
9
1
5
1
45
tr
tr
tr
tr
tr
7
(247)
(247)
(247)
(247)
(247)
(247)
(247)
(247)
(247)
(S5)
(N5)
(N5)
(N5)
(N5)
Typical Size
Profile Chemical
Size % Weight Composition
>5 cm 100 (266) Coke
<5 cm tr (266) Si02
FeO
ZnO
PbO
CuO
As203
CdO
SeO
(247)
(247)
(174)
(174)
(174)
(N5)
(174)
(174)
(174)
Data shown in this table are for the actual input feed material.
Emissions from material handling during input are not addressed.
-------
TABLE XL
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-LEAD BLAST FURNACE
(Continued)
Numbers in parentheses are references
Control Point
Flow Rate
1000 SCFM
Avg Range
Gas Temperature
°F
Avg Range
Chemical Composition
of Gas
Chemical % Volume
NJ
*.
ISJ
Control Point No. 1
(After blast furnace,
before cooler and
conditioner and
joining other gases)
17.9 (163) 8.5-26.2 (163) 358° (163) 300-450°(163) S02
H20
02
Others
0.07
nil
4.8
95.13
-------
to
4V
U
TABLE XL
SELEC5EEB CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-LEAD BLAST FURNACE
1 (Concluded)'
Numbers in parentheses .are references
Control Point ", Srain Loadl?is
. : . AVE . Range
Control -Point No. 1 8,5 gr/SCF 1-11 gr/SCF
(After blast furnace, (163) (43)
before cooler and
- conditioner and
joining other gases)'
% Weight Analysis
of Chemicals
Chemical '% Weight
Coke dust
SiO,
Zn
Pb
Cu
As
Cd
F
Se
N.R,
N.R.
N.R.
N.R.
tr
tr
tr
tr
tr
(N5)
(N5)
(NS)
(N5)
(N5)
Typical Size
Profile Chemical
Size 7. Weight . . Composition
< .,3 u 100 (43) PbO
Pb3o4
ZnO
CdO
Coke
PbS
Fed
CuO
SeO
SiO,
A.J,
(43)
(43)
(174)
(174)
(43)
(43)
(174)
(N5)
(174)
(247)
(174)
-------
0.3 microns and are thus in the fine particulate category.
5.5 Steelmaking Furnaces
Figure 39 depicts the basic operational flow in the
iron and steel industry
5.5.1 Open Hearth Furnaces
5.5.1.1 Process Description
5.5.1.1.1 With Oxygen Lance. In the open hearth process
the charge is melted in a shallow rectangular basin or hearth enclosed
by walls and roof constructed of refractory brick. Fuel is burned
at one end with the flame traveling the length of the furnace. Brick
structures for absorbing heat from the hot gases extend out from both
sides of the furnace. These units are called checkers and contain
a large number of passageways for the hot gases. In some cases, the
gases leaving the checkerwork pass to a waste heat boiler for further
extraction of heat. An illustration of an open hearth furnace appears
in Figure 40.
The raw materials used in this process are scrap iron, scrap
steel, pig iron, and sometimes limestone. During the melting period,
the direction of the flame is reversed every 15 or 20 minutes. This
is possible because all the elements of the combustion system burners,
checkwork, and flues are duplicated at each end of the furnace. When
the charge has melted, molten pig iron is added by pouring it through
a spout in the furnace door. This is followed by the ore and lime boil,
which is caused by the oxidized gases rising to the surface of the
melt. The ore boil is a gentle boiling action caused by the generation
of carbon monoxide. When carbon dioxide is released by the calcination
244
-------
Wl
i
i
RR
CAR
1*
.IMESTONE
INS
1
J
*
*
i-
LUMP
ORE
1 1 -
*
COKE
PILE
-*+ v + *«-
BLAST **
FURNACE
1
** *+ 1
COKE
BREEZE
ORE RR
FINES CAR
»1« * 1
H«
SINTER
MACHINE
y.
_fc SCREEN AND RR
COOLER CAR
* 1 1 •
~\*
#
t*
COKE
FINEE
EEN
t*
•X-
GRINDER
t
•* M
#•* M
S
BY-PRODUCT
RECOVERY
t
QUENCHING
TOWER
. * COKE **
* OVEN
t*
SCRAP
PILE
A*
^*
1 %
•Jf-*
OPEN
HEARTH
FURNACE
** **
BASIC : ELECTRIC
OXYGEN ARC
FURNACE , FURNACE
1 1 1
> FROM THE MINE SITE
*
4,
SOAKING
PITS
^
* COAL f * RR
PILE ' ; CAR
INOR EMISSION POINT
AJOR EMISSION POINT
OURCE: MRI
*"*
^
PICKLING
*+ i*
FURTHER
PROCESSING
FIGURE 39
BASIC OPERATIONS-IRON & STEEL INDUSTRY
-------
CHARGING PORTS
OXYGEN LANCE
MOLTEN METAL
TAP-HOLE
.KJ
^REVERSIBLE
GAS EXHAUST
FIGURE 40
OPEN HEARTH FURNACE WITH OXYGEN LANCING
-------
of the limestone, a more turbulent boil, called lime boil, results.
Oxygen lances which extend through the roof of the furnace are
used to inject gaseous oxygen into the bath. This speeds the
oxidation reactions and shortens the heat time. Typical heat time
for an open hearth furnace with an oxygen lance is 8 hours. These
lances are frequently used throughout the heat with the exception
of the charging and hot-metal-addition periods. When the heat has
been completed, the tap-hole is opened and the molten steel drains
into ladles.
5.5.1.1.2 Without Oxygen Lance. An open hearth furnace
without oxygen lance is identical to the one with an oxygen lance
sketched in Figure 40, except that the lance in the roof is not
present. The operation minus the oxygen lancing stage is the same
as that described above for open hearth furnaces with oxygen lance.
The only major difference is that it takes about 4 hours longer
(or a total of 12 hours) to complete one heat when not using an oxygen
lance.
5.5.1.2 Chemical and Physical Characteristics of Input Feed
and Effluents
5.5.1.2.1 With Oxygen Lancing. Little difference exists
between the characteristics of emissions from input feed at the open
hearth furnace regardless of whether or not oxygen lance is used.
Table XLI presents the data for the process with lancing. The
additional oxygen only accounts for 2% of the total gas. Grain loadings
247
-------
Numbers in parenthesis are references
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED AND EFFLUENTS-
OPEN HEARTH STEEL FURNACE WITH OXYGEN LANCE
Ni
•b.
00
FLOW RATE GAS TEMPERATURE CHEMICAL COMPOSITION GRAIN LOADINGS % WEIGH! ANALYSIS TYPICAL SIZE CHEMICAL
CONTROL POINT 1000 SCFM °F OF GAS OF CHEMICALS* PROFILE COMPOSITION
Avg. Range Avg. Range Chemical % Volume Avg. Range Chemical %Weight Size ^Weight
Input feed 64 (N5) 45-200 100 80-150 CO neg
(N5) (N5) (N5) CO neg
0 20
1C 73
0.6 rate of SO DRY neg
oxygen NOX AIR neg
injection OtfiersJ 1
(239) HO (Steam) 4
0, (Lance) 2
2.
(N5) Does not apply CaCO 6 (57,65) Liquid or
(N5) Fe 0 3 (57,65) Large Pieces 100 (183) CaCO
(65) Fe I Dust NEG (183) Fe 0^
(65) Zn Fe
(N5) Mn SCRAP Zn
(N5) Cu STEEL Mn
(65) Pb AND 35(65) Cu
(65) Ni FERRO Pb
(65) Cr ALLOY Ni
Others] Cr
Fe
Zn
Mn
Cu
Ni
Cr
Pb
Sn
Ba
V
F
Others .
Pb
Sn
Ba
V
52(65) SiF2
MOLTEN
IRON
Fuel Oil- 4 (65)
(65)
(65)
(65)
(N5)
(N5)
(N5)
(N5)
(N5)
(N5)
(N5)
(N5)
(N5)
(N5)
(N5)
This is a typical example. Many other mixtures are possible.
-------
TABLE XLI
Numbers in__parenthesis are references
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED AND EFFLUENTS-
OPEN HEARTH STEEL FURNACE WITH OXYGEN LANCE
(Concluded)
>0
CONTROL POINT
(After furnace) .
After Electro-
static Preci-
pitator
FLOW RATE GAS TEMPERATURE CHEMICAL COMPOSITION
1000 SCFM °F OF GAS
• Avg. Range Avg,. Range Chemical % Volume
64(65) 45-200 Not 400-2000 CO neg
(43) Reported (43) CO 8-9
0 j 8-9
N, Balance
SO tr
NO* tr
F * tr
H,0 12
L
64(N5) 45-200 450 300-600 Same as abov.e
(N5) (N5) (N5)
(N5)
(43)
(43)
(43)
(43)
(43)
(43)
(57)
GRAIN LOADINGS
AVg. Range
1.9 at
hot 0.1-2.5
metal
addition (214)
2.7 at lime
boil
<5 at lancing
6.21 at
refining
(65)
.029 at hot metal
addition
% WEIGHT ANALYSIS TYPICAL SIZE CHEMICAL
OF CHEMICALS PROFILE COMPOSITION
Chemical %W,eight Size %Weight
Fe 0
FeV
SiO
Al 0
CaS 3
MgO
MnO
CuO
ZnO
P9°^
cl 5
Ni
Pb
Sn
Ba
V
88.8(65) >40
2.5 (65.) 20-40
0.90(65) iO-20
0.60(65) 5-10
0.96(65) 2-5
0.39(65) <2
0.62(65)
0,14(65)
0.72(65)
0.83(65)
tr (N5)
tr (N5)
tr (N5)
tr (N5)
tr (N5)
tr (N5)
Same as
above
7 Fe 0
8 Fe 0J
17 SiO
22 Al 6
26 Ca'V
20 Mg 0
(239) Mn 0
Cu 0
Zn 0
P, 0
Cr 0^
Ni 0
Pb 0
Sn 0
Ba 0
V2°5
(65)
(65)
(65)
(65)
(65)
(65)
(65)
(65)
(65)
(65)
(N5)
(N5)
(N5)
(N5)
(S5)
(N5)
Same as
above
.041 at lime boil
.075 at lancing
.003 at refining
<239)
-------
are not applicable because the input feed is a combination of molten
metal and large pieces of scrap steel.
