EPA 600/2-77 023w
February 1977
Environmental Protection Technology Series
INDUSTRIAL PROCESS PROFILES FOR
ENVIRONMENTAL USE: Chapter 23.
Sulfur, Sulfur Oxides and
Sulfuric Acid
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into five series. These five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies ,
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to develop and
demonstrate instrumentation, equipment, and methodology to repair or prevent
environmental degradation from point and non-point sources of pollution. This
work provides the new or improved technology required for the control and
treatment of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfiefd, Virginia 22161.
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EPA-600/2-77-Oa3w
February 1977
INDUSTRIAL PROCESS PROFILES
FOR ENVIRONMENTAL USE
CHAPTER 23
SULFUR, SULFUR OXIDES AND SULFURIC ACID
by
Richard W. Gerstle and Vishnu S. Katari
PEDCo-Environmental Specialists, Inc.
Cincinnati, Ohio 45246
Terry Parsons and Charles Hudak
Radian Corporation
Austin, Texas 78766
Contract No. 68-02-1319
Project Officer
Alfred B. Craig
Metals and Inorganic Chemicals Branch
Industrial Environmental Research Laboratory
Cincinnati, Ohio 45268
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been reviewed by the Industrial Environmental Research
Laboratory - Cincinnati, U.S. Environmental Protection Agency, and approved
for publication. Approval does not signify that the contents necessarily
reflect the views and policies of the U.S. Environmental Protection Agency,
nor does mention of trade names or commercial products constitute endorsement
or recommendation for use.
n
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TABLE OF CONTENTS
Page
INDUSTRY DESCRIPTION 1
Raw Materials 2
Products 3
Companies 4
Envi ronmental Impact 6
Bibliography 11
INDUSTRY ANALYSIS 13
Elemental Sulfur Production 14
Process No. 1 Gas Desiilfurization and Sulfur
Recovery = 17
Process No. 2 Tail Gas Treatment , 22
Process No. 3 Frasch Process Sulfur Production 27
Sulfuric Acid and Sulfur Dioxide Production 29
Process No. 4 Sulfur Combustion 31
Process No. 5 Roasting of Pyrites , 32
Process No. 6 Spent Acid Combustion 34
Process No. 7 Gas Cleaning 35
Process No. 8 Absorption and Stripping 37
Process No. 9 Converter 38
Process No. 10 Absorption Tower , 39
Process No. 11 Distillation , , 45
Process No. 12 Acid Concentrator., 46
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TABLE OF CONTENTS (Continued)
Page
APPENDIX A - Companies and Their Products 49
APPENDIX B - Product Uses and Properties 61
APPENDIX C - References for Appendices 65
iv
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LIST OF FIGURES
No. Page
la Sulfur Production from Gas Treatment. 16
Ib Sulfur Production and Frasch Sulfur 16
2 Sul fur Oxi des Product! on 30
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LIST OF TABLES
Table Page
1 Leading Producers of Frasch-Sulfur and Their
Production Capacities 5
2 Five Largest Recovered-Sulfur Producers 5
3 Major Sulfuric Acid Producers 7
4 Domestic Sulfur Dioxide Producers 8
5 Material Flow for Example Claus Sulfur Plants... 19
6 Fuel Requirements 20
7 Claus Sulfur Plant Tail Gas 20
8 Typical Feed for Pyrite Roasting 32
9 Typical Utility Requirements of Smelter Gas Purifi-
cation and Contact Acid Production Plants
(For Process 6 and 9 to 11) 35
10 Characteristics of Tail Gas Emissions from
Conventional Sulfuric Acid Plants , 41
11 Emission Factors for Sulfuric Acid Plants 42
12 Particle Size Distributions in Selected Sulfuric
Acid Plant Absorber Effluents 43
13 Utility Requirements of a Drum-Type Sulfuric Acid
Concentrator 46
14 Emissions from Acid Drum Concentrators 47
vi
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ACKNOWLEDGMENTS
This catalog entry was prepared for EPA by PEDCo-Environmental
Specialists, Inc., under Contract No. 68-02-1321, Task 25. Vishnu
S. Katari and Richard W. Gerstle were the co-authors of this report.
vii
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SULFUR. SULFUR OXIDES AND SULFURIC ACID INDUSTRY
INDUSTRY DESCRIPTION
The sulfur, sulfur oxides and sulfuric acid plants comprise
a large and important chemical industry. The principal product of the
sulfur industry3 is concentrated sulfuric acid which serves as a raw
material in numerous applications. Sulfuric acid accounts for over
90 percent of domestic sulfur production. Other products of impor-
tance include, but are not limited to, sulfur dioxide and oleum.
The sulfur industry has experienced steady growth during the
previous 25 years, with an increase in total annual production for 6.1
2
to 11.2 million metric tons since 1950. Forecasts indicate that
the domestic sulfur demand will increase to between 23 to 38 million
tons by the year 2000. Despite this long term trend, production in
2
1975 slipped 1.4 percent of the 1974 levels. Exports and imports
are roughly equivalent and represent only 10 percent of domestic
2
consumption.
The sulfur industry can be divided into two basic groups according
to the types of products. Chemical processes yielding elemental
sulfur either from naturally occurring deposits or from HLS containing
gas streams, comprise the first group. The elemental sulfur serves
as one of the main raw materials for the sulfur oxides and sulfuric
acid production plants which comprise the second major category.
The Frasch Process continues to be the dominant source of elemental
2
sulfur, accounting for 64 percent of domestic production in 1975.
This process, which is technically similar to the original process
introduced in the 1890's, provides an economical supply of high purity
(99.5 + %) sulfur. Impurities such as hydrocarbons and ash generally
3
are present in quantities less than 0.15 percent each. There are
presently 13 Frasch mines in the United States, all located in Texas
a
and Louisiana. The annual quantities of Frasch sulfur produced
throughout this report the term "sulfur industry" will apply to all
components of the elemental sulfur, sulfur oxides and sulfuric acid
industries.
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domestically have been relatively stable at 5 to 6 metric tons during
2
the last ten years. Nevertheless, the share of the elemental sulfur
market has declined steadily during this period due to increases in
recovered sulfur.
Recovered elemental sulfur from both natural gas purification and
petroleum processing accounted for 26 percent of domestic 1975 production.
Quantities from both sources have approximately doubled in the previous
2
5 years. Unlike the Frasch process, which is concentrated in a small
geographical region, recovered sulfur plants are widely distributed.
There are approximately 140 plants, located in all major industry regions
of the country. Such plants tend to be small, with only five of the
140 plants having production capacities in excess of 100,000 tons per
year.
There are approximately 166 sulfuric acid plants with an annual
production capacity of 37.5 million tons; 7 plants produce more than
a million tons annually. Of the 28.8 million tons of sulfur acid
produced in 1973, 99.6 percent was by the contact process and the
remainder by the chamber process. About 68 percent of contact process
sulfuric acid was produced from elemental sulfur, 4.5 percent from
iron pyrites» 9 percent from smelter tail-gas, and 18.5 percent from
hydrogen sulfide spent alkylation acid, and acid sludge from refin-
4
eries. Additionally, by-product sulfuric acid is produced by several
copper, lead and zinc smelters.
In 1974, there were about eight sulfur dioxide producers with a
4
total capacity of 204,000 tons. About 45 percent of the total sulfur
dioxide was used in producing hydrosulfites and other chemicals, 25
percent in paper manufacturing, and the remainder in soybean protein
production, oil refining, metal and ore refining, and other miscellaneous
processes.
Raw Materials
The main source of raw elemental sulfur is the large sulfur de-
posits in the coastal plains of Louisiana and Texas. The Frasch
sulfur produced in this region accounted for 64 percent of domestic
2
sulfur production in 1975. Recovered elemental sulfur from natural
-------
gas and petroleum processing provided 26 percent of domestic production,
and recovered sulfuric acid accounted for the remaining 10 percent.
There has been a modest but steady decline during the last 25 years
in the fraction of elemental sulfur provided by the Frasch process.
In 1950, over 85 percent of sulfur was produced by the Frasch process
w
2
p
while the present level is only 64 percent. There was a drop from
69 percent to 64 percent in the previous year alone.'
Treatment of sour natural gas and refining of petroleum results
in the recovery of hydrogen sulfide as a by-product, which subsequently
can be used for production of sulfur and sulfur oxides. The quantities
of elemental sulfur recovered at natural gas plants and petroleum
)t
2
2
refineries are approximately equal. Both sources have experienced
rapid growth during the last five years.'
Concentrated sulfur dioxide in the gaseous effluent of non-ferrous
smelters is a third major sulfur source. These gases generally contain
4 to 8 more percent SOg. There is a long term trend toward more
recovery of S02 from smelters and power plants due partially to environ-
mental control requirements.
Products
Sulfuric acid is the major product of the sulfur chemicals in-
dustries, accounting for over 90 percent of total domestic sulfur con-
2
sumption. Other products include oleum, sulfur dioxide and sulfur.
One relatively minor by-product of this industry is iron calcite
produced when pyrites are used as a raw material.
Elemental sulfur is chemically stable and can be stored for long
periods of time without any appreciable product quality degradation.
It has a characteristic yellow color and is generally shipped in the
liquid form to facilitate handling and to reduce environmental impact.
All but a small fraction of elemental sulfur is ultimately consumed
for production of sulfuric acid.
Sulfuric acid is a colorless, corrosive, oily liquid obtained in
a variety of different commercial grades. Table B-l in the appendices
shows the major users of sulfuric acid by industry group. It can be
seen that fertilizers are by far the major end products. Oleum or
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fuming sulfuric acid is a solution of sulfur trioxide in 100 percent
sulfuric acid. Oleum, which reacts very violently with water, is
highly toxic. It is used as a sulfating and sulfonating agent; as a
dehydrating agent in nitrations; in the dye, explosive, and petroleum
refining industries; and as a laboratory reagent. Table B-2 gives
properties of the commercial grades of sulfuric acid and oleum.
Sulfur is a colorless gas with a pungent odor which is primarily
used in the food and chemical industries. Anhydrous grade sulfur
dioxide is at least 99.98 percent pure.
Physical properties of sulfur, sulfur oxides and sulfuric acid
are summarized in Table B-3.
Companies
There is a very large and diverse set of companies involved in
the production of sulfur chemicals. In addition to the elemental sulfur
companies using the Frasch process, there are oil companies, chemical
companies and non-ferrous smelting companies which recover sulfur or
sulfur oxides.
The leading producers of Frasch sulfur and the corresponding pro-
duction capacities are listed in Table 1. Freeport Sulfur Company and
Texas Gulf Sulfur Company together accounted for 60 percent of the
4
total sulfur production in 1973. It is apparent that this segment of
the industry is concentrated entirely in the Gulf Coast area, where
large deposits of sulfur bearing ore are available. Frasch sulfur
production facilities are generally large scale operations due to the
utilities requirements.
There are over fifty companies actively involved in the production
of elemental sulfur from either sour natural gas or petroleum. A list
of plants and production capacities is provided in Appendix A-l. It is
apparent that such plants tend to have smaller production capacities
than the Frasch sulfur facilities. Only 5 of the elemental sulfur re-
covery plants had capacities in excess of 100,000 tons per year while
all but one of the Frasch plants is substantially larger than this amount.
Approximately 55 percent of the sulfur recovery plants was produced at
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Table 1. LEADING PRODUCERS OF FRASCH-SULFUR AND
THEIR PRODUCTION CAPACITIES
(SOURCE: REFERENCE 4)
Producer
Arco Chemical, Fort Stockton, Texas
Duval , Culberson County, Texas
Freeport, Garden Island, La.
Freeport, Grand Ecaille, La.
Freeport, Grand Isle, La.
Freeport, Lake Pel to, La.
Jefferson Lake, Long Point, Texas
Pan American Petroleum, High Island, Texas
Texas Gulf, Bullycamp, La.
Texas Gulf, Fannett, Texas
Texas Gulf, Moss Bluff, Texas
Texas Gulf, Newgulf, Texas
Texas Gulf, Spindletop, Texas
Total
Capacity,
103 metric ton/yr
183
2,540
813
1,422
1,524
610
305
51
305
178
305
1,524
686
10,446
Table 2. FIVE LARGEST RECOVERED-SULFUR PRODUCERS - 1973
(ADAPTED FROM REFERENCE 4)
Producer
Exxon Company
Getty Oil Company
Shell Oil Company
Standard Oil Company of California
Standard Oil Company of Indiana
Total
Capacity,
103 metric ton/vr
260
231
1,077
165
464
2,197
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petroleum refineries (38 companies total) and 45 percent at natural
2
gas purification plants (29 companies total). The five largest
recovered sulfur produced (both petroleum and natural gas processing)
are listed in Table 2. Due partially to the relatively high sulfur
content of some mideastern crude oil, there should be continual growth
in sulfur recovery. Since 1970, the quantities produced from both
2
natural gas and petroleum have doubled.
There are three general categories of companies involved in the
production of sulfuric acid; the elemental sulfur (Frasch) companies,
chemical companies and non-ferrous smelting companies. Thfe capacities
and raw materials vary significantly as illustrated in Table 3.
