Supplement no. 11 for Compilation of Air Pollutant Emission Factors


                                        AP-42
                                  Supplement 11
       SUPPLEMENT NO. 11
                  FOR

          COMPILATION
      OF AIR POLLUTANT
      EMISSION FACTORS,
THIRD  EDITION (INCLUDING)
       SUPPLEMENTS 1-7)
       I >. KM IRO1MIMENTAI. I'KOI K< I ION \(,KM
          Office nl \ir ami \\a-lr Maiiairrmcul
        Offici- of \ir Onalil\ l'lainiiiiarrh Trianuli' I'.irk. Nnrlli ( arolina 2771 I

                October 1980

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This document is issued by the Environmental Protection Agency
to report technical data of interest to a limited number of
readers.  Copies are available free of charge to Federal
employees, current EPA contractors and grantees, and nonprofit
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Services Office (MD 35), U. S. Environmental Protection Agency,
Research Triangle Park, North Carolina  27711; or, for a fee,
from the National Technical Information Service, 5285 Port
Royal Road, Springfield, Virginia  22161.  This document is
also for sale to the public from the Superintendent of
Documents, U. S. Government Printing Office, Washington, DC.
                     Publication No. AP-42
               U,G. environmental Protection Agency

                              ii

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INSTRUCTIONS FOR INSERTING SUPPLEMENT 77

INTO AP-42
Pag a* JuiJi thuough v H.ep£ac.e *ame. New Contend.
Page* \)Jui and vJiLi n.e.p£a.ce. &ame. New Publication* In
Page. 2.0-1 n.e.ptac.e* p. 2-1. Editorial. Change*.
Page* 2.1-1 through 2.1-5
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CONTENTS

Page
INTRODUCTION
I. EXTERNAL COMBUSTION SOURCES
1.1 BITUMINOUS COAL COMBUSTION
.2 ANTHRACITE COAL COMBUSTION
.3 FUEL OIL COMBUSTION ..
1.4 NATURAL GAS COMBUSTION
.5 LIQUIFIED PETROLEUM CAS COMBUSTION
.6 WOOD WASTE COMBUSTION IN BOILERS .
1.7 LIGNITE COMBUSTION
.8 BAGASSE COMBUSTION IN SUGAR MILLS
.9 RESIDENTIAL FIREPLACES
1-
1-
2-
3-
.4-
5-
6-
7-
8-
9
1.10 WOODSTOVES ............................. 1.10-
1.11 WASTE OIL DISPOSAL ........................ 111-
2. SOLID WASTE DISPOSAL ...... ................ 20-
2.1 REFUSE INCINERATION ........................ 21-
2.2 AUTOMOBILE BODY INCINERATION ..................... 22
2.3 CONICAL BURNERS ............................... 23-
2.4 OPEN BURNING ................................. 2.4-
2.5 SEWAGE SLUDGE INCINERATION ...................... 2.5-
3. INTERNAL COMBUSTION ENGINE SOURCES ................ 3-
GLOSSARY OF TERMS .................................. 3-
3.1 HIGHWAY VEHICLES ............... ......... 31-
3.2 OFF-HIGHWAY MOBILE SOURCES .............................. 3.2-
3.3 OFF-HIGHWAY STATIONARY SOURCES ..................... 3.3-
4. EVAPORATION LOSS SOURCES ........................... 4.1-
4.1 DRY CLEANING .............................. 41-
4.2 SURFACE COATING .............................. 4.2-
4.3 STORAGE OF PETROLEUM LIQUIDS ............................... 43-
4.4 TRANSPORTATION AND MARKETING OF PETROLEUM LIQUIDS ........... 44-
4.5 CUTBACK ASPHALT, EMULSIFIED ASPHALT AND ASPHALT CEMENT ....... 45
4.6 SOLVENT DECREASING ............................... 46-
4.7 WASTE SOLVENT RECLAMATION ........................... 4.7
4.8 TANK AND DRUM CLEANING .............................. 48-
5. CHEMICAL PROCESS INDUSTRY ................................ 51-
5.1 ADIP1C ACID .................................................. 5.1-
5.2 SYNTHETIC AMMONIA ..................................... 52-
5.3 CARBON BLACK ................... ................... 53-
5.4 CHARCOAL ................................................ 54-
5.5 CH LOR- ALKALI ............................................. 5.5-
5.6 EXPLOSIVES .................................................. 5.6-
5.7 HYDROCHLORIC ACID ..................................... 5.7-
5.8 HYDROFLUORIC ACID ................................. 58-
5.9 NITRIC ACID .......................................... 59-
5.10 PAINT AND VARNISH ....................................... 510-
5.1 1 PHOSPHORIC ACID ............................................. 5.11-
5.12 PHTHALIC ANHYDRIDE .................................... 5.1 2-
5.13 PLASTICS .............................................. 5.13-
5.14 PRINTING INK ............................................ 5.14-
5.15 SOAP AND DETERGENTS ..................................... 5.15-
5.16 SODIUM CARBONATE ....................................... 5.16-
5.17 SULFURIC ACID ............................................ 5.17-
5.18 SULFUR RECOVERY ................................. 5.18-
5.19 SYNTHETIC FIBERS ........................................ 519-
5.20 SYNTHETIC RUBBER ...................................... 5.20-
5.21 TEREPHTHALIC ACID ...................................... S 21-
5.22 LEAD ALKYL .............................................. 5 22-
5.23 PHARMACEUTICALS PRODUCTION ........................................ 5.23-
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Page

6. FOOD AND AGRICULTURAL INDUSTRY 6.1-
6.1 ALFALFA DEHYDRATING 6.1-
6.2 COFFEE ROASTING 62-
6.3 COTTON GINNING 6.3-
6.4 FEED AND GRAIN MILLS AND ELEVATORS 6.4-
6.5 FERMENTATION 6.5-
6.6 FISH PROCESSING 6.6-
6.7 MEAT SMOKEHOUSES 6.7-
6.8 AMMONIUM NITRATE FERTILIZERS 6.8-
6.9 ORCHARD HEATERS 6.9-
6.10 PHOSPHATE FERTILIZERS 6.10-
6.11 STARCH MANUFACTURING 6.11-
6.12 SUGAR CANE PROCESSING 6.12-
6.13 BREAD BAKING 6.13-
6.14 UREA 6.14-
6.15 BEEF CATTLE FEEDLOTS 6.15-
6.16 DEFOLIATION AND HARVESTING OF COTTON 6.16-
6.17 HARVESTING OF GRAIN 6.17-
7. METALLURGICAL INDUSTRY 7.1-
7.1 PRIMARY ALUMINUM PRODUCTION 7.1-
7.2 COKE PRODUCTION 7.2-
7.3 PRIMARY COPPER SMELTING 7.3-
7.4 FERROALLOY PRODUCTION 7.4-
7.5 IRON AND STEEL PRODUCTION 7.5-
7.6 PRIMARY LEAD SMELTING 7.6-
7.7 ZINC SMELTING 77-
7.8 SECONDARY ALUMINUM OPERATIONS 7.8-
7.9 SECONDARY COPPER SMELTING AND ALLOYING 7.9-
7.10 GRAY IRON FOUNDRIES • 7.10-
7.11 SECONDARY LEAD SMELTING 7.11-
7.12 SECONDARY MAGNESIUM SMELTING 7.12-
7.13 STEEL FOUNDRIES 7.13-
7.14 SECONDARY ZINC PROCESSING 7.14-
7.15 STORAGE BATTERY PRODUCTION 7.15-
7.16 LEAD OXIDE AND PIGMENT PRODUCTION 7.16-
7.17 MISCELLANEOUS LEAD PRODUCTS 7.17-
7.18 LEADBEARING ORE CRUSHING AND GRINDING 7.18-
8. MINERAL PRODUCTS INDUSTRY 8.1-
8.1 ASPHALTIC CONCRETE PLANTS 8.1-
8.2 ASPHALT ROOFING 8.2-
8.3 BRICKS AND RELATED CLAY PRODUCTS 8.3-
8.4 CALCIUM CARBIDE MANUFACTURING 8.4-
8.5 CASTABLE REFRACTORIES 8.5-
8.6 PORTLAND CEMENT MANUFACTURING 8.6-
8.7 CERAMIC CLAY MANUFACTURING 8.7-
8.8 CLAY AND FLY ASH SINTERING 8.8-
8.9 COAL CLEANING 8.9-
8.10 CONCRETE BATCHING 8.10-
8.11 GLASS FIBER MANUFACTURING 8.11-
8.12 FRIT MANUFACTURING 8.12-
8.13 GLASS MANUFACTURING 8.13-
8.14 GYPSUM MANUFACTURING 8.14-
8.15 LIME MANUFACTURING 8.15-
8.16 MINERAL WOOL MANUFACTURING 8.16-
8.17 PERLITE MANUFACTURING 8.17-
8.18 PHOSPHATE ROCK PROCESSING 8.18-
8.19 SAND AND GRAVEL PROCESSING 8.19-
8.20 STONE QUARRYING AND PROCESSING 8.20-
8.21 COAL CONVERSION 8.21-
8.22 TACONITE ORE PROCESSING 8.22-
9. PETROLEUM INDUSTRY 9.1-
9.1 PETROLEUM REFINING 9.1-
9.2 NATURAL GAS PROCESSING 9.2-

IV
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Page

10. WOOD PRODUCTS INDUSTRY 10-1-
10.1 CHEMICAL WOOD PULPING 101-
10.2 PULPBOARD 10 2-
10.3 PLYWOOD VENEER AND LAYOUT OPERATIONS ... 10.3-
104 WOODWORKING WASTE COLLECTION OPERATIONS 10.4-
II. MISCELLANEOUS SOURCES 111-
11.1 FOREST WILDFIRES 111-
11.2 FUGITIVE DUST SOURCES 112-
11.3 EXPLOSIVES DETONATION 113-
APPENDIX A. MISCELLANEOUS DATA AND CONVERSION FACTORS A-
APPENDIX B. EMISSION FACTORS AND NEW SOURCE PERFORMANCE STANDARDS
FOR STATIONARY SOURCES B-l
APPENDIX C. NEDS SOURCE CLASSIFICATION CODES AND EMISSION
FACTOR LISTING . C-l
APPENDIX D. PROJECTED EMISSION FACTORS FOR HIGHWAY VEHICLES D-l
APPENDIX E TABLE OF LEAD EMISSION FACTORS . . E-l
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PUBLICATIONS IN SERIES
Issuance

Compilation of An Pollutant Emission Factors. Thud Edition
(Including Supplements 1-7)

Supplement No. 8
Intioduction
Section 1 10 Wood Stoves
Section 2 I Refuse Incineration
Section 2.4 Open Burning
Section 3.0 Internal Combustion Engine Souiccs. Notice
Section 3.3 Off-Highway Stationary Souices
Section 6 3 Cotton Ginning
Section 68 Ammonium .Nmaie Femlixers
Section 7.3 Pi unary Copper Smelting
Section 7.9 Secondaiy Coppei Smelting and Alloying
Section 8.1 Asphaltic Concrete Plants
Section 8.2 Asphalt Roofing
Section 813 Glass Manufacturing
Section 9.1 Petroleum Refining
Section I 1.2.1 Unpaved Roads (Dirt and Gravel)
Section 11.2.5 Paved Roads
Release Date

8/77

12/77
Supplement No. 9
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section 10.4
Section 11.2.5
Appendix C
Appendix E
1.11
4.4
4.5
4.6
5.2
5.3
5.17
5.22
69
6.13
6.14
6.15
6.16
7.3
7.9
7 15
7.16
7.17
7.18
8 10
7/79
Bituminous Coal Combust ion
Transportation and Marketing of Pctioleum Liquids
Cutback Asphalt, Emulsified Asphalt and Asphalt Cements
Solvent Degreasing
Synthetic Ammonia
Carbon Black
Sulfunc Acid
Lead Alkyl
Orchard Heaters
Bread Baking
Urea
Beef Cattle Feedlots
Defoliation and Harvesting of Cotton
Primary Copper Smelting
Secondary Copper Smelting and Alloying
Storage Battery Production
Lead Oxide and Pigment Production
Miscellaneous Lead Products
Lead bearing Ore Crushing and Grinding
Concrete Batching
Woodworking Waste Collection Operations
Fugitive Dust - Paved Roads
NEDS Source Classification Codes and Emission Factor Listing
Table of Lead Emission Factors
VII
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PUBLICATIONS IN SERIES (CONT'D)
Issuance
Supplement No. 10
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section 10.3
Section 10.4
Section 11.3
Appendix A
3.2.1
4.7
4.8
5.8
5.11
5.18
6.5.2
6.17
7.6
8.9
8.11
8.18
8.21
8.22
Release Date

2/80
Introduction
Internal Combustion Engine Sources - Aircraft
Waste Solvent Reclamation
Tank and Drum Cleaning
Hydrofluoric Acid
Phosphoric Acid
Sulfur Recovery
Fermentation • Wine Making
Harvesting of Grain
Primary Lead Smelting
Coal Cleaning
Glass Fiber Manufacturing
Phosphate Rock Processing
Coal Conversion
Taconite Ore Processing
Plywood Veneer and Layout Operations
Woodworking Waste Collection Operations
Explosives Detonation
Miscellaneous Data and Conversion Factors
Supplement No. 11
10/80
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
5.9
5.23
5.24
6.10.1
6.10.2
6.10.3
7.2
7.3
7.5
7.11
9.1
Nitric Acid
Pharmaceuticals Production
Maleic Anhydride
Normal Superphosphates
Triple Superphosphates
Ammonium Phosphates
Coke Production
Primary Copper Smelting
Iron and Steel Production
Secondary Lead Smelting
Petroleum Refining
Vlll
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2. SOLID WASTE DISPOSAL
As defined in the Solid Waste Disposal Act of 196S, the term "solid waste" means garbage, refuse, and other
discarded solid materials, including solid-waste materials resulting from industrial, commercial, and agricultural
operations, and from community activities It includes both combustibles and noncombustibles.

Solid wastes may be classified into four general categories urban, industrial, mineral, and agricultural.
Although urban wastes represent only a relatively small part of the total solid wastes produced, this category has
a large potential for air pollution since in heavily populated areas solid waste is often burned to reduce the bulk
of material requiring final disposall The following discussion will be limited to the urban and industrial waste
categories.

An average of 5.5 pounds (2.5 kilograms) of urban refuse and garbage is collected per capita per day in the
United States.2 This figure does not include uncollected urban and industrial wastes that are disposed of by other
means. Together, uncollected urban and industrial wastes contribute at least 4.5 pounds (2.0 kilograms) per
capita per day. The total gives a conservative per capita generation rate of 10 pounds (4.5 kilograms) per day of
urban''and industrial wastes. Approximately 50 percent of all the urban and industrial waste generated in the
United States is burned, using a wide variety of combustion methods with both enclosed and open
burning3. Atmospheric emissions, both gaseous and paniculate, result from refuse disposal operations that use
combustion to reduce the quantity of refuse. Emissions from these combustion processes cover a wide range
because of their dependence upon the refuse burned, the method of combustion or incineration, and other
factors. Because of the large number of variables involved, it is not possible, in general, to delineate when a higher
or lower emission factor, or an intermediate value should be used For this reason, an average emission factor has
been presented.
References

1. Solid Waste • It Will Not Go Away. League of Women Voters of the United States Publication Number 675.
April 1971.

2. Black, R.J., H.L. Hickman, Jr., A.J. Klee, A.J. Muchtck, and R.D. Vaughan. The National Solid Waste
Survey: An Interim Report. Public Health Service, Environmental Control Administration. Rockville, Md.
1968.

3. Nationwide Inventory of Air Pollutant Emissions, 1968 US. DHEW, PHS, EHS, National Air Pollution
Control Administration. Raleigh, N.C. Publication Number AP-73. August 1970.
12/77 Solid Waste Disposal 2.0-1
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2.1 REFUSE INCINERATION

2.1.1 Process Description1'4

The most common types of incinerators consist of a refractory-lined chamber with a grate upon which refuse
is burned. In some newer incinerators water-walled furnaces are used. Combustion products are formed by
heating and burning of refuse on the grate. In most cases, since insufficient underfire (undergrate) air is provided
to enable complete combustion, additional over-fire air is admitted above the burning waste to promote complete
gas-phase combustion. In multiple-chamber incinerators, gases from the primary chamber flow to a small
secondary mixing chamber where more air is admitted, and more complete oxidation occurs. As much as 300
percent excess air may be supplied in order to promote oxidation of combustibles Auxiliary burners are
sometimes installed in the mixing chamber to increase the combustion temperature. Many small-size incinerators
are single-chamber units in which gases are vented from the primary combustion chamber directly into the
exhaust stack. Single-chamber incinerators of this type do not meet modern air pollution codes.

2.1.2 Definitions of Incinerator Categories1

No exact definitions of incinerator size categories exist, but for this report the following general categories
and descriptions have been selected:

1. Municipal incinerators — Multiple-chamber units often have capacities greater than 50 tons (45.3 MT) per
day and are usually equipped with automatic charging mechanisms, temperature controls, and movable
grate systems. Municipal incinerators are also usually equipped with some type oi particulale control
device, such as a spray chamber or electrostatic precipitator.

2. Industrial/commercial incinerators — The capacities of these units cover a wide range, generally between
50 and 4,000 pounds (22.7 and 1,800 kilograms) per hour. Of either single- or multiple-chamber design,
these units are often manually charged and intermittently operated. Some industrial incinerators are
similar to municipal incinerators in size and design. Better designed emission control systems include gas -
fired afterburners or scrubbing, or both.

3. Trench incinerators— A trench incinerator is designed for the combustion of wastes having relatively high
heat content and low ash content. The design of the unit is simple: a U-shaped combustion chamber is
formed by the sides and bottom of the pit and air is supplied from nozzles along the top of the pit. The
nozzles are directed at an angle below the horizontal to provide a curtain of air across the top of the pit and
. to provide air for combustion in the pit. The trench incinerator is not as efficient for burning wastes as the
municipal multiple-chamber unit, except where careful precautions are taken to use it for disposal of low-
ash, high-heat-content refuse, and where special attention is paid to proper operation. Low construction
and operating costs have resulted in the use of this incinerator to dispose of materials other than those for
which it was originally designed. Emission factors for trench incinerators used to burn thr»e such
materials7 are included in Table 2.1-1

4. Domestic incinerators — This category includes incinerators marketed for residential use. Fairly simple in
design, they may have single or multiple chambers and usually are equipped with an auxiliary burner 10
aid combustion.