During the feeding MITRE estimates that the metals which are
present in the molten metal will be given off as fumes. Although,
they probably form oxides quickly, they would be emitted as metals.
When the fumes are released from the furnace, oxides of these metals
are present. Ferric oxide makes up most of the weight of the
particulate emissions. After passing through an electrostatic
precipitator, the emission stream shows the same chemical composition
and chemical distributions. However, the grain loadings show a
significant decline driving each of the four process steps, hot
metal addition, lime boil, lancing and refining.
The flow rate after the electrostatic precipitator was estimated
to be the same as before the precipitator, because there are no
conditions present which would cause a change in this factor. The
gas temperature range is lowered before reaching the precipitator.
The extremes of the range were averaged in order to come up with a
value for the average gas temperature.
5.5.1.2.2 Without Oxygen Lancing. Approximately 74% of
the dry air escaping from the input feed point of the open hearth
furnace without the oxygen lancing operation is nitrogen. The only
other chemical present to any significant degree is oxygen.
For particulates, the chemical analysis by weight can vary from
plant to plant and depending on the desired output, so only a typical
250
-------
example has been shown. For this example, 46% of the input is scrap
steel and 48% is estimated to be molten iron with the remainder being
fuel oil. Emissions resulting from the charging of these materials
are either liquid or large pieces and a negligible amount of dust.
The factors shown in Table XLII are for emissions resulting
after the furnace operation. Again the major component of the gas
emitted is nitrogen. The metals which are present in the particulate
emissions include iron, zinc, chromium, nickel, lead, tin, copper,
maganese, barium, and vanadium. All of these are found in the form
of oxides. The same is true of the emissions which occur after an
electrostatic precipitator. The only characteristics which do differ
are the grain loadings which radically decrease and the temperature
which must be lowered before the gases can be sent through the
precipitator.
5.5.2 Basic Oxygen Steel-Making Furnace
5.5.2.1 Process Description. The basic oxygen furnace (EOF)
is a pear-shaped vessel with an opening at the top and a capacity of
about 200 tons. A typical EOF has been sketched in Figure 41.
Making steel in this type of furnace is a batch operation taking
about 55 minutes.
Scrap is loaded first and then molten iron is added. Oxygen
is blown into the vessel by a water-cooled lance thrust vertically
down into the vessel and held slightly above the surface of the bath.
The oxygen is blown onto the surface at high velocity, resulting in
251
-------
TABLE XLII
Numbers in parenthesis are references
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED AND EFFLUENTS-
OPEN HEARTH STEEL FURNACE WITHOUT OXYGEN LANCE
to
Cn
to
FLOW RATE GAS TEMPERATURE CHEMICAL COMPOSITION GRAIN LOADINGS % WEIGHT ANALYSIS TYPICAL SIZE CHEMICAL
CONTROL POINT 1000 SCFM °F OF GAS OF CHEMICALS* PROFILE COMPOSITION
Avg. Range Avg. Range Chemical 7« Volume Avg. Range Chemical ^Weight Size %Weight
Input feed Not 25-100 100 80-150 CO neg
Reported (N5) (N5) (N5) CO neg
0 20
N2 DRY -j^
SO AIR neg
NO neg
n-K !
Others
HO (Steam) 5
*
(N5) Does not apply CaCO 6(65) Liquid or
(N5) Fe,°, ?(65) Large Pieces 100(183) CaCO (65)
(65) Fe Dust NEG(183) Fe^^S)
(65) Zn I SCRAP Fe (65)
(N5) Mn 1 STEEL Zn (N5)
(N5) Cu AND ^officN Mn (N5>
(65) Pb FERRO •"t-b:i; Cu (N5)
Ni ALLOYS Pb (N5)
Cr Ni (N51
,,t-\ *-*L V"-*/
165 ' OthersJ Cr (N5)
Fe
Zn
Mn
Cu
Ni
Cr
Pb
Sn
Ba
V
F
Others
Pb (N5)
Sn (N5)
Ba (N5)
V (N5)
SiF2 (N5)
48(65)
MOLTEN
IRON
Fuel Oil 6(65)
*This is a typical example. Many other mixtures are possible.
-------
SABLE xtil
Numbers in paren1th.esis are references
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT. FEED AND EFFLUENTS-
OBEN HEARTH STEEL FURNACE WITHOUT 'OXYGEN LANCE
(Concluded)
FLOW SATE GAS TEMPERATURE CHEMICAL COMPOSITION GRAIN LOADINGS
CONTKSL POINT 1000 SCfM °F OF GAS
Avg. Range Avg. Range Chemical %Volume Avg. Range
(After furnace) Not 25-100 1300(214) 460-1800 CO
Reported (43) 500 after (63) H.O
waste heater 0*
boiler (214) CO
N
SO
NOX
FX
6i Aftei? Electro- 25-100 450 300-600 Same
CJ static Preci- (N5) (N5) (N5)
pita tor
neg
12
8-9
8-9
(N5) 0.4(239) 0.1-2.0
(57) (214)
(43)
(43)
Balance (43)
tr
tr
tr
as ab
(43).
(43)
(43)
ove 8.006(239)
% WEIGHT ANALYSIS TYPICAL SIZE CHEMICAL
OF CHEMICALS PROFILE COMPOSITION
Chemical Weight Size %Weight
Fe
Zn
Cr
Ni
Pb
Sn
Cu
Mn.
Ba
V
Others
Same as
56-61
10-15
2
2
: 5
1
0.5
• 0,.5
tr
tr
23-28
above
(57) 1-3
(57) 0.5-1.0
(57) 0.15-0.5
(57) <0.15
(57)
(57)
(57)
(57)
(57)
(57)
(57)
7.3 (183) FeO (43)
28.4 (183) Sio; (43)
49.5 (183) Al.O (43)
14.8 (183) CaO J(43)-
M.nO (43)
P,0 (43)
ZnO (183)
Cr 0 (N5)
NlV(N5)
Pb 0 (N5)
Sn 0 (N5)
Cu 0 (H5)
Ba 0 (N5)
V 0 (N5)
M| 3 (65)
Same as
above
-------
MOLTEN METAL
BATH
HOOD
RETRACTABLE
OXYGEN LANCE
REFRACTORY
LINING
HIGH-PURITY
OXYGEN AT
SUPERSONIC
SPEED
CONVERTER
VESSEL
BASIC DIMENSIONS OF BOF:
OUTSIDE DIAMETER 24 ft.
OUTSIDE HEIGHT 38 ft.
CAPACITY: 200 TONS/BATCH
FIGURE 41
BASIC-OXYGEN STEEL-MAKING FURNACE
254
-------
violent agitation and complete mixing of the oxygen with the molten
pig iron. No external heat is supplied because the heat generated by
the oxidation is sufficient to carry the process to completion and
produce steel. When the heat has been completed, the furnace is
tilted and the steel is poured into a ladle. Gases are drawn off
through a hoo.d over the mouth of the furnace.
5.5.2.2 Chemical and Physical Characteristics of Input Feed
and Effluents. A table was prepared for BOF emissions from two
points: the point at which the raw materials are put into the furnace
and the point at which the product leaves the furnace. (See Table XLIII)..
In this process the input feed consists of scrap steel in large
pieces, a negligible amount of dust, and molten iron. Flux is also
added. The chemical composition of the emission is the same as the
composition of the input feed. A % weight analysis was specified a
little differently in two separate reference sources. One gave the
initial charge as 30% scrap steel and 70% molten iron. The other
specified the charge components in terms of ranges: 22-31% scrap
steel and 69-78% molten iron.
The second table describes the gases and particulates emitted
from the furnace. Majority of the gas emissions is carbon monoxide,
while 90% of the particulate emissions is in the form of ferric
oxide. The ranges of both gas flow rate and temperature are quite
broad, and averages were not available in the literature so MITRE
estimates were made. The flow rate value is simply an average of the
255
-------
TABLE XLIII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED AND EFFLUENTS-
BASIC OXYGEN STEEL FURNACE
Numbers in parenthesis are references
NO
<-n
0»
Control Point Flow Rate Gas Temperature Chemical Composition Grain Loadings % Weight Analysis Typical Size Chemical
1000 SCFM °F of Gas of Chemicals Profile Composition
Avg Range Avg Range Chemical %Volume Avg Range Chemical 7, Weight Size 7. Weight
Initial Charge
Input Feed - - - - — - Does not apply Fe Liquid or
Mn
Zn
Cu
Scrap 30 (270) £«f Pleces
Steel 22-31 (65)
Others
Fe
Mn
Zn
70 (270)
Molten
Cu 1 Iron 69-78 (65)
Others
Flux Charge
Fe2°3
Ca (OH)
100% F£ , .
(N5) l";
Neg. Mn (65)
Zn (65)
Cu (65)
FS2°3 (65)
Ca(OH)2(270)
CaCo3 (270)
•J Tr.,,.i' «K1 a f)-jn\
Ca CO.
-------
TABLE XLIII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED AND EFFLUENTS-
BASIC OXYGEN STEEL FURNACE
(Concluded)
Numbers in parenthesis, are references
Control Point Flow (Rate Gas Temperattt-re Chemical Composition
1000 -gOFM -°F of Gas -
Avg Range Avg Range Chemical %Vbluine ...
