EPA-600/2-77-023p
February 1977
Environmental Protection Technology Series
INDUSTRIAL PROCESS PROFILES FOR
ENVIRONMENTAL USE: Chapter 16.
The Fluorocarbon-Hydrogen
Floride Industry
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, Springfield, Virginia 22161.
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EPA-60U/2-77-023p
February 1977
INDUSTRIAL PROCESS PROFILES
FOR ENVIRONMENTAL USE
CHAPTER 16
THE FLUOROCARBON-HYDROGEN FLUORIDE INDUSTRY
by
Dow Chemical U.S.A.
Michigan Division
Midland, Michigan
Contract No. 68-02-1329
Project Officer
Irvin A. Oefcoat
Industrial Environmental Research Laboratory
Research Triangle Park, North Carolina 27711
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.
ii
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TABLE OF CONTENTS
CHAPTER 16
Page
INDUSTRY DESCRIPTION 1
Raw Materials 2
Products 3
Companies 3
Environmental Impact 4
Bibliography 5
INDUSTRY ANALYSIS 6
Fluorocarbon Production Processes 7
Process No. 1. Liquid Phase Fluorination 11
Process No. 2. Distillation from Liquid Phase
Fluorination 15
Process No. 3. Separation, Neutralization, Drying
of Products from Liquid Phase Fluorination ... 17
Process No. 4. Vapor Phase Fluorination 21
Process No. 5. Distillation from Vapor Phase
Fluorination 25
Process No. 6. Separation, Neutralization,
Drying of Products from Vapor Phase
Fluorination 27
Process No. 7. Electrochemical Fluorination. ... 30
Process No, 8. Separation, Neutralization, Drying
of Products from Electrochemical Fluorination. . 34
Process No. 9. Bromination of Fluorohydrocarbons . 37
Process No. 10. Purification of Bromo-
f luorocarbons 39
Process No. 11. Pyrolysis of Chlorodifluoromethane 42
Process No. 12. Pyrolysate Scrubber, Separator,
Drier 44
111
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TABLE OF CONTENTS (Continued^
CHAPTER 16
P^ge
Process No. 13. Reductive Dechlorination of
1,1,2-Trichlorotrifluoroethane 47
Process No. 14. Separation and Purification of
Products from Dechlorination of 1,1,2-Tri-
chlorotrifluoroethane 49
Process No. 15. Addition of Halogens to
Perfluoroalkenes 52
Process No. 16. Dimerization of Fluoroolefins. ... 54
Process No. 17. Oxidation of Ch ;-r^fluoroolefins . . 57
Process No. 18. Production of Fluoroaxcrhols by
Catalytic Hydrogenation 60
Process No. 19. Preparation of Perfluoroalkyl
Iodides 63
Process No. 20. HF Addition to Acetylene 66
Process No. 21. Separation and Purification of
Fluorohydrocarbons from HF Addition 68
Process No. 22. Chlorination of 1,1-Difluoroethane . 70
Process No. 23. Dehydrochlorination of 1-Chloro-l,
1-Difluoroethane 72
Process No. 24. Production of Fluoroaromatic
Compounds 75
HF Production Processes 77
Process No. 25. Mining of Fluorspar 80
Process No. 26. Fluorspar Beneficiation 82
Process No. 27. Agglomeration of Fluorspar 85
Process No. 28. Hydrogen Fluoride Generation .... 88
Process No. 29. Hydrogen Fluoride Purification ... 90
Appendix A - Raw Materials 93
Appendix B - Products and By-Products 95
Appendix C - Producers and Products 99
iv
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LIST OF FIGURES
CHAPTER 16
Figure Page
1 Chemical Trees of Fluorocarbons ......... 8
2 Flowsheet for Production of Fluorocarbons by
Liquid Phase Fluorination ........... 10
3 Flowsheet for Production of Fluorocarbons By
Vapor Phase Fluorination .... ....... 20
4 Flowsheet for the Production of Fluorocarbons
By Electrochemical Fluorination ........ 29
5 Flowsheet for the Production of Bromofluoro-
carbons .................... 36
6 Flowsheet for the Pyrolysis of Chlorodi-
fluoromethane (FC-22) ............. 41
7 Flowsheet for the Reductive Dechlorination
of 1,1,2-Trichlorotrifluoroethane ....... 46
8 Flowsheet for the Reactions of Fluoroolefins . . 51
9 Flowsheet for the Oxidation of Chlorofluoro-
olef ins .................... 56
10 Flowsheet for the Production of Fluoroalcohols
By Catalytic Hydrogenation .......... 59
11 Flowsheet for the Production of Perfluoro-