5. Flue-fed incinerators — These units, commonly found in large apartment houses, are characterized by the
charging method of dropping refuse down the incinerator flue and into the combustion chamber Modified
flue-fed incinerators utilize afterburners and draft controls to improve combustion efficiency and reduce
emissions.
12/77 Solid Waste Disposal 2.1-1
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10
Table 2.1-1. EMISSION FACTORS FOR REFUSE INCINERATORS WITHOUT CONTROLS"
EMISSION FACTOR RATING: A
Incinerator type
Municipal6
Multiple chamber, uncontrolled
With settling chamber and
water spray system'
1 ndustnal/commercial
Multiple chamber^
Single chamber1
Trench'
Wood
Rubber tires
Municipal refuse
Controlled air m
Flue-fed single chamber"
Flue-fed (modified)0-?
Domestic single chamber
Without primary burner"
With primary burner'
Pathological5
Particulates
Ib/ton

30
14

7
15

13
138
37
1.4
30
6

35
7
8
kg/MT

15
7

35
75

65
69
18.5
07
15
3

175
3.5
4
Sulfur oxides'3
Ib/ton

25
25

25h
25h

0.1k
NA
25h
1 5
05
0.5

05
05
Neg
kg/MT

1.25
1.25

1 25
1.25

005
NA
125
0.75
025
0.25 '

0.25
0.25
Neg
Carbon monoxide
Ib/ton

35
35

10
20

NA1
NA
NA
Neg
20
10

300
Neg
Neg
kg/MT

17.5
175

5
10

NA
NA
NA
Neg
10
5

150
Neg
Neg
OrganlcS0
Ib/ton

1.5
1.5

3
15

NA
NA
NA
Neg
15
3
-
100
2
Neg
kg/MT

075
0.75

1.5
7.5

NA
NA
NA
Neg
7.5
1.5

50
1
Neg
Nitrogen oxidesd
Ib/ton

3
3

3
2

4
NA
NA
10
3
10

1
2
3
kg/MT

1.5
1 5

1 5
1

2
NA
NA
5
1 5
5

0.5
1
1 5
PI
2
i
aAverage factors given based on EPA procedures for incinerator stack testing
''Expressed as sulfur dioxide
cExpressed as methane
Expressed as nitrogen dioxide
e References 5 and 8 through 14
Most municipal incinerators are equipped with at least this much control see Table
2 1 -2 for appropriate efficiencies for other controls
^References 3.5. 10.13. and IS
Based on municipal incinerator data
'References 3.5.10, and 15
' Reference 7
kBased on data for wood combustion in conical burners
Not available
mReference 9
"References 3.10.11.13.15. and 16
°With afterburners and draft controls
^References 3,11, and 15
^References 5 and 10.
r Reference 5
5 References 3 and 9
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6. Pathological incinerators — These are incinerators used to dispose of animal remains and other organic
material of high moisture content. Generally, these units are m a size range of 50 to 100 pounds (22.7 to
45.4 kilograms) per hour. Wastes are burned on the hearth in the combustion chamber. The units are
equipped with combustion controls and afterburners to ensure good combustion and minimal emissions.

7. Controlled air incinerators — These units operate on a controlled combustion principle in which the waste
is burned in the absence of sufficient oxygen for complete combustion in the main chamber. This process
generates a highly combustible gas mixture that is then burned with excess air in a secondary chamber,
resulting in efficient combustion. These units are usually equipped with automatic charging mechanisms
and are characterized by the high effluent temperatures reached at the exit of the incinerators.

2.1.3 Emissions and Controls1

Operating conditions, refuse composition, and basic incinerator design have a pronounced effect on
emissions. The manner in which air is supplied to the combustion chamber or chambers has, among all the
parameters, the greatest effect on the quantity of particulate emissions. Air may be introduced from beneath the
chamber, from the side, or from the top of the combustion area. As underfire air is increased, and increase in fly-
ash emissions occurs. Erratic refuse charging causes a disruption of the combustion bed and a subsequent release
of large quantities oflparticulates. Large quantities of uncombusted particulate matter and carbon monoxide are
also emitted for an extended period after charging of batch-fed units because of interruptions in the combustion
process. In continuously fed units, furnace particulate emissions are strongly dependent upon grate type. The use
of rotary kiln and reciprocating grates results in higher particulate emissions than the use of rocking or traveling
grates.14 Emissions of oxides of sulfur are dependent on the sulfur content of the refuse. Carbon monoxide and
unburned hydrocarbon emissions may be significant and are caused by poor combustion resulting from improper
incinerator design or operating conditions. Nitrogen oxide emissions increase with an increase in the temperature
of the combustion zone, an increase in the residence time in the combustion zone before quenching, and an
increase in the excess air rates to the point where dilution cooling overcomes the effect of increased oxygen
concentration.14

Hydrochloric acid emissions were found to approximate 1.0 Ib/ton of feed in early work14 and 1.8 Ib/ton in
more recent work.23 The level can be sharply increased in areas where large quantities of plastics are consumed.
Methane levels found in recent work" range from 0.04 to 0.4 Ib/ton of feed.

Table 2.1-2 lists the relative collection efficiencies of particulate control equipment used for municipal
incinerators. This control equipment has little effect on gaseous emissions. Table 2.1-1 summarizes the
uncontrolled emission factors for the various types of incinerators previously discussed.

Table 2.1-2. COLLECTION EFFICIENCIES FOR VARIOUS TYPES OF
MUNICIPAL INCINERATION PARTICULATE CONTROL SYSTEMS"
Type of system
Settling chamber
Settling chamber and water spray
Wetted baffles
Mechanical collector
Scrubber
Electrostatic precipitator
Fabric filter
Efficiency, %
Oto30
30 to 60
60
30 to 80
80 to 95
90 to 96
97 to 99
References 3. 5. 6. and 1 7 through 21
12/77 Solid Waste Disposal 2.1-3
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References for Section 2.1

1. Air Pollutant Emission Factors. Final Report. Resources Research Incorporated, Reston. Virginia. Prepared
for National Air Pollution Control Administration, Durham, N.C., under Contract Number CPA-22-69-119.
April 1970.

2. Control Techniques for Carbon Monoxide Emissions from Stationary Sources. U.S. DHEW, PHS, EHS,
National Air Pollution Control Administration. Washington, D.C. Publication Number AP-65. March 1970.

3. Danielson, J.A. (ed.). Air Pollution Engineering Manual. U.S. DHEW, PHS, National Center for Air
Pollution Control. Cincinnati, Ohio, Publication Number 999-AP-40. 1967. p. 413-503.

4. De Marco. J. et al. Incinerator Guidelines 1969. U.S. DHEW, Public Health Service. Cincinnati, Ohio. SW-
13TS. 1969. p. 176.

5. Kanter, C. V., R. G. Lunche, and A. P. Fururich. Techniques for Testing Air Contaminants from
Combustion Sources. J. Air Pol. Control Assoc. 6(4): 191-199. February 1957.

6. Jens, W. and F.R. Rehm. Municipal Incineration and Air Pollution Control. 1966 National Incinerator
Conference, American Society of Mechnical Engineers. New York, May 1966.

7. Burkle, J.O., J.A. Dorsey, and B. T. Riley. The Effects of Operating Variables and Refuse Types on
Emissions from a Pilot-Scale Trench Incinerator. Proceedings of the 1968 Incinerator Conference.
American Society of Mechanical Engineers. New York. "May 1968. p. 3441.

8. Fernandas. J. H. Incinerator Air Pollution Control. Proceedings of 1968 National Incinerator Conference,
American Society of Mechanical Engineers. New York. May 1968. p. 111.

9. Unpublished data on incinerator testing. U.S. DHEW, PHS, EHS, National Air Pollution Control
Administration. Durham, N. C. 1970.

10. Stear, J. L. Municipal Incineration: A Review of Literature. Environmental Protection Agency, Office of Air
Programs. Research Triangle Park, N.C. GAP Publication Number AP-79. June 1971.

11. Kaiser, E.R. et al. Modifications to Reduce Emissions from a Flue-fed Incinerator. New York University.
College of Engineering. Report Number 552.2. June 1959. p. 40 and 49.

12. Unpublished data on incinerator emissions. U.S. DHEW, PHS, Bureau of Solid Waste Management.
Cincinnati, Ohio. 1969.

13. Kaiser, E. R. Refuse Reduction Processes in Proceedings of Surgeon General's Conference on Solid \V iste
Management. Public Health Service. Washington, D.C. PHS Report Number 1729. July 10-20, 1967.

14. Nissen, Walter R. Systems Study of Air Pollution from Municipal Incineration. Arthur D Little, Inc.
Cambridge, Mass. Prepared for National Air Pollution Control Administration, Durham, N.C., under the
Contract Number CPA-22-69-23 March 1970.

15. Unpublished source test data on incinerators Resources Research, Incorporated. Reston, Virginia. 1966-
1969.
2.1-4 EMISSION FACTORS 12/77
-------
16. Communication between Resources Research, Incorporated, Reston, Virginia, and Maryland State
Department of Health, Division of Air Quality Control, Baltimore, Md. 1969.

17. Rehm, F. R. Incinerator Testing and Test Results. J. Air Pol. Control Assoc. 6:199-204. February 1957.

18. Stenburg, R. L. et al. Field Evaluation of Combustion Air Effects on Atmospheric Emissions from Municipal
Incinerations. J. Air Pol. Control Assoc. 72:83-89. February 1962.

19. Smauder, E. E. Problems of Municipal Incineration. (Presented at First Meeting of Air Pollution Control
Association, West Coast Section, Los Angeles, California. March 1957.)

20. Cerstfe, R. W. Unpublished data: revision of emission factors based on recent stack tests. U.S. DHEW,
PHS, National Center for Air Pollution Control. Cincinnati, Ohio. 1967.

21. A Field Study of Performance of Three Municipal Incinerators. University of California, Berkeley,
Technical Bulletin. 6:41, November 1957

22. Driscol, J. et al. Evaluation of Monitoring Methods and Instrumation for Hydrocarbons and Carbon
Monoxide in Stationary Source Emissions. Publication No. EPA-R2-72-106. November 1977.

23. Jahnke, J. A., J. L. Chaney, R. Rollins, and C. R. Fortune. A Reasearch Study of Gaseous Emissions from a
Municipal Incinerator. J. Air Pollut. Contr. Assoc. 27:747-753, August 1977.
12/77 Solid Waste Disposal 2.1-5
-------
Table 5.8-1. EMISSION FACTORS FOR HYDROFLUORIC ACID MANUFACTURE
Type of Operation
and Control
a
Spar drying
Uncontrolled
Fabric filter
Spar handling
silosb
Uncontrolled
Fabric filter
Transfer operations
Uncontrolled
Covers, additives
Tail gasc
Uncontrolled

Caustic scrubber

Control
efficiency
(%)

0
99

0
80

Emissions
Gases
Ib/ton acid

25.0 (HF)
30.0 (SiFiJ
45.0 (S02)
0.2 (HF)
0.3 (SiFi,)
0.5 (S02)
kg/MT acid

12.5 (HF)
15.0 (SiFiJ
22.5 (S02)
0.1 (HF)
0.2 (SiFjJ
0.3 (S02)
Particulates (Spar)
Ib/ton
Fluorospar

75.0
0.8

60.0
0.6

6.0
1.2

kg/MT
Fluorospar

37.5
0.4

30.0
0.3

3.0
0.6

Emission
Factor
Rating

Reference 1. Averaged from information provided by four plants. Hourly fluorospar input calculated
from reported 1975 year capacity, assuming stoichiometric amount of calcium fluoride and 97.5%
content in fluorospar. Hourly emission rates calculated from reported baghouse controlled rates.
Values averaged were:
Plant 1975 capacity Emissions Ib/Ton Fluorospar
1
2
3
4
Information as in Note a.
emissions.
Information as in Note a.
in Reference 4.
15,000 ton HF
20,000 ton HF
50,000 ton HF
11,000 ton HF
106
130
42
30
Four plants averaged for silo emissions, two plants for transfer operations

Three plants averaged. HF and SiFi^ emission factors verified by information
-------
processing. The precondenser removes water vapor and sulfuric acid
mist, and the condenser, acid scrubber and water scrubbers remove all
but small amounts of hydrogen fluoride, silicon tetrafluoride, sulfur
dioxide and carbon dioxide from the tail gas. A caustic scrubber is
employed to reduce further the levels of these pollutants in the tail
gas.

Dust emissions result from the handling and drying of the fluorospar,
and they are controlled with bag filters at the spar storage silos and
drying kilns, their principal emission points.

Hydrogen fluoride emissions are minimized by maintaining a slight
negative pressure in the kiln during normal operations. Under upset
conditions, a standby caustic scrubber or a bypass to the tail gas
caustic scrubber are used to control hydrogen fluoride emissions from
the kiln.

Fugitive dust emissions from spar handling and storage are con-
trolled with flexible coverings and chemical additives.

Table 5.8-1 lists the emission factors for the various process
operations. The principal emission locations are shown in the process
flow diagram, Figure 5.8-1.

References for Section 5.8

1. Screening Study on Feasibility of Standards of Performance for'
Hydrofluoric Acid Manufacture. EPA-450/3-78-109, U.S. Environmental
Protection Agency, Research Triangle Park, NC, October 1978.

2. "Hydrofluoric Acid", Kirk-Othmer Encyclopedia of Chemical
Technology. Vol. 9, Interscience Publishers, New York, 1965.

3. W. R. Rogers and K. Muller, "Hydrofluoric Acid Manufacture",
Chemical Engineering Progress. 59(5);85-8. May 1963.

4. J. M. Robinson, et al., Engineering and Cost Effectiveness Study
of Fluoride Emissions Control. Vol. 1. PB 207 506, National Technical
Information Service, Springfield, VA, 1972.
5.8-4 EMISSION FACTORS 2/80
-------
5.9 NITRIC ACID

5.9.1 Process Description

Weak Acid Production - Nearly all the nitric acid produced in the
United States is manufactured by the catalytic oxidation of ammonia
(Figure 5.9-1). This process typically consists of three steps, each of
which corresponds to a distinct chemical reaction. First, a 1:9 ammonia/
air mixture is oxidized at high temperature (1380 - 1470°F or
750 - 800°C) as it passes through a platinum/rhodium catalyst, according
to the reaction:

4NH3 + 502 -»• 4NO + 6H20 (1)
Ammonia Oxygen Nitric • Water
oxide

After the process stream is cooled to 100°F (38°C) or less by passage
through a cooler/condenser, the nitric oxide reacts with residual oxygen
to form nitrogen dioxide:

2NO + 02 -> 2N02 *• N204
Nitrogen "*" Nitrogen (2)
dioxide tetroxide

Finally, the gases are introduced into a bubble cap plate absorption
column for contact with a countercurrent stream of water. The exothermic
reation that occurs is:

3N02 + H20 -J- 2HN03 + NO (3)

The production of nitric oxide in Reaction 3 necessitates the intro-
duction of a secondary air stream into the column to oxidize it into
nitrogen dioxide, thereby perpetuating the absorption operation.

In the past, nitric acid plants have been operated at a single
pressure, ranging from 14.7 to 176 pounds per square inch (100 - 1200 kPa)
However, since Reaction 1 is favored by low pressures and Reactions 2
and 3 are favored by higher pressures, newer plants tend to be operating
two pressure systems, incorporating a compressor between the oxidizer
and the condenser.

The spent gas flows from the top of the absorption tower to an
entrainment separator for acid mist removal, through a heat exchanger in
the ammonia oxidation unit for energy absorption by the ammonia stream,
through an expander for energy recovery, and finally to the stack. In
most plants, however, the tail gas is treated to remove residual nitrogen
oxides before release to the atmosphere.

High Strength Acid Production - The nitric acid concentration
process consists of feeding strong sulfuric acid and 50 - 70 percent
nitric acid to the top of a packed dehydrating column at approximately
atmospheric pressure. The acid mixture flows downward counter to ascend-
ing vapors. Concentrated nitric acid leaves the top of the column as 98

10/80 Chemical Process Industry 5.9-1
-------
AIR
EMISSION
POINT
COMPRESSOR
EXPANDER
EFFLUENT
STACK
— NOX EMISSIONS —
CONTROL
CATALYTIC REDUCTION
AIR
PREHEATER
NITRIC OXIDE
GAS
WASTE
HEAT
BOILER
NITRIC
ACID GAS
PLATINUM
FILTER
ABSORPTION
TOWER
COOLING
WATER
SECONDARY AIR
ENTRAINEP
MIST
SEPARATOR
COOLER
CONDENSER PRODUCT
(50 • 70%
HN03)

Figure 5.9-1. Flow diagram of typical nitric acid plant using pressure process (high strength
acid unit not shown).
5.9-2
EMISSION FACTORS
10/80
-------
percent vapor, containing a small amount of N02 and Q£ from dissociation
of nitric acid. The concentrated acid vapor leaves the column and goes
to a bleacher and countercurrent condenser system to effect the conden-
sation of strong nitric acid and the separation of oxygen and nitrogen
oxide byproducts. These byproducts then flow to an absorption column
where the nitric oxide mixes with auxiliary air to form NC>2, which is
recovered as weak nitric acid. Unreacted gases are vented to the atmo-
sphere from the top of the absorption column.

TABLE 5.9-1. NITROGEN OXIDE EMISSIONS FROM NITRIC ACID PLANTS3

EMISSION FACTOR RATING: B
Control Emissions
Source Efficiency, % Ib/ton Acid kg/MT Acid
Weak Acid Plant Tail Gas

0
(14 - 86) (7 - 43)
Uncontrolled15 0 43 22
Catalytic reduction

Natural gas 99.1 0.4 0.2
(0.05 - 1.2) (0.03 - 0.6)
Hydrogen0 97 - 99.8 0.8 0.4
(0 - 1.5) (0 - 0.8)
Natural gas/hydrogen
(25%/75%) 98 - 98.5 1.0 0.5
(0.8 - 1.1) (0.4 - 0.6)
Extended absorption 95.8 1.8 0.9
(0.8 - 2.7) (0.4 - 1.4)

High Strength Acid Plant6 NAf 10 5

Based on 100% acid. Production rates are in terms of total weight of
product (water and acid). A plant producing 500 tons (454 MT)/day of
55 wt. % nitric acid is calculated as producing 275 tons (250 MT)/day
,of 100% acid. Ranges in parentheses. NA: Not Applicable.
Reference 3. Based on a study of 18 plants.
References 1 and 2. Based on data from 2 plants with these process
conditions: production rate, 130 tons (118 MT)/day at 100% rated
capacity; absorber exit temperature, 90°F (32°C); absorber exit
.pressure, 87 psig (600 kPa); acid strength, 57%.
References 1 and 2. Based on data from 2 plants with these process
conditions: production rate, 208 tons (188 MT)/day at 100% rated
capacity; absorber exit temperature, 90°F (32°C); absorber exit
presure, 80 psig (550 kPa); acid strength, 57%.
References 1 and 2. Based on a unit that produces 3000 Ib/hr (6615
kg/hr) at 100% rated capacity, of 98% nitric acid.
10/80 Chemical Process Industry 5.9-3
-------
The two most common techniques used to control absorption tower
tail gas emissions are extended absorption and catalytic reduction. The
extended absorption technique reduces emissions by increasing the effi-
ciency of the absorption tower. This efficiency increase is achieved by
increasing the number of absorber trays, operating the absorber at
higher pressures, or cooling the weak acid liquid in the absorber.

In the catalytic reduction process (often termed catalytic oxidation),
tail gases are heated to ignition temperature, mixed with fuel (natural
gas, hydrogen, carbon monoxide or ammonia) and passed over a catalyst.
In the presence of the catalyst, the fuels are oxidized, and the nitrogen
oxides are reduced to N2> The extent of reduction of NC>2 and NO to N£
is a function of plant design, fuel type operating temperature and
pressure, space velocity through the reduction catalytic reactor, type
of catalyst, and reactant concentration. .See Table 5.9-1.