Control Point 270(N5) 35-500 700(N5) 560-3000(43) CO 74-90.5(65)
No. 1 (after (43,65,239)
BOF) H20 Neg(N5)
02 Neg(N5)
C02 5-16(65)
N2 3-8 (65)
10
Ui
N|
Grain Loadings % Weight Analysis Typical Size
of Chemicals Profile
Avg Range Chemical Weight Size %Weight
3.59 2.02-4.96 Fe203 90.0(239) l-15(i 15
(65) (65) Mn304 4.4(239) 0.5-1.0 65
FeO 1.5(239) <0.5 20
SiO 1.3(23S) (239)
Ca02 0.4(239)
P205 0.3(239)
A1203 0.2.(239)
C 0.1-0.15(262)
Zn tr-2.2(65)
Cu 0.03(65)
MgO tr (262)
Chemical
Composition
Fe203(239)
Mn304(239)
FeO (239)
Si02(239)
Ca02 (239)
P205(23,9)
A1203 (239)
MgO (65)
CaO(65)
-------
range. The average gas temperature estimate is based on the fact
that some natural cooling in the duct work will occur before the
point at which the control device will be applied.
5.5.3 Electric-Arc Furnace
5.5.3.1 Process Description. Electric-arc furnaces are used
for both the production of common steels and special alloy steels.
The furnace is cylindrical with large carbon electrodes extending
through the roof. Newer vessels are approximately 30 feet in
diameter and have a 200 ton capacity. A sketch of such a furnace
is shown in Figure 42.
The first step is to open the top of the furnace to allow the
charging of scrap into the furnace. The roof is then closed and
electrodes lowered, which form the electric arc that generates the
heat to melt the charge. Oxygen-fuel gas burners may also be used
during the scrap meltdown period. This increases the uniformity of
scrap meltdown and decreases the power consumption. In 1 1/2 to 4
hours the steel is ready. The slag containing the impurities is
either raked or poured off the surface by tilting the furnace. Then
the furnace is tilted to pour the steel into a ladle, from which it
is transferred into molds.
5.5.3.2 Chemical and Physical Properties of the Input Feed
and Effluents. Emission characteristics were compiled for two control
points at electric arc furnaces. Table XL1V gives the characteristics
at the input feed point, and also presents the characteristics where
the product leaves the furnace.
258
-------
INSIDE DIAMETER: 7 TO 30 ft.
CAPACITY: 2 TO 250 TONS/BATCH
ELECTRODES
REFACTORY LINING
MOLTEN METAL
FIGURE 42
ELECTRIC-ARC FURNACE
259
-------
TABLE XLIV
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED AND EFFLUENTS-
ELECTRIC-ARC STEEL FURNACE
IO
Ov
o
jjumbers in parenthesis are referenr_&g
1000 SCFM °F
Avg Range Avg Range
Input feed - - -
Chemical Composition Grain Loadings % Weight Analysis Typical Size Chemical
of Gas of Chemicals Profile Composition
Chemical % Volume Avg Range Chemical % Weight Size % Weight
Does not apply CaCO,
C
Fe203
Fe
Zn
Mn
Cu
Pb
Hi
Cr
Others
Large Pieces 100%(N5) CaCOj (57)
57. (57) Dust Neg.(N5) C (57)
Fe203 (57)
Fe (57)
Zn (57)
Mn (57)
Scrap Cu (57)
Steel 957.(57) Pb (57)
Ni (57)
Cr (57)
C (57)
-------
TABLE XLIV
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED AND EFFLUENTS-
ELECTRIC-ARC STEEL FURNACE
(Concluded)
Numbers in parenthesis are references
Control Point Flow Rate Gas Temperature Chemical Composition Grain Loadings Z Weight Analysis Typical Size
1000 SCFM °F of Gas of Chemical Profile
Avg Range -Avg Range Chemical % Volume Avg Range Chemical Avg Range size Weight
Control Point #1 20.5 10.3-38.4 145 129-172 CO 8-85(43) .42 .35-. 51 FeO
(after electric
arc) (57) (57) (57) (57) HjO Neg (43) (57) (57) Fe203
02 Neg (N5) Cr203
C02 5-15(43) MnO
N2 5-85 (43) NiO
PbO
IO ZnO
o
— • Si02
CaO
MgO
C
4.2(65) 4-10(43) > 40 (j. 4
48(65) 19-53(43,65) 20-40^ 5
4.9(65)
7.1(65,239)
0.9(65)
2.2(65)
5.4(65)
5.4(65,239)
7.8(65,239)
6.5(65,239)
5.0(65,239)
2.3(65)
0-12(43) 10-20fi 5
3-12(43) 5-lOji 22
0-3(43) <5U 64
0-4(43) (57)
0-44(43)
2-9(43)
1-15(43,65)
2-22(43,65)
2-15(43,65)
2-4(43)
Chemical .
Composition
ZnO (239)
CaO(239)
MnO(239)
A1203(239)
Si02(239)
MgO(239)
CuO(239)
P2°5(239)
PbO(65)
NiO(65)
Cr203(65)
Fe203 (65)
Fe 0(65)
C(43)
-------
As in the case of the basic oxygen furnace, no gases are emitted
at the input feed point. Virtually all of the particulate emissions
are large pieces of scrap steel. However, at control point number
one, after the melting process is complete, roughly 64% of the
particulate emissions are less than 5 microns in size. Although,
the percent of ferric oxide present in these emissions is considerably
less than it was in the case of the basic oxygen furnace, it makes
up the largest percentage of the particulate weight analysis. With
the exception of carbon, all the other components of the particulate
emissions are oxides.
5.6 The Chlor-Alkali Industry
5.6.1 Chlorine Manufacture in Mercury Cells
5.6.1.1 Process Description. The mercury all consists of two
basic sections, the electrolyzer and the decomposer. In the electrolyzer,
two layers of liquid flow from one end of the cell to the other. The
lower layer is mercury and acts as the cathode, with a stream of brine
flowing on top of it. The anodes are usually horizontal graphite
plates that hang on insulated rods from the top of the cell. A typical
mercury cell is shown in Figure 43 and a flow diagram of the process
in Figure 44. Purified and nearly saturated brine is fed continuously
into the electrolyzer. Chlorine gas is evolved at the anodes and is
discharged from the electrolyzer to the purification and liquefaction
units. Sodium ions are drawn into the mercury to form an amalgam.
The amalgam flows to a decomposing unit where it reacts with water
262
-------
CHLORINE
ELECTROLIZER
SPENT
BRINE
Fl!D> BRINE
N3
C*
to
WATER
AMALGAM
BASIC DIMENSIONS OF MERCURY CELL:
WIDTH 4.6 TO 6.7 ft.
LENGTH 40.7 TO 66.9 ft.
'CAPACITY: 1.16 TO 1.45 TONS/DAY
FIGURE 43
MERCURY CELL WITH HORIZONTAL DECOMPOSER
-------
KJ
O>
TO VACUUM PUMPS
AND LIQUEFACTION
Cl + AIR
FIGURE 44
FLOW DIAGRAM OF MERCURY CELL CHLOR/ALKALI MANUFACTURE
-------
to yield hydrogen, sodium hydroxide and mercury. These three products
are easily separated since the hydrogen is a gas and the mercury is
immiscible in the water solution of sodium hydroxide.
According to Reference 91, in most mercury-cell plants about
10 to 15 percent of the sodium chloride is decomposed as the brine
passes through the cell. The depleted brine contains chlorine in
solution and must be dechlorinated before recycle. The depleted
brine is first sent to a surge tank for storage and then is pumped
to a reaction tank where it is usually acidified with hydrochloric
acid and reacted with sodium hyppchlorite in the brine. These
reactions form some free chlorine which is vented to the vacuum pumps
and liquefaction unit along with the main chlorine stream. The brine
is then pumped to a stripping unit where it is subjected to vacuum
degassing or is air blown, or both, to remove most of the remaining
chlorine. This gas is either recycled to the mercury cell or passed
through control devices and vented to the atmosphere. After
dechlorination the brine is resaturated and recycled to the mercury
cell.
5.6.1.2 Chemical and Physical Properties of the Input Feed
and Effluent. Table XLV shows the chemical and physical properties
of the input feed and effluent for the mercury cell manufacture of
chlorine. Data shown were taken directly from the literature cited
except as discussed below.
Gas temperatures were estimated based on the average of the
positive inlet temperatures reported in Reference 91. It was estimated
265
-------
TABLE XLV
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-MERCURY CELL CHLOR/ALKALI MANUFACTURE
CONTROL POINT
Input feed
Control Point #1
(After Acidification
of depleted Brine)
After using Alkali
Scrubber
Control Point #2
(After Vacuum Degassing
of Brine)
After using Alkali
Scrubber
Control Point #3
(After Air Blowing
of Brine)
After using Alkali
Scrubber
INPUTS - % WEIGHT
ANALYSIS
CHEMICAL
Nad
H20
Hg
C12
H20
C12
H20
C12
H20
C12
C12
C12
H20
% WEIGHT
26-27 (49)
73-74 (49)
Neg.
100 (49,91)
Neg. (N5)
100 (49,91)
Neg. (N5)
Unk (49,91)
Unk (N5)
Unk (49,91)
Unk (N5)
Unk (49,91)
Unk (N5)
Unk (49,91)
Unk (N5)
GAS TEMPERATURE
AVG.
80 (91, N5)
60(N5)
80 (N5)
60(N5)
80 (N5)
60 (N5)
RANGE
NO
68-100(91,N5)
50-75 (N5)
68-100 (N5)
50-75 (N5)
68-100 (N5)
50-75 (N5)
FLOW RATE
SCFM
AVG.
INPUT GAS
. 81(49, N4)
. 02(24, N4)
. 64(49, N4)*
Unk (N5)
. 02(24, N4)»
Unk (N5)
. 27(49, N4)*
Unk (N5)
. 008(24, N4)
Unk (N5)
RANGE
.01-3. 2(49, N4)
-------
in all cases that the alkali scrubber would cause a reduction in gas
temperature of about 20°F. This is an annual average and would be
highly dependent on the conditions under which the alkali scrubber
solution is stored prior to use. These conditions are most likely
to vary with the geographical location and the season of the year.
The flow rates for the various control points indicated were
calculated from information on emissions and liquid flows contained
in References 49 and 91. Each of these calculations will be discussed
be low.