A comparison of the totals of raw materials listed in Table 3
indicate that Frasch sulfur now accounts for only slightly more than
half of total sulfur consumed. This trend toward more recovered sulfur
and reclaimed sulfuric acid should continue due to environmental regu-
lations. During the next ten years coal and oil fired utility boilers
equipped with certain S02 control systems could become sulfur and
sulfuric acid sources.
Sulfur dioxide is produced by 6 companies at eight sites in Table
4. It is apparent that this volume of sulfur dioxide produced is
an order of magnitude lower than sulfuric acid.
In 1974, four companies were manufacturing sulfur trioxide:
Allied Chemical Corporation, (Industrial Chemical Division); E.I.
du Pont Company, (Industrial Chemicals Division); Cities Service Com-
pany; and Stauffer Chemical Company, (Industrial Chemical Division).
More complete lists of producers of elemental sulfur, sulfur
dioxide, sulfur trioxide, sulfuric acid, and other products are listed
in Tables A-l through A-5 in the appendices.
Environmental Impact
Atmospheric emissions of H2S, S02 and sulfuric acid mist consti-
tute the main environmental problem with the various sulfur chemical
industries. In sulfuric acid production the SC^ emissions vary in-
versely with the SOg to SOg conversion efficiency. For older sulfur-
burning plants with three-stage converters, conversion efficiencies
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Table 3. MAJOR SULFURIC ACID PRODUCERS
(Adapted from reference 4)
Producer
Chemical companies
Stauffer Chemical Co.
Allied Chemical Co.
E.I. duPont
C.F. Industries
Farmland Industries, Inc.
Gardinier, Inc.
Elemental sulfur companies
Freeport Minerals, Inc.
Texasgulf, Inc.
Non-ferrous smelters
American Smelting and
Refining
Kennecott Copper
Phelps Dodge
St. Joe Mineral
Anaconda
Bunker Hill
Total
Quantities of Sulfuric Acid, 1000 metric tons/year
Using
Elemental
Sulfur
710
1,197
1,095
2,086
1,179
1,361
1,542
1,343
-
-
-
_
_
-
10,513
Using
Smelter
Gas
(S02)
-
-
-
-
-
-
-
-
636
975
426
350
313
287
2,981
Using sludge
pyrites,
hydrogen sulfide
2,972
1,539
1,302
-
-
-
-
-
-
-
-
-
_
-
5,813
Total
capacity
3,682
2,736
2,397
2,086
1,179
1,361
1,542
1,343
363
975
426
350
313
281
19,307
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Table 4, DOMESTIC SULFUR DIOXIDE PRODUCERS
(Source: Reference 4)
Producer
Ansul , Marinette, Wise.
Asarco, Tacoma, Washington
Cities Service, Copperhill, Tenn.
Essex, Newark, N.J.
Stauffer, Baton Rouge, La.
Stauffer, Hammond, Ind.
Virginia Chemicals, W. Norfolk, Va.
Virginia Chemicals, Selby, Calif.3
Total
3 Capacity
10 metric ton/yr
15
61
35
15
13
10
41
14
204
May be shut down.
8
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are typically 95 to 96 percent, with corresponding emissions of approxi-
mately 22 to 37 kilograms of 502 per ton of acid produced (approximately
7800 to 15,600 mg/m3 (3000 to 6000 ppm).8'9 Conversion of efficiencies
for four-stage converters range from 96 to 98 percent, with SO/, emissions
o
between 11 and 29 kilograms per ton (approximately 3900 to 10,400 mg/m ,
8 9
1500 to 4000 ppm). ' Plants utilizing elemental sulfur as feed generally
have lower emissions compared to plants using other sulfur-bearing feed
streams. Dual absorption plants can achieve conversion efficiencies
higher than 99 percent, with resulting S02 emissions of less than 2.0
kilograms per ton of acid. The corresponding SO? concentration are
3
less than 1300 mg/m (500 ppm) with such plants. Acid mist emissions
are in the range of 0.5 to 6 kg per ton of acid without controls and
are independent of conversion efficiencies.
Sulfur dioxide emissions from new sulfuric acid plants are limited
by Federal regulations to 2.0 kg per ton of acid produced; acid mist
emissions are limited to 0.075 kg per ton of acid.
Some odorous compounds are emitted from plants that utilize feed-
stocks with large amounts of organic compounds such as refinery acid
sludges. These organic compounds are largely oxidized in the combustion
and conversion stages of the sulfuric acid manufacturing process, but
trace amounts may be emitted.
Chamber-type sulfuric acid plants generally release lower concen-
trations of sulfur dioxide as compared to contact plants. The exit gases
in the chamber plant, in addition to S0~, contain between 1230 to 2460
•3 C-
mg/m (1000 to 2000 ppm) of nitrogen oxides. The air pollution impact
caused by chamber processes is limited by the small quantities produced
in this manner. Chamber type production accounts for only 0.4 percent
of the total sulfuric acid production.
Emissions from Claus type plants used to process H,,S recovered
from natural gas or petroleum include hLS, S07, carbonyl sulfide and
in
carbon disulfide. For a typical 100 metric ton per day, operating
at 94 percent efficiency, H9S and SO, concentration would be 11,900
"\ c. e. -,-,
and 23,900 mg/m (8500 and 9200 ppm), respectively. Carbonyl sulfide
-------
3
and carbon disulfide concentrations are estimated at roughly 1250 mg/m
(500 ppm) each. Conventional treatment practice is incineration in
order to reduce potential odor problems in the vicinity of the Glaus
plant. This results in a substantial increase in S02 emission rates
and concentration. There are a variety of tail-gas treatment problems
under development to alleviate these atmospheric problems. Most of these
processes recover sulfur pollutant compounds in a chemical form that can
be used. These tail-gas processes generally reduce sulfur compound
emissions by 80 percent or greater. Literature concerning the operating
conditions and performance characteristics of these processes is provided
in references 10, 11, 12, 13, 14 and 15.
Liquid and solid waste impacts caused by this industry are minimal.
Accidental spills of sulfuric acid which is shipped by rail, train
and barge can cause physical damage to the surrounding areas.
10
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Bibliography
1. Merwin, R. W. and W. F. Keyes. Sulfur and Pyrites. Bureau of
Mines Minerals Yearbook, U.S. Department of the Interior. 1973.
2. Sulfur in 1975. Division of Nonmetallic Minerals. In:
Mineral Industry Surveys, U.S. Department of the Interior,
Bureau of Mines. Washington, D.C. July 10, 1976. 17 p.
3. Lowenheim, F. A. and M. K. Moran. Faith, Keyes and darks'
Industrial Chemicals, fourth edition, Wiley Interscience, 1975.
4. Stanford Research Institute. 1974 Dictionary of Chemical Pro-
ducers - United States of America. California, 1974.
5. Chemical Economics Handbook. Manual of Current Indicators.
Stanford Research Institute. California, February 1975.
6. Chemical Profile - Sulfur Dioxide. In: Chemical Marketing
Reporter, No. 9. August 26, 1974. Schnell Publishing Co., Inc.
New York.
7. Hawley, G. G. The Condensed Chemical Dictionary. Eighth edition.
Van Nostrand-Reinhold Company. New York, 1971.
8. Background Information for Proposed New-Source Performance
Standards: Sulfuric Acid Plants. EPA Office of Air Programs,
Research Triangle Park, N.C. August 1971. Report No. APTD-0711.
9. Chemical Construction Corp., Engineering Analysis of Emissions
Control Technology for Sulfuric Acid Manufacturing Process.
NTIS No. PB190393. March 1970.
10. Semrau, K. T. Control of Sulfur Oxide Emissions from Primary
Copper, Lead, and Zinc Smelters—A Review. (For Presentation
at the 63rd Annual Meeting of the Air Pollution Control
Association. Missouri. June 14-18, 1970.)
11. Genco, J. M. and S. S. Tarn. Characterization of Sulfur Recovery
from Refinery Fuel Gas. EPA Contract No. 68-02-0611. June 1974.
12. Beavon, D. K. and R. N. Fleck. Beavon Sulfur Removal Process
for Claus Plant Tail Gas. In: Sulfur Removal and Recovery
from Industrial Processes, John B. Pfeiffer (ed.). Washington,
D.C., Advances in Chemistry Series 139, American Chemical Society,
1975. p. 93-99.
13. Barthel, Yves, et al. Sulfur Recovery in Oil Refineries Using
IFP Processes. In: Sulfur Removal and Recovery from Industrial
Processes, John B. Pfeiffer (ed.). Washington, D.C., Advances
in Chemistry Series 139, American Chemical Society, 1975.
p. 100-110.
11
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14. Swaim, C. D., Jr. The Shell Claus Offgas Treating (SCOT)
Process. In: Sulfur Removal and Recovery feom Industrial
Processes, John B. Pfeiffer (ed.). Washington, D.C., Advances
in Chemistry Series 139, American Chemical Society, 1975.
p. 111-119.
15. Kim, B., Genco, J. M., Oxley, J. and P. Choi. Development
of Information for Standards of Performance for the Fossil
Fuel Conversion Industry. EPA-450/3-75-029, October 1974.
12
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INDUSTRY ANALYSIS
The sulfur, sulfur oxides and sulfuric acid industries are logically
divided into two segments. The production of elemental sulfur from
either naturally occurring deposits or hydrogen sulfide containing gas
streams constitutes the first group of processes. The elemental sul-
fur produced serves as the main raw material to the sulfur acid and
sulfur dioxide industries which comprise the second major group.
Elemental sulfur is produced primarily by Frasch Process recovery
of natural deposits or Glaus Process recovery from sour gas streams.
Power plant desulfurization processes may eventually be another source
of elemental sulfur, however, these processes have not yet achieved
commercial status in the United States. For this reason, such desul-
furization processes are not discussed.
Sulfuric acid is produced by the contact process from burning
sulfur, or H2S, from metallurgical smelter gases, roaster gases,
burning of acid sludges, and other minor sources. In all cases the
same overall reaction mechanisms occur. The chamber process of pro-
ducing sulfuric acid is not discussed, because the process is becoming
obsolete and presently accounts for only 0.4 percent of production.
13
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ELEMENTAL SULFUR PRODUCTION
Elemental sulfur is produced by two general methods: 1) the
Frasch Process of recovery of naturally occurring sulfur and 2) the
Claus Process of oxidation of hLS recovered from natural gas plants
and petroleum refinery. The Frasch Process continues to be the
dominant process despite recent gains in recovered sulfur production.
Due to the high sulfur content of some Mideast oil and to stringent
environmental regulations, the trend in favor of recovered sulfur should
continue. Generalized process flowsheets for these two techniques
are presented in Figures la and Ib.
The hydrogen sulfide recovery process has been subject to rapid
technological development due to the increasing cost of Frasch sulfur
and to the need for such processes in coal gasification. The process
actually encompasses a series of steps, including removal of h^S from
a gas stream, oxidation of the H2S, and recovery of the elemental
sulfur. These have been lumped into one process block since there
are generally no major waste streams from the HpS removal processes.
The discussion of gas stream desulfurization is limited to the various
amine techniques since it is the dominant approach at the present.
It should be noted that there are a large number of other processes
which could be used and that the input materials and utilities require-
ments will vary.
Hydrogen sulfide oxidation and elemental sulfur recovery is
typically done in a Claus plant. Due to the predominance of this
general technique, it is the only process discussed. The Stretford
Process is a possible alternative to the Claus Process, particularly
in applications with a low H^S concentration gas stream from the desul-
furization process.
Gaseous emissions from the Claus plant have generally been incin-
erated to convert I^S to the less odorous compound SOp. Increasing
concern over ambient S02 levels has resulted in greater interest in
tail gas treatment processes for removal of all sulfur compounds.
There are relatively few commercial installations in the United States
despite the fact that a number of processes have been successfully
14
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operated In Europe. A general discussion of these processes is pre-
sented since there are too many to cover separately. Useful references
which provide a convenient entry to the technical literature concerning
tail gas processes is also presented.
The Frasch Process is a highly developed commercial process not
subject to rapid technological changes. Furthermore, this industry
does not have the diversity which characterizes the sulfur recovery
industry.
15
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CATALYST'
SOLVENTS
COOLING WATER
CONTAINING—*-
GAS
DESULFURIZATION1
AND
RECOVERY PROCESS
TAIL GAS
TREATMENT PROCESS
Figure la. Sulfur production from gas treatment.
HOT WATER
DRILLING3
FRASCH PROCESS
SULFUR PRODUCTION
GASEOUS EMISSIONS
LIQUID WASTE
SOLID HASTE
Figure Ib. Sulfur production from Frasch sulfur.
16
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ELEMENTAL SULFUR PRODUCTION PROCESS NUMBER 1
_Gas Desulfurization and Sulfur Recovery
1. Function - This process comprises a series of steps designed to remove
sulfur compounds from a natural gas plant or petroleum refinery gas
stream and to convert those sulfur compounds to elemental sulfur. De-
sulfurization may be accomplished in a variety of techniques, however,
recovery using ethanamine is the most common. Applicable chemical
reactions for this process are shown below.