Two seldom used alternative control devices for absorber tail gas
are molecular sieves and wet scrubbers. In the molecular sieve technique,
tail gas is contacted with an active molecular sieve which catalyticly
oxidizes NO to N02 and selectively adsorbs the N02. The N0£ is then
thermally stripped from the molecular sieve and returned to the absorber.
In the scrubbing technique, absorber tail gas is scrubbed with an aqueous
solution of alkali hydroxides or carbonates, ammonia, urea or potassium
permanganate. The NO and N0£ are absorbed and recovered as nitrate or
nitrite salts.

Comparatively small amounts of nitrogen oxides are also lost from
acid concentrating plants. These losses (mostly N02) are from the
condenser system, but the emissions are small enough to be controlled
easily by inexpensive absorbers.

Acid mist emissions do not occur from the tail gas of a properly
operated plant. The small amounts that may be present in the absorber
exit gas streams are removed by a separator or collector prior to entering
the catalytic reduction unit or expander.

Emissions from acid storage tanks may occur during tank filling.
The displaced gases are equal in volume to the quantity of acid added to
the tanks.

Nitrogen oxide emissions (expressed as N02) are presented for weak
nitric acid plants in Table 5.9-1. The emission factors vary consider-
ably with the type of control employed and with process conditions. For
comparison purposes, the EPA New Source Performance Standard for both
new and modified plants is 3.0 pounds per ton (1.5 kg/MT) of 100 percent
acid produced, maximum 3 hour average, expressed as N02.
5.9-4 EMISSION FACTORS 10/80
-------
5.9.2 Emissions and Controls

Emissions from nitric acid manufacture consist primarily of nitric
oxide, nitrogen dioxide (which accounts for visible emissions) and trace
amounts of nitric acid mist. By far, the major source of nitrogen
oxides is the tail gas from the acid absorption tower (Table 5.9-1). In
general, the quantity of NOx emissions is directly related to the
kinetics of the nitric acid formation reaction and absorption tower
design.

The two most common techniques used to control absorption tower
tail gas emissions are extended absorption and catalytic reduction. The
extended absorption technique reduces emissions by increasing the effi-
ciency of the absorption tower. This efficiency increase is achieved by
increasing the number of absorber trays, operating the absorber at
higher pressures, or cooling the weak acid liquid in the absorber.

In the catalytic reduction process (often termed catalytic oxidation),
tail gases are heated to ignition temperature, mixed with fuel (natural
gas, hydrogen, carbon monoxide or ammonia) and passed over a catalyst.
In the presence of the catalyst, the fuels are oxidized, and the nitrogen
oxides are reduced to N2> The extent of reduction of NC>2 and NO to N2
is a function of plant design, fuel type operating temperature and
pressure, space velocity through the reduction catalytic reactor, type
of catalyst, and reactant concentration. See Table 5.9-1.

Two seldom used alternative control devices for absorber tail gas
are molecular sieves and wet scrubbers. In the molecular sieve technique,
tail gas is contacted with an active molecular sieve which catalyticly
oxidizes NO to N02 and selectively adsorbs the N02. The N02 is then
thermally stripped from the molecular sieve and returned to the absorber.
In the scrubbing technique, absorber tail gas is scrubbed with an aqueous
solution of alkali hydroxides or carbonates, ammonia, urea or potassium
permanganate. The NO and N02 are absorbed and recovered as nitrate or
nitrite salts.

Emissions from acid storage tanks may occur during tank filling.
The displaced gases are equal in volume to the quantity of acid added to
the tanks.

10/80 Chemical Process Industry 5.9-5
-------
new and modified plants is 3.0 pounds per ton (1.5 kg/MT) of 100 percent
acid produced, maximum 3 hour average, expressed as NC^.

References for Section 5.9

1. Control of Air Pollution from Nitric Acid Plants. Office of Air
Quality Planning and Standards, U.S. Environmental Protection
Agency, Research Triangle Park, NC, August 1971. Unpublished.

2. Atmospheric Emissions from Nitric Acid Manufacturing Processes,
999-AP-27, U.S. Department of Health, Education and Welfare,
Cincinnati, OH, 1966.

3. Marvin Drabkin, A Review of Standards of Performance for New
Stationary Sources - Nitric Acid Plants. EPA-450/3-79-013, U.S.
Environmental Protection Agency, Research Triangle Park, NC, March
1979.

4. "Standards of Performance for Nitric Acid Plants", 40 CFR 60. G.
5.9-6 EMISSION FACTORS 10/80
-------
5.23 PHARMACEUTICALS PRODUCTION

5.23.1 Process Description

Thousands of individual products are categorized as Pharmaceuticals.
These products usually are produced in modest quantities in relatively
small plants using batch processes. A typical pharmaceutical plant will
use the same equipment to make several different products at different
times. Rarely is equipment dedicated to the manufacture of a single
product.

Organic chemicals are used as raw materials and as solvents, and
some chemicals such as ethanol, acetone, isopropanol and acetic anhyd-
ride are used in both ways. Solvents are almost always recovered and
used many times.

In a typical batch process, solid reactants and solvent are charged
to a reactor where they are held (and usually heated) until the desired
product is formed. The solvent is distilled off, and the crude residue
may be treated several times with additional solvents to purify it. The
purified material is separated from the remaining solvent by centrifuge
and finally is dried to remove the last traces of solvent. As a rule,
solvent recovery is practiced for each step in the process where it is
convenient and cost effective to do so. Some operations involve very
small solvent losses, and the vapors are vented to the atmosphere through
a fume hood. Generally, all operations are carried out inside buildings,
so some vapors may be exhausted through the building ventilation system.

Certain Pharmaceuticals - especially antibiotics - are produced by
fermentation processes. In these instances, the reactor contains an
aqueous nutrient mixture with living organisms such as fungi or bacteria.
The crude antibiotic is recovered by solvent extraction and is purified
by essentially the same methods described above for chemically synthe-
sized Pharmaceuticals. Similarly, other Pharmaceuticals are produced by
extraction from natural plant or animal sources. The production of
insulin from hog or beef pancreas is an example. The processes are not
greatly different from those used to isolate antibiotics from fermen-
tation broths.

5.23.2 Emissions and Controls

Emissions consist almost entirely of organic solvents that escape
from dryers, reactors, distillation systems, storage tanks and other
operations. These emissions are exclusively nonmethane organic compounds.
Emissions of other pollutants are negligible (except for particulates in
unusual circumstances) and are not treated here. It is not practical to
attempt to evaluate emissions from individual steps in the production
process or to associate emissions with individual pieces of equipment,
because of the great variety of batch operations that may be carried out

10/80 Chemical Process Industry 5.23-1
-------
at a single production plant. It is more reasonable to obtain data on
total solvent purchases by a plant and to assume that these represent
replacements for solvents lost by evaporation. Estimates can be refined
by subtracting the materials that do not enter the air because of being
incinerated or incorporated into the pharmaceutical product by chemical
reaction.

If plant-specific information is not available, industrywide data
may be used instead. Table 5.23-1 lists annual purchases of solvents by
U.S. pharmaceutical manufacturers and shows the ultimate disposition of
each solvent. Disposal methods vary so widely with the type of solvent
that it is not possible to recommend average factors for air emissions
from generalized solvents. Specific information for individual solvents
must be used. Emissions can be estimated by obtaining plant-specific
data on purchases of individual solvents and computing the quantity of
each solvent that evaporates into the air, either from information in
Table 5.23-1 or from information obtained for the specific plant under
consideration. If solvent volumes are given, rather than weights,
liquid densities in Table 5.23-1 can be used to compute weights.

Table 5.23-1 gives for each plant the percentage of each solvent
that is evaporated into the air and the percentage that is flushed into
the sewer. Ultimately, much of the volatile material from the sewer
will evaporate and will reach the air somewhere other than the pharma-
ceutical plant. Thus, for certain applications it may be appropriate to
include both the air emissions and the sewer disposal, in an emissions
inventory that covers a broad geographic area.

Since solvents are expensive and must be recovered and reused for
economic reasons, solvent emissions are controlled as part of the normal
operating procedures in a pharmaceutical industry. In addition, most
manufacturing is carried out inside buildings, where solvent losses must
be minimized to protect the health of the workers. Water or brine
cooled condensers are the most common control devices, with carbon
adsorbers in occasional use. With each of these methods, solvent can be
recovered. Where the main objective is not solvent reuse but is the
control of an odorous or toxic vapor, scrubbers or incinerators are
used. These control systems are usually designed to remove a specific
chemical vapor and will be used only when a batch of the corresponding
drug is being produced. Usually, solvents are not recovered from
scrubbers and reused, and of course, no solvent recovery is possible
from an incinerator.

It is difficult to make a quantitative estimate of the efficiency
of each control method, because it depends on the process being con-
trolled, and pharmaceutical manufacture involves hundreds of different
processes. Incinerators, carbon adsorbers and scrubbers have been
reported to remove greater than 90 percent of the organics in the
control equipment inlet stream. Condensers are limited, in that they
can only reduce the concentration in the gas stream to saturation at the
5.23-2 EMISSION FACTORS 10/80
-------
condenser temperature, but not below that level. Lowering the temper-
ature will, of course, lower the concentration at saturation, but it is
not possible to operate at a temperature below the freezing point of one
of the components of the gas stream..
TABLE 5.23-1.
SOLVENT PURCHASES AND ULTIMATE DISPOSITION BY
PHARMACEUTICAL MANUFACTURERS3
Solvent
Acetic Add
Acetic Anhydride
Acetone
Acetonltrlle
Amyl Acetate
Amyl Alcohol
Benzene
Blendan (AMOCO)
Butanol
Carbon Tetrachlorlde
Chloroform
Cyclohexylamine
o- 01 chl ore benzene
Dlethylamine
Dlethyl Carbonate
Dimethyl Acetamide
Dimethyl Fonnamide
Dimethyl sulf oxide
1 ,4-Dloxane
Ethanol
Ethyl Acetate
Ethyl Bromide
Ethyl ene Glycol
Ethyl Ether
Formaldehyde
Fomamlde
Freons
Hexane
Isobutyraldehyde
Isopropanol
Isopropyl Acetate
Isopropyl Ether
Nethanol
Methyl Cellosolve
Methylene Chloride
Methyl Ethyl Ketone
Methyl Formate
Methyl Isobutyl Ketone
Polyethylene Glycol 600
Pyrldlne
Skelly Solvent B (hexanes)
Tetrahydrofuran
Toluene
Trlchloroethane
Xylene
Annual
Purchase
(metric tons)
930
1,265
12.040
35
285
1.430
1.010
530
320
1.850
500
3.930
60
50
30
95
1,630
750
43
13.230
2.380
45
60
280
30
440
7,150
530^
85
3,850
480
25
7.960
195
10.000
260
415
260
3
3
1.410
4
6.010
135
3.090
Ultimate Disposition (percent)
Air
Emissions
1
1
14
83
42
99
29
-
24
11
57
-
2
94
4
7
71
1
5
10
30
-
.
85
19
-
0.1
17
50
14
28
SO
31
47
53
65
-
BO
-
-
29
-
31
100
6
Sewer
82
57
22
17
58
-
37
-
6
7
5
-
98
6
71
-
3
28
-
6
47
100
100
4
77
67
.
_
50
17
11
50
45
53
5
12
74
-
-
100
2
-
14
-
19
Incineration
—
-
38
.
.
.
16
-
1
82
.
-
-
-
-
-
20
71
-
7
20
.
'
-
-
-
-
15
-
17
61
-
14
_
20
23
-
-
-
-
69
100
26
-
70
Solid Haste or
Contract Haul
.
.
7
.
.
.
8
.
36
.
38
-
-
-
-
93
6
-
95
1
3
-
-
11
\ -
26
-
68
-
7
-
-
6
,
22
-
12
-
-
-
-
-
29
-
5
Product
17
42
19
.
.
1
10
100
31
_
.
100
-
-
25
-
-
-
-
76
-
.
-
-
4
7
99.9
.
-
45
-
-
4
-
-
-
14
20
100

~
Liquid Density
Ib/gal * 68°F
8.7
9.0
6.6
6.6
7.3
6.8
7.3
NA
6.8
13.3
12.5
7.2
10.9
5.9
8.1
7.9
7.9
11.1
8.6
6.6
7.5
12.1
9.3
6.0
b
9.5
c
5.5
6.6
6.6
7.3
6.0
6.6
8.7
11.1
6.7
8.2
6.7
9.5
8.2
5.6
7.4 "
7.2
11.3
7.2
These data were reported by 26 member companies of the Pharmaceutical
Manufacturers Association, accounting for 53 percent of pharmaceutical
sales in 1975.
Sold as aqueous solutions containing 37% to 50% formaldehyde by weight.
Some Freons are gases, and others are liquids weighing 12 - 14 Ib/gal.
10/80
Chemical Process Industry
5.23-3
-------
Reference for Section 5.23

1. Control of Volatile Organic Emissions from Manufacture of
Synthesized Pharmaceutical Products, EPA-450/2-78-029, U. S.
Environmental Protection Agency, Research Triangle Park, NC,
December 1978.
5.23-4 EMISSION FACTORS 10/80
-------
5.24 MALEIC ANHYDRIDE

5. 2 A.I General1

The predominant end use of maleic anhydride (MA) is in the pro-
duction of unsaturated polyester resins for a variety of uses. These
laminating resins, which have high structural strength and good dielec-
tric properties, are used in automobile bodies, building panels, molded
boats, chemical storage tanks, lightweight pipe, machinery housings,
furniture, radar domes, luggage, and bathtubs. Other end products are
fumaric acid, agricultural chemicals, alkyd resins, lubricants, copoly-
mers, plastics, succinic acid, surface active agents, and other products.
In the United States, the primary raw material used in the production of
MA is benzene, with one plant using only n-butane and a second plant
using n-butane for 20 percent of its feedstock needs. The MA industry
is exhibiting trends to convert the old benzene plants and to build new
plants that use n-butane. MA also is a byproduct of the production of
phthalic anhydride. It is a solid at room temperature but is a liquid
or gas during production. It is a strong irritant to skin, eyes and
mucous membranes of the upper respiratory system.

The model MA plant, as described in this section, has a benzene to
MA conversion rate of 94.5 percent, has a capacity of 20,600 tons
(22,700 MT) of MA produced per year, and runs 8000 hours per year.

Because of a lack of data, this discussion covers only the benzene
oxidation process, and not the n-butane process.
2
5.24.2 Process Description

The following chemical reaction illustrates how MA is produced by
the benzene oxidation process .
2 C6H6 + 9 02 > 2 (^203 + H20 +4 C02
Benzene Oxygen - * •* Maleic Water Carbon
anhydride dioxide

Vaporized benzene and air are mixed and heated before entering the
tubular reactor. Inside the reactor, the benzene/air mixture is reacted
in the presence of a catalyst which contains approximately 70 percent
vanadium pentoxide (V20s) , with usually 25 to 30 percent molybdenum
trioxide (MoOs), forming a vapor of MA, water and carbon dioxide. The
vapor, which may also contain oxygen, nitrogen, carbon monoxide, benzene,
maleic acid, formaldehyde, formic acid and other compounds from side
reactions, leaves the reactor and is cooled and partially condensed so
that about 40 percent of the MA is recovered in a crude liquid state.
The effluent is then passed through a separator which directs the liquid
to storage and the remaining vapor to the product recovery absorber.
10/80 Chemical Process Industry 5.24-1
-------
The absorber contacts the vapor with water, producing a liquid of about
40 percent maleic acid. The 40 percent mixture is converted to MA,
usually by azeotropic distillation with xylene. Some processes may use
a double effect vacuum evaporator at this point. The effluent then
flows to the xylene stripping column where the xylene is extracted.
This MA is then combined in storage with that from the separator. The
molten product is aged to allow color forming impurities to polymerize.
These are then removed in a fractionation column, leaving the finished
product. The flow diagram shown in Figure 5.24-1 represents a typical
process.

MA product is usually stored in liquid form, although it is some-
times flaked and pelletized into briquets and/or bagged.

Table 5.24-1. EMISSION FACTORS FOR MALEIC ANHYDRIDE PRODUCTION3

EMISSION FACTOR RATING: C

Benzene VOC
Type of source _ Ib/ton _ kg/MT _ Ib/ton _ kg/MT

Product recovery
absorber and refining
vacuum system combined
vent

Uncontrolled 134.0 67.0 172.20 86.10
With carbon adsorption0 0.68 0.34 0.68 0.34
With incineration 0.68 0.34 0.86 0.43

Storage and handling
emissions d d d d

Fugitive emissions e e e e

Secondary emissions _ - _ - _ - _ -
*No data are available for catalytic incineration or for plants
, converted to n-butane.
For recovery absorber and refining vacuum, VOC can be MA and xylene;
for storage and handling, MA, xylene and dust from briquet ing
operations; for secondary emissions, residual organics from spent
catalyst, excess water from dehydration column, vacuum system water,
and fractionation column residues. VOC also includes benzene.
CBefore the exhaust gas stream goes into the carbon adsorber, it is
scrubbed with caustic to remove organic acids and water soluble
.organics. Benzene is the only likely VOC remaining.
See Section 4.3.
Section 9.1.3.
Secondary emission sources are excess water from dehydration column,
vacuum system water, and organics from fractionation column. No
data are available on the quantity of these emissions.

5.24-2 EMISSION FACTORS 10/80
-------
00
o
r-i
O
O
ft)
CO
CO
0-

en
AIR
MAKEUP
WATER
DEHYDRATION
COLUMN
EXCESS
WATER
AGED ANHYDRIDE
STORAGE
KEY
A - PRODUCT RECOVERY ABSORBER VENT
B - VACUUM SYSTEM VENT
C -STORAGE AND HANDLING EMISSIONS
D -SECONDARY EMISSION POTENTIAL
Figure 5.24-1. Process flow diagram for uncontrolled model plant.
-------
2
5.24.2 Emissions and Controls

The predominant pollutant in MA production, benzene, is emitted as
a gas. Essentially all emissions will be from the main process vent of
the product recovery absorber. This is the largest vent. Emissions
here will include any unreacted benzene, which can constitute 3 to 10
percent of the total benzene feed. The only other exit for process
emissions is the refining vacuum system vent. These emissions amount to
0.62 Ib/hr (0.28 kg/hr) of MA and xylene.

Emissions also result from the storage and handling of benzene,
xylene and MA. The reader is referred to Section 4.3 for an explanation
on how to calculate these emissions. MA emissions in the form of dust
can result from the briqueting operation, but no data are available on
the quantity of such emissions.

Fugitive emissions can contain benzene, xylene, MA and maleic acid.
The reader is referred to Section 9.1.3 for fugitive emissions.

Table 5.24-2. UNCONTROLLED EMISSIONS FROM PRODUCT RECOVERY ABSORBER3
Component Wt.% Ib/ton kg/MT
Nitrogen
Oxygen
Water
Carbon Dioxide
Carbon Monoxide
Benzene
Formaldehyde
Maleic Acid
Formic Acid
73.37
16.67
4.00
3.33
2.33
0.33
0.05
0.01
0.01
42,812.0
9,726.0
2,334.0
1,944.0
1,360.0
134.0
28.8
5.6
5.6
21,406.0
4,863.0
1,167.0
972.0
680.0
67.0
14.4
2.8
2.8
Total 58,350.0 29,175.0

Reference 2.

Potential sources of secondary emissions are spent reactor catalyst,
excess water from the dehydration column, vacuum system water, and
fractionation column residues. The small amount of residual organics in
the spent catalyst after washing have low vapor pressure and produce a
small percentage of total emissions. Xylene is the principal organic
contamination in the excess water from the dehydration column and the
vacuum system water. The residues from the fractionation column are
relatively heavey organics, with a molecular weight greater than 116,
and they produce a small percentage of total emissions.