Alkyl Iodides ................. 62
v
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LIST OF FIGURES (Continued)
CHAPTER 16
Figure
12 Flowsheet for the Production of Fluorocarbons
from Acetylene 65
13 Flowsheet for the Production of Fluoroaromatic
Compounds 74
14 Flowsheet for the Production of Fluorspar .... 79
15 Flowsheet for the Production of Hydroge,
Fluoride 87
VI
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LIST OF TABLES
CHAPTER 16
Table Page
1 Process Descriptions for Fluorocarbon
Production.. 9
2 Fluorocarbons Produced from Chlorocarbons ... 22
3 Input Materials and Products from Electro-
chemical Fluorination 31
4 Typical Fluoroaromatic Compounds and Input
Materials 75
5 Processes for HF Production 78
A-l List of Raw Materials 94
B-l List of Products and By-Products 96
C-l Company/Product List TOO
C-2 Producers of Fluorocarbons 107
C-3 Speciality Fluorochemicals List 103
C-4 Producers of Hydrogen Fluoride 109
vii
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ACKNOWLEDGEMENTS
This chapter was prepared for EPA by Dow Chemical U.S.A.,
Michigan Division, Contract Projects Laboratory. The con-
tribution of H. E. Doorenbus is gratefully acknowledged.
Helpful review comments from Marcus E. Hobbs and Edward A.
Tyczkowski were received and incorporated into this chapter,
vm
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FLUOROCARBONS - HYDROGEN FLUORIDE INDUSTRY
INDUSTRY DESCRIPTION
The materials of the fluorocarbon-hydrogen fluoride industry
consist primarily of chemically and thermally stable organo-
fluoro compounds which generally have nontoxic and nonflammable
qualities. Most of the fluorocarbons are aliphatic compounds,
although recently there has been an increased interest in the
use of aromatic fluorocompounds.
The industry is composed of two major segments. One segment is
the production of hydrogen fluoride for use as a raw material.
Another segment involves reacting the hydrogen fluoride with
raw materials to form the fluorocarbon products.
As shown on the process flowsheets, the raw materials of this
industry are primarily chlorocarbons, such as carbon tetrachloride
and chloroform, and anhydrous hydrogen fluoride. The bulk of
the products from this industry is formed by allowing the chloro-
carbons and hydrogen fluoride to react in the liquid or vapor
phase or in an electrochemical cell; the fluorocarbons and hydrogen
chloride are the usual products.
Fifteen different companies manufacture fluorocarbons at 23
locations. The manufacturing facilities vary in size from 50 kg
to 50 million kg per year. An estimated 450 million kg of fluoro-
carbon compounds are produced annually in this industry.
The manufacturing locations of this industry are primarily
throughout the eastern, midwestern, and southern parts of the
U.S. Many of these facilities are located near large cities and
most are associated with other industries at that same location.
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The growth rate of the industry from 1963 to 1973 averaged nearly
9% per year. A growth rate of 6.5% per year through 1977 was
projected in January 1973. However, with increasing regulatory
pressure being exerted due to the possible health and safety
hazards of aerosol sprays, the current projected growth rate
is nearer 4-570 per year for the next five years.
The hydrogen fluoride (HF) used in the fluorocarbon industry is
generated to a large extent by the fluorocarbon producers pri-
marily for use in this industry, and approximately 45% of the
HF made in the U.S. is so used. The HF industry is therefore
considered part of the fluorocarbon industry. Another 3870 of
the HF is used in the aluminum industry for the production of
sodium aluminum fluoride, synthetic cryolite. L sser amounts
are used for petroleum refining (5-6%), stainless rteel pickling
(3-4%) , uranium hexafluoride for nuclear fuels (2-370) and other
minor applications.