2 RNH2
(RNH3)2 S
The term R in these equations represents a variety of organic groups.
Principal amine compounds used in these processes are monoethanolamine
(MEA), diethyltmol amine (DEA), diisopropanol amine (DIPA), and 2(2-
aminethoxy ethanol) (DEA). The choices of amine sometimes depends on
the presence of other sulfur compounds. Diethylanolamine is used for
refining gas (10 to 20 percent aqueous solution) while monoethanolamine
is generally used for purification of natural gas (10 to 30 percent
aqueous solution).
The regenerated acid gas stream composed primarily of C02 and
H2S can be treated in a Claus unit for production of elemental sulfur.
There are a variety of process configurations which can be used depending
on the H2S concentration in the inlet gas stream. These include total
acid gas combustion and split stream combustion. The basic chemical
processes in all of these systems are similar and are presented below.
2 H2S + S02 - -3 S + 2 H20
Overall H2S + \ 02 - *S + H20
In total combustion, the acid gas stream is mixed with the theore-
tical amount of air and burned in a cambustion chamber. Products of
combustion containing sulfur vapor, steam, S02, and H2$ are passed through
a heat recovery boiler, where partial cooling of combustion gases occurs
17
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and a portion of the sulfur vapor is condensed and separated. Effluent
gases are passed to a two- or three-stage catalytic converter with
provision for intermediate condensation and reheating. The reaction is
carried out in the presence of a bauxite catalyst and additional
sulfur vapor is formed and condensed. All the product sulfur formed
in the heat recovery boiler and condensers is passed to a liquid sulfur
storage tank after passing through a coalescer.
The split-stream combustion process consists of burning one-third
of the feed acid gas stream in the furnace to produce SOo. This S02
is then combined with the remaining two-thirds of feed material and
passed to a catalytic reactor where the reaction between S02 and H2S
occurs. The reaction products enter a heat exchanger where the sulfur
is condensed. The reaction gas is then passed through a coalescer to
remove any entrained droplets of sulfur which could interfere with
subsequent gas treatment equipment (incineration or tail-gas purifica-
tion systems).
Usually the sulfur recovery in Glaus units is 94 to 97 percent,
the percentage being affected by the number of catalyst stages. About
85 percent conversion is achieved in a one-stage converter, 94 percent
in a two-stage converter, and 97 percent in a three-stage converter.
Recovery efficiency also varies directly with the H2S concentration of
the feed gas. The sulfur recovered from gases in a Glaus-type recovery
plant usually is above 99.9 percent pure and is free of metallic con-
taminants such as arsenic, selenium and tellurium.
2. Input Materials - A gas stream containing H2S from natural gas
plants, petroleum refineries or other sources is the main input stream.
Steam from H?S stripping is required along with make-up amine solution.
3
Air requirements for the Glaus plant are approximately 1800 m
per metric ton of sulfur recovered.
Feed to the sulfur recovery plant primarily contain hydrogen sulfide
o
and carbon dioxide with about 1 to 2 mole percent of hydrocarbons.
Table 5 shows material flow quantities for typical Glaus sulfur plants
2
on a petroleum refinery gas stream.
18
-------
Table 5. MATERIAL FLOW FOR EXAMPLE CLAUS SULFUR PLANT
Feed quantity
m^/day
Feed composition,
mole %
H2S
co2
Hydrocarbons
Sulfur production,
metric tons/day
3
Air, m /metric ton
65,000
90
8
2
122
1,800
The catalyst used is a natural bauxite that has been activated by
heating to a temperature between 370 to 400°C and calcined to a residual
4
water content of 6 percent. For split-stream combustion a ratio by
5
volume of catalyst to H2S to be converted may be 1:2 or more. The
catalyst is usually replaced annually.
3. Operating Parameters - H2S absorption is generally performed at
40°C and atmospheric pressure while stripping is done at roughly 110°C.
The Claus plant operates an atmospheric pressure with an intake gas
temperature of 40°C. The temperature in the burner reaches 1100°C. After
passing through a waste heat boiler, the gas temperature is about 370°C.
The temperature of the gas in the converter is maintained between 230 and
245°C. The condenser gas exit temperature is 150°C.
4- Utilities - Approximately 2 horsepower per ton of product is needed
for lighting and miscellaneous purposes. Fuel gas is required for
start-up of the sulfur plant. Boiler feed water requirements of Claus
plants are: 1300 kg/hr for a plant of 10 tons/day recovery, 12,000 kg/hr
for a plant of 100 tons/day capacity, 58,000 kg/hr for a plant of
500 tons/day capacity, and 111,000 kg/hr for a plant of 1000 ton/day
capacity.8 Table 6 gives fuel requirements and steam generation for
g
the plants described in Table 5.
19
-------
Table 6. FUEL REQUIREMENTS
3
Fuel gas, m /day
Steam generated,
kg/hr
Plant A
14,200
15,000
Plant B
5,400
16,000a
Plant C
7,000
4,000
aConsisting of about 12,000 kg/hr of 21.1 kg/cm steam and
about 400 kg/hr of 3.5 kg/cm* steam.
The reactions are highly exothermic. Most of the heat generated in
the burner and reaction chamber is removed by generating high-pressure
steam, and the condenser heat is removed by generating low-pressure
steam.10
5. Waste Streams - Waste streams for this process are based on a single-
stage recovery unit with one catalytic reactor. The vent gases from the
sulfur recovery unit may contain 1 to 3 mole percent of unconverted H0S
4 e-
and SOp. Unrecovered sulfur appears in tail gases principally as H^S,
sulfur vapor and SO,,. A typical tail gas from a properly designed and
operated Claus unit will contain C02, N2 and H^O plus sulfur compounds
in concentrations shown in Table 7.
Table 7. CLAUS SULFUR PLANT TAIL GAS
Components
H2S
so2
cs2
COS
Sg (vapor)
ppm dry basis
5,000 to 12,000
2,500 to 6,000
300 to 5,000
300 to 5,000
100 to 200
mg/m°
7,000 to 17,000
6,500 to 16,000
950 to 16,000
730 to 12,250
1,000 to 2,000
Because the feed gas may contain carbon/sulfur compounds, reactions
in the process will result in carbonyl sulfide and carbon disulfide.
Increasing hydrocarbon content of the feed stream will tend to increase
the formation of COS and CS2. These carbon/sulfide compounds can be
minimized but not eliminated by reducing the hydrocarbon content of the
20
-------
feed. COg can also be a source of carbon for forming sulfides.
Many methods are available to control the emissions. The methods .
used most often in the United States are flaring and incineration which
convert the sulfides to sulfur dioxide. Tail gas clean-up processes
are now commercially available to aid in reducing sulfur emissions.
Solid waste in the form of inactive catalyst is also generated at
Claus plants.
6. EPA Source Classification Code - None exists.
7. References -
1. Kim, B., Genco, J. M., Oxley, J. and P. Choi. Development of
Information for Standards of Performance for the Fossil Fuel
Conversion Industry. EPA-450/3-75-029, October 1974.
2. Air Pollution Engineering Manual. U.S. Environmental Protection
Agency Report AP-40, 1972.
3. Grekel, H., Palm, J. W. and J. W. Kilmer. Why Recover Sulfur
from H2S? In: The Oil and Gas Journal. October 28, 1968.
4. Graff, R. A. Sulfur Recovery from Petroleum Gases Eliminates
an Air-Pollution Problem and Puts a Profit in the Till. The
Oil and Gas Journal. November 17, 1960.
5. U.S. Patent No. 2092386. Hans Baehr and Carl Braus, issued
May 14, 1940.
6. Giusti, G. P. Petroleum Major Sulfur Source. The Oil and Gas
Journal. February 22, 1975.
7. Information Provided by Ford Bacon and Davis Sulfur Recovery
Plants. In: Beers, W. D. Characterization of Claus Plant
Emissions. EPA-R2-73-188. April 1973.
8. Information Provided by J. F. Pritchard and Co. In: Beers,
W. D. Characterization of Claus Plant Emissions. EPA-R2-73-
188. April 1973.
9. Beers, W. D. Characterization of Claus Plant Emissions. EPA-
R2-73-188. April 1973.
10. Genco, J. M. and S. S. Tarn. Characterization of Sulfur Recovery
from Refinery Fuel Gas. EPA Contract No. 68-02-0611. June 1974.
11. Pearson, M. J. Developments in Claus Catalysts. Hydrocarbon
Processing. February 1973.
21
-------
ELEMENTAL SULFUR PRODUCTION PROCESS NUMBER 2
Tail Gas Treatment
1. Function - The principal function of tail gas treatment processes
is the removal of gaseous sulfur compounds in the effluent of the Claus
plant (Process Number 1). These pollutants are generally converted to
either elemental sulfur or SOo and put back into the main product stream.
Sulfur recovery is a secondary function of these processes. A partial
list of commercial tail gas treatment processes is provided below.
Beavon
Cleanair
IFP-1
SCOT
Sulfreen
Well man-Lord
Chiyoda Throughbred 101
2. Input Materials - Specific input requirements for the commercial
treatment processes are briefly summarized below. Quantity data is
generally not readily available in the open literature.
Beavon: A limited quantity of make-up absorber liquor is required
for the Stretford process which is an integral part of the Beavon process
(= 0.0131 to 0.131 L/sec for a 100 MT/D Claus plant). This solution
contains anthraquiamine disulphonic acid, sodium meta vandate, sodium
3
potassium titrate, soda ash, and other compounds. The cobalt
4
molybate catalyst must be replaced every three years.
Cleanair: Detailed technical information is proprietary, however,
make-up catalyst and absorber liquor are probably required.
IFP-1: A catalyst composed of mixed alkali salts of an organic acid
are used along with a glycol solvent and an ammonium sulfite absorber
•3
liquor. Make-up requirements are unknown.
SCOT: Limited quantities of cobalt-molybdenum catalyst and alkanol-
amine solution are required.
Sulfreen: A catalyst composed of either activated carbon or alumina
is required at a rate of 5.6 or 11.0 kg/hr, respectively for a 100 MT/D
22
-------
Claus plant off-gas. Nitrogen gas is also required (- 40 Nm/hr).
Well man-Lord: 3.7 metric tons of 100% NaOH is required for a
3
100 metric ton per day Claus plant off-gas.
Chiyoda Throughbred 101: Ferric sulfate catalyst and limestone are
required. Limestone quantities are 21 MT/D for a 100 MT/D claus plant.
3. Operating^ Conditions - The operating conditions of the various tail
gas treatment processes are briefly discussed below.
Beavon: Hydrolysis and hydrogeneration are performed at approxi-
3 4
mately the same temperature and pressure as the Claus plant. ' The
Stretford unit operates at approximately 50°C.
Cleanair: No information readily available.
IFP-1: No information readily available.
SCOT: The reactor operates at approximately 300°C and atmospheric
pressure. Absorption is done at ambient temperatures following water
quenching of the gas stream.
Sulfreen: The reactor operates at 127 to 149°C. Desorption of
sulfur is accomplished at 400°C.
Wellman-Lord: Absorption of the S02 containing gas stream from
the incinerator is done at 38°C and approximately
atmospheric pressure.
Chiyoda Throughbred 101: Absorption of an S02 containing gas stream
from an incinerator is done at 55°C and approximately atmospheric
pressure.
4- Utilities - The utility requirements for the various tail gas
treatment processes are summarized on the following page. It is readily
apparent that there are major differences. The data in the table
is based on a 100 metric ton per day Claus plant off-gas. Steam
produced in the process is not included in the table.
23
-------
Approximate Utility Requirements
Process
4
Beavon
Ceanair
IFP-15
SCOT6
Sulfreen
Wellmen-Lord
Chiyoda
Throughbred 103
Electrical
power
kWh/day
7,200
N.D.
4,600
815
2,000
2,230
10,200
Natural
gas
MM Btu/day
125
N.D.
-
70
15
3,500
55,000
Water
cooling
M liters/day
-
N.D.
19,000
16,300
-
12,900
21 ,200
Steam
kg/hr
-
N.D.
2,500
2,900
(50 PSIG)
1,770
-
0
Boiler
feed water
M liters/day
N.D.
N.D.
N.D.
95
60
260
285
5. Waste Streams - The waste streams for the tail gas treatment processes
are briefly summarized in the table below. The basis for the quantities
shown in the table is a 100 MT/D Claus plant off-gas.