Benzene oxidation process emissions can be controlled at the main
vent by means of carbon adsorption, thermal incineration or catalytic
5.24-4 EMISSION FACTORS 10/80
-------
incineration. Benzene emissions can be stopped by conversion to the n-
butane process. Catalytic incineration and conversion from the benzene
process to the n-butane process are not discussed for lack of data. The
vent from the refining vacuum system is combined with that of the main
process, as a control for refining vacuum system emissions. A carbon
adsorption system or an incineration system can be designed and operated
at a 99.5 percent removal efficiency for benzene and volatile organic
compounds with the operating parameters given in Appendix D of Reference 2.

Fugitive emissions from pumps and valves may be controlled by an
appropriate leak detection system and maintenance program. No control
devices are presently being used for secondary emissions.

References for Section 5.24

1. B. Dmuchovsky and J. E. Franz, "Maleic Anhydride", Kirk-Othmer
Encyclopedia of Chemical Technology, Volume 12, John Wiley and
Sons, Inc., New York, NY, 1967, pp. 819-837.

2. J. F. Lawson, Emission Control Options for the Synthetic Organic
Chemicals Manufacturing Industry; Maleic Anhydride Product Report,
EPA Contract No. 68-02-2577, Hydroscience, Inc., Knoxville, TN,
March 1978.
10/80 Chemical Process Industry 5.24-5
-------
6.5 FERMENTATION
6.5.1 Process Description'

For the purpose of this report only the fermentation industries associated with food will be considered This
includes the production of beer, whiskey, and wine.

The manufacturing process for each of these is similar The four mam brewing production stages and their
respective sub-stages are. (1) brewhouse operations, which include (a) malting of the barley, (b) addition of
adjuncts (corn, grits, and rice) to barley mash, (c) conversion of starch in barley and adjuncts to maltose sugar by
enzymatic processes, (d) separation of wort from grain by straining, and fe) hopping and boiling of the wort,(2)
fermentation, which includes (a) cooling of the wort, (b) additional yeast cultures, (c) fennentai'on for 7 to 10
days, (d) removal of settled yeast, and (e) filtration and carbonation, (3) aging, which lasts from I to 2 months
under refrigeration, and (4) packaging, which includes (a) bottling-pasteunzation, and(b) tacking draft beer
The major differences between beer production and whiskey production arc the purification and distillation
necessary to obtain distilled liquors and the longer period of aging. The primary difference between wine making
and beer making is that grapes are used as the initial raw material in wine rather than grams
As the following Subsection 652. Wine Making, implies, the
FERMENTATION Section is being expanded as new informa-
tion is obtained
Except for the Wine Making information.
mains valid until further nonce

2/80
Table 6.5-1 re-
2/72
Food and Agricultural Industry
65-1
-------
Table 6.5-1. EMISSION FACTORS FOR FERMENTATION PROCESSES
EMISSION FACTOR RATING: E
Type of product
Beer
Grain handling3
Drying spent grains, etc a
Whiskey
Grain handling8
Drying spent grains, etc.3
Aging
Wine
Particulates
Ib/ton

3
5

kg/MT

1.5
2.5

Hydrocarbons
Ib/ton

NAb

—
NA
Iff

kg/MT

—
NA
0.024d

aBased on section on grain processing
bNo emission factor available, but emiss.ons do occur
'Pounds per year per barrel of whiskey stored 2
"Kilograms per year per liter of whiskey stored.
eIMo significant emissions
References for Section 6.5

1. Air Pollutant Emission Factors. Final Report. Resources Research, Inc. Reston, Va. Prepared for National
Air Pollution Control Administration, Durham, N.C., under Contract Number CPA-22-69-119. April 1970.

2. Shreve, RN Chemical Process Industries, 3rd Ed. New York, McGraw-Hill Book Company. 1967. p.
591-608.
6.5-2
EMISSION FACTORS
2/72
-------
6.10 PHOSPHATE FERTILIZERS
6.10.1 NORMAL SUPERPHOSPHATES1

6.10.1.1 General

The term "normal superphosphate" is used to designate a fertilizer
material containing 15 - 21 percent P20s. It is prepared by reacting
ground phosphate rock with 65 - 75 percent sulfuric acid. Rock and acid
are mixed in a reaction vessel, held in an enclosed area (den) while the
reaction mixture solidifies, and transferred to a storage pile for
curing. Following curing, the product is most often ground and bagged
for sale as run-of-the-pile product. It can also be granulated, for
sale as granulated superphosphate or granular mixed fertilizer. However,
this accounts for less than 5 percent of total production. To produce a
granular normal superphosphate material, run-of-the-pile material is
first fed to a pulverizer to be crushed, ground, and screened. Screened
material is sent to a rotary drum granulator and then through a rotary
dryer. The material goes through a rotary cooler and on to storage bins
for sale as bagged or bulk product. Superphosphate fertilizers are
produced at 79 plants in the United States. A generalized flow diagram
of the process for the production of normal superphosphate is shown in
Figure 6.10.1-1.

6.10.1.2 Emissions and Controls

Sources of emissions at a normal superphosphate plant include rock
unloading and feeding, mixer (reactor), den, curing building, and fertil-
izer handling operations. Rock unloading, handling and feeding generate
particulate emissions of phosphate rock dust. The mixer, den and
curing building emit gaseous fluorides (HF and SiF4) and particulates
composed of fluoride and phosphate material. Fertilizer handling oper-
ations release fertilizer dust.

At a typical normal superphosphate plant, the rock unloading,
handling and feeding operations are controlled by a baghouse. The mixer
and den are controlled by a wet scrubber. The curing building and
fertilizer handling operations normally are not controlled.

Emission factors for the production of normal superphosphate are
presented in Table 6.10.1-1. These emission factors are averages based
on recent source test data from controlled phosphate fertilizer plants
in Florida.
10/80 Food and Agricultural Industry 6.10.1-1
-------
PMTICUU1E
EMISSIONS
8 AC HOUSE
GROUND
PHOSPHATE ROCK
ROCK FEEDER
SYSTEM
SULfURIC-
ACID
ROCK BIN PARTICULATE
EMISSIONS
I
10 GYPSUM
POND
PARTI CUWTl
ANOauOftlK
••EMISSIONS
(UNCONTBOU.au
PARTICULAR
AND FLUORIDE
EMISSIONS
PRODUCT
Figure 6.10.1-1. Normal superphosphate process flow diagram.
6.10.1-2
KHSSION FACTORS
10/30
-------
TABLE 6.10.1-1. EMISSION FACTORS FOR THE PRODUCTION OF
NORMAL SUPERPHOSPHATE3

EMISSION FACTOR RATING: A
Emission factor
Emission point Pollutant Ib/ton P-0,. kg/MT
Rock unloading
Rock feeding
Mixer and den

Curing building

Particulate
Particulate
Particulate
Fluoride
Particulate
Fluoride
0.56
0.11
0.52
0.20
7.20
3.80
0.28
0.06
0.26
0.10
3.60
1.90

^Reference 1, pp. 74-77, 169.
Factors are for emissions from baghouse with an estimated collection
efficiency of 99%.
Factors are for emissions from wet scrubbers with a reported 97%
.control efficiency.
Uncontrolled.

Silicon tetrafluoride and hydrogen fluoride emissions, and partic-
ulate from the mixer, den and curing building are controlled by scrubbing
the offgases with recycled water. Gaseous silicon tetrafluoride in the
presence of moisture reacts to form gelatinous silica which has the
tendency to plug scrubber packings. The use of conventional packed
countercurrent scrubbers and other contacting devices with small gas
passages for emissions control is therefore limited. Scrubber types
that can be used are cyclonic,venturi, impingement, jet ejector and
spray crossflow packed. Spray towers also find use as precontactors for
fluorine removal at relatively high concentration levels (greater than
3,000 ppm, or 4.67 g/m3).

Air pollution control techniques vary with particular plant designs.
The effectiveness of abatement systems in removal of fluoride and
particulate also varies from plant to plant, depending on a number of
factors. The effectiveness of fluorine abatement is determined by (1)
inlet fluorine concentration, (2) outlet or saturated gas temperature,
(3) composition and temprature of the scrubbing liquid, (4) scrubber
type and transfer units, and (5) effectiveness of entrainment separation.
Control efficiency is enhanced by increasing the number of scrubbing
10/80 Food and Agricultural Industry 6.10.1-3
-------
stages in series and by using a fresh water scrub in the final stage.
Reported efficiencies for fluoride control range from less than 90
percent to over 99 percent, depending on inlet fluoride concentrations
and the system employed. An efficiency of 98 percent for particulate
control is achievable.

Reference for Section 6.10.1

"1. J. M. Nyers, et al., Source Assessment: Phosphate Fertilizer
Industry. EPA-600/2-79-019c, U. S. Environmental Protection Agency,
Research Triangle Park, NC, May 1979.
6.10.1-4 EMISSION FACTORS 10/80
-------
6.10.2 TRIPLE SUPERPHOSPHATES

6.10.2.1 General

Triple superphosphate is a fertilizer material of P20s content over
40 percent, made by reacting phosphate rock and phosphoric acid. The
two principal types of triple superphosphate are run-of-the-pile (40
percent of total production) and granular (60 percent of total produc-
tion) . Run-of-the-pile material is essentially a pulverized mass of
variable particle size produced in a manner similar to normal super-
phosphate. Thus, phosphoric acid (50 percent P20s) is reacted in a cone
mixer with ground phosphate rock. The resultant slurry begins to
solidify on a slow moving conveyer (den) en route to the curing area.
At the point of discharge from the den, the material passes through a
rotary mechanical cutter that breaks up the solid mass. Coarse run-of-
the-pile product is sent to a storage pile and cured for a period of 3
to 5 weeks. The final product is then mined from the "pile" in the
curing shed, and then crushed, screened, and shipped in bulk. Granular
triple superphosphate yields larger, more uniform particles with improved
storage and handling properties. Most of this material is made with the
Dorr-Oliver slurry granulation process, illustrated in Figure 6.10.2-1.
In this process, ground phosphate rock is mixed with phosphoric acid in
a reactor or mixing tank. The phosphoric acid used in this process is
appreciably lower in concentration (40 percent P20s) than that used to
manufacture run-of-the-pile product, because the lower strength acid
maintains the slurry in a fluid state during a mixing period of 1 to 2
hours. A thin slurry is continuously removed and distributed onto
dried, recycled fines, where it coats the granule surfaces and builds up
its size.

Pugmills and rotating drum granulators are used in the granulation
process. A pugmill is composed of a u-shaped trough carrying twin
contrarotating shafts, upon which are mounted strong blades or paddles.
Their action agitates, shears and kneads the solid/liquid mix and trans-
ports the material along the trough. The basic rotary drum granulator
consists of an open ended slightly inclined rotary cylinder, with retain-
ing rings at each end and a scraper or cutter mounted inside the drum
shell. A rolling bed of dry material is maintained in the unit while
the slurry is introduced through distributor pipes set lengthwise in the
drum under the bed. Slurry-wetted granules then discharge onto a
rotary dryer, where excess water is evaporated and the chemical reaction
is accelerated to completion by the dryer heat. Dried granules are then
sized on vibrating screens. Oversize particles are crushed and recircu-
lated to the screen, and undersize particles are recycled to the granu-
lator. Product size granules are cooled in a countercurrent rotary
drum, then sent to a storage pile for curing. After a curing period of
3 to 5 days, granules are removed from storage, screened, bagged and
shipped.
10/30 Food and Agricultural Industry 6.10.2-1
-------
ro
•

NJ
w
t— !f

R
o
S!
o
EO
CO
RECVClED
POND WATER
ELEVATOR
CURING IUIIDING

ISIORACt ISHIPPIWI
Figure 6.10.2-1. Dorr-Oliver process flow diagram for

granular triple superphosphate production.
CO
o
-------
6.10.2.2 Emissions and Controls

Emissions of fluorine compounds and dust particles occur during the
production of granular triple superphosphate. Silicon tetrafluoride and
hydrogen fluoride are released by the acidulation reaction and they
evolve from the reactors, den, granulator, dryer and cooler. Evolution
of fluorides continues at a lower rate in the curing building, as the
reaction preceeds. Sources of particulate emissions include the reactor,
granulator, dryer, cooler, screens, mills, and transfer conveyors.
Additional emissions of particulate result from the unloading, storage
and transfer of ground phosphate rock.

At a typical plant, emissions from the reactor, den and granulator
are controlled by scrubbing the effluent gas with recycled gypsum pond
water. Emissions from the dryer, cooler, screens, mills, product trans-
fer systems, and storage building are sent to a cyclone separator for
removal of a portion of the dust before going to wet scrubbers. Bag-
houses are used to control the fine rock particles generated by the
preliminary ground rock handling activities.

Emission factors for the production of run-of-the-pile and granular
triple superphosphate are given in Table 6.10.2-1. These emission
factors are averages based on recent source test data from controlled
phosphate fertilizer plants in Florida.

Particulate emissions from ground rock unloading, storage and
transfer systems are controlled by baghouse collectors. These cloth
filters have reported efficiencies of over 99 percent. Collected solids
are recycled to the process. Emissions of silicon tetrafluoride, hydrogen
fluoride, and particulate from the- production area and curing building
are controlled by scrubbing the offgases with recycled water. Exhausts
from the dryer, cooler, screens, mills, and curing building are sent
first to a cyclone separator and then to a wet scrubber.

Gaseous silicon tetrafluoride in the presence of moisture reacts to
form gelatinous silica, which has the tendency to plug scrubber packings.
The use of conventional packed countercurrent scrubbers and other con-
tacting devices with small gas passages for emissions control is there-
fore limited. Scrubber types that can be used are (1) spray tower, (2)
cyclonic, (3) venturi, (4) impingement, (5) jet ejector, and (6) spray-
crossflow packed.

Spray towers are used as precontactors for fluorine removal at
relatively high concentration levels (greater than 3,000 ppm, or 4.67
g/m3).

Air pollution control techniques vary with particular plant designs.
The effectiveness of abatement systems for the removal of fluoride and
particulate also varies from plant to plant, depending on a number of
factors. The effectiveness of fluorine abatement is determined by (1)

10/80 Food and Agricultural Industry 6.10.2-3
-------
TABLE 6.10.2-1.
ho
CONTROLLED EMISSION FACTORS FOR THE PRODUCTION OF TRIPLE SUPERPHOSPHATES

EMISSION FACTOR RATING: A
a

Controlled emission factor

M
C/i
OT
M
i
FACTORS

Process
Run-of-the-pile triple
superphosphate

Granular triple
superphosphate

Emission point
Rock unloading
Rock feeding
Cone mixer, den
and curing building0
Rock unloading
Rock feeding
Reactor, granulatorj
dryer, cooler and
screens
Curing building

Pollutant
Particulate
Particulate
Particulate
Fluoride
Particulate
Particulate
Particulate
Fluoride
Particulate
Fluoride
Ib/ton P.05
0.14
0.03
0.03
0.20
0.18
0.03
0.10
0.24
0.20
0.04
kg/MT P205
0.07
0.01
0.02
0.10
0.09
0.02
0.05
0.12
0.10
0.02
00
o
^Reference 1, pp. 77-80, 168, 170-171.
Factors are for emissions from baghouses with an estimated collection efficiency of 99%.
Factors are for emissions from wet scrubbers with an estimated 97% control efficiency.
-------
inlet fluorine concentration, (2) outlet or saturated gas temperature,
(3) composition and temperature of the scrubbing liquid, (4) scrubber
type and transfer units, and (5) effectiveness of entrainment separation.
Control efficiency is enhanced by increasing the number of scrubbing
stages in series and by using a fresh water scrub in the final stage.
Reported efficiencies for fluoride control range from less than 90
percent to over 99 percent, depending on inlet fluoride concentrations
and the system employed. An efficiency of 98 percent for particulate
control is achievable.

Reference for Section 6.10.2

1. J. M. Nyers, et al., Source Assessment; Phosphate Fertilizer
Industry. EPA-600/2-79-019c, U. S. Environmental Protection Agency,
Research Triangle Park, NC, May 1979.
10/80 Food and Agricultural Industry 6.10.2-5
-------
6.10.3 AMMONIUM PHOSPHATES

6.10.3.1 General

Ammonium phosphates are produced by reacting phosphoric acid with
anhydrous ammonia. Both solid and liquid ammonium phosphate fertilizers
are produced in the United States. Ammonia ted superphosphates are also
produced, by adding normal superphosphate or triple superphosphate to
the mixture. This discussion covers only the granulation of phosphoric
acid with anhydrous ammonia to produce granular fertilizers. The produc-
tion of liquid ammonium phosphates and ammonia ted superphosphates in
fertilizer mixing plants is considered a separate process. Two basic
mixer designs are used by ammonia tion-granulation plants, the pugmill
ammonia tor and the rotary drum ammoniator. Approximately 95 percent of
ammoniation-granulation plants in the United States use a rotary drum
mixer developed and patented by the Tennessee Valley Authority (TVA) .
In the TVA process, phosphoric acid is mixed in an acid surge tank with
93 percent sulfuric acid (used for product analysis control) and with
recycle and acid from wet scrubbers (see Figure 6.10.3-1). Mixed acids
are then partially neutralized with liquid or gaseous anhydrous ammonia
in a brick lined acid reactor. All phosphoric acid and approximately 70
percent of ammonia are introduced into this vessel.
A slurry of NHi^^PO^ and 22 percent water is produced and sent
through steam- traced lines to the ammonia tor-granulator. Ammonia rich
offgases from the reactor are wet scrubbed before exhausting to the
atmosphere. Primary scrubbers use raw material-mixed acids as scrubbing
liquor, and secondary scrubbers use gypsum pond water.

The basic rotary drum ammoniator-granulator consists of a slightly
inclined open end rotary cylinder with retaining rings at each end, and
a scraper or cutter mounted inside the drum shell. A rolling bed of
recycled solids is maintained in the units. Slurry from the reactor is
distributed on the bed, and the remaining ammonia (approximately 30
percent) is sparged underneath. Granulation, by agglomeration and by
coating particules with slurry, takes place in the rotating drum and is
completed in the dryer. Ammonia rich offgases pass through a wet
scrubber before exhausting to the atmosphere.

Moist ammonium phosphate granules are transferred to a rotary
cocurrent dryer and then to a cooler. Before exhausting to the atmo-
sphere, these offgases pass through cyclones and wet scrubbers. Cooled
granules pass to a double deck screen, in which oversize and undersize
particles are separated from product particles.

6.10.3.2 Emissions and Controls

Air emissions from production of ammonium phosphate fertilizers by
ammoniation granulation of phosphoric acid and ammonia result from five
process operations. The reactor and ammoniator granulator produce
10/80 Food and Agricultural Industry 6.10.3-1
-------
ISJ

FILTERED PHOSPH
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Figure 6.2.3-1. Ammonium phosphate process flow diagram.
03
O
-------
emissions of gaseous ammonia, gaseous fluorides (HF and SiF^) and partic-
ulate ammonium phosphates. These two exhaust streams generally are
combined and passed through primary and secondary scrubbers.