Acidification stage - According to Reference 49 the acidification
stage reduces the Cl_ content in the depleted brine from an average
of 0.55 gm per liter to 0.3 gm per liter. Thus 0.25 gm per liter of
Chlorine is released. Reference 91 gives the liquid flow rates for
the acidification stage in mercury cell plants as a range from 2 to
600 gal. per minute. The average of the data is 156 gal. per minute.
The combination of the data from these two references yields chlorine
emissions which average 10 gm per minute and range from .13 to 39
gfi per minute. Conversion of these emissions to volumes using
Avagadro's law yields an average flow rate of the chlorine gas of
.81 SCFM. The range becomes .01 to 3.2 SCFM. The flow shown for
after the alkali scrubber was based on a scrubber efficiency of 97%
given in Reference 24»
Vacuum degassing of brine - Reference 49 also gives the chlorine
Content of the liquid flow before and after vacuum degassing. These
267
-------
data are 0.3 gm per liter and 0.1 gm per liter respectively resulting
in a chlorine release of 0.2 gm per liter during degassing. Calculations
performed in the same manner as for the acidification stage yield an
average chlorine flow rate of .64 SCFM and a range of .006 to 2,56 SCFM.
These flows are for the chlorine gas only and do not include any air
or water vapor in the system. The scrubber efficiency is the same as
used above.
Air blowing of brine - The chlorine contents of the brine before
and after air blowing are 0.3 gm per liter and 0.1 gm per liter. This
results in emissions of 0.2 gm Cl? per liter of depleted brine. These
emissions would yield an average flow rate for the chlorine gas of .27
SCFM and a range of .003 to 1.02 SCFM. As stated previously, these
flows do not include any dilution air or water vapor. The scrubber
efficiency was the same as in previous stages.
5.6.2 Chlorine Manufacture in Diaphragm Cells
5.6.2.1 Process Description. An illustration of one kind of
diaphragm cell, the Hooker cell, appears as Figure 45. The cell
consists of essentially three parts, an anode compartment, a cathode
compartment, and an asbestos diaphragm separating the two. The anode
section consists of an assembly of closely spaced graphite blades cast
in lead. Extending through the side of the bottom are copper bus
bars to conduct current into the lead. The cathode compartment is
constructed of a steel plate with fingers of wire screen coated with
an asbestos diaphragm. Hot, purified, saturated brine is fed continuously
268
-------
KJ
o-
XD
CONCRETE
CELL TOP
ANOLYTE (BRINE)
CHLORINE
OUTLET
HYDROGEN
OUTLET
CATHODE
BUS BAR A_
A
GRAPHITE ANODE
CONCRETE
CELL BOTTOM
LEAD POUR
JOINING ANODES
ASBESTOS-COVERED
CATHODE FINGER
OUTSIDE WIDTH
OUTSIDE LENGTH
OUTSIDE HEIGHT
5.84 ft.
6.70 ft.
6.57 ft.
BRINE INLET
(ORIFICE FEED)
MANOMETER
CATHODE
FRAME
CELL LIQUOR
OUTLET
A
MASTIC SEALER
7AND INSULATOR
ANODE BUS BAR
BASIC DIMENSIONS OF DIAPHRAGM CELL
CAPACITY: 0.3 TO 1.0 TON/DAY
FIGURE 45
HOOKER DIAPHRAGM CELL
-------
into the anode compartment and is in direct contact with graphite
anodes. When electric current is applied, chlorine is produced at
the positively charged anode, leaving the cell saturated with water
vapor. The dissolved sodium ions are attracted to the negatively
charged cathode. Here the caustic soda and the hydrogen gas are
produced. The porous diaphragm allows the ions to pass through by
electrical migration, but reduces diffusion of products from one
compartment to the other. From the cathode compartment the liquor
goes to evaporators where the excess salt precipitates out. The
salt is then filtered, washed, and returned as a slurry to the brine
system. The diaphragm cell produces a lower grade caustic than the
mercury cell does, so in some cases the caustic must be concentrated
and purified before being used. A flow diagram of the basic operations
in the diaphragm cell chlor-alkali process is shown in Figure 46.
5.6.2.2 Chemical and Physical Properties of Input Feed and
Effluents. The feed to a diaphragm cell consists only of brine, no
gases. The composition of the brine is 26 to 27 percent sodium chlorine
and the rest water. The charging of this fuel does not cause any
particulate or gaseous emissions. Gases are emitted after the vacuum
distillation of the caustic solution, but information on the
characteristics was not reported in the literature. MITRE estimated
the range of temperatures to be 68 to 100°F with an average temperature
of 80°F. This estimate is based on data reported for the mercury
cell in Reference 91 and converted from centigrade to Fahrenheit.
270
-------
ro
N
MINOR EMISSION POINT
MAJOR EMISSION POINT
RECOVERED BRINE
HOT CAUSTIC
CAUSTIC
STORAGE
TANK
ATMOSPHERE
f**
VACUUM
EVAPORATOR
^
SALT
SEPARATOR
LIQ1
JOR
T
r
COOLER
±
BLEACH
SOURCE: ENGINEERING SCIENCE, INC.
FIGURE 46
BASIC OPERATIONS-DIAPHRAGM CELL CHLOR-ALKALI
-------
No attempts were made to estimate the flow rate or chemical composition
of the emissions. The complete data set is shown in Table XLVT.
5.6.3 Chlorine Liquefaction
5.6.3.1 Process Description. The chlorine gas produced by both
the diaphragm cell and the mercury cell is liquefied in the same way.
First the gas is cooled by direct contact with water packed in a tower,
and then it is dried with sulfuric acid. Finally, the gas is compressed,
passed through a demister and liquefied. This is all done at the same
location as where the gas is produced. A typical plant produces a total
of between 100 and 200 tons of chlorine per day-
5.6.3.2 Chemical and Physical Properties of Input Feed and
Effluent. Table XLVII shows the chemical and physical properties
of the input feed and effluent from chlorine liquefaction when the
chlorine gas comes from the mercury cell and when it comes from the
diaphragm cell. Because the liquefaction process emits only gases,
this table does not have columns for particulate emission characteristics,
The main sources of data for this table are References 49 and 91.
When the input feed is from a mercury cell the gas emissions were
reported to have an average temperature of 90°F. Flow rates were
not found in the literature, so they were computed based on the output
flow rates and the percent of flow reduction resulting from a scrubber.
The average percentage of reduction based on data from diaphragm cells,
was 18.6 percent. Consequently, the outflow scrubber flow rates were
divided by 81.4 percent to obtain the flow rates for the input feed.
272
-------
TABLE XLVI
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-DIAPHRAGM CELL CHLOR/ALKALI MANUFACTURE
CONTROL POINT
Input feed
Control Point #1
(After Vacuum
Distillation of
Caustic Solution)
INPUTS 7, WEIGHT
ANALYSIS
CHEMICAL
NaCl
H20
% WEIGHT
26-27(49)
73-74(49)
GAS TEMPERATURE
°F
AVG.
80 (N5)
RANGE
68-100 (N5)
FLOW RATE
AVG.
- NO INPU
N.R*
RANGE
T GAS -
N.R.*
CHEMICAL COMPOSITION
CHEMICAL
C12
H-0
% VOLUME
N.R.*
N.R.*
CJ
*N.R. = Not Reported
-------
TABLE XLVII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENT-CHLORINE LIQUEFACTION
CONTROL POINT
Input from
Mercury Cell
After Caustic
or Lime
Scrubber
Input from
Diaphragm Cell
After Caustic or
Lime Scrubber
GAS TEMPERATURE
°F
AVG.
90° (91)
86° (91)
20° (91)
*
60°(91)
RANGE
14 - 212° (91)
77-104° (91)
68°- 104° (91)
-76° to 95°(91)
14° to 90° (91)
FLOW RATE
SCFM
AVG.
489 (N4)
398(91)
306 (N4)
249 (91)
RANGE
456-4140(91)
147-737 (N4)
120-600(91)
10-1324 (N4)
8-1078(91)
CHEMICAL COMPOSITION
CHEMICAL % VOLUME
C12
CO 2
CO
H20
ci2
C02
CO
C12
CO 2
N
02
H2
CO
C12
C02
N2
02
H2
CO
20-50 (49)
15 (91)
0.4 (91)
Balance (N5)
0.0001 (49)
Balance (49)
96.3 }
1.6
1.3 (49)
0.7
0.1
0.02J
0.0001 (49)
43 }
35
19 (N4)*
2.5
.5
*0n a dry basis.
-------
The gas emitted is composed of chlorine, carbon dioxide, and carbon
monoxide. The balance of the emissions has been estimated to be
water vapor. This determination was based on the fact that this is
a wet process. After having passed through a caustic or lime scrubber,
the average gas temperature decreased slightly and the range of
temperatures narrowed. The average flow rate after a scrubber is 398
standard cubic feet* Reference 49, indicates that the percent volume
of chlorine gas drops to a mere 0.0001 percent of the total volume
after the scrubber with the rest of the volume being composed of
carbon monoxide, carbon dioxide, and water vapor.
The temperature of the gas emitted when the input feed comes
from a diaphragm cell has been reported to be as low as -76°F with the
average value being 20°F. The flow was given in the literature for
four measurements taken at one plant. These values were used to
compute the percent the flow decreases after the gas passes through
a scrubber. The average decrease based on these four measurements
was 18.4%. Using this fact and the after scrubber flow rates for
other diaphragm cells, flow rates were computed for emissions
before the scrubber. The range of these values was large 10 to 1324
standard cubic feet per minute, with the average being 306 standard
cubic feet per minute. The chemical composition broken down by
percent volume by given in Reference 49 and showed that 96.3 percent
of the total volume was chlorine gas. After going through a caustic
or lime scrubber this percentage had dropped to only 0.0001. The rest
275
-------
of the volume was estimated to have the same distribution among the
other gases present, as it had before the scrubber. Average temperature
after the scrubber was 60°F, with a narrower range of temperature.