Process
Waste Streams
Airborne waste
Aqueous waste
Solid waste
Beavon'
0.065 MT/D sul-
fur compound
(=26 mg/m3)
Cleanair
Gaseous sulfur
compound emissions
quantities probably
similar to Beavon
Process
l)Sour water
condensate,
250 M liters/day
50 mg/L H2S
2)Stretford
purge solution
4-40 M liters/day
(for typical
composite -
see ref. 3)
Stretford purge
solution, quan-
tities probably
similar to
Beavon Process
Unknown
Unknown
24
-------
Process
Waste Streams
Airborne waste
Aqueous waste
Solid waste
IFP-r
scor
Sulfreen*
Well man-Lord"
Chiyoda 3
Throughbred 101
0.993 MT/D of
sulfur, primarily
S02 @ 546 mg/m3
0.08 MT/D sulfur
primarily as S02
with slight quan-
tities of H2$;S02
concentration
- 500 mg/m3,
concentration
14 mg/m3
1.7 MT/D of sulfur.
Primarily as S02
at a concentration
of 7800 mg/m3
0.134 MT/D of sul-
fur. Primarily as
S02 at concentra-
tion of 550 mg/nr
Intermittent
catalyst wash
waste
Sour waste con
densate * 43 M
gas/day, with
H2S @ 30 mg/L
Catalyst
waste
Catalyst waste
and small
amounts of
amine sludge
0.5 MT/D of sulfur
Primarily as S02
at concentration
of 2000 mg/nr
No major waste
l)Sodium sulfate/
sulfite purge,
75 M liters/day
2)Acid water con-
densate, 115 M
liters/day: pH 2.
Acidic purge stream
50 M liters/day
Catalyst waste
Unknown
By-product
gypsum, 35 MT/D.
6. EPA Source Classification Codes - None exists.
7. References -
1. Semrau, K. Controlling the Industrial Process Sources of Sulfur
Oxides. In: Sulfur Removal and Recovery from Industrial Processes,
John B. Pfeiffer (ed.). Washington, D.C., Advances in Chemistry
Series 139, American Chemical Society, 1975. p. 1-24.
2. Kim, B., Genco, J. M., Oxley, J. and P. Choi. Development of
Information for Standards of Performance for the Fossil Fuel
Conversion Industry. EPA-450/3-75-029, October 1974.
3. Genco, J. M. and S. S. Tarn. Characterization of Sulfur Recovery
from Refinery Fuel Gas. EPA Contract No. 68-02-0611. June 1974.
25
-------
4. Beavon, D. K. and R. N. Fleck. Beavon Sulfur Removal Process
for Claus Plant Tail Gas. In: Sulfur Removal and Recovery from
Industrial Processes, John B. Pfieffer (ed.). Washington, D.C.
Advances in Chemistry Series 139, American Chemical Society,
1975. p. 93-99.
5. Swaim, C. D., Or. The Shell Claus Offgas Treating (SCOT)
Process. In: Sulfur Removal and Recovery from Industrial Pro-
cesses, John B. Pfieffer (ed.). Washington, D. C., Advances
in Chemistry Series 139, American Chemical Society, 1975.
p. 111-119.
26
-------
ELEMENTAL SULFUR PRODUCTION PROCESS NUMBER 3
Frasch Process Sulfur Production
1. Function - Almost all of the elemental sulfur produced by the
Frasch process is obtained from sulfur bearing porous limestone deposits
in the salt dome rocks of Texas and Louisiana. Holes are bored to the
bottom of the sulfur bearing strata at depths from 150 to 760 meters.1'2'3
Three concentric pipes with diameters of 20, 10 and 2.5 cm (8, 4 and 1
inch) within a 25 cm (10 inch) casing are placed in the hole. Hot water
is passed down the space between the 20 cm and 10 cm pipes to melt the
sulfur from the rocks. The molten sulfur, being heavier than water,
sinks to form a pool around the base of the well and is forced up to
the surface through the 10 cm pipe by an airlift created by blowing air
123
down the 2.5 cm pipe. ' ' The product sulfur is collected in steam-
heated sumps where the air bubbles out.
2. Input Materials - The primary input material is raw sulfur containing
less than 0.15 percent ash and less than 0.05 to 1.0 percent hydrocarbons.
Large quantities of hot water and air are also required.
3. Operating Parameters - Temperature of the hot water is maintained
" ;- ' n
at about 160 to 165°C. Air is compressed to 28 to 42 kg/cnr (400 to
600 pounds per square inch). A heating period of 24 hours or longer
is required to accumulate a liquid sulfur pool.
4- Utilities - Large quantities of hot water and compressed air are
necessary. Water requirements vary from 4 to 50 metric tons per metric
ton of sulfur produced. The equivalent heat content of this water is
560,000 to 7,000,000 kcal per metric ton of sulfur.
5. Waste Streams - Blended well water is withdrawn at approximately
the same rate as hot water is passed into the sulfur deposits. This
waste contains appreciable quantities of hydrogen sulfide and is highly
corrosive. At some facilities, the H2S is stripped with hot air in
countercurrent towers. Atmospheric emissions of \\2$ result from this
operation. H^S is also evolved from air by air bubbles passing out of
the liquid sulfur. The aqueous waste can be treated for hardness and
chlorides for reuse or can be discharged.
27
-------
6. EPA Source Classification Code - None exists.
7. References
1. Shreve, R. N. Sulfur and Sulfuric Acid. In: Chemical
Process Industries. New York, McGraw Hill Book Company.
1967.
2. Lowenheim, F. A. and M. K. Moran. Faith, Keyes and darks'
Industrial Chemicals, fourth edition, Wiley Interscience.
1975.
3. Chemical Technology: An Encyclopedic Treatment. T. J. W. van
Thoor (ed.), Barnes and Noble, Inc., 1968.
28
-------
SULFURIC ACID AND SULFUR DIOXIDE PRODUCTION
The processes necessary for production of sulfuric acid and sulfur
dioxide involve one or more of the following; S02 formation by S02
oxidation, S03 absorption, oleum distillation and sulfuric acid concen-
tration. S02 formation can be done by a variety of alternative pro-
cesses including combustion of elemental sulfur, spent acid combustion,
roasting of pyrites, or direct recovery for smelter gases. The latter
two sources are becoming more important as supplies of elemental sulfur
become more expensive. The generalized flowsheets for the processes
are shown in Figure 1.
The chemical reactions which are the basis for process design
and operating requirements are presented below.
S + 02 ^* S02
2 S02 + 02 ^ 2 S03
S03 + H20 »~ H2S04
The reversibility of the second reaction has been a major factor
affecting total sulfur oxide emissions. During the last 13 years, a
variety,of processes have been commercialized to achieve greater S02
conversion by a two stage SOo absorption, and S02 conversion technique.
This development has both environmental and economical advantages.
tJttier than the development of this dual absorption technology, changes
in this industry are comparatively gradual.
29
-------
co
o
DRY
Isu
q
C
r
AIR
SULFUR 4
COMBUSTION
LFUR
RITES
ROASTING
FER
SPENT ACID 6
COMBUSTION
WATER
/-xf
V / 1*" A
ACID SLUDGE
FUEL
LTER GAS
CASEOUS EMISSIONS
LIQUID WASTE
SOLID WASTE
Figure 2. Sulfur oxides production.
-------
SULFUR OXIDES PRODUCTION PROCESS NUMBER 4
Sulfur Combustion
1. Function - Elemental sulfur Is burned with dry air to form gaseous
sulfur dioxide with a concentration of 8 to 11 mole percent. If the
sulfur is in solid form, it is heated to a molten state and settled
or filtered to remove ash before it is pumped into the refractor-lined
burner. The hot combustion products are passed through waste heat
boilers where the gas is cooled and high-pressure steam is generated
before it is sent to the absorber or the converter (Process Numbers
8 and 9).
2. Input Materials - The stochiometry of the sulfur oxidation reaction
o
indicates that approximately % kilogram of sulfur and 1.2 Nm of air
are required per kilogram of S02 produced.
3. Operating Parameters - If molten sulfur is to be combusted, the
handling equipment must be steam jacketed to maintain the sulfur
temperature at 135 to 150°C (275 to 310°F). The temperature of the gas
leaving the combustion chamber ranges from 700 to 1000°C. The gas is
then cooled to a temperature between 400 and 450°C. The pressure is
p
maintained between 1400 and 4200 kg/m (2 to 6 psig) depending on design,
rate of operation, and cleanliness of equipment.
4- Utilities - The sulfur combustion processes involves an exothermic
chemical reaction which yields useful steam energy at an estimated rate
of 1100 kcal (4360 Btu) per kilogram of S02 produced. Utility require-
ments are minor.
5. Waste Streams - Emissions from combustion chambers are negligible
if there are no leaks in heat exchanges. All of the gases formed
(S02, C02, 02, N2) are passed to the absorber or to the converter
through a closed system.
6. EPA Source Classification Code - None exists.
7. References -
1. Kirk-Othmer. Sulfur Compounds. In: Encyclopedia of Chemical
Technology. New York, John WiTey & Sons, Inc., 1969.
2. U.S. Department of Health, Education and Welfare. Atmospheric
Emissions from Sulfuric Acid Manufacturing Processes. Public
Health Service Publications No. 999-AP-13. 1965.
31
-------
SULFUR OXIDES PRODUCTION PROCESS NUMBER 5
Roasting of Pyrites
!• Function - Pyrite or pyrrhotite is fed at a controlled rate to a
fluidized-bed roaster as a slurry with water or as small crushed particles,
Combustion air is also fed into the roaster. During roasting at high
temperatures the sulfide ores form metallic oxides and sulfur dioxide.
The resulting iron oxide by-product is marketed for use in blast
furnaces. Flash roasters or multiple-hearth roasters are also in use.
The gases formed in this process are then cleaned (Process No. 7).
2. Input Materials - As a rule, maximum allowable carbon content and
minimum sulfur content of the pyrite used for acid production are 8
percent and 42 percent, respectively. Table 8 gives typical feed
requirements for the roasting operation.
Table 8. TYPICAL FEED FOR PYRITE ROASTING
Material
Pyrite feed
Sulfur content
Carbon content
Water
Quantity
1 ton
46 percent
5 percent
250 liters
3. Operating Parameters - The roasting temperature is controlled by
water sprays or cooling tubes located in the fluidized bed. The SOo-
containing gases leave the roaster at 800 to 900°C. Air for oxidation
o
and for fluidizing the bed is drawn from the atmosphere by a blower.
4. Utilities - Roasting of pyrites requires the following per metric
ton of feed ore: 115 kWh of electrical energy, 20,000 liters of
cooling water. Roasting also produces about 250 kWh of electrical
energy per ton of pyrite charged.
5. Waste Streams - Since the entire roaster gas product stream is
passed to the absorption or conversion process, the atmospheric emissions
are negligible except for leaks which have not been quantified.
32
-------
6. EPA Source Classification Code - None exists.
7. References -
1. Pollution Control and By-Product Sulfur Too. Engineering and
Mining Journal. June 1968.
2. Chemical Construction Corporation. Sulfuric Acid from Pyrite
or Pyrrhotite. In: Modern Contact Sulfuric Acid Processes.
Bulletin No. 116. New York.
33
-------
SULFUR OXIDES PRODUCTION PROCESS NUMBER 6
Spent Acid Combustion
1. Function - Spent acid, sludge, or other feed Is pumped to a com-
bustion furnace along with air where it is decomposed at a high temper-
ature to produce sulfur dioxide and small amounts of carbon dioxide and
water. The resulting combustion gas is cooled in waste heat boilers
and then cleaned (Process Number 7).
2. Input Materials - The spent acid usually contains about 90 percent
1 2
suIfuric acid, 4 to 5 percent water, and 5 to 6 percent hydrocarbons. '
Some quantities of hydrogen sulfide or sulfur are also burned when make-
up acid is required.
3. Operating Parameters - Furnace temperature is maintained at about
1000 to 1100°C. The gas is cooled to a temperature of 370°C.1
4. Utilities - The hydrocarbons in the spend acid provide part of the
fuel. Additional heat is provided by burning fuel oil or gas in the
presence of air. The fuel requirements increase with increasing water
content of the feed material.
5. Waste Streams - Emissions are negligible because the entire product
formed from burning spent acid is sent to a gas cleaning unit.
6. EPA Source Classification Code - None exists.
7. References -
1. Chemical Construction Corporation. Sulfuric Acid from Spent
Acids. In: Modern Contact Sulfuric Acid Processes. Bulletin
No. 116. New York.
2. Shreve, R. N. Sulfur and Sulfuric Acid. In: Chemical
Process Industries. New York, McGraw Hill Book Company.
1967.
34
-------
SULFUR OXIDES PRODUCTION PROCESS NUMBER 7
Gas Cleaning
1- Function - Because off-gases from nonferrous smelting operations and
spent acid combustion contain considerable amounts of particulate material,
they are scrubbed with weak acid. The gas is then cooled and passed
through an electrostatic precipitator for removal of dust and sulfuric
acid mist. The cleaned gas is dried with 93 percent acid in a drying
tower before it enters a converter in the acid plant.
2- Input Materials - The sulfur dioxide content of gases from smelting
operations ranges from 4 to 14 percent.1 Weak acid (10% H2S04) is also
required for the scrubbing liquor.
3. Operating Parameters - In the drying tower smelting gases are cooled
from 70°C to 37°C to reduce the moisture content.2 Temperature of
roasting gases is reduced from 900°C to 350°C.3
4. Utilities - Table 9 gives typical utility requirements for a
n
smelting gas purification process and contact sulfuric acid plant.