Exhaust gases from the dryer and cooler also contain ammonia,
fluorides and particulates, and these streams commonly are combined and
passed through cyclones and primary and secondary scrubbers. Partic-
ulate emissions and low levels of ammonia and fluorides from product
sizing and material transfer operations are controlled the same way.

Emission factors for ammonium phosphate production are summarized
in Table 6.10.3-1. These emission factors are averages based on recent
source test data from controlled phosphate fertilizer plants in Florida.

Exhaust streams from the reactor and ammoniator-granulator pass
through a primary scrubber, in which phosphoric acid recovers ammonia
and particulate. Exhaust gases from the dryer, cooler and screen go
first to cyclones for particulate recovery, and from there to primary
scrubbers. Materials collected in the cyclone and primary scrubbers are
returned to the process. The exhaust is sent to secondary scrubbers,
where recycled gypsum pond water is used as a scrubbing liquid to control
fluoride emissions. The scrubber effluent is returned to the gypsum
pond.

Primary scrubbing equipment commonly includes venturi and cyclonic
spray towers, while cyclonic spray towers, impingement scrubbers, and
spray-crossflow packed bed scrubbers are used as secondary controls.
Primary scrubbers generally use phosphoric acid of 20 to 30 percent as
scrubbing liquor, principally to recover ammonia. Secondary scrubbers
generally use gypsum and pond water, for fluoride control.

Throughout the industry, however, there are many combinations and
variations. Some plants use reactor-feed concentration phosphoric acid
(40 percent PaOs) ^n both primary and secondary scrubbers, and some use
phosphoric acid near the dilute end of the 20 to 30 percent PZ^S range
in only a single scrubber. Existing plants are equipped with ammonia
recovery scrubbers on the reactor, ammoniator-granulator and dryer, and
particulate controls on the dryer and cooler. Additional scrubbers for
fluoride removal are common but not typical. Only 15 to 20 percent of
installations contacted in an EPA survey were equipped with spray-
crossflow packed bed scrubbers or their equivalent for fluoride removal.

Emission control efficiencies for ammonium phosphate plant control
equipment have been reported as 94 - 99 percent for ammonium, 75 - 99.8
percent for particulates, and 74 - 94 percent for fluorides.
10/80 Food and Agricultural Industry 6.10.3-3
-------
TABLE 6.10.3-1. AVERAGE CONTROLLED EMISSION FACTORS FOR THE
PRODUCTION OF AMMONIUM PHOSPHATES3

EMISSION FACTOR RATING: A

Emission Point
Reactor/ammonia tor-granula tor
Fluoride (as F)
Particulates
Ammonia
Dryer/cooler
Fluoride (as F)
Particulates
Ammonia
Product sizing and material transfer
Fluoride (as F)C
Particulates
Ammonia
Total plant emissions
Fluoride (as F)d
Particulates
Ammonia
Controlled
Ib/ton P20t

0.05
1.52
b

0.03
1.50
b
0.01
0.06
b
0.08
0.30
0.14
Emission Factors
. kg/MT P205

0.02
0.76
b

0.02
0.75
b
0.01
0.03
b
0.04
0.15
0.07
^Reference 1, pp. 80-83, 173.
No information available. Although ammonia is emitted from these unit
operations, it is reported as a total plant emission.
.Represents only one sample.
EPA has promulgated a fluoride emission guideline of 0.03 g/kg P2°5
input.
Based on limited data from only 2 plants.

Reference for Section 6.10.3

1. J. M. Nyers, et al., Source Assessment; Phosphate Fertilizer
Industry, EPA-600/2-79-019c, U.S. Environmental Protection Agency,
Research Triangle Park, NC, May 1979.
6.10.3-4 EMISSION FACTORS 10/80
-------
7.2 COKE MANUFACTURING

7.2.1 Process Description

Coking is the process of destructive distillation, or the heating
of coal in an atmosphere of low oxygen content. During this process,
organic compounds in the coal break down to yield gases and a relatively
involatile residue. The primary method for the manufacture of coke is
the byproduct method, which accounts for more than 98 percent of U.S.
coke production.

The byproduct method is oriented to the recovery of gases produced
during the coking cycle. Narrow rectangular slot-type coking ovens are
constructed of silica brick, and a battery is commonly made up of a
series of 40 to 70 of these ovens interspaced with heating flues. A
larry car runs along the top of the coke battery, charging the ovens
with coal through ports. After each charging, the ports are sealed, and
heat is supplied to the ovens by combustion of gases passing through the
flues between the ovens. The fuels used in the combustion process are
natural gas, coke oven gas or blast furnace gas. In the ovens, coke is
formed first near the brick walls and then toward the center, where
temperatures are 2000° - 2100°F (1100° - 1150°C). After a period of
16 - 20 hours, the coking process is complete. Coke is pushed by a ram
from the oven into a quenching car. The quenching car of hot coke is
moved by rail to the quench tower, where several thousand gallons of
water are used to cool the coke. The coke is allowed to dry and is
separated into various sizes for future use. See Figure 7.5-1 of this
document for a flow diagram of an integrated iron and steel plant which
contains the coking operations.

7.2.2 Emissions

Particulates, volatile organic compounds, carbon monoxide and other
emissions originate from the following byproduct coking operations: (1)
coal preheating (if used), (2) charging of coal into the incandescent
ovens, (3) oven leakage during the coking period, (4) pushing the coke
out of the ovens, (5) quenching the hot coke and (6) combustion stacks.
Gaseous emissions from the byproduct ovens during the coking process are
drawn off to a collecting main and are subjected to various operations
for separating ammonia, coke oven gas, tar, phenol, light oil (benzene,
toluene, xylene) and pyridine. These unit operations are potential
sources of volatile organic compounds.

Oven charging operations and leakage around poorly sealed coke oven
doors and lids are major sources of emissions from byproduct ovens.
Emissions also occur when finished coke is pushed into the quench cars
and during the quenching operation. The combustion process is also a
source of pollutant emissions. As the combusting gases pass through the
coke oven heating flues, emissions from the ovens may leak into the
stream. Also, if the coke oven gas is not desulfurized, the combustion
process will emit sulfur dioxide. Figure 7.2-1 is a depiction of a coke
oven battery showing the major air pollution sources.
10/80 Metallurgical Industry 7.2-1
-------
o
o
TYPES OF AIR POLLUTION EMISSIONS
FROM COKE-OVEN BATTERIES
(T) Pushing emissions
(2) Charging emissions
(3) Door emissions
(3) Topside emissions
(5) Battery underfire emissions

///////////////////////////////////////7////S.
(Courtesy of the Western
Pennsylvania Air Pollution
Control Association)
-------
CO
o
I-J
00
H-
O
03
0
C-

Ul
Table 7.2-1. EMISSION FACTORS FOR COKE MANUFACTURE3
EMISSION FACTOR RATING: D (except particulates)

K
Particulates"
Type of Operation
Coal Preheaters
Uncontrolled
Controlled by scrubber
Coal Charging
Uncontrolled
Controlled larry car vented
to scrubber
Sequential charging
Door Leaks (Uncontrolled)
Coke Pushing
Suspended particulates
Uncontrolled (measured in
duct venting coke side shed)
Controlled (water sprays)
Total particulates (suspended
plus dust fall)
Uncontrolled
Controlled (water sprays)
Controlled (enclosed coke car
and guide, vented
to scrubber)
Quenching (Controlled by Baffles)
Combustion Stacks (Uncontrolled)
Ib/ton

7.0
0.65

0.85

0.02
0.016
0.51

0.47
0.39

2.0
1.2

0.024
1.0
0.58
kg/MT

3.5
0.325

0.425

0.01
0.008
0.255

0.235
0.195

1.0
0.6

0.012
0.5
0.29
^Emission factors expressed as units per weight of
Reference 1.
^References 2 and 3.

Emission Factor Sulfur Carbon Volatile .
C C CO
Rating Dioxide Monoxide Organics '
Ib/ton kg/MT Ib/ton kg/MT Ib/ton kg/MT

C ______
C ______

C 0.02 0.01 0.6 0.3 2.5 1.25

C ______
C ______
B 0.6 0.3 1.5 0.75

A ______
A ______

B - 0.07 0.035 0.2 0.1
B ______

C ______
A ______
B 4.0e 2.0 - - - -
coal charged. Dash indicates no available data.

Nitrogen c
Oxides (N02; Ammonia
Ib/ton kg/MT Ib/ton kg/MT

_
- - - -

0.03 0.015 0.02 0.01

_
-
0.01 0.005 0.06 0.03

_
_

0.1 0.05
_

- - - -
_
_

eReference 4. The sulfur dioxide factor is based on the following representative conditions: (1) sulfur content of coal charged to oven is
0.8 weight %; (2) about 33 weight % of total sulfur in the coal charged to oven is transferred to the coke oven gas; (3) about 40% of coke
oven gas is burned during the underfiring operation, and the remainder is used in other parts of the steel operation, where the rest of the
sulfur dioxide is discharged - about 6 Ib/ton (3 kg/MT) of coal charged; and (4) gas used in underfiring has not been desulfurized.
tsa

_o
-------
Associated with the byproduct coke oven process are open source
fugitive dust operations. These include material handling operations of
unloading, storing, grinding and sizing of coal, and the screening,
crushing, storing and loading of coke. Fugitive emissions also come
from vehicles traveling on paved and unpaved surfaces. These emissions
and the parameters that influence them are discussed in more detail in
Section 7.5 and Chapter 11 of this document. The emission factors for
coking operations are summarized in Table 7.2-1. Extensive information
on the data used to develop the particulate emission factors is found in
Reference 1.

References for Section 7.2

1. Particulate Emission Factors Applicable to the Iron and Steel Industry,
EPA-450/4-79-028, U.S. Environmental Protection Agency, Research
Triangle Park, NC, September 1979.

2. Air Pollution by Coking Plants, United Nations Report: Economic
Commission for Europe, ST/ECE/Coal/26, 1968.

3. R. W. Fullerton, "Impingement Baffles To Reduce Emissions from Coke
Quenching", Journal of the Air Pollution Control Association,
r7:807-809, December 1967.

4. J. Varga and H. W. Lownie, Jr., Final Technological Report on: A
Systems Analysis Study of the Integrated Iron and Steel Industry,
HEW Contract No. PH 22-68-65, Battelle Memorial Institute, Columbus,
OH, May 1969.
7.2-4 EMISSION FACTORS 10/80
-------
7.3 PRIMARY COPPER SMELTING

7.3.4 Lead Emission Factors

Lead particulate emissions occur during roasting, smelting, convert-
ing and refining operations. In converting, some control is effected by
moveable hoods placed over the converter mouth. Emissions from this
phase, high in particulate and sulfur dioxide, are ducted to electrostatic
precipitators or cyclones for particle removal and then to single or
double contact sulfuric acid plants.

Significant fugitive emissions occur during materials handling and
furnace charging and tapping. Fugitive gases and dust from roasting and
smelting (calcine transfer) are usually controlled by cyclones, precip-
itators, or in newer plants, baghouses.

Some operations are intermittant, like calcine transfer to furnaces
and copper matte and slag tapping from furnaces.

No emission data are available for refining operations and con-
trolled smelting, and only one data point for roasting controlled by a
precipitator.

Table 7.3-4 shows potential lead emission factors from these
sources.

Table 7.3-4. LEAD EMISSION FACTORS FOR PRIMARY COPPER SMELTERS
EMISSION FACTOR RATING: B
Emission Factor
Operation Ib/ton kg/MT

Roasting
Uncontrolled 0.0536 0.0268
(0.0087 - 0.0994) (0.0043 - 0.0497)
Controlled 0.1386 0.0693

Smelting 0.0579 0.0289
(0.0016 - 0.2368) (0.0008 - 0.1184)

Converting
Uncontrolled 0.1233 0.0617
(0.0135 - 0.2065) (0.0068 - 0.1033)
Controlled 0.0785 0.0393
(0.0067 - 0.1377) (0.0034 - 0.0689)

Refining NA NA
a '
. Reference 16. Ranges in parentheses. NA: no data available.
Only datum available.

10/80 Metallurgical Industry 7.3-9
-------
Additional Reference for Section 7.3

16. D. Ringwald and T. Rooney, Copper Smelters; Emission Test Report -
Lead Emissions, EMB Report 79 CUS-14, U. S. Environmental Protection
Agency, Research Triangle Park, NC, September 1979.
7-3-10 EMISSION FACTORS 10/80
-------
7.5 IRON AND STEEL PRODUCTION

1 2
7.5.1 Process Description and Emissions '

Iron and steel manufacturing may be grouped into eight generic
process operations: (1) coke production, (2) sinter production,
(3) iron production, (4) steel production, (5) semi-finished product
preparation, (6) finished product preparation, (7) heat and electricity
supply and (8) handling and transport of raw, intermediate and waste
materials. Figure 7.5-1, a general flow diagram of the iron and steel
industry, interrelates these categories. The first category, coke
production, is discussed in detail in Section 7.2 of this publication,
and additional information on the handling and transport of materials is
found in Chapter 11.

Sinter Production - The sintering process converts fine sized raw
materials such as fine iron ore, coke breeze, fluxstone, mill scale, and
flue dust into an agglomerated product of suitable size for charging
into the blast furnance. The materials are mixed with water to provide
cohesiveness in a mixing mill, then placed on a continuous moving grate
called the sinter strand. A burner hood above the front third of the
sinter strand ignites the coke in the mixture. Once ignited, combustion
is self supporting and provides sufficient heat, 2400 - 2700°F
(1300 - 1480°C), to cause surface melting and agglomeration of the mix.
On the underside of the sinter machine lie windboxes that draw the
combusted air down through the material bed into a common duct which
leads to a particulate control device. The fused sinter is discharged
at the end of the sinter machine, where it is crushed and screened. The
undersize portion is recycled to the mixing mill. The remaining sinter
is cooled in the open air by water spray or by mechanical fan to draw
off the heat from the sinter. The cooled sinter is screened for a final
time, with the fines being recycled and the rest being sent to charge
the blast furnaces.

Emissions occur at several points in the sintering.process. Points
of particulate generation are (1) the windbox, (2) the discharge (sinter
crusher and hot screen), (3) the cooler and (4) the cold screen. In
addition to these sources, there are the inplant transfer stations,
which generate emissions which can be controlled by localized enclosures.
All the above sources except the cooler are normally vented to one or
two control systems.

Iron Production - Iron is produced in blast furnaces, which are large
refractory-lined chambers into which iron as natural ore, or agglom-
erated products such as pellets or sinter, coke, and limestone, are
charged and allowed to react with large amounts of hot air to produce
molten iron. Slag and blast furnace gases are byproducts of this
operation. The average charge to produce one unit weight of iron
requires 1.7 unit weights of iron bearing charge, 0.55 unit weights of
coke, 0.2 unit weights of limestone, and 1.9 unit weights of air.
Average blast furnace byproducts consist of 0.3 unit weights of slag,
10/80 Metallurgical Industry 7.5-1
-------
Ln
FROM ORE
KREEIIRW DPI RATIO!
co
CO
ELECTRIC-ARC
FURRAICI
(ALTERNATE!
CLEANED BLAST FURNANC!
GAS TO BE USED AS FUEL
(TO MITER OR
BLAST FURHANCEI
Figure 7.5-1. General flow diagram for the iron and steel industry.
w
o
-------
0.05 unit weights of flue dust, and 3.0 unit weights of gas per unit of
iron produced. The flue dust and other iron ore fines from the process
are converted into useful blast furnace charge by the sintering operation.

Because of its high carbon monoxide content, this blast furnace gas
has a low heating value, about 75 - 90 BTU/ft3 (2790 - 3350 J/l3) and
is used as a fuel within the steel plant. Before it can be efficiently
oxidized, however, the gas must be cleaned of particulate. Initially,
the gases pass through a settling chamber or dry cyclone to remove about
60 percent of the particulate. Next, the gases undergo a one or two
stage cleaning operation. The primary cleaner is normally a wet scrubber,
which removes about 90 percent of the remaining particulate. The second-
ary cleaner is a high energy wet scrubber (usually a venturi) or an
electrostatic precipitator, either of which can remove up to 90 percent
of the particulate that has passed through the primary cleaner. Applied
together, these control devices provide a clean fuel of less than 0.02
gr/ft3 (0.05 g/m3) for use within the steel plant.

Emissions occur during the production of iron when there is a blast
furnace "slip" and during hot metal transfer operations in the cast
house. All of the gas generated in the blast furnace is normally cleaned
and used for fuel. Conditions such as "slips", however, can cause
instantaneous emissions of carbon monoxide and particulates. Slips
occur when a stratum of the material charged to a blast furnace does not
settle with the material below it, thus leaving a gas filled space
between the two portions of the charge. When this unsettled stratum of
charge collapses, the displaced gas may cause the top gas pressure to
increase above the safety limit, thus opening a counter-weighted bleeder
valve to the atmosphere. Improvements in techniques for handling blast
furnace burden have greatly reduced these occurrences.

Steel Making Process - Basic Oxygen Furnace - The basic oxygen process
is employed to produce steel, from a furnace charge typically composed
of 70 percent molten blast furnace metal and 30 percent scrap metal, by
use of a stream of commercially pure oxygen to oxidize the impurities,
principally carbon and silicon. Most of the basic oxygen furnaces (BOF)
in the United States have oxygen blown through a lance in the top of the
furnace. However, the Quiet-Basic Oxygen Process (Q-BOP), which is
growing in use, has oxygen blown through tuyeres in the bottom of the
furnace. Cycle times for the basic oxygen process range from 25 to 45
minutes.

The large quantities of carbon monoxide (CO) produced by the
reactions in the BOF can be combusted at the mouth of the furnace and
then vented to gas cleaning devices, as with open hoods, or the combustion
can be suppressed at the furnace mouth, as with closed hoods. The term
"closed hood" is actually a misnomer, since the opening at the furnace
mouth is large enough to allow approximately 10 percent of theoretical
air to enter. Nearly all the Q-BOPs in the United States have closed
hoods, and most of the new top blown furnaces are being designed with
closed hoods. Most furnaces installed before 1975 are of the open hood
design.
10/80 Metallurgical Industry 7.5-3
-------
TABLE 7.5-1. SILT CONTENT VALUES APPLICABLE TO THE
IRON AND STEEL INDUSTRY3.4

Number of
Source tests
Unpaved roads
Paved roads
Material handling
activities and
storage pile wind
erosion
Coal
Iron ore pellets
Lump iron ore
Coke breeze
Slag
Blended ore
Sinter
Limestone
Flue dust
12
9

7
10
9
1
3
1
1
1
2
Range of silt
content
(%)
4
1.1

2
1.4
2.8

14
- 13
- 13

- 7.7
- 13
- 19
-
- 7.3
-
-
—
- 23
Average silt
(%)
7.3
5.9

5.0
4.9
9.5
5.4
5.3
15.0
0.7
0.4
18.0
TABLE 7.5-2.
SURFACE MOISTURE CONTENT VALUES APPLICABLE TO THE
IRON AND STEEL INDUSTRY3.1*

Number of
Source tests
Material handling
activities and
storage pile
wind erosion
Coal
Iron ore pellets
Lump iron ore
Coke breeze
Slag
Blended ore
Flue dust

6
8
6
1
3
1
1
Range of surface
moisture content

2.8
0.64
1.6
0.25

- 11
- 3.5
- 8.1
- 2.2
—
Average surface
moisture content

4.8
2.1
5.4
6.4
0.9
6.6
12.4
7.5-4
EMISSION FACTORS
10/80
-------
There are several sources of emissions in the basic oxygen furnace
steel making process. The emission sources are (1) the furnace mouth
during refining - collected by local full (open) or suppressed (closed)
combustion hoods, (2) hot metal transfer to charging ladle, (3) charging
scrap and hot metal, (4) dumping slag and (5) tapping steel.