The flow rates were reported in Reference 91 and served as the basis
for computing the flow rates before the scrubber as explained above.
5.6.4 Hydrochloric Acid Manufacture
5.6.4.1 Process Description. According to Reference 310 commercial
hydrochloric acid is manufactured by one of the following four major
processes,
o Byproduct of the chlorination of both aromatic and aliphatic
hydrocarbons.
o The reaction of sodium chloride and sulfuric acid or niter
cake (sodium bisulfate).
o Direct combustion of hydrogen and chlorine.
o The Hargreaves process which combines sodium chloride, sulfur
dioxide, oxygen and water to form sodium sulfate and hydrogen
chloride.
The byproduct method accounts for about three-fourths of the acid
commercially produced. The salt/sulfuric acid process and the direct
combustion process each account for almost half of the remainder. The
Hargreaves process is used in only one plant but that one is the
largest single plant in the country.
The basic steps in the production of by-product acid include the
removal of any unchlorinated hydrocarbon from the gas, followed by the
276
-------
absorption of the HC1 in water. In all four major processes the
absorption of gaseous HC1 in water is a principal step. Figure 47
shows a diagram of a typical absorbing unit. Since the chlorination
of hydrocarbons emits large amounts of heat, special equipment is
necessary for control of the temperature of the reaction.
The reactions of the salt-sulfuric acid process are endothermic.
Thus sulfuric acid (or niter cake) and sodium chloride are roasted in
a furnace to form hydrogen chloride and sodium sulfate (salt cake).
A flow diagram of this process is shown in Figure 48. The hot hydrogen
chloride, contaminated with droplets of sulfuric acid and particles of
salt cake, is cooled by passing it through a series of S~shaped coolers,
cooled externally by water.
The cooled gas is then passed upward through a coke tower to
remove suspended foreign materials. Purified hydrogen chloride from
the top of the coke tower is absorbed in water in a tantalum or
Karbate absorber. Finished hydrochloric acid is withdrawn from the
bottom of the absorber, and any undissolved gas passing out the top
of the absorber is scrubbed out with water in a packed tower.
The synthetic or direct combustion process generates hydrogen
chloride by burning chlorine in a few percent excess of hydrogen.
The purity of the ensuing acid is dependent upon the purity of the
hydrogen and chlorine. However, since both of these gases are
available in a very pure state from the electrolytic process for caustic
soda, this synthetic method produces the purest hydrogen chloride of -
*••
277
-------
VENT
COOLING
WATER
FEED
WATER
COOLING
WATER
GAS FLOW
LIQUID FLOW
COOLING WATER
STRONG
ACID
FIGURE 47
DIAGRAM OF A KARBATE ALL-CARBON HYDROCHLORIC ACID COOLER-ABSORBER
(NATIONAL CARBON CO. MODEL)
278
-------
SULFURIC
ACID
SODIUM
CHLORIDE
FURNACE
SALT CAKE
i
\
k
r
COOLING
TOWER
^
r
WATER
ABSORBER
i
r
HYDROCHLORIC
ACID (STRONG)
**MAJOR EMISSION POINT
SOURCE: CHEMICAL PROCESS INDUSTRIES
SCRUBBER
HC1
HYDROCHLORIC
ACID (WEAK)
FIGURE 48
BASIC OPERATIONS-HYDROCHLORIC ACID MANUFACTURE
-------
all the processes. The cooling and absorption are very similar to
that employed in the salt process. Anhydrous hydrogen chloride is
generally manufactured by burning chlorine in water. The aqueous
solution is stripped of hydrogen chloride under slight pressure, giving
strong gaseous hydrogen chloride, which is dehydrated to 99.5% hydrogen
chloride by cooling to 10°F.
In the Hargreaves process the combination of sodium chloride,
sulfur dioxide, oxygen and water produces an aqueous solution of
sodium and gaseous hydrogen chloride. Absorption of the hydrogen
chloride in water is done in the same way as in the other processes. An
advantage of this process is that both products of the reaction, the
hydrochloric acid and the sodium sulfate,are readily marketable.
5.6.4.2 Chemical and Physical Properties of Input Feed and
Effluent. Table XLVIII shows the chemical and physical properties
of the input feed and effluent for a hydrogen chloride water absorption
tower of the Karbate type. For the purpose of calculations it was
assumed that the hydrogen chloride was produced as a byproduct of the
chlorination of benzene to pheyl chloride, a common industrial chemical
procedure. The data shown in the table were taken directly from the
references cited except as discussed below.
The average flow rate for the input gases was calculated from data
contained in Reference 282 which stated that the flow to the absorption
tower was 2300 pounds per hour of HC1 and 867 pounds per hour of other
gases. If the molecular weight of HC1 is taken as 36.5 and the average
280
-------
TABLE XLVIII
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
/AND EFFLUENTS-HYDROCHLORIC ACID MANUFACTURE
CONTROL POINT
Input Gases
•n
Control Point #1
(After Water
Absorption)
After Water
Scrubber
GAS TEMPERATURE
: AVG.
80(282)
72(98)
80(91)
RANGE
' N.R.
50-100(98)
40-180(91)
FLOW RATE
; SCFM
AVG:
540 (N4)
70(N5)
40(98)
RANGE
15-1650(N5)
5-1350 (N5)
5-550(98)
CHEMICAL COMPOSITION
CHEMICAL
HC1
C12
N2 ;
H2
Organics
HC1
C12
N2
H2
Organic
HC1
C12
H2
Organics
% VOLUME
40-80(49)
6-12(49)
Balance (49)
;<1%(49) range 0-54% (49)
10-59(N4)
89-40 (N4)
<0.5(98)
.3-2.0(N4)
Balance (N4)
Ki
OO
-------
molecular weight of the balance as,
Cl 71 estimated average
1
N0 28 i based on relative
2 \
H 2 32 proportions
Benzene 78 )
then the flow of gas per hour becomes,
HC1 28,643 moles
Other gases 12,315 moles
Total 40,958 moles
Using Avagadro's law (1 mole occupies 22.4 liters at standard conditions)
yields a total of 917,459 liters per hour. This converts to 540
SCFM.
The range for the flow rates was estimated by using the ratio of
the total gas flow to the non-HCl gas which is 3.326. It was assumed
that except for chlorine gas all the other gases pass through the
scrubber without absorption. To account for the chlorine absorbed
the ratio was reduced arbitrarily to 3 to 1. Reference 98 reports
an after scrubber flow range of 5 to 550 SCFM. This was tripled to
give the input flow range.
The flow rates for the gases entering the scrubber were calculated
by assuming as above that the N?, H and organics are unaffected by the
scrubber. Thus the total weight of these gases is unchanged before
and after the scrubber. Knowledge of this constant total weight, the
percentage by volume of the constituents before and after the scrubber,
282
-------
and the flow rate after the scrubber is sufficient for calculating the
flow rate entering the scrubber. Based on the percent volume data
given in the table and. the average flow rate of 40 SCFM given in
Reference 98 for the exit flow from the scrubber, the flow entering
the scrubber would average approximately 70 SCFM. The range of flows
shown were based on the extremes shown for the flow and percent volume
data.
The percent volume of the gases after passing through the Karbate
absorption tower may be calculated by using the assumption that only
the HCl gas remains in the absorption tower solution. Thus the flow
of the other gases remains constant through the absorption tower.
Reference 49 reports the percent volume of HC1 as 40 to 80% entering
the tower and averaging 1% after passing through the tower. Since
the other gases remain constant their percent volumes after the tower
can be calculated by normalizing the input values to 99%.
The percent volumes after passage through the water scrubber
were calculated by using the following scrubber efficiencies,
Gas % Efficiency of Scrubber Reference
HCl 93 49
Cl 97 91
Others 0 N5
Application of these efficiencies to the data shown for control point
number 1 yields the results shown for chlorine and the balance of the
gases. Reference 98 reports a direct measurement of the HCl volume as
less than 0.5 percent.
283
-------
5.6.5 Chlorine Bleach Manufacture
5.6.6.1 Process Description. According to Reference 49 a typical
commercial strength chlorine bleach contains from 12 to 15% available
chlorine. Chlorine bleach which is the common name for sodium hypochlorite
solution is prepared in a batch process by reacting chlorine with
sodium hydroxide solution to produce sodium hypochlorite and hydrogen
chloride. This reaction is exothermic and irreversible if high
temperature and low pH are avoided. A typical batch requires 3 to 5
hours to reach optimum chlorination.
5.6.6.2 Chemical and Physical Properties of Input Feed and
Effluents. Table XLIX shows the chemical and physical properties
of the input feed and effluents for a commercial strength chlorine
bleach manufacture. Reference 49 gives the amount of chlorine used
per day in the manufacture of chlorine bleach in the U.S. as 250 tons.
Since there are approximately 100 plants involved the average is 2.5
tons per day per plant. Stoichiometric calculations require that the
chlorine be added to 1 Ton/day of sodium hydroxide and 1.9 tons/day
of water. These weights convert to the percentages shown in the table.
The flow rate for the HC1 offgas was also based on Stoichiometric
calculations and subsequent conversion to volume. The flow rate for
the gas after the scrubber was based on a scrubber efficiency of 93%
as stated in Reference 49.
284
-------
TABLE XLIX
SELECTED CHEMICAL AND PHYSICAL PROPERTIES OF INPUT FEED
AND EFFLUENTS-CHLORINE BLEACH MANUFACTURE
(COMMERCIAL 12-15% AVAILABLE Cl)
CONTROL POINT
Input Feed
Control Point
(After mixing tank)
*Flow for HC1 gas only;
After Water
Scrubber
INPUTS - % WEIGHT
ANALYSIS
CHEMICAL
NaOH
H20
C12
NaOH
H20
does not if
% WEIGHT
2.5 Tons/day
1 Ton/ day
1.9 Tons/ day
46%, (N4)
19% (N4)
35% (N4)
tclude dilutio
GAS TEMPERATURE
°F
AVG.