Hydrogen fluoride (HF) is generated from the reaction between
sulfuric acid and acid grade (>97%) fluorspar (CaF2) and is the
sole major product of this segment of the fluorocarbon industry.
The bulk of the hydrogen fluoride is manufactured in the anhydrous
state. If hydrofluoric acid is desired, the anhydrous material
is dissolved in water. Ten different companies manufacture hydro-
gen fluoride at 14 locations. The manufacturing facilities vary
in size from 4000 to 98,000 metric tons/year. A total of 350,000
metric tons of hydrogen fluoride is produced annually from
1,220,000 metric tons of fluorspar.
Raw Materials
The raw materials used for the production of hydrogen fluoride
are sulfuric acid and fluorspar (977o CaF2) . Most of the fluorspar
is mined in Mexico, Canada, and Europe; a small amount is mined
in Illinois and a few other states. Fluorspar usually occurs as
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veins associated with limestone and sandstone, but is sometimes
associated with galena, sphalerite, calcite, or barite.
The major chlorocarbon raw materials used in this industry are
carbon tetrachloride, chloroform, and tetrachloroethylene -
products of the Industrial Organic Chemicals Industry. Since
the reactions to produce the fluorocarbons are carried out in
closed systems, there is minimum danger from the chlorocarbons,
although some of these raw materials are toxic at high concen-
trations. The basic raw materials are given in Appendix A.
Products
The industry began with the discovery that certain fluorocarbons
make excellent refrigerants. The production of refrigerants and
aerosols currently constitutes approximately 75% of total pro-
duction. Other applications include solvents, blowing agents
for plastic foam (10%) , feedstocks for fluoropolymers (570) and
fire extinguishants. The two most important products of this
industry are trichlorofluoromethane and dichlorodifluoromethane
(fluorocarbon 11 and 12, respectively) with a combined production
of approximately 8070 of the total. Excluded from examination in
this study are fluorocarbon compounds marketed primarily as phar-
maceutical products, insecticides, surfactants, explosives, dyes
and intermediates. A list of products of this industry as defined
is given in Appendix B.
Companies
The major companies in this industry are some of the largest
chemical manufacturing companies in the U.S. These include:
Allied Chemical Corporation
E.I. du Pont de Nemours & Co., Inc.
Kaiser Aluminum and Chemical
Penwalt Corporation
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Racon, Inc.
Union Carbide Corporation
Appendix C gives a comprehensive company listing.
Environmental Impact
Most of the solid wastes from this industry are buried in the
ground. The liquid products are usually scrubbed with water
or aqueous castic and dried with a desiccant. The liquid wastes
can be neutralized and sent to a waste pond or stream.
A large quantity of hydrogen chloride by-product is normally
produced in the anhydrous gaseous state. This i^ usually trans-
ferred to other plant uses. Aqueous hydrochloric acid can also
be transferred and is rarely discarded.
Gaseous fluorocarbon emissions during manufacture and processing
are kept to a minimum by the industry. However, the users of
many of these products do allow them to escape into the atmosphere
Measurements of the effect of these gases on our environment are
incomplete at present.
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Bibliography
(1) Sittig, Marshall, "Fluorinated Hydrocarbons and Polymers",
Chemical Process Monograph, No. 22, Noyes Development
Corporation, 118 Mill Road, Park Ridge, N.J. 07656, 1966.
(2) Stull, D. R., Westrum, E. F., Jr., and Sinke, G. C., "The
Chemical Thermodynamics of Organic Compounds", John Wiley
and Sons, Inc., N.Y., 1969.
(3) CEH Manual of Current Indicators, Aug. 1974.
(4) Chemical Marketing Reporter, Aug. 21, 1972.
(5) Oil, Paint, and Drug Reporter, March 16, 1970.
(6) Chemical Horizons Intelligence File.
(7) Chemical Week, Aug. 23, 1972, p. 14.
(8) Literature from Producing Companies of Fluorocarbons.
(9) MacMillan, R. T., Fluorine, In: Mineral Facts and Problems,
Bureau of Mines Bulletin No. 650, United States Department
of the Interior, Washington, D.C., 1970.