TABLE 7.5-3. SURFACE LOADING ON TRAVELED LANES OF PAVED ROADS
IN IRON AND STEEL PLANTS 3»1*
Number of Range of surface loading Average surface loading
tests (Ib/mile) (Ib/mile)

9 65 - 17,000 2,700
Steel Making Process - Electric Arc Furnaces - Electric arc furnaces
(EAF) are used to produce carbon and alloy steels. The charge to an EAF
is nearly always 100 percent scrap. Direct arc electrodes extending
through the roof of the furnace melt the scrap. An oxygen lance may or
may not be used to speed the melting and refining process. Cycles range
from 1 1/2 to 5 hours for carbon steel and from 5 to 10 hours for alloy
steel.

There are several sources of emissions in the electric arc furnace
steel making process. They are (1) emissions from the melting and
refining often vented through a hole in the furnace roof, (2) charging
scrap, (3) dumping slag and (4) tapping steel. In interpreting and
using emission factors for EAFs, it is important to know what configu-
ration one is dealing with. For example, if an EAF has a building
evacuation system, the emission factor before the control device would
represent all melting, refining, charging, tapping and slagging emissions
which ascended to the building roof. Reference 2 has additional details
on various configurations used to control electric arc furnaces.

Steel Making Process - Open Hearth Furnaces - In the open hearth furnace
(OHF), a mixture of scrap iron and steel and hot metal (molten iron) is
melted in a shallow rectangular basin or "hearth". Burners producing a
flame above the charge provide the heat necessary for melting. The
mixture of scrap and hot metal can vary from 100 percent scrap to 100
percent hot metal, but a half and half mixture is a reasonable industry-
wide average. The process may or may not be oxygen lanced, affecting
the process cycle times, which are approximately 8 hours and 10 hours
respectively.

There are several sources of emissions in the open hearth furnace
steel making process. The activities generating emissions are (1)
transferring hot metal, (2) melting and refining the heat, (3) charging
of scrap and/or hot metal, (4) dumping slag and (5) tapping steel.

Semifinished Product Preparation - After the steel has been tapped, the
molten metal is teemed into ingots which are later heated to form other
shapes, such as blooms, billets or slabs. The molten metal may also
10/80 Metallurgical Industry 7.5-5
-------
TABLE 7.5-4. PARTICULATE EMISSION FACTORS FOR IRON AND STEEL MILLS
a,b
01
Source
Units
Emission Factors
Emission Factor
Rating
GO
GO
H
i
H
§
to
Blast Furnances

Slips
Uncontrolled cast house
emissions
Monitor
Tap hole and trough
(not runners)

Sintering
Windbox emissions

Uncontrolled
Leaving grate
After coarse particu-
late removal
Controlled by dry ESP
Controlled by wet ESP
Controlled by scrubber
Controlled by cyclone
Sinter discharge (breaker
and hot screens)

Uncontrolled
Controlled by baghouse
Controlled by orifice
scrubber

Windbox and discharge

Controlled by baghouse
lb(kg)/slip

Ib/T (kg/MT) hot metal
Ib/T (kg/MT) finished
sinter
Ib/T (kg/MT) finished
sinter
Ib/T (kg/MT) finished
sinter
87.0 (39.5)

0.6 (0.3)

0.3 (0.15)
11.1
(5.56)
B

B
B
8.7
1.6
0.17
0.47
1.0
6.8
0.1
0.59
0.3
(4.35)
(0.8)
(0.085)
(0.235)
(0.5)
(3.4)
(0.05)
(0.295)
(0.15)
A
B
B
B
B
B
B
A
A
oo
o.
-------
Table 7.5-4 (cont.). PARTICULATE EMISSION FACTORS FOR IRON AND STEEL MILLS**b
oo
o
Source
Units
Emission Factors
Emission Factor
Rating
s
ft
01
M
M
C
OQ
H-
O
0>
3
a.
c
en
rt
»>1
•

I
Basic Oxygen Furnaces
Top blown furnace melting
and refining
Uncontrolled
Controlled by open hood
vented to:
ESP
Scrubber
Controlled by closed hood
vented to:
Scrubber

Q-BOP melting and refining
Controlled by scrubber

Charging
At source
At building monitor

Tapping
At source
At building monitor

Hot metal transfer
At source
At building monitor

EOF monitor (all sources)

Electric Arc Furnaces
Melting and refining
Uncontrolled
Carbon steel
Ib/T (kg/MT) steel
Ib/T (kg/MT) steel
Ib/T (kg/MT) hot metal
Ib/T (kg/MT) steel
Ib/T (kg/MT) hot metal
Ib/T (kg/MT) steel
Ib/T (kg/MT) steel
28.5
0.13
0.09
0.056

0.6
0.142

0.92
0.29

0.19
0.056
0.5
(14.25)
(0.065)
(0.045)
0.0068 (0.0034)
(0.028)

(0.3)
(0.071)

(0.46)
(0.145)

(0.095)
(0.028)
(0.25)
B
A
B
A

A
B

B
38.0
(19.0)
-------
Table 7.5-4 (cont.). PARTICULATE EMISSION FACTORS FOR IRON AND STEEL MILLS
a,b
Ol

00
Source
Units
Emission Factors
Emission Factor
Rating
Wl
M

i
H

3
CO
Charging, tapping and
slagging
Uncontrolled emissions
escaping monitor
Melting, refining, charging,
tapping and slagging
Uncontrolled
Alloy steel
Carbon steel
Controlled by:
Configuration 1
(building evacuation
to baghouse for alloy
steel)
Configuration 2
(DSE plus charging
hood vented to common
baghouse for carbon
steel)

Open Hearth Furnaces

Melting and refining
Uncontrolled
Controlled by ESP
Roof monitor emissions

Teeming

Leaded steel
Uncontrolled (as measured
at the source)
Controlled by side-draft
hood vented to baghouse
Ib/T (kg/MT) steel
Ib/T (kg/MT) steel
Ib/T (kg/MT) steel
Ib/T (kg/MT) steel
1.4 (0.7)
11.3 (5.65)
50.0 (25.0)
0.3 (0.15)
0.043 (0.0215)
21.1 (10.55)
0.28 (0.14)
0.168 (0.084)
0.81 (0.405)

0.0038 (0.0019)
A
C
A
A
C
A

A
oo
o
-------
Table 7.5-4 (cont.). PARTICULATE EMISSION FACTORS FOR IRON AND STEEL MILLS
a,b
00
o
Source
Units
Emission Factors
Emission Factor
Rating
if
rt
to
h-1
M

00
H-
n
3
O.
en
Unleaded steel
Uncontrolled (as measured
at the source)
Controlled by side-draft
hood vented to baghouse

Machine Scarfing

Uncontrolled

Controlled by ESP
Miscellaneous Combustion
Sources^
Boilers, soaking pits and
slab reheat furnaces
Blast furnace gas
Coke oven gas
Ib/T (kg/MT) metal through
scarfer
lb/106 Btu (kg/109J)
0.07 (0.035)

0.0016 (0.0008)
0.1 (0.05)
0.023 (0.0115)
0.035 (0.015)
0.012 (0.0052)
A

A
B
A
D
D
Reference 2. ESP: Electrostatic precipitator. DSE: Direct shell evacuation.
3For fuels such as coal, fuel oil and natural gas, use the emission factors presented in Chapter 1 of
this document. The rating for these fuels in boilers is A, and in soaking pits and slab reheat
furnaces is D.
vo
-------
bypass this entire process and go through a continuous casting operation.
The product next goes through a process of surface preparation of semi-
finished steel (scarfing). A scarfing machine removes surface defects
from the steel billets, blooms and slabs before shaping or rolling by
applying jets of oxygen to the surface of the steel, which is at orange
heat, thus removing a thin upper layer of the metal by rapid oxidation.
Scarfing can normally be performed by machine on hot semifinished steel
or by hand on cold or slightly preheated semifinished steel. Emissions
occur during teeming as the molten metal is poured. Emissions also
occur when the semifinished steel products are manually or machine
scarfed to remove surface defects.

Miscellaneous Combustion Sources - Iron and steel plants require energy
in the form of heat or electricity for every plant operation. Some
energy intensive operations that produce emissions on plant property are
boilers, soaking pits and slab furnaces, burning such fuels as coal, No.
2 fuel oil, natural gas, coke oven gas or blast furnace gas. In soaking
pits, ingots are heated such that the temperature distribution over the
cross section of the ingots is acceptable and the surface temperature is
uniform for further rolling into semifinished products (blooms, billets
and slabs). In slab furnaces, a slab is heated before being rolled into
finished products (plates, sheets or strips). The emissions from the
combustion of natural gas, fuel oil or coal for boilers can be found in
Chapter 1 of this document. Emissions from these same fuels used in
soaking pits or slab furnaces can be estimated to be the same as those
for boilers, but since this is an estimate, the factor rating drops to
D.

Emission factor data for blast furnace gas and coke oven gas are
not available and therefore must be estimated. There are three facts
available for making the estimation. First, the gas exiting the blast
furnace passes through primary and secondary cleaners and can be cleaned
to less than 0.02 gr/ft3 (0.05 g/m3). Second, nearly one third of the
coke oven gas is methane. Lastly, there are no blast furnace gas consti-
tuents that generate particulate when burned. The combustible constituent
of blast furnace gas is CO, which burns clean. Based on facts one and
three, the emission factor for the combustion of blast furnace gas is
equal to the particulate loading of that fuel, 2.9 pounds per million
cubic feet (0.05 g/m3).

Emissions for combustion of coke oven gas can be estimated in the
same fashion. Assume that cleaned coke oven gas has as much particulate
as cleaned blast furnace gas. Since one third of the coke oven gas is
methane, the main component of natural gas, it is assumed that the
combustion of this methane in coke oven gas generates 3.3 lb/106 ft3
(0.06 g/m3) of particulate. Thus, the emission factor for the combustion
of coke oven gas is the sum of the particulate loading and that gen-
erated by the methane combustion, or 6.2 pounds per million cubic feet
(0.1 g/m3).
7.5-10 EMISSION FACTORS 10/80
-------
Open Dust Sources - In addition to process emission sources, open dust
sources contribute to the atmospheric particulate burden. Open dust
sources include (1) vehicular traffic on paved and unpaved roads, (2)
raw material handling outside of buildings and (3) wind erosion from
storage piles and exposed terrain. Vehicular traffic consists of plant
personnel and visitor vehicles, plant service vehicles, and trucks
handling raw materials, plant deliverables, steel products and waste
materials. Raw material is handled by clamshell buckets, bucket/ladder
conveyors, rotary railroad dumps, bottom railroad dumps, front end
loaders, truck dumps, and conveyor transfer stations, all of which
disturb the raw material and expose fines to the wind. Even fine
material resting on flat areas or in storage piles is exposed and is
subject to wind erosion. It is not unusual to have several million tons
of raw materials stored at a plant and to have in the range of 10 to 100
acres of flat exposed area there.

Table 7.5-5. UNCONTROLLED CARBON MONOXIDE EMISSION FACTORS FOR
IRON AND STEEL MILLS3

EMISSION FACTOR RATING: C
Source Ib/ton kg/MT

Sintering
windbox 44 22

Basic oxygen furnace 138 69

Electric arc furnace 18 9

rReference 5.
Founds/kilograms per ton/metric ton of finished sinter.

Empirically derived predictive emission factor equations for open
dust sources have been developed and are presented in Chapter 11 of this
document. The predictive emission factor equations in Chapter 11 can be
used for all facilities having open dust sources, not just for iron and
steel plants. However, there are several independent parameters in
these equations for which data have been obtained from iron and steel
plants. These parameters are raw material silt and moisture content,
paved and unpaved road material silt content, and total surface dust
loading on paved roads. Tables 7.5-1 through 7.5-3 show the results of
silt, moisture and loading analysis of collected field samples. The
number of samples obtained, the range of values measured and the mean
values of the parameters are given for each type of material. Samples
listed in Tables 7.5-1 through 7.5-3 were collected at as many as twelve
different iron and steel plants, in a wide range of geographic locations.
NOTICE: The above mention of equations in Chapter 11 refers to equations in revisions still
impending when this printing went to press. In the interim, please see Reference 2 for the
correct equations.

10/80 Metallurgical Industry 7.5-11
-------
Particulate emission factors for iron and steel plant processes are
found in Table 7.5-4. These emission factors are a result of an exten-
sive investigation by EPA and the American Iron and Steel Institute.2
Emission factors for carbon monoxide are found in Table 7.5-S.5
References for Section 7.5

1. H. E. McGannon, ed., The Making, Shaping and Treating of Steel,
U. S. Steel Corporation, Pittsburgh, PA, 1971.

2. T. A. Cuscino, Jr., Particulate Emission Factors Applicable to the
Iron and Steel Industry, EPA-450/4-79-029, U.S. Environmental
Protection Agency, Research Triangle Park, NC, September 1979.

3. R. Bohn, et al., Fugitive Emissions from Integrated Iron and Steel
Plants, EPA-600/2-78-050, U. S. Environmental Protection Agency,
Research Triangle Park, NC, March 1978.

4. C. Cowherd, Jr., et al., Iron and Steel Plant Open Source Fugitive
Emission Evaluation, EPA-600/2-79-103, U. S. Environmental
Protection Agency, Research Triangle Park, NC, May 1979.

5. Control Techniques for Carbon Monoxide Emissions from Stationary
Sources, AP-65, U. S. Department'of Health, Education and Welfare,
Washington, DC, March 1970.
7.5-12 EMISSION FACTORS 11/80
-------
7.11 SECONDARY LEAD PROCESSING

7.11.1 Process Description

The secondary lead industry processes a variety of leadbearing
scrap and residue to produce lead and lead alloy ingots, battery lead
oxide, and lead pigments (PbsOij and PbO). Processing may involve scrap
pretreatment, smelting and refining/casting. Processes typically used
in each operation are shown in Figure 7.11-1.

7.11.1.1 Scrap pretreatment is the partial removal of metal and non-
metal contaminants from leadbearing scrap and residue. Processes used
for scrap pretreatment include battery breaking, crushing and sweating.
Battery breaking is the draining and crushing of batteries followed by
manual screening to separate the lead from nonmetallic materials. This
separated lead scrap is then mixed with other scraps and smelted in
reverberatory or blast furnaces. Oversize pieces of scrap and residues
are usually crushed by jaw crushers. Sweating separates lead from high-
melting metals in direct gas or oil fired rotary or reverberatory
furnaces. Rotary furnaces are typically used to process low lead content
scrap and residue, while reverberatory furnaces are used to process high
lead content scrap. The partially purified lead is periodically tapped
for further processing in smelting furnaces or pot furnaces.

7.11.1.2 Smelting is the production of purified lead by melting and
separating lead from metal and nonmetallic contaminants and by reducing
oxides to elemental lead. Reverberatory smelting furnaces are used to
produce a semisoft lead product that typically contains 3-4 percent
antimony. Blast furnaces produce hard or antimonial lead containing
about 10 percent antimony.

A reverberatory furnace produces semisoft lead from a charge of
lead scrap, metallic battery parts, oxides, drosses and other residues.
The furnace consists of a rectangular shell lined with refractory brick
and fired directly with oil or gas to a temperature of 2300°F (1250°C).
The material to be melted is heated by direct contact with combustion
gases. The furnace can process about 50 tons per day (45 MT/day).
About 47 percent of the charge is typically recovered as lead product
and is periodically tapped into molds or holding pots. Forty-six
percent of the charge is removed as slag and subsequently processed in
blast furnaces. The remaining 7 percent of the furnace charge escapes
as dust or fume.

Blast furnaces produce hard lead from charges containing siliceous
slag from previous runs (typically about 4.5 percent of the charge),
scrap iron (about 4.5 percent), limestone (about 3 percent), coke (about
5.5 percent), and oxides, pot furnace refining drosses, and reverberatory
slag (comprising the remaining 82.5 percent of the charge). The propor-
tions of rerun slags, limestone and coke vary respectively to as high as
8 percent, 10 percent, and 8 percent of the charge. Processing capacity
of the blast furnace ranges from 20 - 80 tons per day (18 - 73 MT/day).
10/80 Metallurgical Industry 7.11-1
-------
Similar to iron cupolas, the furnaces consist of vertical steel cyl-
inders lined with refractory brick. Combustion air at 0.5 - 0.75 psig
is introduced at the bottom of the furnace through tuyeres. Some of the
coke combusts to melt the charge, while the remainder reduces lead
oxides to elemental lead. The furnace exhausts at temperatures of
1200 - 1350°F (650 - 730°C).

As the lead charge melts, limestone and iron float to the top of
the molten bath and form a flux that retards oxidation of the product
lead. The molten lead flows from the furnace into a holding pot at a
nearly continuous rate. The product lead constitutes roughly 70 percent
of the charge. From the holding pot, the lead is usually cast into
large ingots, called pigs or sows.

About 18 percent of the charge is recovered as slag, with about 60
percent of this being a sulfurous slag called matte. Roughly 5 percent
of the charge is retained for reuse, and the remaining 7 percent of the
charge escapes as dust or fume.

7.11.1.3 Refining/casting is the use of kettle type furnaces in remelt-
ing, alloying, refining and oxidizing processes. Materials charged for
remelting are usually lead alloy ingots which require no further process-
ing before casting. The furnaces used for alloying, refining and oxidiz-
ing are usually gas fired, and operating temperatures range from
700 - 900°F (375 - 485°C).

Alloying furnaces simply melt and mix ingots of lead and alloy
material. Antimony, tin, arsenic, copper and nickel are the most common
alloying materials.

Refining furnaces remove copper and antimony to produce soft lead,
and they remove arsenic, copper and nickel to produce hard lead. Sulfur
may be added to the molten lead bath to remove copper. Copper sulfide
skimmed off as dross may subsequently be processed in a blast furnace to
recover residual lead. Aluminum chloride flux may be used to remove
copper, antimony and nickel. The antimony content can be reduced to
about 0.02 percent by bubbling air through the molten lead. Residual
antimony can be removed by adding sodium nitrate and sodium hydroxide to
the bath and skimming off the resulting dross. Dry dressing consists of
adding sawdust to the agitated mass of molten metal. The sawdust
supplies carbon to help separate globules of lead suspended in the dross
and to reduce some of the lead oxide to elemental lead.

Oxidizing furnaces are either kettle or reverberatory furnaces
which oxidize lead and entrain the product lead oxides in the combustion
air stream. The product is subsequently recovered in baghouses at high
efficiency.
7-11-2 EMISSION FACTORS 10/80
-------
145
7.11.2 Emissions and Controls ' '

Emission factors for uncontrolled processes and fugitive partic-
ulate emissions are in Tables 7.11-1 and 7.11-2, respectively.

Reverberatory and blast furnaces account for about 88 percent of
the total lead emissions from the secondary lead industry. Most of the
remaining processes are small emission sources with undefined emission
characteristics.