5- Waste Streams - Waste water results from this process. This water
is treated to remove particulate material. Quantitative waste water
data are not readily available.
The exit gases are contained and processed further to recover the
sulfur, thus eliminating all but fugitive emissions.
Table 9. TYPICAL UTILITY REQUIREMENTS OF SMELTER GAS
PURIFICATION AND CONTACT ACID PRODUCTION PLANTS
(FOR PROCESS 6 AND 9 TO 11)
(Basis: 1 ton of HSO produced)
Utility
Electric power for all
electric motor drives
Water for gas cooling at 29°C
Water for acid cooling
Quantity
52 kWh
15,000 liters
40,000 liters
35
-------
6. EPA Source Classification Code - None exists.
7. References
1. Rinckhoff, J. B. Sulfuric Acid Plants for Copper Converter Gas.
In: Sulfur Removal and Recovery from Industrial Processes.
John B. Pfeiffer (ed.), Washington, D.C., Advances in Chemistry
139, American Chemical Society, 1975. p. 48-59.
2. Semrau, K. T. Control of Sulfur Oxide Emissions from Primary
Copper, Lead, and Zinc Smelters--A Review. (For Presentation
at the 63rd Annual Meeting of the Air Pollution Control Associa-
tion. Missouri. June 14-18, 1970).
3. Chemical Construction Corporation. Sulfuric Acid from Pyrite
or Pyrrhotite. In: Modern Contact Sulfuric Acid Processes.
Bulletin No. 116. New York.
36
-------
SULFUR OXIDES PRODUCTION PROCESS NUMBER 8
Absorption and Stripping
1. Function - To make product grade S02, the cooled gas from the com-
bustion chamber is contacted and absorbed by water in a packed tower
absorber. When the S02 is obtained from other sources, such as smelter
gases, the S02 is cleaned and then is absorbed by anhydrous dimethyl -
aniline in a bubble cap tower. The cool, absorbed liquor is stripped
by heating with low-pressure steam to produce a gaseous mixture of
sulfur dioxide and water vapor which is dried with sulfuric acid and
finally compressed and liquified. The final product, liquid S02, con-
tains less than 50 ppm of water. The commercial grade of the liquid
product is 99.98 percent pure sulfur dioxide.
2. Input Materials - From 50 to 100 tons of water are required per ton
of sulfur dioxide produced. Consumption of dimethyl aniline is about
2
0.5 kg/ton of S02 produced.
3. Operating Parameters - The absorption is carried out at approxi-
mately atmospheric pressure.
4. Utilities - Not available.
5. Waste Streams - Gaseous emissions from this process are composed
mainly of water vapor. Exit gases from packed towers contain from
0.02 to 0.1 percent sulfur dioxide.2 The liquid waste from the
2
stripping process contains about 0.01 percent S02 by weight.
6. EPA Source Classification Code - None exists.
7. References
1. Chemical Technology: An Encyclopedic Treatment. T. J. W. van
Thoor (ed.), Barnes and Noble, Inc., 1968.
2. Kirk-Othmer. Sulfur Compounds. In: Encyclopedia of Chemical
Technology. New York, John Wiley and Sons, Inc. 1969.
37
-------
SULFUR OXIDES PRODUCTION
PROCESS NUMBER 9
Converter
1. Function - Cooled sulfur dioxide gas passes through a converter and
is converted to sulfur trioxide in the presence of excess oxygen and
vanadium pentoxide catalyst. Converters usually incorporate two, three
or four stages. Various types of gas coolers are used between converter
stages. The converter exit gases are cooled before further processing
in the absorption tower.
Most new plants operate with a dual absorption system where partially
converted gas is passed through an intermediate absorption tower, back
to a converter and then to the final absorber, This system achieves
S02 to SOg conversion efficiencies greater than 99.5 percent.
2. Input Materials - S02 content of gases entering the converter range
from 6.0 to 12 percent, depending on the source. Efficiency of the
conversion to SO, is between 95 and 98 percent for 3- or 4-stage con-
verters. If the sulfur dioxide is produced from a source other than
elemental sulfur, it may also contain arsenic, chlorine, and fluorine.
Vanadium pentoxide catalyst requirements are listed below:
Number of
stages
2
3
4
Conversion
efficiency, %
94
96
98
Catalyst required,
liters/day/ton of acid
120
145
165
3. Operating Parameters - Inlet feed gas temperature normally ranges
from 425 to 450°C. The processes operate at approximately atmospheric
pressure. The gas is cooled between converter stages and finally exits
between 230 and 260°C.1
4. Utilities - No utilities are required. Heat released from this
process may be recovered as steam.
5. Waste Streams - Since all the converter gases are passed to the
absorption tower, there are only fugitive emissions. Disposal of
catalyst waste is required.
38
-------
6. EPA Source Classification Code - None exists.
7. References
1. Shreve, R. N. Sulfur and Sulfuric Acid. In: Chemical Process
Industries. New York, McGraw Hill Book Company. 1967.
2. Personal communication with Mr. Bruce Varner. Emission Standards
and Engineering Division. Environmental Protection Agency.
Research Triangle Park, North Carolina.
39
-------
SULFUR OXIDES PRODUCTION PROCESS NUMBER 10
Absorption Tower
1. Function - The cooled effluent from the converter is passed into an
absorption tower for the production of sulfuric acid or an oleum tower
for the production of oleum. Sulfuric acid (98 to 99 percent) is
circulated in the absorption tower. The sulfur trioxide combines with
the water in the acid to form more acid at nearly 100 percent absorption
efficiency. If oleum (sulfur trioxide dissolved in 100 percent sulfuric
acid) is to be produced, the sulfur trioxide stream from the converter
is cooled further before it is passed through an absorber which is then
called an oleum tower. In the oleum tower some of the SO, is absorbed
in the presence of recirculating acid. The equipment involved in
the absorption and oleum towers is similar with differences in the
methods of operation. Recirculation in the oleum tower allows more
absorption of sulfur trioxide to take place. The effluent gases from
the tower are passed through another absorber for recovery of the
residual sulfur trioxide.
2. Input Materials - The gases from the converter are the main input
material. Concentration of SOg is in the 4 to 12 percent range. The
entering gases also contain unconverted SOo, traces of moisture and
carbon dioxide. The moisture and C02 incomplete drying of combustion
air and burning of hydrocarbons in the sulfur.
3. Operating Conditions - The absorption tower inlet gas temperature
is between 230 and 260°C and less than 225°C for an oleum tower.1
4. Utilities - Not available.
5. Waste Streams - Waste gas from the absorber is the major source of
emissions from contact sulfuric acid plants. The effluent gas contains
some unreacted sulfur dioxide, unabsorbed sulfur trioxide, and sulfuric
acid mist. Uncontrolled emissions from an absorber vary as shown in
Table 10 and average about 30 kilograms of S09, 1.5 to 6 kilograms of
2
acid mist, and 0.1 kilograms of S03 per ton of sulfuric acid produced.
The gases may also contain nitrogen oxides which result from nitrogen
compounds in the raw materials used, spent acid being the feedstock
40
-------
Table 10. CHARACTERISTICS OF TAIL GAS EMISSIONS
FROM CONVENTIONAL SULFURIC ACID PLANTS
Feedstock
Sulfur
H2S
Pyri tes
Acid sludge
Copper
converter gas
Roaster gas
Exit gas flow,a
nr/ton of acid
(as 100% H2S04)
3- stage
conversion
2870
3120
3400
3710
5990
4520
4-stage
conversion
2840
3090
3370
3670
5740
4460
S02 content
ppm
3- stage
conversion
3000 to 5000
3000 to 5000
2500 to 5000
2500 to 5000
2000 to 10000
2000 to 5000
4-stage
conversion
1500 to 4000
1500 to 4000
1500 to 4000
1500 to 4000
2000 to 7000
1000 to 4000
SOo emissions,
kg/ ton of acid
3-stage
conversion
22 to 37
24 to 40
22 to 44
24 to 48
31 to 156
23 to 46
4-stage
conversion
11 to 29
12 to 32
13 to 35
14 to 38
30 to 104
12 to 46
Acid mist,
mg/nr
99%
acid
70 to 700
70 to 700
70 to 700
70 to 700
70 to 700
70 to 700
Oleum
180 to 1800
180 to 1800
180 to 1800
180 to 1800
180 to 1800
180 to 1800
aThese are maximum values. Flow will vary with plant design and excess air used.
Number of conversion stages does not effect mist emissions. Plants using high purity sulfur yield lower mist
emissions. These are uncontrolled mist emissions. Divide by approximately 250 to convert to kg/metric ton.
-------
most likely to produce them. For a given mass emission rate, pollutant
concentrations are a function of the volume of air fed to the process.
The air volume in turn depends on the SOp concentration in the gas stream
fed to the converters. The conversion efficiency and thereby the emissions
are affected by the number of catalyst stages, the amount of catalyst
used, the temperature, and the concentrations of the reactants and
sulfur dioxide. Table 11 gives emission factors for sulfuric acid plants
4
with different rates of conversion of S02 to SO.,. Concentration of the
acid mist emissions in the stack gas range from 70 to 700 milligrams
per cubic meter for a plant producing no oleum and from 180 to 1800 milli-
5
grams per cubic meter for an oleum plant. The reported values for
unabsorbed sulfur trioxide range from less than 20 to 1700 milligrams per
cubic meter. Mesh mist eliminators or electrostatic precipitators are
used to reduce mist emissions.
Table 11. EMISSION FACTORS FOR SULFURIC ACID PLANTS
Conversion of S02
to S03, %
93
94
95
96
97
98
99
99.5
99.7
100
S02 emissions
Ib/ton of 100%
H2S04
96
82
70
55
40
27
14
7
4
0
kg/MT of 100%
H2S04
48.0
41.0
35.0
27.5
20.5
13.0
7.0
3.5
2.0
0.0
Mist particles range from 0.3 to 5.0 microns in diameter. Table
12 shows a particle size distribution for sulfuric acid mist at plants
5
producing acid, 20 percent ojeum, and 32 percent oleum.
42
-------
Table 12. PARTICLE SIZE DISTRIBUTIONS IN
SELECTED SULFURIC ACID PLANT ABSORBER EFFLUENTS
Particle diameter,
microns
0.2
0.4
0.6
0.8
1.0
1.5
2.0
Cumulative weight percent smaller than
Acid production
only
1
7
12
21
40
20% oleum
production
0.4
2
4.8
8
11.6
48
84.5
32% oleum
production
3.6
16
30
42
53
86.5
97
Exit plumes from oleum-producing sulfuric acid plants usually are
more highly visible than those of acid-producing plants. The visibility
is more a function of the extremely fine particle size than of total
mist concentration.
Dual absorption will substantially reduce the S02 content of the
exit gases, but does not affect mist emissions.
6. EPA Source Classification Code - The following SCC codes apply to
entire contact sulfuric acid plants.
3-01-023-01 for 99.7% conversion of S02 to S03
3-01-023-04 for 99.5% conversion of S02 to S03
3-01-023-06 for 99.0% conversion of S02 to S03
3-01-023-08 for 98.0% conversion of S02 to S03
3-01-023-10 for 97.0% conversion of S02 to S03
3-01-023-12 for 96.0% conversion of S02 to S03
3-01-023-14 for 95.0% conversion of S02 to S03
3-01-023-16 for 94.0% conversion of S02 to S03
3-01-023-18 for 93.0% conversion of S02 to S03
7. References
1 Atmospheric Emissions from Sulfuric Acid Manufacturing Processes.
U.S. Department of Health, Education and Welfare. Public Health
Service Publication No. 999-AP-13. Cincinnati, 1965.
43
-------
2. Guidelines for Limitation of Contact Sulfuric Acid PTant Emis-
sions. Office of Air Pollution Control Publication No. APTD-
0602, Environmental Protection Agency, Research Triangle Park,
North Carolina. January 1971.
3. Engineering Analysis of Emissions Control Technology for Sul-
furic Acid Manufacturing Processes. Chemical Construction
Corporation. NTIS Publication No. PB190393.
4. Compilation of Air Pollution Emission Factors. EPA Publication
No. AP-42. Environmental Protection Agency. Research Triangle
Park, North Carolina. April 1973.
5. Varner, B. A., Bunyard, F. L. and 6. B. Crane. State Guidelines
for Standards of Performance for Existing Sulfuric Acid Plants.
Environmental Protection Agency, Research Triangle Park,
North Carolina. January 1975.
6. Brink, J. A., Jr., Burggrable, W. F. and L. E. Greenwell.
Mist Eliminators for Sulfuric Acid Plants. Chemical Engineering
Progress. November 1968.
44
-------
SULFUR OXIDES PRODUCTION PROCESS NUMBER 11
Distillation
1. Function - Sulfur trioxide product is produced by heating 20 percent
or stronger oleum to the boiling point in either an indirect-fired
vessel or a high-pressure steam-heated vessel and distilling sulfur
trioxide. Entrained acid mist is removed with mist filters or similar
equipment. The distilled product is then cooled and condensed to liquid.