(10) Wood, H. B., Fluorspar and Cryolite, In: Minerals Year
Book, U.S. Bureau of Mines, 1971.
(11) Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd
Edition, Interscience Publishers, New York, 1966, Volume
9, pp. 506-847.
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INDUSTRY ANALYSIS
The data presented herein are taken primarily from the patent
literature. Ancillary data are taken from recent trade publi-
cations, related books, and company brochures. Much of the
thermal data on the heating or cooling requirements for processes
had to be calculated and/or estimated since this information was
not available in the literature. Due to the present economic
climate and the potential fluorocarbon-ozone problem, actual
production data presented may vary from the reported values.
Other variations in production data may be caused by improvements
in processing techniques since the data were printed. This, of
course, would be considered as a trade secret by the manufacturing
companies, and there is no open access to this information.
Research findings also play a role in the quantities of certain
fluorocarbons being manufactured. For example, production of
aromatic fluorocarbons was recently begun due to new applications
or uses. While production is very small now, it may continue to
grow and expand in the future.
The industry has been divided into two segments for analysis:
Fluorocarbon Production and HF Production. Process flowsheets
and process descriptions are given for the processes involved
in these segments of the industry with operating parameters,
input materials, utilities, and waste streams defined for each
process.
In general, manufacturing companies treat production techniques
as proprietary information and are reluctant to divulge specific
information relating to methods used. The process descriptions
contained in this section reflect data for selected reactions
considered typical for fluorocarbon production. The reader must
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be aware that, in some cases, the reaction specified may not be
the method of choice for commercial production of the indicated
fluorocarbon, or may be one of several alternate routes to the
product.
Producer/product data compiled from the 1976 Directory of Chemical
Producers differs somewhat from data received from producers and
from industry experts. Limited attempts to resolve this inconsis-
tency were unsuccessful. The data are presented as compiled, with
footnoes to indicate inconsistencies .
FLUQROCARBON PRODUCTION PROCESSES
The primary raw materials for the preparation of the principal
fluorocarbons are the chlorocarbons. Certain fluorocarbons are
also prepared from acetylene. Many of the incompletely fluorinated
products are subjected to additional chemical reactions (processes)
to give other useful produces.
Chemical trees shown in Figure 1 illustrate the sequences of
reactions in which fluorocarbons are prepared from hydrocarbon
raw materials. Table 1 lists the process descriptions given for
this segment.
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CC14 > CFC13 + CF2C12 + CF3C1
CBr2F2
CF3CFC1-CF2C1 CF3»CFBr-CF2Br
CF2Br-CF2Br
CC12=CC12 —> CF2C1-CFC12+CFC12-CFC12+CF2C1-CF2^1+CF3CF2C1+CF3CF3
CF2=CFC1
CF3CC13 —-> CF3COC1 —> CF3COOH
CH3CHF2+CH2=CHF
CH3CC1F2 — > CH2=CF2
Cl Cl
CC12=C-C=CC12 > F3C-C=C-CF3 -> F3C-COOH > F3CI
Cl
Cl
F3C-CH?OH
F3C-C=C-CF-, F.C-CF.-CF.-CF,
V
FIGURE 1. CHEMICAL TREES OF FLUOROCARBONS
8
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Table 1. PROCESS DESCRIPTIONS FOR
FLUOROCARBON PRODUCTION
1. Liquid Phase Fluorination
2. Distillation from Liquid Phase Fluorination
3. Separation, Neutralization, Drying of Products from
Liquid Phase Fluorination
4. Vapor Phase Fluorination
5. Distillation from Vapor Phase Fluorination
6. Separation, Neutralization, Drying of Products from Vapor
Phase Fluorination
7. Electrochemical Fluorination
8. Separation, Neutralization, Drying of Products from
Electrochemical Fluorination
9. Bromination of Fluorohydrocarbons
1O. Purification of Bromofluorocarbons
11. Pyrolysis of Chlorodifluoromethane
12. Pyrolysate Scrubber, Separator, Drier
13. Reductive Dechlorination of 1,1,2-Trichlorotrifluoroethane
14. Separation and Purification of Products from Dechlorination
of 1,1,2-Trichlorotrifluoroethane
15. Addition of Halogens to Perfluoroalkenes
16. Dimerization of Fluoroolefins
17. Oxidation of Chlorofluoroolefins
18. Production of Fluoroalcohols by Catalytic Hydrogenation
19. Preparation of Perfluoroalkyl Iodides
2O. HF Addition to Acetylene
21. Separation and Purification of Fluorohydrocarbons from
HF Addition
22. Chlorination of 1,1-Difluorbethane
23. Dehydrochlorination of l-Chloro-l,l-difluoroethane
24. Production of Fluoroaromatic Compounds
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Heat
Refrig.