ALL INP
72° (N5)
n air.
80° (N5)
RANGE
UTS ARE LIQ
50-100(N5)
40-80° (N5)
FLOW RATE
AVG.
JID
18SCFM*(N4)
approx. 1 S
(N5)
RANGE
N.R.
CFM*
CHEMICAL COMPOSITION
CHEMICAL
C12
HC1
H20
Dilution
Air
C12
HC1
Dilution
Air
% VOLUME
Neg (49)
Unk
Unk
Unk
Neg (N5)
Unk
Unk
Unk
IsJ
CO
-------
APPENDIX
During initial work on this study flbw diagramsof the basic
operations of various processes were drawn. These diagrams also
show estimates Of the emissions points of hazardous pollutants.
those diagrams which have not been previously presented are contained
in this appendix.
287
-------
to
00
00
TO STEEL
MILL
TO STEEL
MILL
* MINOR EMISSION POINT
** MAJOR EMISSION POINT
SOURCE: MRI
FIGURE 49
BASIC OPERATIONS-IRON ORE PELLET PLANT
-------
BLAST **
OR
ELECTRIC
FURNACE
FERROALLOY
INGOTS
GRINDING
FINISHED
INGOTS
MINOR EMISSION POINT
MAJOR EMISSION POINT
SOURCE: MITRE
FIGURE 50
BASIC OPERATIONS-FERRO-ALLOYS (INCL. SILICOMANGANESE)
289
-------
ATMOSPHERE
ISJ
X)
ALUMINA
ROOF fr
MONITOR
*
\ \
t S
ROOM CONTROL
AIR HOOD
V'
PPFBAKK
t "]
ROOM CONTROL
AIR HOOD
A ^ k
nnpT7nraTAT
ANODE SODERBERG
CELL CELL
CONTROL J *
DEVICES
! ATMOSPHERE
fc CONTROL J * -X-
^ P DEVICES
ROOM CONTROL
AIR HOOD
^-[ "
,. OPTICAL CHLORINE
SODERBERG
CELL
ELECTRIC T } T r T M
POWER
11 «. RAW >. CASTING*
^ ALUMINUM ^ FURNACE
MINOR EMISSION POINT
MAJOR EMISSION POINT
SOURCE: MITRE
FIGURE 51
BASIC OPERATIONS-PRIMARY ALUMINUM
-------
AL (OH)
PRIMING
* MINOR EMISSION POINT'
Jfc * MAJO'R EMISSION POINT
mi
CALCINED COMMERCIAL
ALUMINA.
FIGURE 52
BASIC OPERATIONS-MANUFACTURE OF ALUMINA
-------
10
•o
PHOSPHATE
ROCK
LJ
It
"I
J
SULFURIC
ACID
r
MIXER
i
DEN
1
r
CURING
1
J
^^•H
1 ATMOSPHERE
A * *
CONTROL
DEVICES
ATMOSPHERE ^
t-b * P0;
* * 1 COI
J*_
3SIBLE
TCROL
POMTPHT 1 DEVICES
^ LONiROL AMMONIA '
^ DEVICES niuwnLa
irt t* *t
^ AMMONIATOR ^ ™>VT?T> ^ rnni va
" GRANULATOR " ^
*
r
GRINDER
*
RUN OF PILE
"* PRODUCT
t
k "
GI
PI
T *
GREENING
JANULATED
IODUCT
MINOR EMISSION POINT
MAJOR EMISSION POINT
SOURCE: MRI
FIGURE 53
BASIC OPERATIONS-NORMAL SUPERPHOSPHATE MANUFACTURE
-------
CHIPS
63
STEAM FOR PROCESS
AMD POWER
*-*
MULTIPLE-EFFECT
EVAPORATORS
SULFUR BURNER AND
GAS COOLER
* MINOR EMISSION POINT
* * MAJOR EMISSION POINT
SOURCE: MRI
FIGURE B4
BASIC OPERATIONS-SULFITE PULPING PROCESS, AMMONIA BASE
-------
to
Mg(HS03)2 + H2S03 COOKING LIQUOR
TO ATMOSPHERE
CHIPS
TO STACK
COOLED GASES
** MgO SLURRY
DIGESTER
BLOW
PULP
* MINOR EMISSION POINT
** MAJOR EMISSION POINT
SOURCE: MRI
l-l
ABS.
TOWER
" U
ABS.
TOWER
Mg(HS03)2 Mg(HS03)2
SCRUBBER
SULPHUR
MAKE-UP
CONC'D
RED LIQUOR
MgO SLURRY
RECOVERY
FURNACE
WATER
FIGURE 55
BASIC OPERATIONS-SULFITE PULPING PROCESS, MAGNESIA BASE
-------
CONTROL
I DEVICES I
I
MINOR EMISSION POINT
MAJOR EMISSION POINT
SOURCE: MRI
FIGURE 56
BASIC OPERATIONS-RAW CERAMIC CLAY MANUFACTURE
295
-------
GAS
BURNER
GAS
PIPELINE
K)
•O
o«
MINOR EMISSION POINT
! MAJOR EMISSION POINT
SOURCE: AIR POLLUTION ENGINEERING MANUAL
TO
ATMOSPHERE
OIL
KNOCKOUT
TANK
^
STACK
FINISHED
PRODUCT
STORAGE
FIGURE 57
BASIC OPERATIONS-TYPICAL ASPHALT AIR-BLOWING PROCESS
-------
COAL
TRUCK
•&
k
COAL
STOCKPILE
*t
FURNACE
FEEDING
MECHANISM
*
->
ATMOSPHERE
1**
OIL
TRUCK
*
OIL
STORAGE
USUALLY GRAVITY
FEED
^-
FURNACE
fc.
STACK
KJ
>O
XI
GAS
PIPELINE
•X- MINOR EMISSION POINT
MAJOR EMISSION POINT
SOURCE: MITRE
FIGURE 58
BASIC OPERATIONS-COMMERCIAL/RESIDENTIAL COMBUSTION
-------
to
S3
00
RAILROAD
CAR
COAL
TRUCK
OIL
TANKERS
OIL
TRUCKS
OIL
PIPELINE
GAS
PIPELINE
^^w
•••M
*
COAL
STOCKPILE
OIL
STORAGE
k
FURNACE
FEEDING
MECHANISM
OIL
PUMPS
1 *
COMBUSTIBLE
WASTE
GAS FROM
PROCESS
ATMOSPHERE
|#-3f
STACK
1 (OCNL) ^
^ f~ OCNL 1
FURNACE
i r
ASH
F01
b CONTROL 1 Dp
DEVICES M
| (OCNL)
* ^
ASH LIQUID
Abtl WASTE
1 1
ASH *
DISPOSAL
ASH *
DISPOSAL
ICED
tfT
' !
* MINOR EMISSION POINT
•X-X-MAJOR EMISSION POINT
SOURCE: MITRE
FIGURE 59
BASIC OPERATIONS-INDUSTRIAL COMBUSTION
-------
*
ATMOSPHERE
KJ
"O
V
ANY SINGLE OR COMBINATION
OF FUELS POSSIBLE
MINOR EMISSION POINT
MAJOR EMISSION POINT
SOURCE: MITRE
FIGURE 60
BASIC OPERATIONS- POWER PLANT COMBUSTION
-------
OIL OR GAS
FIRED
PRIMARY
BURNER
OIL OR GAS
FIRED
SECONDARY
BURNER
MANUAL
CHARGING
CHARGING
CHUTE
PRIMARY
BURNING
CHAMBER
SECONDARY
BURNING
CHAMBER
EXHAUST
FLUE
AND
STACK
PRIMARY
DRAFT '
MANUAL **
ASH
REMOVAL
4 1
AFTERBURNER I
(OPTIONAL)
I
I #*
ATMOSPHERE
* MINOR EMISSION POINT
* * MAJOR EMISSION POINT
SOURCE: AIR POLLUTION ENGINEERING MANUAL
I J
FIGURE 61
BASIC OPERATIONS-TYPICAL APARTMENT HOUSE TYPE INCINERATOR
300
-------
TRUCK *
UNLOADING
STORAGE
PIT
GRAB
BUCKET
CHARGING
HOPPER
ATMOSPHERE
#•*
STACK
t
STACK
CONTROL
DEVICES
FEEDING
AND
DRYING
STOKER
|
PRIMARY
COMBUSTION
1
SECONDARY
COMBUSTION
FORCED
DRAFT
FAN
ASH
CONVEYOR
;
ASH *
REMOVAL
r
ASH '
REMOVAL I
(OCNL) I
I
I LIQUID I
• WASTE |
REMOVAL |
L (OCNL) j
•Jf MINOR EMISSION POINT
•X--X- MAJOR EMISSION POINT
SOURCE:
AIR POLLUTION
ENGINEERING
MANUAL
FIGURE 62
BASIC OPERATIONS-TYPICAL MUNICIPAL INCINERATOR
301
-------
VI. BIBLIOGRAPHY
DOCUMENT
W. E. Davis and Associates, National Inventory of Sources
and Emissions: Cadmium, Nickel, and Asbestes - 1968
Cadmium - Section I, Feb. 1970, APTD 68, PB 192-250
Nickel - Section II, Feb. 1970, APTD 69, PB 192-251
Asbestos - Section III, Feb. 1970, APTD 70, PB 192-252
W. E. Davis and Associates, National Inventory of Sources
and Emissions: Arsenic, Beryllium, Manganese, Mercury,
and Vanadium - 1968
Arsenic - Section I, June 1971
Beryllium - Section II, June 1971
Manganese - Section II, June 1971
Mercury - Section IV, June 1971
Vanadium - Section V, June 1971
W. E. Davis and Associates, National Inventory of Sources
and Emissions; Barium, Boron, Copper, Selenium, and Zinc
1969
Barium - Section I, APTD 1140, PB 210-676
Boron - Section II, APTD 1159, PB 210-677
Copper - Section III, APTD 1129, PB 210-678
Selenium - Section IV, APTD 1130, PB 210-679
Zinc - Section V, APTD 1139, PB 210-680
Litton Systems, Incorporated, Oct. 1969,
Preliminary Air Pollution Survey of:
Aeroallergens, APTD 69-23, PB 188-076
303
-------
NUMBER
BIBLIOGRAPHY (CONT'D)
DOCUMENT
15 Aldehydes, APTD 69-24, PB 188-081
16 Ammonia, APTD 69-25, PB 188-082
17 Arsenic, APTD 69-26, PB 188-071
18 Asbestos, APTD 69-27, PB 188-080
19 Barium, APTD 69-28, PB 188-083
20 Beryllium, APTD 69-29, PB 188-078
21 Biological Aerosals, APTD 69-30, PB 188-084
22 Boron, APTD 69-31, PB 188-085
23 Cadmium, APTD 69-32, PB 188-086
24 Chlorine Gas, APTD 69-33, PB 188-087
25 Chromium, APTD 69-34, PB 188-075
26 Ethylene, APTD 69-35, PB 188-069
27 Hydrochloric Acid, APTD 69-36, PB 188-067
28 Hydrogen Sulfide, APTD 69-37, PB 188-068
29 Iron, APTD 69-38, PB 188-088
30 Manganese, APTD 69-39, PB 188-079
31 Mercury, APTD 69-40, PB 188-074
32 Nickel, APTD 69-41, PB 188-070
33 Odorous Compounds, APTD 69-42, PB 188-089
34 Organic Carcinogens, APTD 69-43, PB 188-090
35 Pesticides, APTD 69-44, PB 188-091
36 Phosphorous, APTD 69-45, PB 188-073
37 Radioactive Substances, APTD 69-46, PB 188-092
304
-------
BIBLIOGRAPHY (CONT'D)
NUMBER