Usually some stabilizer such as a mixture of several boron compounds and
dimethyl sulfate is added to eliminate any traces of moisture. The final
liquid sulfur trioxide product is stored and maintained between the
freezing point (34°C) and the boiling point (45°C).1 The distallate
residue is returned to absorption towers as 10 percent oleum.
2. Input Materials - 20 percent or stronger oleum is used. The quantity
of stabilizer used is very small with a resulting boron content of
between 0.0005 to 0.1 weight percent expressed as boron oxide.
3. Operating Conditions - Distillation is carried out at atmospheric
pressure.
4. Utilities - Heat is required to bring oleum to its boiling point.
5. Waste Streams - Vent gases are generally scrubbed with strong or
absorbing strength (98-99.5 percent) sulfuric acid before discharge.
Quantitative emission data are not available.
6. EPA Source Classification Code - None exists.
7. References
1. Kirk-Othmer. Encyclopedia of Chemical Technology. New York,
John Wiley & Sons, Inc. 1966.
45
-------
SULFUR OXIDES PRODUCTION PROCESS NUMBER 12
Acid Concentrator
1. Function - Spent sulfuric acid may be concentrated ifi one of the two
types of concentrators: a vacuum or a drum concentrator. The vacuum
concentrator operates under high vacuum with heat applied indirectly;
the drum concentrator operates with heat applied directly in the form
1 2
of combustion gases.
In the vacuum concentrator, the hot acid is concentrated by evap-
oration in a flash chamber. The vapors consisting of water and some
HgSO* are liquified in a condenser. The drum concentrator, the more
popular of the two for plants with large capacities and high acid con-
centrations, provides a countercurrent contact of a hot gas mixture
and the weak acid. The number of drums determines the number of
stages. H2SO^ vapor formed in a high concentration stage is partly
condensed in the following stages. The product acid is passed through
an acid cooler before being sent to storage.
2. Input Materials - Inlet acid concentrations range from 65 to 93
percent.
3. Operating Conditions - Vacuum concentrators operate at 69 to 75
^
centimeters Hg.
4. Utilities - Table 13 gives a typical utility requirement of a
drum-type sulfuric acid concentrator.
Table 13. UTILITY REQUIREMENTS OF A DRUM-TYPE
SULFURIC ACID CONCENTRATOR
(Basis: 1 ton of sulfuric acid concentrate
from 65 to 93 percent acid)
Utility
Fuel
Electric power
Cooling water
Quantity
554,000 kilocalories
36 kilowatt-hours
5,000 liters
46
-------
5. Waste Streams - Vacuum concentrators yield negligible emissions.
Emissions from drum concentrators contain acid mist. Since the main
function of concentrators is to remove water from the acid, the exit
gases contain large amounts of water vapor which condense to form a
visible fog. Emissions also contain acid mist and negligible quantities
of S09, Before being discharged to the atmosphere, the exit gas is
3
treated in scrubbers. Table 14 gives emissions from acid drum con-
centrators with different operating capacities.4
Table 14. EMISSIONS FROM ACID DRUM CONCENTRATORS4
Operating rate,
percent of capacity
Acid mist concentration
mg/m3
Acid mist emission quantity
metric ton/ day
Particle size wt % < 3 microns
55
82
7034
85
73
no
2401
86
100
150
2334
57a
aAt maximum capacity more large particles are entrained.
6. EPA Source Classification Code - None exists.
7. References
1. Chemical Construction Corporation. Sulfuric Acid from Pyrite
or Pyrrhotite. In: Modern Contact Sulfuric Acid Processes.
Bulletin No. 116. New York.
2. Shreve, R. N. Sulfur and Sulfuric Acid. In: Chemical Process
Industries. New York, McGraw Hill Book Company. 1967.
3. Chemical Construction Corporation. Engineering Analysis of
Emissions Control Technology for Sulfuric Acid Manufacturing
Processes. PB 190 393. New York. March 1970.
4. Atmospheric Emissions from Sulfuric Acid Manufacturing Processes.
Public Health Service Publication No. 999-AP-13. U.S. Department
of Health, Education and Welfare. Cincinnati, 1965.
47
-------
APPENDIX A
COMPANIES AND THEIR PRODUCTS
49
-------
Table A-l. PRODUCERS OF ELEMENTAL SULFUR, THEIR ANNUAL
CAPACITY AND RAW MATERIALS1
' Company
Alaska Interstate Co.
Anlin Co. of Illinois, subsid.
Anlin Co. of New Jersey, subsid.
Allied Chem. Corp.
Indust. Chems. Div.
Amanllo Oil Co.
Amerada Hess Corp.
American Cyanamid Co.
Organic Chems. Div
American Petrofma. In',.
American Petrodria Co. of Texas.
subsid.
Cosden Oil & Chem Co.. subsid.
American Smelting and Relining Co.
Arkansas Louisiana Gas Co.
Arkla Chem. Corp . subsid.
Ashland Oil. Inc.
Ashland Chem. Co , div.
Petrochems. Div.
Northwestern Refining Co.. subsid.
Atlantic Richfield Co
ARCO Chem. Co.. d.v.
Bethlehem Steel Corp
The Charter Co.
Charter Oil Co., su'. s>d.
Charter Internal 1 Oil Co.. subsid.
Chem-Gas Products Co.
Cities Service Co.. Inc
Columbian Div.
North American Pefoleum Group
Climax Chem. Co.
Coastal States Gas Corp
Coasial States Marketing. Inc.. subsid.
Continental Oil Co.
Douglas Oil Co.. sui>s:rl.
Diamorrl Shamrock Co'p.
Diamond Shamrm k Oil and Gas Co.
Dorchester Gas Cmp
Doichesler Gas ("reducing Co..
subsid
El Paso Natural Gas Co.
El Paso Products Co.. subsid.
Odessa Natural Gasoline Co..
subsid.
Exxon Corp.
Exxon Co., U.S.A.
Location
Wood River. III.
Perth Amboy. NJ.
Elizabeth. N.J.
Goldsmith. Tex.
Port Reading. NJ.
Purvis. Miss.
Bound Brook. NJ.
Mt. Pleasant. Tex.
Port Arthur. Tex.
Big Spring. Tex.
El Paso. Tex.
Magnolia. Ark.
Canton. Oh.o
North Tonawanda, N.Y.
St. Paul Park. Minn.
Artesia. N.M.
Fashing, Tex.
Forl Stockton, Tex.
Cherry Point, Wash.
East Chicago. Ind.
Houston. Tex.
Philadelphia, Pa.
Wilmingtoi , Calif.
Burns Harbor. Ind.
Lackawanna, N.Y.
Sparrows Point. Md.
Houston. Tex.
Worland. Wyo.
Seagraves, Tex.
Cochran County. Tex.
Dawson County, Tex,
Lake Charles. La.
Milnesand. N.M.
Myrtle Springs Tex.
Monument, N.M.
Corpus Christi. Tex.
Paramount. Calif.
Dumas, Tex.
Reagan County. Tex.
Odessa. Tex.
Baton Rouge, La.
Baytown. Tex.
Bemcia. Calif.
Flomaton, Ala.
Jay. Fla.
Jourdanton. Tex.
Linden. N J.
Annual capacity
1000 of tons
54
18
20
4
15
11
n.a.
4
20
5
n.a.
7
n.a.
16
6
5
3
152
41
n.a.
31
36
25
n.a.
n.a.
14
15
7
8
2
2
16
8
122
13
25
31
5
2
10
71
ri.a
51
51
25
6
51
Raw material
and remarks
Refinery
Refinery
Refinery. May be closed.
Natural gas
Refinery
Refinery
Carbon bisulfide plant effluent
Natural gas
Reiinery
Ret;nery
Smelter gases: pilot plant
Natural gas may be closed
Refinery
Refinery
Natural gas
Natural gas
Frasch
Reiinery
Refinery
Refinery
Refinery. Some sulfur valufi
trom refinery HjS are recove-fd
directly as acid at Philadelphia
Refinery
Coke oven gas
Coke Oven gas
Coke oven gas
Refinery
Natural gas
Natural gas
Natural gas
Natural gas
Hodnery
Natural gas
Natural gas
Natural gas: may be closed o>
may use as direct feed lor
sulfuric acid plant
Natural gas
Refinery
Natural gas and crude oil
Natural gas
Natural gas
Refinery
Refinery
Refinery
Natural gas
Natural gas
Refinery
ftefmery
Capacity expressed In metric tons.
50
-------
Table A-1(continued). PRODUCERS OF ELEMENTAL SULFUR, THEIR
ANNUAL CAPACITY AND RAW MATERIALS1
Company
Farmers Union Central Exchange Inc.
Farmland Indus!.. Inc.
CRA. Inc.. subsid.
Freeport Minerals Co
Freeport Sulphur Co.. div.
Getty Oil Co.
The Goodyear Tire & Rubber Co.
Chem. Div.
Gulf Oil Corp.
Gulf Oil Chems. Co.. div.
Petrochems. D>v
Warren Petroleum Corp.. div.
Husky Oil Co.
Intratex Gas Co.
Kwr-McGee Corp.
Kerr-McGee Chem. Corp.. subsid.
Koch Indust.. Inc.
Koch Refining Co.. subsid.
Marathon Oil Co.
Mobil Oil Corp.
North American Oiv.
Monsanto Co.
Monsanto Indusl. Chems. Co.
Montana Sulphur & Chem. Co.
National Steel Corp.
Weirton Steel Div.
Northern Natural Gas Co.
Occidental Petroleum Corp.
Occidental Chem. Co . subsid.
Jefferson Lake Su'phur Co.. div.
The Oil Shale Corp.
lion On Co.. subsid
Olin Corp.
Indust. Products and Services Div.
Pisco. Inc
Pennzoil Co
Ouval Corp.. subsid.
Phillips Petroleum Co.
Pioneer Natural Gas Cu
Powerme Oil Co.
Shell Chem Co.
Petrocicms. Div.
The Signal Companies. Inc.
Signal Oil and Gas Co.. subsid.
Location
Laurel. Mont.
Coffeyville. Kans.
Chauvin, La.
Grand Isle. la.
Port Sulphur. La.
Venice. La.
Delaware City. Del.
Scoggms, Tex.
Teas Field. Tex.
Akron. Ohio
Alliance. 1 a
Philadelphia. Pa.
Port Arthur. Tex.
Santa Fe Springs. Calif.
Toledo. Ohio
Campbellton, Tex.
Como. Tex.
Sand Hills. Tex.
Waddell. Tex.
Cody. Wyo.
Pecos. Tex.
Indian Basin. N.M.
Pine Bend. Minn.
Artesia. N.M.
Detroit. Mich.
Iraan, Tex.
Robinson, III
Coyanosa. Tex
Joliet. Ill
Paulsboro. N J
Torrancfi, Calif.
Avon. Calif
East Billings. Mont.
Weirton. W.Va.
Hobbs. N.M
Long Point Dome. Tex.
El Dorado, Ark.
Beaumont, Tex.
Sinclair. Wyo.
Pecos, Tex.
Artesia, N.M.
Borger, lex
Crane. Tex.
Goldsmith. Tex.
Kansas City, Kans.
Sweeny. Tex.
Madill. Okla.
Santa l"e Springs, Calif.
Biandoi.. MISS.
Bryan s Mill. Tex.
Deer P.«k. Tex.
Martinet. Calif.
Norco. 'La.
Persons. Tex.
Thomasville. Miss.
Tioga. N.D.
Annual capacity
1000 of tons
5
2
610
1524
1331
B33
124
41
n.a.
n.a
16
53
11
n.a.
15
36
12
31
17
6
10
47
13
41
5
15
102
25
140
56
36
n.a.
5
330
5
15
9
1524
4
15
35
30
13
10
4
7
157
66
51
15
23
8
457
51
Raw material
and remarks
Refinery
Refinery
Fiasch
f-rasch
Piasch
f-f asch
Refinery may be expanded
Natuial gas
Natural gas
By-product sulfur dioxide
Refinery
Refinery
Refinery
Natural gas
Natural gas
Natural gas
Natural gas
Natural gas
Natural gas
Natural gas
Refinery
Natural gas
Refinery
Natural gas
Refinery
Natural gas. may be closed
Refinery
Refinery
Refinery
Relmery
Rednery
Natural gas
Frasch
Refinery
Refinery
Natural gas
Expandable to 2500
Natural gas
Refinery
Natural gas
Natural gas
Refinery
Refinery
Natural gas
Refinery
Natural gas
Natural gas
Refinery
Refinery
Refinery
Natural gas
Sour gas
Natural gas
51
-------
Table A-1(continued). PRODUCERS OF ELEMENTAL SULFUR, THEIR
ANNUAL CAPACITY AND RAW MATERIALS1
Company
Skally OH Co.
Standard Oil Co. of California
Standard Oil Co. (Indiana)
Amoco Oil Co.. subsid.
Amoco Production Co.. subsid
The Standard Oil Co. (Ohio)
BP Oil Corp.. subsid.