n
liquid Thase
Fluorlnation
sbCl3
h-1
O
Heat
[To other plant uses]
Heat
Distillation from
Liquid Phase
Fluorination 2
Recycle
£hloro and
[chlorofluor
carbons
r
Cooling
Water
\ Sep.,Neut.,
— ^- of Prods, f
/ Liq.-Ph.Flu
/
^
^
f
1
Dry'g.
orln. 3
t
FIGURE 2. FLOWSHEET FOR PRODUCTION OF FLUOROCARBONS BY
LIQUID PHASE FLUORINATION
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FLUOROCARBON PRODUCTION PROCESS NUMBER 1
Liquid Phase Fluorination
1. Function
To convert chlorocarbons to fluorocarbons by means of flu-
orination with anhydrous hydrogen fluoride together with a
catalyst. The reactor may be made of steel, various stain-
less alloys, Monel or nickel clad steel.
a. Carbon tetrachloride is converted into dichlorodi-
fluoromethane (FC-12) and trichlorofluoromethane
(FC-11).
b. Chloroform is converted into chlorodifluoromethane
(FC-22) and dichlorofluoromethane (FC-21).
c. Tetrachloroethylene and chlorine are converted
into trichlorotrifluoroethane (FC-113), tetrach-
lorodifluoroethane (FC-112), and dichlorotetra-
fluoroethane (FC-114).
d. Hexachlorobutadiene is converted into 2,3-dichloro-
hexafluorobutene-2. Perfluorobutene-2, and perfluoro-
butane are made from 2,3-dichlorohexafluorobutene-2
by subsequent and different reactions.
2. Input Materials
Assuming a production capabity of 68 million kg of product
per year, and a production rate of one kg of product per kg
of catalyst per hour, the quantities of raw materials re-
quired for (a) above are:
CCi 9798 kg/hr
HF 4 2077 kg/hr
11
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for (b) above:
CHC13 --------- 13066 kg/hr
HF --------- 2077 kg/hr
and for (c) above:
CC12=CC12 ----- 7610 kg/hr
HF --------- 4500 kg/hr
clz --------- 3250 kg/hr
Since the process can be operated to prepare more of one prod-
uct than another, the feed ratio of HF to chlorocarbon may
vary depending upon what product is desired.
The catalyst consists of 2885 kg SbCl5, 290 kg SbCl3 and 7938
kg CC13F. The efficiency of HF utilization is estimated to be
9770 and that of CCU is estimated to be "j-98%.
Operating Parameters
Satisfactory operating conditions cover wide ranges. The
pressures may vary from 0 to 35 kg/cm2 , the temperatures from
45-200°C, catalyst concentrations from 10 to 90 weight per
cent, and product take-off temperatures from -30° to +100°C.
A typical example uses CC1,, and HF, a pressure of 7 kg/cm , a
reactor temperature of 80°C, a catalyst concentration of 60
weight percent in CC13F (400 parts SbCls, 40 parts SbCl3>
660 parts CC13F), and a reflux condenser temperature set at
-5°C. Under these conditions, the products will consist
primarily of CHI and CC12F2 (all CC14 and CC13F being returned
to the reactor) . Increasing the reflux condenser temperature
to +5°C allows some of the CC13F to escape to form a 9:1 ratio
of CC12F2 to CC13F. An increase in pressure will allow an
increase in condenser temperatures without altering the pro-
duct composition. Thus, a range of variables is possible with-
out a change in product composition. In general, an increase
in temperature and pressure will result in an increase in rate.