DOCUMENT
38
39
40
41
42
43
44
45
46
47
48
49
50
Selenium, APTD 69-47, PB 188-077
Vandium, APTD 69-48, PB 188-093
Zinc, APTD 69-49, PB 188-072
Midwest Research Institute, Particulate Pollutant
System Study:
Vol. I - Mass Emissions, May 1, 1971
APTD 0743, PB 203-128
Vol. II - Fine Particulate Emissions, Aug. 1, 1971
APTD 0744, PB 203-521
Vol. Ill - Emissions, Effluents, and Control Practices
for Stationary Particulate Pollution Sources, APTD 0745,
PB 203-522, Nov. 1, 1971
Battelle, Columbus Labs; E. P. Stambaugh, E. H. Hall,
R. H. Cherry, Jr. and S. R. Smothson, Jr.; Topical
Report on Basis for National Emissions Standards on
Cadmium (no date)
Battelle, Columbus Labs; Control Techniques for Emissions
Containing Chromium, Manganese, Nickel, and Vanadium,
June 9, 1972
EPA, GAP, Control Techniques for Mercury Emissions,
January, 1972
EPA, OAP, Control Techniques for Lead Emissions,
(no date)
GCA Corp., Control Techniques for Polycyclic Organic
Matter Emissions, August 1970
EPA, OAP, Control Techniques for Chlorine and Hydrogen
Chloride Emissions, March 1971
TRW Systems Group, Engineering and Cost Effectiveness
Study of Fluoride Emissions Control, Robinson, Graber,
Lusk, and Santy, January 1972. Volumes I and II,
PB 207-506, PB 209-647
305
-------
BIBLIOGRAPHY (CONT'D)
.NUMBER
DOCUMENT
51
52
53
54
55
56
57
BuMines, Pittsburgh, D. C. Diehl, et al.,
Fate of Trace Mercury in the Combustion of Coal,
BuMines TPR 54, May 1972, PB 210-226
Oak Ridge National Lab, Environmental Pollution; Use of
Neutron Activation Analysis to Determine the Fate of
Trace Elements from Fossil Fuel Combustion, 1971
CONF-720413-1
Rahn, Kenneth A., Sources of Trace Elements in Aerosols:
An Approach to Clean Air, May, 1971
Joensuu, Oiva I., "Fossil Fuels as a Source of Mercury
Pollution," Science, Vol. 172, June 4, 1971, pp. 1027-28
Minerals Yearbook, 1968, Vol. I-II: Metals, Minerals
and Fuels. U. S. Bureau of Mines, 1969
Mineral Facts and Problems, 1970, U.S. Bureau of Mines,
1970
John A. Danielson (ed.), Air Pollution Engineering
Manual. Los Angeles County Air Pollution Control District,
1967, PHS-999-AP-40
306
-------
BIBLIOGRAPHY (CONT'D)
NUMBER
DOCUMENT
58
TRW, McLean, Virginia, Engineering and Cost Effectiveness
Study of Flouride Emissions Control, Vol. II, 1972.
59
U.S. Department of Commerce, 1967 Census of Manufactures
Vol. II.
60
Department of Health, Education, and Welfare, National
Emission Standards Study, Vol I.
61
Department of Health, Education, and Welfare, National
Emission Standards Study, Vol. II.
62
Department of Health, Education, and Welfare, National
Emission Standards Study, Vol. III.
63
Engineering Science, Inc., Exhaust Gases From Combustion
and Industrial Processes, 1971.
64
Battelle, Columbus Laboratories, A Cost Analysis of Air
Pollution Controls in the Integrated Iron and Steel Industry,
1969.
65
Battelle, Columbus Laboratories, A System Analysis Study of
the Integrated Iron and Steel Industry. 1969.
66
Battelle, Columbus Laboratories, Evaluation of Process
Alternatives to Improve Control of Air Pollution from
Production of Coke, 1970.
67
NAPCA, Air Pollution Aspects of Brass and Bronze Smelting
and Refining Industry, 1969.
68
Department of Interior, Mercury Contamination in the Natural
Environment, 1970.
307
-------
BIBLIOGRAPHY (CONT'D)
NUMBER
DOCUMENT
69
70
71
72
73
74
75
76
77
78
Copley International Corporation, National Survey of the
Odor Problem - Phase I of a Study of the Social and
Economic Impact of Odors, 1970.
Copley International Corporation, National Survey of the
Odor Problem - Phase I of a Study of the Social and
Economic Impact of Odors, Appendix, 1970
Public Health Service, Cincinnati, Ohio, Atmospheric
Emissions from Petroleum Refineries; a Guide for
Measurement and Control, 1960
A. T. Kearney and Company, Chicago, Illinois, Systems
Analysis of Emissions and Emissions Control in the Iron
Foundry Industry, Vol. I, 1971
A. T. Kearney and Company, Chicago, Illinois, Systems
Analysis of Emissions and Emissions Control in the Iron
Foundry Industry, Vol. II, 1971
A. J. Kearney and Company, Chicago, Illinois, Systems
Analysis of Emissions and Emissions Control in the Iron
Foundry Industry, Vol. Ill, 1971
EPA, Durham, Secondary Zinc Industry Emission Control
Problem Definition Study Part I, 1971
A. T. Kearney and Company, Air Pollution Aspects of the
Iron Foundry Industry. 1971
Arthur D. Little, Inc., Evaluation of Community Odor
Exposure, 1971
Karolinska Institute, Stockholm, Sweden, Mercury in the
Environment, 1971
308
-------
BIBLIOGRAPHY (CONT'D)
NUMBER
DOCUMENT
79
Illinois Institute for Environmental Quality, Chicago,
Asbestos Air Pollution Control, 1971.
80
Illinois Institute for Environmental Quality, Chicago,
A Study of Environmental Pollution by Lead, 1971.
81
EPA, Air Pollution Control Office, Beryllium and Air
Pollution; An Annotated Bibliography, February, 1971.
82
EPA, OAP, Air Pollution Aspects of Emission Sources;
Petroleum Refineries - A Bibliography with Abstracts,
July, 1972.
83
EPA, OAP, Air Pollution Aspects of Emission Sources; Iron
and Steel Mines - A Bibliography with Abstracts, May, 1972.
84
EPA, Environmental Lead and Public Health, 1971.
85
Department of Health, Education, and Welfare, Air Pollution
and the Kraft Pulping Industry, 1963.
86
EPA, Asbestos and Air Pollution, An Annotated Bibliography.
1971.
87
National Academy of Sciences, Asbestos - The Need for and
Feasibility of Air Pollution Controls, 1971.
88
EPA, Air Pollution Aspects of Emission Sources; Cement
Manufacturing - A Bibliography with Abstracts, 1971.
89
Economics Priorities Report, Paper Profits: Pollution
Audit 1972, Vol. 3, No. 3, July/August 1972.
309
-------
BIBLIOGRAPHY (CONT'D)
NUMBER
DOCUMENT
90
EPA, Paint Technology and Air Pollution; A Survey and
Economic Assessment, 1972.
91
EPA, Atmospheric Emissions from Chlor-Alkali Manufacture,
1971.
92
EPA, Chlorine and Air Pollution; An Annotated Bibliography,
1971^
93
National Academy of Sciences, Lead-Airborne Lead in Perspective,
1972.
94
EPA, Air Pollution Aspects of Emission Sources; Municipal
Incineration - A Bibliography with Abstracts, 1971.
95
Department of Health, Education, and Welfare, Cincinnati,
Ohio, Survey of Lead in the Atmosphere of Three Urban
Communities, 1965.
96
National Center for Air Pollution Control, Cincinnati, Ohio,
Atmospheric Emissions from the Manufacture of Portland
Cement, 1967.
97
Environmental Engineering, Control of Atmospheric Emissions
in the Wood Pulping Industry, Vol. I, 1970.
98
NAPCA, Atmospheric Emissions from Hydrochloric Acid^
Manufacturing Processes, 1969.
99
Karolinska Institute, Stockholm, Sweden, Cadmium in the
Environment - A Toxicological and Epidemiological Appraisal,
1971.
310
-------
BIBLIOGRAPHY (CONT'D)
NUMBER
DOCUMENT
100
Illinois Institute for Environmental Quality, Mercury Vapor
Emissions; Report on Aerial Survey of Sources Potentially
Affecting the Air in Illinois, 1971.