Stauller Chem. Co.
Indust Chem. Div.
Speedily Chem Div.
Sun Oil Co
Sun Oil Co. of Penr • ylvania. &jbsid.
Puerto Rico Sun O ' Co.. sulmd.
Yahucoa Sun Oil Co.. suhvd.
Texaco in'
TXL Oil Corp.. subsifi
Texas Amcncan Oil Corp.
Texas American Sulphur Co.. subsid.
Texasgulf. Inc.
Agricultural Div.
Total Leonard. Inr
Trans-Jed Chem Corp.
Union Carbide Coip
Umon Carbide Canbe. Inc.. subsid.
Union Oil Co. of California
Union Pacific Corp
Champlm Petroleum Co.. subsid.
United States Steel Corp.
USS Chems.. div.
Location
El Dorado, Kans.
El Segundo. Calif.
Sugai Creek, Mo.
Whilmg. Ind.
Yorktown. Va.
Andrews. Tex.
Artesia. N.M.
Edgowood. Tex.
Frankel City. Tex.
Goldsmith. Tex.
Powell. Wyo.
Riverton. Wyo.
Sundown, Tex.
Yantis. Tex.
Marcus Hook. Pa.
Bay town. Tex.
Freeport. Tex.
Jay, Fla.
Marcus Hook. Pa.
Toledo, Ohio
Yabucod. P R.
Andrews \.ounty. Tex.
Ector County. Tex.
Eddy County. N.M.
Franklin County, Tex.
Hockley County. Tex.
Hopkins County, 1«;».
Port Arthur. Tex.
Vermillion Parish, La.
Westville. NJ.
Wilmington. Calif.
Wood C'lunty, Tex.
Lignite. N.H
Sand Hills. Tex.
Beaumont, Tex.
Bullycamp Dome. La.
Hamshire, Tex.
Liberty. Tex.
Newgull. Tex.
Alma, Mich.
Tilden. Tex.
Penuelas. P.R.
Arroyo Grande. Calif.
lemont. III.
Rodeo. Calif.
San Juan County. Utah
Wilmington. Calif.
Wilmington. Calif.
Clairton, Pa.
Annual capacity
1000 of tons
16
165
X
66
23
4
8
214
5
7
27
26
18
30
n.a.
36
n.a.
13
15
10
20
2
<1
.-1
15
3
2
10
<1
1
31
<1
2
6
660
ass
178
253
1626
4
30
n.a.
19
11
19
5
41
10
15
Raw material
and remarks
Refinery
Refinery
Refinery
Refinery
Refinery
Natural gas
Natural gas
Natural gas
Natural gas
Natural gas
Natural gas
Natural gas
Natural gas
Natural gas
Refinery
Rehnery
Natural gas
Refinery
Refinery
Refinery
Natural gas
Natural gas
Natural gas
Natural gas
Natural gas
Natural gas
Refinery
Natural gas
Refinery
Refinery
Natural gas
Natural gas
Natural gas
Frasch
Frasch
Frasch
Frasch
Frasch
Refinery
Natural gas
Refinery
Refinery
Refinery
Natural gas
Refinery
Refinery
Coke oven gas
TOTAL
>13366
These listings include only those plants designed to produce or recover new sulfur in elemental loim. Excluded are a number of facilities that
recover new sulfur values directly as sulfunc acid or SO,-without intermediate isolation of the sulfur in elemental form. This includes recovery
directly as acid from H,S (from refinery gases, sour natural gas, and/or coke-oven gas) and recovery directly as acid or SO, from smelter oases and
pyrites. Also excluded are companies that mine pyrites and low-to-medium grade sulfur ores.
Source: Compiled in association with the Chemical Economics Handbook.
52
-------
Table A-2. PRODUCERS OF SULFUR DIOXIDE, THEIR ANNUAL CAPACITY1
Company
American Cyanamtd Co.
Organic Chems. Div.
American Smelting and Refining Co.
The A'-sul Co.
Chem. Div.
Cities Service Co . Inc.
North American Chems. and Metals
Gro! r
Indus!. Chems. Div.
Essex Chem. Corp
Chems. Div.
Olm Corp.
Indust. Products and Services Div.
Rohm and Haas Co.
Scott Paper Co.
Packaged Products Div.
Stauffer Chem. Co.
Indust. Chem. Div.
Virginia Chems. Inc.
Indust. Chems. Dept.
Location
Bound Brook. NJ.
Tacoma, Wash.
Marinette, Wise.
Copperhill. Tenn.
Newark. NJ.
Paulsboro, NJ.
Bristol. Pa.
Anacortes. Wash.
Everett. Wash.
Oconto Falls. Wise.
Winslow. Me.
Baton Rouge. La.
Hammond. Ind.
Portsmouth. Va.
Annual capacity
1000 of tons
1
60
14
45
14
M
»
M
M
M
Hi
12
1}
40
Remarks
Captive
All captive
Captive
Captwe
Captive
Captive
TOTAL
200
Sources: Oil. Pamt and Drug Reporter. December 2!. 1970: Sulfur. March/Apr,, 197): and correspondence.
53
-------
Table A-3. PRODUCERS OF SULFUR TRIOXIDE1
Company
Location
Allied Chem. Corp.
Indus!. Chems. Oiv.
Cities Service Co.. Inc.
North American Cherts, and Meta's
Group
Indust. Chems. Htv
E. I du Pont de Nemours & Co.. Inc.
Indust Chems Depi
Stauffer Chem. Co.
Indust. Chem. Div.
Buffalo. N.Y.
Chicago. HI.
East St. Louis. HI.
El Segundo. Calif.
Copperhill. Tenn.
East Ctin Hgo. Ind.
Linden. N.J.
North Bend, Ohio
Dommguez. Calif.
Hammond. Ind.
Manchester. Tex.
54
-------
Table A-4. PRODUCERS OF SULFURIC ACID, THEIR ANNUAL
CAPACITY AND RAW MATERIALS1
Company
Alaska Interstate Co.
Anhn Co. of Illinois, subsid.
Allied Chem. Corp.
Indust. Chems. Oiv.
American Cyanamid Co.
Indust. Chems. and Plastics Div.
Organic Chems. Div.
American Metal Climax. Inc.
AMAX Lead & Zinc. Inc.. div.
AMAX Lead Co. of Missouri, subsid.
Amax-Homestake Lead Tollers
American Smelting and Refining Co.
The Anaconda Co.
Primary Metals Div.
Arkansas Louisiana Gas Co.
Arkla Chem. Corp.. subsid.
Beker Indust. Corp.
Agricultural Products Corp.. subsid.
National Phosphate Corp. subsid.
Bethlehem Steel Corp.
Borden Inc.
Borden Chem. Div.
Smith-Douglass
CF Indust.. Inc.
Bartow Phosphate Complex
Plant City Phosphate Complex
Chem. Producers Co.
Cities Service Co.. Inc.
Columbian Div.
North American Chems. and Metals
Group
Indust. Chems. Div.
North American Petroleum Group
Climax Chem. Co.
Columbia Nitrogen Corp.
Commonwealth Oil Refining Co., Inc.
Corwerv. Inc.
Conterv Chems. Div.
Location
Wood River. III.
Anacortes. Wash,
Baton Rouqe, La.
Buffalo. N.Y.
Chicago. III.
Cleveland. Ohio
East St. Louis. III.
Elizabeth. NJ.
Front Royal. Va.
Geismar. La.
Hopewell, Va.
Newell. Pa.
Nitro. W.Va.
North Claymont. Del.
Pittsburg. Calif.
Richmond. Calif.
Hamilton, Ohio
Joliet. III.
Kalamazoo. Mich.
Linden. NJ.
New Orleans, La.
Savannah. Ga.
Bound Brook. NJ.
Sauget. III.
Boss. Mo.
Columbus. Ohio
Corpus Christi. Tex.
El Paso, Tex.
Hayden. Ariz.
Tacoma. Wash.
Anaconda, Mont.
Weed Heights. Nev.
Helena. Ark.
Conda. Idaho
Marseilles, III.
Taft. La.
Sparrows Point. Md.
Norfolk. Va.
Piney Point, Fla.
Streator. III.
Bartow. Fla.
Plant City. Fla.
El Paso. Tex.
Monmouth Junction. NJ.
Augusta. Ga.
Copperhill. Tenn.
Lake Charles, La.
Monument, N.M.
Moultrie. Ga.
Penuelas, P.R.
Nichols. Fla.
Annual capacity
1000 of tons
78
73
91
177
145
118
172
181
14S
454
181
227
127
3T8
127
200
82
45
23
218
50
204
59
132
50
59
64
154
300
59
313
127
136
272
231
463
82
73
445
36
1542
644
n
X
118
1143
136
68
18
Z7
363
Raw material
and remarks
Spent acids
Elemental; sludge:
hydrogen sulfide
Elemental: sludge
Elemental: sludge;
hydrogen sulfide
Elemental; sludge
Elemental
Elemental
Elemental; sludge
Elemental
Elemental
Elemental: may be expanded.
Sludge: pyrites
Elemental
Sludge: pyrites
Elemental; sludge
Sludge: hydrogen
sulfide
Elemental
Elemental
Elemental
Elemental
Elemental
Elemental
Elemental
Smelter gases
Smelter gases
Smelter gases
Smelter gases
Smelter gases
Smelter gases
Smelter gases
Smelter gases
Elemental; sulfur ore; smelter
gases - May be closed
Elemental
Elemental
Elemental
Elemental
Pyrites: hydrogen sulfide
Elemental
Elemental
Elemental
Elemental
Elemental
Elemental: sludge
Elemental
Pyrites: smelter gases
Sludge; hydrogen
sulfide
Elemental: hydrogen sul'ide
Elemental. May be closed.
Elemental: sludge:
hydrogen sulfide
Elemental
-------
Table A-4(continued). PRODUCERS OF SULFURIC ACID,
THEIR ANNUAL CAPACITY AND RAW MATERIALS1
Company
Coutton Chetn. Corp.
Xs Mines Corp.
jdad Copper Co.. div.
Delta Chems.. Inc.
Detroit Chem. Works
Pressure Vessel Services, div.
Diamond Shamrock Corp.
Diamond Shamrock Oil and Gas Co.
E. 1. du Pont de Nemours & Co.. Inc.
Biochems. Dept.
Indus!. Chems. Dept.
Organic Chems. Dept.
Dyes and Chems. Div.
Polymer Intermediates Dept.
Eagle Picher IndusI . Inc.
Agricultural Chems. Div.
Eastman Kodak Co.
Eastman Chem. Products, Inc.. subsid.
Distillation Products Indus!., div.
Esntark. Inc.
Swift Chems. Co. Operation
tssex Chem. Corp.
Chems. Div.
Farmland Indus!.. Inc.
First Mississippi Corp.
First Miss, Inc.. subsid.
Freeport Minerals Co.
Freeport Chem. Co.. div.
Gardmier. Inc.
U. S Phosphoric Products
Georgia-Pacific Corp
Chem. Div.
W. R. Grace & Co.
Agricultural Chems Group
Ochoa Fertilizer Co.. Inc., subsid
Gulf Oil Corp.
Gulf Oil Chems. Co.. div.
Petrochems. Div.
Gulf Resources & Chem. Corp.
The Bunker Hill Co . subsid.
Gulf ^ Western IndusI.. Inc.
The New Jersey Zinc Co., subsid.
Illinois Power Co
Inspiration Consolidated Copper Co
Internat'l Minerals & Chem. Corp.
Marion Mfg. Corp., subsid.
Kennecott Copper Corp.
Metal Mining Div.
Chmo Mines Div.
Ray Mines Div.
Utah Copper Div.
Kerr-McGee Corp.
Kerr-McGee Chem. Corp., subsid.
1. J. R M. La Place Co.
Location
Oregon, Ohio
Bagdad. Ariz.
Searsport. Me.
Detroit, Mich.
Dumas. Tex.
La Porte. Tex.
Burnside, La.
Cleveland. Ohio
Cornwe'ls Heights, Pa.
East Chicago. Ind.
Gibbstown. N.J.
Linden. N.J.
North Bend. Ohio
Richmond. Va.
Wurtland. Ky.
Deepwater, N.J.
Newport, Ind,
Galena, Kans.
Rochester. N.Y.
Dothan. Ala.
Norfolk. Va.
Wilmington, N.C.
Newark. N.J.
Rumford, R.I.
Green Bay. Fla.
Fort Madison. Iowa
Port Sulphur, La.
Uncle Sam, La.
Tampa, Fla.
Bellmgham. Wash.
Bartow. Fla.
Charleston. S.C.
Guanica, P.R.
Port Arthur. Tex.
Kellogg. Idaho
Palmerton, Pa.
-
Wood River, III.
Inspiration. Ariz.
Indianapolis. Ind.
Hurl.ey. N.M.
Hayden, Ariz.
Salt Lake City. Utah
Grants, N.M.
Baltimore, Md.
Cottondale. Fla.
Edison. N.J.