12
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Based on a plant having a production capacity of 68 million
kg of product per year, and a production rate of one kg of
product per kg catalyst per hour, the catalyst bed size is
estimated to be 1 meter2 x 6 meters.
4. Utilities
The reactor is normally heated by steam to a temperature of
80°C. Assuming again a production capacity of 68 million kg
of product per year and a production rate of one kg of product
per kg of catalyst per hour, for conversions (a), (b), and
(c) above:
(a) Approximately 400,000 kcal of heat per hour are required.
(b) " 740,000 "
(c) " 280,000 "
5. Waste Streams
The reaction is carried out in a closed system--the only dis-
charges to air or water would be due to leaks and spills.
Estimated catalyst losses: 2 x 10 "* kg/kg product. The waste
catalyst can be disposed of by burial.
6. EPA Source Classification Code
7, References
1) Oilman, H., Ed,, "Organic Chemistry", Volume 1, John
Wiley and Sores, New York, 1943, p. 949.
2) Groggins, P.H., "Unit Processes in Organic Syntheses",
McGraw-Hill, New York, 1958, p. 294.
3) Stacey, M., Tatlow, J. C., and Sharpe, A. G., Editors,
"Advances in Fluorine Chemistry," Volume 2, Butterworths,
Washington, DC, 1961, pp 48-51.
13
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4) Stacey, M., Tatlow, J. C., and Sharpe, A. G. , Editors,
"Advances in Fluorine Chemistry", Vol. 3, Butterworths,
Washington, DC, 1963, pp 117-180.
5) Daudt, H.W., and Youker, M.A., U.S. Patent 2,005,705 (1935).
6) Daudt, H.W., and Youker, M.A., U.S. Patent 2,005,708 (1935).
7) Daudt, H.W., and Youker, M.A., U.S. Patent 2,005,710 (1935).
8) Daudt, H.W., and Youker, M.A., U.S. Patent 2,062,743 (1936).
9) Holt, L.C., and Mattison, E.L., U.S. Patent 2,005,713 (1935)
10) Benning, A.F., U.S. Patent 2,450,414 U,<48) .
11) Benning, A.F., U.S. Patent 2,450,415 (1948).
12) Benning, A.F., U.S. Patent 2,478,362 (1949).
14
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FLUOROCARBON PRODUCTION PROCESS NUMBER 2
Distillation from Liquid Phase Fluorination
1. Function
To separate more volatile by-products from the feed and
product materials and to return the catalyst to the fluor-
ination step. Since the by-product is anhydrous hydrogen
chloride, steel or stainless steel alloys may be used.
2. Input Materials
Depending upon the product desired, anhydrous hydrogen
chloride, chlorocarbons, chlorofluorocarbons, and hydrogen
fluoride are present as the feed. Also small traces of the
antimony salts may be present in the feed.
If one assumes that an average of two chlorines per molecule
are replaced by fluorines, then for a plant having a produc-
tion capacity of 68 million kg per year, between 3600 and
8000 kg/hr of anhydrous HC1 would be formed, depending upon
what product is desired.
3. Operating Parameters
As indicated in the fluorination process, the higher the
pressure, the higher the distillation temperature may be.
The actual temperature and pressure used also depend upon
what product(s) is desired. The temperature can thus be
varied from -30° to +100°C and the pressures can be varied
from 3 to 14 kg/cm2.
4. Utilities
The temperature at which the distillation is performed
determines the type of cooling required. When the distil-
lation is performed at temperatures below 20°C, conventional
15
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refrigeration cooling is required. Above 40°C, water cooling
will be adequate. On the above size plant, approximately
500 kcal/hr of heat must be withdrawn.
5. Waste Streams
No emissions should occur in this process. All anhydrous HC1'
is recovered and used in other plant processes. Because this
is a pressurized system, leaks may develop.
6. EPA Source Classification Code
3-01-011-01 BY-Product w/o SCRUB
7., References
1) Stacey, M., Tatlow, J. C., and Sharpe, A. G., Editors,
"Advances in Fluorine Chemistry," Vol. 3, Btitterworths,
Washington, DC, 1963, pp 117-180.