Emissions from battery breaking mainly consist of sulfuric acid
mist and dusts containing dirt, battery case material and lead com-
pounds. Emissions from crushing are also mainly dusts.

Emissions from sweating operations consist of fume, dust, soot
particulates and combustion products, including sulfur dioxide. The
sulfur dioxide emissions are from the combustion of sulfur compounds in
the scrap and fuel. Dusts range in size from 5-20 um, while unagglom-
erated lead fumes range in size from 0.07 - 0.4 um, with an average
diameter of 0.3 ym. Particulate loadings in the stack gas from rever-
beratory sweating range from 1.4 - 4.5 grains per cubic foot (3.2 - 10.3
g/m3). Baghouses usually control sweating emissions, with removal
efficiencies exceeding 99 percent. The emission factors for lead sweat-
ing in Table 7.11-1 are based on measurements at similar sweating furnaces
in other secondary metals processing industries, and are not based on
measurements at lead sweating furnaces.

Reverberatory smelting furnaces emit particulates and oxides of
sulfur and nitrogen. Particulates consist of oxides, sulfides and
sulfates of lead, antimony, arsenic, copper and tin, as well as unagglom-
erated lead fume. Particulate loadings range from 7-22 grains per
cubic foot (16 - 50 g/m3). Emissions are generally controlled with
settling and cooling chambers followed by a baghouse. Control efficien-
cies generally exceed 99 percent, as shown in Table 7.11-3. Wet scrub-
bers are sometimes used to reduce sulfur dioxide emissions. However,
because of the small particles emitted, scrubbers are not as widely used
as baghouses for particulate control.

Two chemical analyses by electron spectroscopy showed the part-
iculates to consist of 38 - 42 percent lead, 20 - 30 percent tin, and
about 1 percent zinc.16 Typically, particulates from reverberatory
smelting furnaces comprise about 20 percent lead.

Emissions from blast furnaces occur at charging doors, the slag
tap, the lead well, and the furnace stack. The emissions are combustion
gases (including carbon monoxide, hydrocarbons, and oxides of sulfur and
nitrogen) and particulates. Emissions from the charging doors and the
slag tap are hooded and routed to the devices treating the furnace stack
emissions. Reverberatory furnace particulates are larger than those
emitted from blast furnaces and are thus suitable for control by scrubbers
10/80 Metallurgical Industry 7.11-3
-------
PRETREATMENT
SMELTING
REFINING/CASTING
BATTERIES
DROSSES. RESIDUES.
OVERSIZE SCRAP
M
§

I
RESIDUES. DIE SCRAP,
LEAD-SHEATHED
CABLE AND WIRE
HIGH LEAD SCRAP
OXIDES. FLUE DUSTS
MIXED SCRAP
PURE SCRAP
O3
O
COLLECTED
PARTICULATE
MATTER
SEMISOFT
LEAD
REVERBERATORY
SMELTING
BATTERY
BREAKING
KETTLE(SOFTENING)
REFINING
SOFT LEAD
INGOTS
ALLOYING
AGENT
KETTLE(ALLOYING)
REFINING
PRETREATED
SCRAP
BLAST(CUPOLA)
FURNACE SMELTING
ROTARY/TUBE
SWEATING
KETTLE
OXIDATION
BATTERY
LEAD OXIDE
(Pb AND PbO
REVERBERATORY
SWEATING
REVERBERATORY
OXIDATION
Figure 7.11-1. Flow scheme of secondary lead processing.
-------
Table 7.11-2. FUGITIVE EMISSION FACTORS FOR SECONDARY LEAD PROCESSING

EMISSION FACTOR RATING: E

Particulates
Source
Sweating
Smelting
Kettle
Refining
Casting0
Ib/ton
1.6 - 3.5
2.8 - 15.7

0.04
0.88
kg/MT
0.8 - 1.8
1.4 - 7.9

0.02
0.44
Ib/ton
0.4 - 1.
0.6 - 3.

0.01
0.2
Leadb
kg/MT
8 0.2 - 0.4
6 0.3 - 1.8

0.005
0.1
a
of the uncontrolled stack emissions. All factors except that for
casting are based on the amount of charge to the process. The casting
factor is based on the amount of lead cast. Reference 14.
Factors are based on an approximation that particulate emissions
^contain 23% lead. References 3 and 5.
'Factors based on limited tests of a roof monitor over casting operations
at a primary smelter.
10/80
Metallurgical Industry
7.11-5
-------
or fabric filters downstream of coolers. Efficiencies for various
control devices are shown in Table 7.11-3. In one application, fabric
filters alone captured over 99 percent of the blast furnace particulate
emissions.

Table 7.11-3. EFFICIENCIES OF PARTICULATE CONTROL EQUIPMENT
ASSOCIATED WITH SECONDARY LEAD SMELTING FURNACES

Control device
Fabric filter3

Dry cyclone plus fabric filter
Wet cyclone plus fabric filter
Settling chamber plus dry
cyclone plus fabric filter
Venturi scrubber plus demister
Furnace Particulate control
type efficiency, %
Blast
Reverberatory
Blast
Reverberatory
Reverberatory
Blast
98.4
99.2
99.0
99.7
99.8
99.3
•1
, Reference 8.
Reference 9.
^
, Reference 10.
Reference 12.

The size distribution for blast furnace particulates recovered by
an efficient fabric filter is reported in Table 7.11-4. Particulates
recovered from another blast furnace contained about 80 - 85 percent
lead sulfate and lead chloride, 4 percent tin, 1 percent cadmium, 1
percent zinc, 0.5 percent each antimony and arsenic, and less than 1
percent organic matter.17

Kettle furnaces for melting, refining and alloying are relatively
minor emission sources. The kettles are hooded, with fumes and dusts
typically vented to baghouses and recovered with efficiencies exceeding
99 percent. Twenty measurements of the uncontrolled particulates from
kettle furnaces showed a mass median aerodynamic particle diameter of
18.9 ym, with particle size ranging from 0.05 - 150 ym. Three chemical
analyses by electron spectroscopy showed the composition of particulates
to vary from 12 - 17 percent lead, 5-17 percent tin, and 0.9 - 5.7
percent zinc.16

Emissions from oxidizing furnaces are economically recovered with
baghouses. The particulates are mostly lead oxide, but they also
contain amounts of lead and other metals. The oxides range in size from
0.2 - 0.5 ym. Controlled emissions have been reported to be as low as
0.2 - 2.8 pounds per ton (0.1 - 1.4 kg/MT).
7.11-6 EMISSION FACTORS 10/80
-------
Table 7.11-1. EMISSION FACTORS FOR SECONDARY LEAD PROCESSING8
Particulates
Source
Battery breaking
Crushing
Sweating
Leaching
Ib/ton
NA
NA
32-70
Neg
kg/MT
NA
NA
16-35
Neg
Lead
Ib/ton
NA
NA
7-16c
Neg
kg/MT
NA
NA
4-8C
Neg
Sulfur Dioxide .
Ib/ton
NA
NA
NA
Neg
kE/MT
NA
NA
NA
Neg
Emission Factor
Rating

Smelting
M
CO
CO
M
i
>
n
1-3
0
pa
rn
Reverberatory
Blast (cupola)
Kettle refining
Oxidation
Kettle

Reverberatory
147 (56-313)
193 (21-381)f
0.88

<40*

NA
74 (28-157)
97 (11-191)E
0.48

<201

NA
34 (13-72T
44 (5-88)c
' 0.2C

NA
17 (6-36)L
22 (2-44)c
o.ic

NA
80 (71-88) c
53 (18-110)£
NA

NA
40 (36-44)c
27 (9-55)f
NA

NA
B
B
B

All emission factors are based on the quantity of material charged to the furnace (except particulate kettle oxidation).
NA = data not available. Neg = negligible.
Reference 1.
Emission factor rating of E. Emission factors for lead emissions are based on an approximation that particulate emissions contain 23%
lead. References 3 and 5.
Numbers in parentheses represent ranges of values obtained.
References 8-11.
References 11 - 13.
Reference 11.
References 1 and 2.
Essentially all of the product lead oxide is entrained in an air stream and subsequently recovered by a baghouse with average collection
efficiencies in excess of 99%. The reported value represents emissions of lead oxide that escape a baghouse used co collect the
lead oxide product. The emission factor is based on the amount of lead oxide produced and represents an approximate upper limit for
emissions.
co
o
-------
Table 7.11-4. PARTICLE SIZE DISTRIBUTION OF PARTICULATES
RECOVERED FROM A COMBINED BLAST AND REVERBERATORY
FURNACE GAS STREAM WITH BAGHOUSE CONTROL3
Particle Size Range, ym
Fabric filter catch, wt %
0 to 1
1 to 2
2 to 3
3 to 4
4 to 16
13.3
45.2
19.1
14.0
8.4
Reference 4, Table 86.

References for Section 7.11

1. William M. Coltharp, et al., Multimedia Environmental Assessment
of the Secondary Nonferrous Metal Industry (Draft), 2 Volumes, EPA
Contract No. 68-02-1319, Radian Corporation, Austin, TX, June 1976.

2. H. Nack, et al., Development of an Approach to Identification of
Emerging Technology and Demonstration Opportunities, EPA-650/2-74-
048, U.S. Environmental Protection Agency, Research Triangle Park,
NC, May 1974.

3. J. M. Zoller, et al., A Method of Characterization and Quantifi-
cation of Fugitive Lead Emissions from Secondary Lead Smelters,
Ferroalloy Plants and Gray Iron Foundries (Revised), EPA-450/3-78-
003 (Revised), U.S. Environmental Protection Agency, Research
Triangle Park, NC, August 1978.

4. John A. Danielson, editor, Air Pollution Engineering Manual, Second
Edition, AP-40, U.S. Environmental Protection Agency, Research
Triangle Park, NC, May 1973, pp. 299-304. Out of Print.

5. Control Techniques for Lead Air Emissions. EPA-450/2-77-012, U.S.
Environmental Protection Agency, Research Triangle Park, NC,
January 1978.

6. Background Information for Proposed New Source Performance Standards,
Volume I; Secondary Lead Smelters and Refineries, APTD-1352, U.S.
Environmental Protection Agency, Research Triangle Park, NC, June
1973.
7.11-8
EMISSION FACTORS
10/80
-------
7. J. W. Watson and K. J. Brooks, A Review of Standards of Performance
for New Stationary Sources - Secondary Lead Smelters (Draft), EPA
Contract No. 68-02-2526, The Mitre Corporation, McLean, VA, June
1978.

8. John E. Williamson, et al., A j>tudy of Five Source Tests pn_ Emissions
from Secondary Lead Smelters, EPA Order No. 2PO-68-02-3326, County
of Los Angeles Air Pollution Control District, Los Angeles, CA,
February 1972.

9. Emission Test No. 72-CI-8, Office of Air Quality Planning and
Standards, U.S. Environmental Protection Agency, Research Triangle
Park, NC, July 1972.

10. Emission Test No. 72-CI-7, Office of Air Quality Planning and
Standards, U.S. Environmental Protection Agency, Research Triangle
Park, NC, August 1972.

11. A. E. Vandergrift, et al., Particulate Pollutant Systems Study,
Volume I; Mass Emissions, APTD-0743, U.S. Environmental Protection
Agency, Research Triangle Park, NC, May 1971.

12. Emission Test No. 71-CI-33, Office of Air Quality Planning and
Standards, U.S. Environmental Protection Agency, Research Triangle
Park, NC, August 1972.

13. Emission Test No. 71-CI-34, Office of Air Quality Planning and
Standards, U.S. Environmental Protection Agency, Research Triangle
Park, NC, July 1972.

14. Technical Guidance for Control of Industrial Process Fugitive
Particulate Emissions, EPA-450/3-77-010, U.S. Environmental
Protection Agency, Research Triangle Park, NC, March 1977.

15. Silver Valley/Bunker Hill Smelter Environmental Investigation
(Interim Report), EPA Contract No. 68-02-1343, PEDCo-Environmental
Specialists, Inc., Cincinnati, OH, February 1975.

16. E. I. Hartt, An Evaluation of Continuous Particulate Monitors at a
Secondary Lead Smelter, M.S. Report No. O.R.-16, Environmental
Protection Service, Environment Canada.

17. J. E. Howes, et al., Evaluation of Stationary Source Particulate
Measurement Methods, Volume V; Secondary Lead Smelters, EPA Contract
No. 68-02-0609, Battelle Columbus Laboratories, Columbus, OH,
January 1979.
10/80 Metallurgical Industry 7.11-9
-------
Table E-1 (continued). UNCONTROLLED LEAD EMISSION FACTORS
AP-42
Section

710

Process
Open hearth
Lancing
No lancing
Basic oxygen furnace (BOF)
Electric arc furnace
Lancing
No lancing
Primary lead smelting
Ore crushing and grinding
Sintering
Blast furnace
Dross reverberatory furnace
Zinc smelting
Ore unloading, storage,
transfer
Sintering
Horizontal retorts
Vertical retorts
Secondary copper smelting
and alloying
Reverberatory furnace
(high lead alloy 58% Pb)
Red and yellow brass
(15%Pb)
Other alloys (7% Pb)
Gray iron foundries
Cupola
Emission
Metric

0.07 kg/MT steel
0.035 kg/MT steel
0 1 kg/MT steel

0 1 1 kg/MT steel
009 kg/MT steel

015 kg/MT ore
4 2-1 70 kg/MT Pb prod
8 7-50 kg/MT Pb prod
1 3-3.5 kg/MT Pb prod

0.0354.1 kg/MT ore
13 5-25 kg/MT ore
1.2 kg/MT ore
2-2 5 kg/MT ore

25 kg/MT prod
6 6 kg/MT prod
2 5 kg/MT prod

0 05-0 6 kg/MT prod
factor8 b
English

0.14 Ib/ton steel
0.07 Ib/ton steel
0 2 Ib/ton steel

0 22 Ib/ton steel
018 Ib/ton steel

0 3 Ib/ton ore
8 4-340 Ib/ton Pb
prod
175-100 Ib/ton Pb
prod
2 6-7 0 Ib/ton Pb
prod

0.07-0.2 Ib/ton ore
27-50 Ib/ton ore
2 4 Ib/ton ore
4-5 Ib/ton ore

50 Ib/ton prod
132 Ib/ton prod
5 Ib/ton prod

0 1-1 1 Ib/ton prod
References

1
1
1,23,25

1.28
1

29
1.21.22,
30-33
1.30.32.
33,35,36
1.18,30.
34,36

1
1,30.38
1.30.38
1.30,38

1,26,39-41
1,26,39-41
1,26,39-41

1,3,26.
42,43
10/80
Appendix E
E-3
-------
Table E-1 (continued). UNCONTROLLED LEAD EMISSION FACTORS
AP-42
Section

711

715

716

717

Process
Reverberatory furnace
Electric induction furnace
Secondary lead smelting
Reverberatory furnace
Blast cupola furnace
Refining kettles
Storage battery production
(total)
Grid casting
Lead oxide mill (baghouse
outlet)
Three-process operations0
Lead reclaim furnace
Small parts casting
Lead oxide and pigment
production
Barton pot (baghouse
outlet)
Calcining furnace
Red lead (baghouse outlet)
White lead (baghouse
outlet)
Chrome pigments
Miscellaneous lead products
Type metal production
Can soldering
Cable covering
Emission
Metric
0006-0 7 kg/MT prod
0.005- 05 kg/MT prod

27 kg/MT Pb prod
28 kg/MT Pb prod
0 1 kg/MT Pb prod
8 kg/103 batteries
04 kg/103 batteries
005 kg/103 batteries
6.6 kg/103 batteries
035 kg/103 batteries
005 kg/103 batteries

0 22 kg/MT prod
7 kg/MT prod
0 5 kg/MT prod
0 28 kg/MT prod
0 065 kg/MT prod

0 13 kg/MT Pb proc
160 kg/106 baseboxes"
prod
0 25 kg/MT proc
factor8-"
English
0012-014lb/ton
prod
0009-0.1 Ib/ton
prod

53 Ib/ton Pb prod
56 Ib/ton Pb prod
0 21 Ib/ton Pb prod
17 7 lb/103 batteries
0.9 lb/103 batteries
012 lb/103 batteries
14 6 lb/103 batteries
077 lb/103 batteries
010 lb/103 batteries

0 44 Ib/ton prod
14 Fb/ton prod
0 9 Ib/ton prod
0 55 Ib/ton prod
0.13 Ib/ton prod

0 25 Ib/ton Pb proc
018 ton/106 base-
boxes prod
0 5 Ib/ton Pb proc
References
1
1

1.38.42-46
38.42-46
46
1.55-58
1.55-58
1,55-58
1,55-58
1,55-58
1.55-58

1.61.62
61
1.54
1,54
1,54

1.63
1
1,3.64
E-4
EMISSION FACTORS
7/79
-------
7.15 STORAGE BATTERY PRODUCTION by Jake Summers, EPA and
Pacific Environmental Services

7.15.1 Process Description

Lead/acid storage batteries are produced from lead alloy ingots and lead oxide. The latter may or may not
be manufactured at the same plant (Section 7.16).
Molten lead is pumped or flows directly from pot furnaces into the molds that form the battery grids.
Batches of lead sulfate paste are blended by mixing lead oxide, water, sulfuric acid, an organic expander
and other constituents. Pasting machines force the stiff mixture into the interstices of the grids (which
are thereafter referred to as plates).

The plates are cured and stacked in an alternating positive and negative block formation, with insulators
between them. They are then fastened together either by a burning operation (welding leads to the tabs of
each pair of positive and negative plates) or by a "cast on strip" process (in which molten lead is poured
around and between the plate tabs). Positive and negative terminals are then welded to each element,
which can go to either the wet or dry battery assembly line. Pot furnaces are used for reclaiming defective
lead parts.

7.15.2 Emissions and Controls1

Grid casting furnaces and machines, paste mixers, plate dryers, reclaim furnaces and parts casting
machines can be controlled by low- to medium-energy impingement and entramment scrubbers. "Three
process" (element stacking, lead burning and battery casting) emissions can be controlled by pulse jet
fabric filters. Waste material caught in control systems is recycled to recover the lead.
7/79 Mclallurfciral Industry 7.15-1
-------
Table 7.15-1. STORAGE BATTERY PRODUCTION EMISSION FACTORS3

EMISSION FACTOR RATING: B
Process
Grid casting
Paste mixing
Lead oxide mill
(baghouse outlet)
Three-process
operation13
Lead reclaim
furnace
Small parts casting
Formation
Storage battery
production (total)
Paniculate emission factor
(kg/103
batteries)
08
1.0

0.10
13.2

0.70
0.09
14.0C

29.9
(lb/103
batteries)
1.8
2.2

0.24
29.2

1.54
' 019
32.0C

67.2
Lead emission factor
(kg/103
batteries)
0.4
0.5

0.05
6.6

0.35
0.05
N/A

8
(lb/103
batteries)
0.9
1.1

012
14.6

0.77
0.10
N/A

17.6
"References 2-6
>>Stacking, lead burning and battery assembly
Table 7.15-2. STORAGE BATTERY PRODUCTION CONTROL EFFICIENCIES9
Process
Storage battery
production (total)

Control
Low- to medium-energy
impingement and
entramment scrubbers
Pulse jet fabric filter
Percent
reduction
85 - 90 +
95 - 99 +
"Reference 1
7.15-2
EMISSION FACTORS
7/79
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9.1.2.7 Process Heaters - Process heaters (furnaces) are used
extensively in refineries to supply the heat necessary to raise the
temperature of feed materials to reaction or distillation level. They
are designed to raise petroleum fluid temperatures to a maximum of about
950°F (510°C). The fuel burned may be refinery gas, natural gas, residual
fuel oils, or combinations, depending on economics, operating conditions
and emission requirements. Process heaters may also use carbon monoxide-
rich regenerator flue gas as fuel.