101
Commins (J. A.) and Associates, A Localized Study of Gray
Iron Foundries to Determine Business and Technical Commonalities
Conductive to Reducing Abatement Costs, 1972.
102
Battelle, Columbus Laboratories, Development of a Rapid
Survey Method of Sampling and Analysis for Asbestos in
Ambient Air, 1972.
103
San Diego Water Utilities Department, Sewage Odor Control by
Liquid-Gas Extraction, 1970.
104
Graphic Arts Technical Foundation, Evaluations of Emissions
and Control Technologies in the Graphic Arts Industries, 1970.
105
Air Force Rocket Propulsion Laboratory, Edwards AFB,
Atmospheric Diffusion of Beryllium, 1971.
106
Oak Ridge National Lab, Mercury in the Environment: An
Annotated Bibliography. 1972.
107
Research Triangle Institute, Estimating Population Exposure
to Selected Metals - Manganese, 1969.
108
Arthur D. Little, Systems Study of Air Pollution From
Municipal Incineration, Vol. I, 1970.
109
Arthur D. Little, Systems Study of Air Pollution From
Municipal Incineration, Vol. II, 1970.
311
-------
BIBLIOGRAPHY (CONT'D)
NUMBER
DOCUMENT
110
Arthur D. Little, Systems Study of Air Pollution From
Municipal Incineration, Vol. III. 1970.
Ill
A. T. Kearney, Study of Economic Impacts of Pollution Control
on the Iron Foundry Industry, Part I, 1971.
112
A. T. Kearney, Study of Economic Impacts of Pollution Control
on the Iron Foundry Industry, Part II, 1971.
113
A. T. Kearney, Study of Economic Impacts of Pollution
Control on the Iron Foundry Industry, Part III, 1971.
114
Charles River Associates, The Effects of Pollution Control
on the Nonferrous Metals Industries, Lead, Part I, 1971.
115
Charles River Associates, The Effects of Pollution Control
on the Nonferrous Metals Industries, Lead, Part II, 1971.
116
Charles River Associates, The Effects of Pollution Control
on the Nonferrous Metals Industries, Lead, Part III, 1971.
117
Charles River Associates, The Effects of Pollution Control
on the Nonferrous Metals Industries, Aluminum, Part I, 1971.
118
Charles River Associates, The Effects of Pollution Control
on the Nonferrous Metals Industries, Aluminum, Part II, 1971.
119
Charles River Associates, The Effects of Pollution Control
on the Nonferrous Metals Industries, Aluminum, Part III, 1971.
120
Charles River Associates, The Effects of Pollution Control
on the Nonferrous Metals Industries, Copper, Part I, 1971.
312
-------
BIBLIOGRAPHY (CONT'D)
NUMBER
DOCUMENT
121
Charles River Associates, The Effects of Pollution Control
on the Nonferrous Metals Industries, Copper, Part II, 1971.
122
Charles River Associates, The Effects of Pollution Control
on the Nonferrous Metals Industries, Copper, Part III, 1971.
123
Charles River Associates, The Effects of Pollution Control
on the Nonferrous Metals Industries, Zinc, Part I, 1971.
124
Charles River Associates, The Effects of Pollution Control
on the Nonferrous Metals Industries, Zinc, Part II, 1971.
125
Charles River Associates, The Effects of Pollution Control
on the Nonferrous Metals Industries, Zinc, Part III, 1971.
126
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127
Arthur D. Little, Economic Impact of Anticipated Paper
Industry Pollution Abatement Costs, Part II, 1971.
128
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Industry Pollution Abatement Costs, Part III, 1971.
129
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130
Dunlap and Associates, Economic Impact of Environmental
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313
-------
BIBLIOGRAPHY (CONT'D)
NUMBER
DOCUMENT
131
Dunlap and Associates, Economic Impact of Environmental
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132
Dunlap and Associates, Economic Impact of Environmental .
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133
Urban Systems Research and Engineering, Inc., The Leather
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134
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135
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136
Boston Consulting Group, The Cement Industry: Economic
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137
Boston Consulting Group, The Cement Industry; Economic
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138
National Center for Air Pollution Control, Cincinnati,
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139
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314
-------
BIBLIOGRAPHY (CONT1 D)
Number
Document
140
141
142
143
144
145
146
147
148
149
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December 1971
Department of Meteorology and Oceanography, Michigan
University, Particle Size Distribution of Chlorine and
Bromine in Mid-Continent Aerosols From The Great
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National Coal Board, London, England,
Reduction of Atmospheric Pollution Vol. I - Main
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National Coal Board, London, England,
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315
-------
BIBLIOGRAPHY (CONT'D)
Number
Document
150
151
152
153
154
155
156
157
158
159
160
161
Sobotka & Co., The Impact of Costs Associated with New
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of Air Pollution - A Survey, June 1970
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316
-------
Number
BIBLIOGRAPHY (CONT'D)
Document
162
163
164
165
166
167
168
169
170
171
172
173
174
175
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Systems Study for Control of Emissions - Primary Nonferrous
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317
-------
Number
BIBLIOGRAPHY (CONT'D)
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176
177
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179
180
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184
185
186
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318
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BIBLIOGRAPHY (CONT'D)
Number
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187 "Electrolytic Zinc Plant Is Latest Addition to Growing TG
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188 "Phase Out At Blackwell, Phase In At Sauget," Base Metals
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189 "Solutions for Feedlot Odor Control Problems," Robert M.
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190 Beryllium, Actual and Potential Resources, Toxicity, and
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191 Air Pollution and Industry, R. D. Ross, 1972.
192 "In Mechanical Dust Collectors, It's the Fabric That Really
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193 "The Fluidized-Bed Sulfate Roasting of Nonferrous Metals,"
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194 Restriction of Emission Copper-Scrap Smelting Plants and Copper
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196 "S0? Laws Force U.S. Copper Smelters Into Industrial Russian
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197 "New Roasters Spur Production of Sulfuric Acid and Zinc
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198 "Sulfuric Acid Production from Ore Roaster Gases," J. R.
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319
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Number
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200 "Zinc," J. R. Alexander, Engineering/Mining Journal, March 1972.
201 "Copper," W. Harmon, Engineering/Mining Journal, March 1972.
202 "Lead," H. T. Fargey, Engineering/Mining Journal, March 1972.
203 Copper - A Material Survey, A. D. McMahon, U. S. Dept. of the
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204 AIME World Symposium on Mining and Metallurgy of Lead and
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205 AIME World Symposium on Mining and Metallurgy of Lead and
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206 A Manual of Electrostatic Precipitator Technology, Part I -
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207 A Manual of Electrostatic Precipitator Technology, Part II -
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208 "Penalization of the Environment Due to Stench - A Study of
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210 Fluorides, National Academy of Sciences, 1971.
211 Environmental Mercury Contamination, Rolf Hartung and Bertram D.
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212 Process Flow Sheets and Air Pollution Controls, American Con-
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213 "The Design and Performance of Cyclone Separators," F.H.H.
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214 "Air Pollution Problems Faced by the Iron and Steel Industry,"
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320
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BIBLIOGRAPHY (CONT'D)
Number
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215 Economic Impact of Air Pollutants on Plants in the United
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216 "Fluosolids Roasting of Copper Concentrates at Copperhill,"
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217 Control Techniques for Particulate Air Pollutants, U.S. Dept.
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218 "Dust and Fume Collection Equipment," Carl R. Fladin, Con-
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219 "Centralized Control Guides Efficient Operations of Inland
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220 Hydrochloric Acid and Air Pollution - An Annotated Biblio-
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221 Control of Sulfur Oxide Emissions in Copper, Lead, and Zinc
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222 Atmospheric Emissions From Wet-Process Phosphoric Acid Manu-
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223 Atmospheric Emissions from Thermal-Process Phosphoric Acid
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224 Handbook of Fabric Filter Technology, Volume I, Fabric Filter
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225 Appendices to Handbook of Fabric Filter Technology, Volume II,
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226 Bibliography, Volume III, Fabric Filter Systems Study, GCA
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227 Final Report, Volume IV, Fabric Filter Systems Study. GCA
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128 "An Inventory of Miscellaneous Sources of Reduced Sulfur
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321
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231 An Encyclopedia of the Iron and Steel Industry, A.K. Osborne,
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234 "Investigation of Emissions from Plywood Veneer Dryers,"
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235 The Impact of Air Pollution Abatement on the Copper Industry
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236 A Dictionary of Mining, Mineral, and Related Terms,
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237 Abatement of Particulate Emissions From Stationary Sources,
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238 Restriction of Emission: Copper-Ore Mills. (VDI), Society
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240 Handbook of Non-Ferrous Metallurgy, Volume 2. D. M. Liddell.
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322
-------
BIBLIOGRAPHY (CONT'D)
NUMBER
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242
243
244
245
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323
-------
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324
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325
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BIBLIOGRAPHY (CONT'D)
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NUMBER DOCUMENT
302 Sonmerlad, Robert S., "Fabric Filtration - State of the Art,"
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303 Schell, T. W., "Cyclone/Scrubber System Quickly Eliminates
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309 Silverman, L., et. al., Journal Air Pollution Control Association,
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310 Silverman, L., et. al., Journal Air Pollution Control Association,
Vol. 6, No. 4, p. 318.
311 Silverman, L., et. al., Journal Air Pollution Control Association,
Vol. 8, No. 3, p. 185.
312 Silverman, L., et. al., Journal Air Pollution Control Association,
Vol. 8, No. 1, p. 53.
313 Kane, L. J., et. al., U.S. Bureau of Mines, Report of Investigations
No. 5672 (1960).
328
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NON-BIBLIOGRAPHIC REFERENCES
N1 Axiomatic
N2 Application of Gay-Lussac's Law
N3 Private Communication
N^ MITRE Corporation: unpublished computations
N5 MITRE estimate
N6 Privileged data source
329
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