2) Benning, A. F., U.S. Patent 2,450,415 (1948).
16
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FLUOROCARBON PRODUCTION PROCESS NUMBER 3
Separation, Neutralization, Drying of
Products from Liquid Phase Fluor inat ion
1. Function
a. To separate the crude products into the desired final
products and recycle materials.
b. To neutralize any acidic materials that may be present
in the final products,
c. To dry the final products prior to end use.
The separation step is usually divided into two steps,
distillation and decantation. Steel or stainless steel
materials of construction may be used.
2. Input Materials
Chlorocarbons , chlorof luorocarbons and anhydrous HF feed into
this process. The quantities of these materials used depend
upon what product is desired. For example, if one wishes to
produce equal amounts of CC12F2 and CC13F as products, then
CClif is fluorinated under conditions such that these two
materials are produced in nearly equal amounts. Along with
this, a small amount (~5%) of unreacted CCI^ and HF also are
fed. This mixture of feed materials is subjected to an azeo-
tropic distillation, during which time the CC12F2 and HF are
removed from the CC13F and
The azeotrope, CC1 F and HF, is then separated further by
decantation and the CC1 F containing a trace of HF is washed,
e.g., by aqueous caustic, then dried, e.g., by molecular
sieves, silica gel, etc., and bottled. Depending upon the end
17
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use, an additional distillation may be performed. The de-
canted HF is recycled to the fluorination process step (proc-
ess 1).
If CC12F2 is the only product desired, the CClgF and CC14 are
recycled back to the fluorination process. If CC13F is also
desired as a product, it may be separated from CC14 by dis-
tillation. Neutralization and drying of CC13F is performed,
as in the case of CC12F2.
Assuming a production capacity of 68 million kg of product per
year and assuming that equal productions of CC12F2 and CC13F
are desired, about 4200 kg of each of these materials, along
with 260 kg of CC14 and 25 kg of HF, per hour are fed into this
process.
3. Operating Parameters
Again assuming that equal productions of CC12F2 and CC13F
are desired as products, the separation by azeotropic distil-
lation may be performed under a variety of pressures and
temperatures. Since the pressure and temperature are directly
related to each other, more pressure will allow an increase
in temperature to be used and hence less condenser cooling
required. However, at higher temperatures CC12F2 dissolves
to a greater extent in HF and HF is also more soluble in
CC12F2. The conditions for separating this azeotrope by
decantation will probably be chosen by the manufacturer based
on cooling capacity, materials of construction, etc.
4. Utilities
Steam requirements for separation by distillation will vary
depending upon what product(s) is desired. Assuming a produc-
tion of 4200 kg per hour of CCl^, an estimated 170,000 kcal/hr
18
-------
of heat are required for the distillation. Only a small
quantity of heat is required for regeneration of the (molecular
sieve) drying agent.
5. Waste Streams
For neutralization of the <1% of the HF present in the CC12F2
following decantation, aqueous caustic may be used. Up to 20
kg/hr of NaOH may be required for neutralization. The spent
caustic (NaF + NaOH) may be discharged to a pond and complete-
ly neutralized.
6. EPA Source Classification Code
None established.
7. References
1) Stacey, M., Tatlow, J. C., and Sharpe, A. G., Editors,
"Advances in Fluorine Chemistry," Vol. 3, Butterworths,
Washington, DC, 1963, pp 117-180.
2) Benning, A. F., U.S. Patent 2,450,415 (1948).
19
-------
(* Metal"!
LFluorideJ
Heat
Vapor Phase
Fluorination 4
Recyc1e
Chloro-
carbons
[To other plant uses]
Cooling
Hater
Heat
Uifl —
Distillation fron
Vapor Phase
Fluorination 5
ifei
Sep.,Neut.,Dry'g.
f\f DvrtHi i/" t c £ v*riri
j T r rOQ UC 1 5 7 rOm
Vapor PH. Fluor. 6
FIGURE 3. FLOWSHEET FOR PRODUCTION OF FLUOROCARBONS BY
VAPOR PHASE FLUORINATION
-------
FLUOROCARBON PRODUCTION PROCESS NUMBER 4
Vapor Phase Fluorination
1. Function
To convert chlorocarbons to fluorocarbons by means of vapor
phase fluorination with anhydrous hydrogen fluoride
and a catalyst.