All the criteria pollutants are emitted from process heaters. The
quantity of these emissions is a function of the type of fuel burned,
the nature of the contaminants in the fuel, and the heat duty of the
furnace. Sulfur oxide can be controlled by fuel desulfurization or flue
gas treatment. Carbon monoxide and hydrocarbons can be limited by more
combustion efficiency. Currently, four general techniques or modifi-
cations for the control of nitrogen oxides are being investigated:
combustion modification, fuel modification, furnace design and flue gas
treatment. Several of these techniques are presently being applied to
large utility boilers, but their applicability to process heaters has
not been established.2*11*

9.1.2.8 Compressor Engines - Many older refineries run high pressure
compressors with reciprocating and gas turbine engines fired with natural
gas. Natural gas has usually been a cheap, abundant source of energy.
Examples of refining units operating at high pressure include hydro-
desulfurization, isomerization, reforming and hydrocracking. Internal
combustion engines are less reliable and harder to maintain than steam
engines or electric motors. For this reason, and because of increasing
natural gas costs, very few such units have been installed in the last
few years.

The major source of emissions from compressor engines is combustion
products in the exhaust gas. These emissions include carbon monoxide,
hydrocarbons, nitrogen oxides, aldehydes and ammonia. Sulfur oxides may
also be present, depending on the sulfur content of the natural gas.
All these emissions are significantly higher in exhaust of reciprocating
engines than from turbine engines.

The major emission control technique applied to compressor engines
is carburetion adjustment similar to that applied on automobiles.
Catalyst systems similar to those applied to automobiles may also be
effective in reducing emissions, but their use has not been reported.

9.1.2.9 Sweetening - Sweetening of distillates is accomplished by the
conversion of mercaptans to alkyl disulfides in the presence of a
catalyst. Conversion may be followed by an extraction step for the
removal of the alkyl disulfides. In the conversion process, sulfur is
added to the sour distillate with a small amount of caustic and air.
The mixture is then passed upward through a fixed bed catalyst counter
to a flow of caustic entering at the top of the vessel. In the conversion
and extraction process, the sour distillate is washed with caustic and
then is contacted in the extractor with a solution of catalyst and

10/80 Petroleum Industry 9.1-9
-------
Table 9.1-2. FUGITIVE EMISSION FACTORS FOR PETROLEUM REFINERIES*
Emission Process
Source Scream
Type6
Pipeline valves'* II

III

Open ended valves >e I

Flanges'1 I

Pump seals'1 III

Compressor seals II

Process drains I

Pressure vessel 11
relief valves ,
(gas service) '
Cooling towers

Oil/water scparacors -

Storage
Loading
"Data from References 2, 4,
NA - Hot Available.
Emission Emission Factors
Factor Uncontrolled
Units Emissions0
Ib/hr-source 0.059 (0.030 - 0.110)
kg/day-source 0 64 (0.32 - 1.19)
0.024 (0.017 - 0.036)
0.26 (0.18 - 0. J9)
0.0005 (0 0002- 0.0015)
0.005 (0.002 - 0.016)
" 0.018 (0.007 - 0.045)
0.20 (0.08 - 0 49)
0.005 (0.0016- 0.016)
0.05 (0.017 - 0.17)
0 00056 (0.0002- 0.0025)
0.0061 (0.002 - 0.027)
0.25 (0.16 - 0.37)
2.7 (1 7 - 4.0)

" 0.046 (0.019 - 0.11)
0.50 (0.21 - 1.2)
1.4 (0.66 - 2.9)
15 (7 1 - 31)

0.11 (0.05 - 0.23)
11 1 2 (0.5 - 2.5)
0.070 (0.023 - 0.20)
0.76 (0.25 - 2.2)
" 0.36 (0.10 - 1.3)
3.9 (1.1 - 14)

lb/106 gal cooling
water 6

kg/106 liters cooling
water 0. 7
lb/103 bbl refinery
feed8 10
kg/103 liters
refinery feed 0.03
lb/103 gal wastevater 5
kg/103 liter waste
water 0.6
lb/103 bbl refinery
feed 200
kg/103 liters refinery
feed 0.6
See Section 4 3
See Section 4 4
12 and 13 except as noted. Overall, less than IX

Controlled
Emissions
NA

Negligible

0.70

0.083

1.2

0.004
0.2

0.024

0.03

by weight of

Applicable Control Technology

Monitoring and maintenance programs

Installation of cap or plug on open end
of valve/line
Monitoring and maintenance programs

Mechanical seals, dual seals, purged
seals, monitoring and maintenance
programs, controlled degassing vents

Traps and covers

Rupture disks upstream of relief
valves and/or venting to a flare

Minimization of hydrocarbon leaks
Into cooling water system. Monitoring
of cooling water for hydrocarbons

Covered separators and/or vapor recovery
Systems

the total VOC emissions are methane

The volatility and hydrogen content of the process streams have a substantial effect on the emission rate of some fugitive emission
The stream Identification
Stream
Identification
Numeral
I
II
numerals and group names and descriptions are*

Stream
Name Stream Group
All streams All streams

Description

Gas streams Hydrocarbon gas/vapor at process

Emission
Factor
Ratine
A

sources

conditions (containing less than SOX hydrogen, by
III
Light liquid and
gas/liquid streams

Heavy liquid streams
Hydrogen streams
volume)

Liquid or gas/liquid stream vith a vapor pressure greater than that of
kerosene (> 0.1 psla @ 100'F or 689 Pa 9 38°C), based on the most volatile class
present at > 20% by volume

Liquid stream with a vapor pressure equal to or less than that of kerosene (^ 0.1
psia @ 100°F or 689 Pa @ 38*C) , based on the most volatile class present at » 20Z
by volume

Gas streams containing more than 50Z hydrogen by volume
'•Numbers In parentheses are the upper and lower bounds of the 95! confidence Interval for the emission factor
Data from Reference 17.
'The downstream side of these valves is open to the atmosphere. Emissions are through the valve scat of the closed valve.
Emission factor for relief valves In gas service is for leakage, not for emissions caused by vessel pressure relief
^Refinery rate is defined as the crude oil feed rate to the atmospheric distillation column.
9.1-10
EMISSION FACTORS
10/80
-------
caustic. The extracted distillate is then contacted with air to convert
mercaptans to disulfides. After oxidation, the distillate is settled,
inhibitors are added, and the distillate is sent to storage. Regeneration
is accomplished by mixing caustic from the bottom of the extractor with
air and then separating the disulfides and excess air.

The major emission problem is hydrocarbons from contact between
the distillate product and air in the "air blowing" step. These emissions
are related to equipment type and configuration, as well as to operating
conditions and maintenance practices.4

9.1.2.10 Asphalt Blowing - The asphalt blowing process polymerizes
asphaltic residual oils by oxidation, increasing their melting temper-
ature and hardness to achieve an increased resistance to weathering.
The oils, containing a large quantity of polycyclic aromatic compounds
(asphaltic oils), are oxidized by blowing heated air through a heated
batch mixture or, in continuous process, by passing hot air counter-
current to the oil flow. The reaction is exothermic, and quench steam
is sometimes needed for temperature control. In some cases, ferric
chloride or phosphorus pentoxide is used as a catalyst to increase the
reaction rate and to impart special characteristics to the asphalt.

Air emissions from asphalt blowing are primarily hydrocarbon vapors
vented with the blowing air. The quantities of emissions are small
because of the prior removal of volatile hydrocarbons in the distilla-
tion units, but the emissions may contain hazardous polynuclear organics.
Emission are 60 pounds per ton of asphalt.13 Emissions from asphalt
blowing can be controlled to negligible levels by vapor scrubbing,
incineration, or both4*13

9.1.3 Fugitive Emissions and Controls

Fugitive emission sources are generally defined as volatile organic
compound (VOC) emission sources not associated with a specific process
but scattered throughout the refinery. Fugitive emission sources
include valves of all types, flanges, pump and compressor seals, process
drains, cooling towers, and oil/water separators. Fugitive VOC emissions
are attributable to the evaporation of leaked or spilled petroleum
liquids and gases. Normally, control of fugitive emissions involves
minimizing leaks and spills through equipment changes, procedure changes,
and improved monitoring, housekeeping and maintenance practices.
Controlled and uncontrolled fugitive emission factors for the following
sources are listed in Table 9.1-2.

0 valves (pipeline, open ended, vessel relief)
0 flanges
0 seals (pump, compressor)
0 process drains
o
oil/water separators (wastewater treatment)
storage
0 transfer operations
0 cooling towers
10/80 Petroleum Industry 9.1-11
-------
9.1.3.1 Valves, Flanges, Seals and Drains - For these sources, a very
high correlation has been found between mass emission rates and the type
of stream service in which the sources are employed. Except for com-
pressed gases, streams are classified into one of three stream groups,
(1) gas/vapor streams, (2) light liquid/two phase streams, and (3)
kerosene and heavier liquid streams. Gases passing through compressors
are classified as either hydrogen or hydrocarbon service. It is found that
sources in gas/vapor stream service have higher emission rates than
those in heavier stream service. This trend is especially pronounced
for valves and pump seals. The size of sources like valves, flanges,
pump seals, compressor seals, relief valves and process drains does not
affect the leak rates.17 The emission factors are independent of process
unit or refinery throughput.

Emission factors are given for compressor seals in each of the two
gas service classifications. Valves, because of their number and relatively
high emission factor, are the major emission source among the source
types. This conclusion is based on an analysis of a hypothetical refinery
coupled with the emission rates. The total quantity of fugitive VOC
emissions in a typical oil refinery with a capacity of 330,000 barrels
(52,500 m3) per day is estimated as 45,000 pounds (20.4 MT) per day.
See Table 9.1-3.

9.1.3.2 Storage - All refineries have a feedstock and product storage
area, termed a "tank farm", which provides surge storage capacity to
assure smooth, uninterrupted refinery operations. Individual storage
tank capacities range from less than 1000 barrels to more than 500,000
barrels (160 - 79,500 m3). Storage tank designs, emissions and emission
control technologies are discussed in detail in Section 4.3.

9.1.3.3 Transfer Operations - Although most refinery feedstocks and
products are transported by pipeline, some are transported by trucks,
rail cars and marine vessels. They are transferred to and from these
transport vehicles in the refinery tank farm area by specialized pumps
and piping systems. The emissions from transfer operations and appli-
cable emission control technology are discussed in much greater detail
in Section 4.4.

9.1.3.4 Wastewater Treatment Plant - All refineries employ some form of
wastewater treatment so water effluents can safely be returned to the
environment or reused in the refinery. The design of wastewater treat-
ment plants is complicated by the diversity of refinery pollutants,
including oil, phenols, sulfides, dissolved solids, and toxic chemicals.
Although the wastewater treatment processes employed by refineries vary
greatly, they generally include neutralizers, oil/water separators,
settling chambers, clarifiers, dissolved air flotation systems, coagu-
lators, aerated lagoons, and activated sludge ponds. Refinery water
effluents are collected from various processing units and are conveyed
through sewers and ditches to the wastewater treatment plant. Most of
the wastewater treatment occurs in open ponds and tanks.
9.1-12 EMISSION FACTORS 10/80
-------
The main components of atmospheric emissions from wastewater treat-
ment plants are fugitive VOC and dissolved gases that evaporate from the
surfaces of wastewater residing in open process drains, wastewater
separators, and wastewater ponds (Table 9.1-2). Treatment processes
that involve extensive contact of wastewater and air, such as aeration
ponds and dissolved air flotation, have an even greater potential for
atmospheric emissions.

The control of wastewater treatment plant emissions involves cov-
ering wastewater systems where emission generation is greatest (such as
covering American Petroleum Institute separators and settling basins)
and removing dissolved gases from wastewater streams with sour water
strippers and phenol recovery units prior to their contact with the
atmosphere. These control techniques potentially can achieve greater
than 90 percent reduction of wastewater system emissions.13

TABLE 9.1-3. FUGITIVE VOC EMISSIONS FROM AN OIL REFINERY17

Source
Valves
Flanges
Pump Seals
Compressors
Relief Valves
Drains
Cooling Towers3
Oil/Water Separators
(uncovered)
TOTAL

Number
11,500
46,500
350
70
100
650
-

VOC
Ib/day
6,800
600
1,300
1,100
500
1,000
1,600

32,100
45,000
Emissions
kg/ day
3,084
272
590
499
227
454
726

14,558
20,408
a
Emissions from the cooling towers and oil/water separators are based on
limited data. EPA is currently involved in further research to provide
better data on wastewater system fugitive emissions.

9.1.3.5 Cooling Towers - Cooling towers are used extensively in refinery
cooling water systems to transfer waste heat from the cooling water to
the atmosphere. The only refineries not employing cooling towers are
those with once-through cooling. The increasing scarcity of large water
supplies required for once-through cooling is contributing to the disappear-
ance of that form of refinery cooling. In the cooling tower, warm
cooling water returning from refinery processes is contacted with air by
cascading through packing. Cooling water circulation rates for refineries
commonly range from 0.3 to 3.0 gallons (1.1 - 11.0 liters) per minute
per barrel per day of refinery capacity.2»^

Atmospheric emissions from the cooling tower consist of fugitive
VOC and gases stripped from the cooling water as the air and water come
into contact. These contaminants enter the cooling water system from

10/80 Petroleum Industry 9.1-13
-------
leaking heat exchangers and condensers. Although the predominant conta-
minant in cooling water is VOC, dissolved gases such as hydrogen sulfide
and ammonia may also be found (Table 9.1-2) ^i1*'17

Control of cooling tower emissions is accomplished by reducing
contamination of cooling water through the proper maintenance of heat
exchangers and condensers. The effectiveness of cooling tower controls
is highly variable, depending on refinery configuration and existing
maintenance practices.

References for Section 9.1

1. C. E. Burklin, et al., Revision of Emission Factors for Petroleum
Refining, EPA-450/3-77-030, U.S. Environmental Protection Agency,
Research Triangle Park, NC, October 1977.

2. Atmospheric Emissions from Petroleum Refineries; A Guide for Measure-
ment and Control, PHS No. 763, Public Health Service, U.S. Depart-
ment of Health, Education and Welfare, Washington, DC, 1960.

3. Background Information for Proposed New Source Standards; Asphalt
Concrete Plants, Petroleum Refineries, Storage Vessels, Secondary
Lead Smelters and Refineries, Brass or Bronze Ingot Production Plants,
Iron and Steel Plants, Sewage Treatment Plants, APTD-1352a, U.S.
Environmental Protection Agency, Research Triangle Park, NC, 1973.

4. John A. Danielson (ed.), Air Pollution Engineering Manual (2nd Ed.),
AP-40, U.S. Environmental Protection Agency, Research Triangle
Park, NC, 1973. Out of Print.

5. Ben G. Jones, "Refinery Improves Particulate Control", Oil and Gas
Journal, 69(26):60-62, June 28, 1971.

6. "Impurities in Petroleum", Petreco Manual, Petrolite Corp., Long
Beach, CA, 1958.

7. Control Techniques for Sulfur Oxide in Air Pollutants, AP-52, U.S.
Environmental Protection Agency, Research Triangle Park, NC,
January 1969.

8. H. N. Olson and K. E. Hutchinson, "How Feasible Are Giant, One-
train Refineries?", Oil and Gas Journal. 70(1):39-43, January 3,
1972.

9. C. M. Urban and K. J. Springer, Study of Exhaust Emissions from
Natural Gas Pipeline Compressor Engines, American Gas Association,
Arlington, VA, February 1975.

10. H. E. Dietzmann and K. J. Springer, Exhaust Emissions from Piston
and Gas Turbine Engines Used in Natural Gas Transmission, American
Gas Association, Arlington, VA, January 1974.

9.1-14 EMISSION FACTORS 10/80
-------
11. M. G. Klett and J. B. Galeski, Flare Systems Study, EPA-600/2-76-
079, U.S. Environmental Protection Agency, Research Triangle Park,
NC, March 1976.

12. Evaporation Loss in the Petroleum Industry, Causes and Control,
API Bulletin 2513, American Petroleum Institute, Washington, DC,
1959.

13. Hydrocarbon Emissions from Refineries, API Publication No. 928,
American Petroleum Institute, Washington, DC, 1973.

14. R. A. Brown, et al., Systems Analysis Requirements for Nitrogen
Oxide Control of Stationary Sources, EPA-650/2-74-091, U.S.
Environmental Protection Agency, Research Triangle Park, NC, 1974.

15. R. P. Hangebrauck, et al., Sources of Polynuclear Hydrocarbons in
the Atmosphere, 999-AP-33, Public Health Service, U.S. Department
of Health, Education and Welfare, Washington, DC, 1967.

16. W. S. Crumlish, "Review"of Thermal Pollution Problems, Standards,
and Controls at the State Government Level", Presented at the
Cooling Tower Institute Symposium, New Orleans, LA, January 30, 1966.

17. Assessment of Atmospheric Emissions from Petroleum Refining,
EPA-600/2-80-075a through -075d, U.S. Environmental Protection
Agency, Research Triangle Park, NC, 1980.
10/80 Petroleum Industry 9.1-15
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TECHNICAL REPORT DATA
(Please read Instnifliam, on the reverse before completing)
1 REPORT NO 2
AP-42, Supplement 11
4 TITLE AND SUBTITLE
Supplement No. 11 for Compilation of Air Pollutant
Emission Factors, Third Edition, AP-42

7 AUTHOR(S)
Monitoring and Data Analysis Division
9 PERFORMING ORGANIZATION NAME AND ADDRESS
J.S. Environmental Protection Agency
Jffice of Air, Noise and Radiation
Jffice of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
12. SPONSORING AGENCY NAME AND ADDRESS
15 SUPPLEMENTARY NOTES
3 RECIPIENT'S ACCESSION NO
\
5 REPORT DATE
fVtnhpr IQflf)
6 PERFORMING ORGANIZATION CODE
s PERFORMING ORGANIZATION REPORT NO
10 PROGRAM ELEMENT NO
11 CONTRACT/GRANT NO
13 TYPE OF REPORT AND PERIOD COVERED
Supplement
14 SPONSORING AGENCY CODE

15 ABSTRACT
In this Supplement for Compilation of Air Pollutant Emission Factors, AP-42,
revised and updated emissions data are presented for Nitric Acid; Pharmaceuticals
'reduction; Maleic Anhydride; Normal and Triple Superphates and Ammonium Phosphates;
;oke Manufacturing; Primary Copper Smelting; Iron and Steel Production; Secondary
Lead Processing; and Petroleum Refining.
17 KEY WORDS AND DOCUMENT ANALYSIS
a DESCRIPTORS b IDENTIFIE
ruel combustion
Emissions
•mission factors
Stationary sources
-• -
RS/OPEN ENDED TERMS C COSATI 1 leld/Croup

* CLASS IT, ,s Report, 21 NO OF PAGES
96
' 'I i -> '55 iT',i* zoxel 2i PRICE
i
FPA
J220-'
4-77,
.
a-2
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