Annual capacity
1000 of tons
>63
-------
Table A-4(continued). PRODUCERS OF SULPURIC ACID,
THEIR ANNUAL CAPACITY AND RAW MATERIALS1
Company
Minnesota Mining and Mfg. Co.
Chem. Resources Div.
Mississippi Chem. Corp.
Mobil Oil Corp.
Mobil Chem. Co.. div.
Minerals Div.
Monsanto Co.
Mon'-anto Commercial Products Co
Agricultural Div.
Monsanto Indust. Chems. Co.
National Distillers and Chem. Corp.
U. S. Indust. Chems. Co.. div.
National Zinc Co
Newmont Mining Corp.
Magma Copper Co.. subsid.
N I Indust.. Inc.
Titanium Pigment Div.
North Star Chems.. Inc.
Occidental Petroleum Corp.
Occidental Chem Co.. subsid.
Eastern Div.
Southwest Region
Occidental of Florida Div.
Western Oiv.
Olin Corp.
Agricultural Chems. Oiv.
Indust. Products and Services Div.
Ozark-Mahoning Co.
Wizer Inc.
C. K. Williams 8. Co.. div.
Phelps Dodge Corp.
Western Nuclear. Inc.. subsid.
Reichhold Chems.. Inc.
Rohm and Haas Co
Rohm and Haas Texas. Inc.. div.
Royster Co.
St. Joe Minerals Corp
J. B. Simplot Co.
Minerals and Chem Div.
Southern States Phosphate
& Fertilizer Co.
Standard Oil Co. of California
Standard Oil Co. (Indiana)
Amoco Oil Co.. subsid.
Location
Copley. Ohio
Pascagoula. Miss.
1
Depue. III.
El Dorado. Ark.
Avon. Calif.
Everett. Mass.
Sauget. III.
De Soto. Kans.
Dubuque. Iowa
Bartlesville. Okla.
San Manuel, Am.
St Louis. Mo.
Sayreville. N.J.
Pine Bend. Minn.
Plamview. Tex.
White Springs. Fla.
Lathrop. Calif.
Pasadena. Tex.
Baltimore. Md.
Beaumont, Tex.
North Little Rock, Ark.
Paulsboro, N.J.
Shreveport. La.
Tulsa. Okla.
Easton. Pa.
East St. Louis. III.
A|0. Ariz.
Hidalgo, N M.
Morenci. Ariz.
Jeffrey City. Wyo.
Riverton. Wyo.
Tuscaloosa. Ala.
Philadelphia. Pa.
Deer Park, Tex.
Chesapeake, Va.
Mulberry. Fla.
Herculaneum. Mo.
Moriaca, Pa.
Pocatello. Idaho
Savannah. Ga.
El Segundo. Calif.
Honolulu. Hawaii
Texas City. Tex.
Annual capacity
1000 of tons
4
361
if!
96
308
11
590
272
ft
91
635
204
ft
\n
M
1ft
IUV
14
14
181
n.a
245
32
Kft
DO
68
82
454
18
39?
2S9
726
36
159
Raw material
and remarks
Elemental
Elemental
Elemental
Elemental
Elemental: sludge;
hydrogen sulfide
Elemental
Elemental
Elemental
Elemental
Elementa; smelter gases
Smelter gases
Elemental
Elemental
Elemental: sludge - May bt
closed
Elemental
Elemental
Elemental
Elemental
Elemental
Sludge: hydrogen sulfide
Elemental
Elemental: sludge
Elemental
Ferrous sulfate - High-purity
iron oxides as by-product
Ferrous sulfate - High-purity
iron oxides ds by-product
Smeller gases
Smelter gases
Elemental
Elemental May be closed
elemental May be closed.
Recovery from methyl
methacrylate
Elemental May be closed
Elemental
Smelter gases
Smelter gascr
Elemental: output cut back
Elemental
Sludge: hydrogen sulfide
Sludgo: other
Elemental: sludge:
hydrogen sulfide
57
-------
Table A-4(continued). PRODUCERS OF SULFURIC ACID,
THEIR ANNUAL CAPACITY AND RAW MATERIALS1
Company
Stauffer Chem. Co.
Fertilizer and Mining Div.
Indust. Chem. Div.
Texaco Inc.
Texasgulf. Inc.
Agricultural Div.
Union Carbide Corp.
Chems. and Plastics Div.
Union Oil Co. of California
Collier Carbon and cuem. Coi'
subsid.
United States Steel Corp.
USS Agri-Chemicals div.
USS Chems.. div.
Valley Nitrogen Producers. Inc.
AFC Co.. subsid.
Weaver Fertilizer Co., Inc.
The Williams Companies
Agnco Chem. Co., subsid.
Wilson Pharmaceutical & Chem. Corp.
INOLEX Chem. Div.
Witco Chem. Corp.
Sonneborn Div.
Wright Chem. Corp,
Location
Pasadena. Tex.
Baton Rouge, La.
Baytown. Tex.
Dommguez, Calif.
Fort Worth. Tex.
Hammond. Ind.
Le Moyne. Ala.
Manchester. Tex.
Martinez. Calif.
Port Arthur, Tex.
Aurora. N.C.
Texas City. Tex.
Wilmington. Calif.
Barlow. Fla.
Fort Meade. Fla.
Wilmington. N.C.
Neville Island. Pa.
Helm. Calif.
Bena. Calif.
Norfolk. Va.
Baltimore, Md.
Bay City. Mich.
Pierce. Fla.
Elwood. III.
Petrolia. Pa.
Acme. N.C.
Annual capacity
1000 of tons
410
i§fi
?S0
295
109
250
191
1270
*
1343
n.a.
127
263
49$
86
45
254
64
23
els
29S
ft
Raw material
and remarks
Elemental
Elemental: sludge
Elemental: sludge.
hydrogen sulfide
Elemental: sludge:
hydrogen suldde
Elemental
Elemental: sludge
Elemental
Elemental: sludge;
hydrogen sulfide
Elemental; sludge
Sludge: hydrogen sulfide
Elemental
Elemental: sludge;
hydrogen sulfide
Elemental
Elemental
Elemental - May be
Elemental;
hydrogen suldde
Elemental
Elemental
Elemental; sludge -
closed
Leased
from U.S. Government - May
close
Sludge
Elemental - May be
closed
TOTAL
37478
Source: Compiled in association with the Chemical Economics Handbook.
58
-------
Table A-5. PRODUCERS OF OLEUM2
Allied Chemical Corp., Industrial Chemicals Division
American Cyanamid Co., Industrial Chemicals and Plastics Division
Corco Chemical Corp.
Stauffer Chemical Co., Industrial Chemical Division
59
-------
Table A-6. SULFUR STATISTICS, 1973-1974C
(Thousands of tons)
Form
Elemental
sulfur
Frasch
Pyrites
Smelter acid
HpS acid and
Other
Production
1973
2455
7725
215
610
neg.
1974
2570
8062
N.A.
N.A.
neg.
Imports
1973
1242
-
1974
2235
N.A.
Exports
1973
1805
1974
2642
-
Stocks
1973
3990
1974
3861
60
-------
APPENDIX B
PRODUCT USES AND PROPERTIES
61
-------
Table B-l. PHYSICAL PROPERTIES OF SULFUR, SULFUR DIOXIDE, SULFUR TRIOXIDE, AND SULFURIC ACID4'5
Property
Physical state
Molecular weight
Specific gravity at 0°C
Melting point in °C
Boiling point
Vapor density (air=l)
Solubility
Sulfur3
32.06
2.06 (a sulfur)
1.96 (3 sulfur)
112.8 (a sulfur)
119 (3 sulfur)
-
-
Insoluble
in water
Sulfur .
dioxide
Colorless gasc
64.07
1.434 (liquid)
-72.7
-10.0
2.3
0.6gm in lOOgm of
H20 at 90°C,
8.5gm in lOOgm at
25 °C and 22.8gm
in lOOgm at 0°C.
Sulfur .
tri oxide
Colorless liquid
or crystals
80.06
16.83
44.8
2.8
Up to 100 percent
sulfuric acid in
water
Sulfuric
acidb
Colorless liquid
98.06
1.834 at 20°C
10.5
ro
Reference 4.
Reference 5.
c The gas has a characteristic taste and odor.
-------
Table B-2. SULFUR USES IN 1972
a,6
Use
Quantity,
million tons
Agriculture (fertilizers)
Plastic and synthetic products
Paper products
Paints
Nonferrous metal production
Explosive
Petroleum refining
Iron and Steel production
Other
5.29
0.55
0.35
0.40
0.44
0.26
0.22
0.11
2.37
Approximately 90 percent of the sulfur consumed was
in the form of sulfuric acid.
63
-------
Table B-3. COMMERCIAL STRENGTHS OF SULFURIC ACID'
For oleums, % means free SOg
Battery acid
Chamber acid, fertilizer acid,
50 acid
Glover or tower acid, 60 acid
Oil of vitriol (0V), concentrated
acid, 66 acid
98 acid
100% H2S04
20% oleum, 104.5 acid
40% oleum, 109 acid
66% oleum
Degrees Be,
60 °f , or
15.6eC
29.0
50
60
66
Specific
gravity,
60°F, or
15.6°C
1.250
1.526
1.706
1.835
1.841
1.835
1.915
1.983
1.992
Sulfuric
acid, %
33.33
62.18
77.67
93.19
98.0
100.0
104.50
109.0
114.6
64
-------
APPENDIX C
REFERENCES FOR APPENDICES
65
-------
REFERENCES FOR APPENDICES
1. Standford Research Institute. 1974 Dictionary of Chemical Prod-
ucers. United States of America. California 1974.
2. Chemical Marketing Reporter. 1974-75 OPD Chemical Buyers Diction-
ary. 62nd Annual Edition C 1974, Schnel Publications Co., Inc. New
York.
3. Chemical Economics Handbook. Manual of Current Indicators. Feb-
ruary 1975.
4. Gessner, G. Hawley. The Condensed Chemical Dictionary. 8th Edi-
tion. New York. Van Nostrand Reinhold Company. 1971.
5. Patty, F. A. Arsenic, Phosphorus, Selenium, Sulfur, and Tellurium.
In: Industrial Hygiene and Toxicology. New York, Interscience
Publishers. 1968.
6. Sulfur. In: Commodity Statement. U.S. Department of Interior.
Bureau of Mines.
7. Shreve, R. N. Sulfur and Sulfuric Acid. In: Chemical Process
Industries. New York, McGraw Hill Book Company. 1967.
66
-------
TECHNICAL REPORT DATA
(Please read .'Hitnictions on the reverse before completinfij
1. REPORT NO.
EPA-600/2r77-023w
4. TITLE AND SUHTITLE
Industrial Process Profiles for Environmental Use:
Chapter 23. Sulfur, Sulfur Oxides and Sulfuric Acid
3. RECIPIENT'S ACCESSION-NO.
6. REPORT DATE
February 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Richard W. Gerstle and Vishnu S. Katari (PEDCo)
Terry Parsons and Charles Hudak, Editors
8. PERFORMING ORGANIZATION REPORT NO.
9 PERFORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
8500 Shoal Creek Boulevard
P.O. Box 99^8
Austin, Texas 78766
10. PROGRAM ELEMENT NO.
1AB015: ROAP 21AFH-025
11. CONTRACT/GRANT NO.
68-02-1319» Task 31*
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Laboratory
Office of Research ana Development
U.S. ENVIRONMENTAL PROTECTION AGENCY
Cincinnati, Ohio 1+5268
13. TYPE OF REPORT AND PERIOD COVERED
Initial: 8/7^-11/76
14. SPONSORING AGENCY CODE
EPA/600/12
15. SUPPLEMENTARY NOTES
16. ABSTHACT
The catalog of Industrial Process Profiles for Environmental Use was developed as an
aid in defining the environmental impacts of industrial activity in the United States.
Entries for each industry are in consistent format and form separate chapters of the
study.
The sulfur industry is divided into two basic parts, according to the types of
products. The first part involves those chemical processes which yield elemental
sulfur either from naturally occurring deposits or from hydrogen sulfide containing
gas streams. The elemental sulfur serves as one of the main raw materials for the
sulfur oxides and sulfuric acid production plants which comprise the second part of
the industry. Three industrial process flow diagrams and twelve process descriptions
have been prepared to characterize the industry. Within each process description
available data have been presented on input materials, operating parameters, utility
requirements and waste streams. Data related to the subject matter, including company
and product data, are included as appendices.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Pollution
Sulfur
Elemental Sulfur
Hydrogen Sulfide
Sulfur Oxides
Sulfuric Acid
Frash Process
Sour Gas
Process Descrip-
tion
b. IDENTIFIERS/OPEN ENDED TERMS
Air Pollution Control
Water Pollution Control
Solid Waste Control
Stationary Sources
Fertilizer Industry
19. SECURITY CLASS (ThisReport)
Unclassified
COSATI Ficld/Gro.up
07B
13B
18. DISTRIBUTION STATEMENT
Release to Public
21. NO. OF PAGES
73
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
67
OUSGPO: 1978 — 757-086/0807
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