Any of a number of chlorocarbons is converted into a number
of fluorocarbons. In this process (as opposed to the liquid
phase fluorination process) less control on the degree of
fluorination is possible; therefore, a larger mixture of
products is obtained. In general, this process is more
suitable for producing the more highly fluorinated compounds.
The reactor consists of a heated tube or series of tubes
filled with a granular catalyst and fed by a vaporized mix-
ture of the chlorocarbon and anhydrous hydrogen fluoride.
A variety of metallic fluorides may be used as catalysts.
These may be in a solid granular or supported form. The re-
actor can be made of steel, stainless steel, or clad or
alloy steel.
2. Input Materials
The quantities and types of materials fed into this process
vary considerably and are dependent upon the product(s) de-
sired. The normal mole ratio of HF to chlorocarbon is 1.1
to 1.5 and the efficiency of HF utilization is usually from
90 to 10O%.
21
-------
A representative list of chlorocarbons which can be converted
into fluorocarbons is given below.
Table 2. FLUOROCARBONS PRODUCED FR011 CHLOROCARBONS
Feed Products
CC14 CC13F, CC12F2, CC1F3, CF4
CHC13 CHClgF, CHC1F2, CHF3
CC12=CC12 + C12 CC12F-CC1F2, CC1F2-CC1F2, CC1F2-CF3
CF3-CF3
0 000
CC13-C-CC13 CC1F2-C-CC1F2, CC1F2-C-CF3, CF3-C-CF3
CBr4 CBrF3, CHF3, CBr2F2, CBr3F
CH3C12 CH2F2, CH2C1F
Assuming & production capacity of 10 million kg of product
per year, and assuming that approximately equal amounts of
CC12F2 and CC13F are desired from CC14, the quantities of
raw materials required are:
CC14 1400 kg/hr
HF 3OO kg/hr
With this ratio of feed, the following quantities of products
would probably be obtained:
CC12F2 64O kg/hr
CC13F 480 kg/hr
CC1F3 13 kg/hr
HCi . 525 kg/hr
3. Operating Parameters
The temperature employed will vary from 100° to 5OO°C.
The fluorination is usually carried out at about atmospheric
pressure (1 kg/cm2). Typical catalysts which may be used are
22
-------
chromium oxyfluoride, chromium oxyfluoride - aluminum fluoride,
A1F3, ZrFij, CrF3, etc. Depending upon what production quantity is
desired, the size of the reactor will vary. A typical example
is seen in the following:
A total of 2O8 g of CC14 and 36 g of HF was vaporized and
passed through a 5 x 30 cm bed of 0.5 x 0.5 cm pellets of
chromium oxyfluoride in a nickel reactor for 30 min. at 550°C
and a contact time of 6.6 sec. The products consisted of 9.6%
CC1F3, 40.9% CC12F2, 13.6% CC13F, and 5.9% CC14. In general,
at any one temperature, a decrease in contact time produces
smaller quantities of the highly fluorinated materials and an
increase in temperature produces greater quantities of the
highly fluorinated materials.
4. Utilities
The reactor is heated by flue gas or by high pressure steam
to a temperature of about 150°C. Assuming a production capac-
ity of 10 million kg of product per year, a total of about 2
million kcal of heat per hour is required. In addition to
this, about 450kWh of electrical energy are required.
5. Waste Streams
Waste streams should be limited to leaks and spills from this
closed system process.
6. EPA Source Classification Code
None established.
7. References
1) Stacey, M., Tatlow, J. C., and Sharpe, A. G., Editors,
"Advances in Fluorine Chemistry," Vol. 3, Butterworths,
Washington, DC, 1963, pp 117-180.
2) Ruh, R. P. and Davis* R. A., U.S. Patent 2,745,886 (1956).
23
-------
3) Foulletier, L., and Dassaud, R., U.S. Patent 2,897,064 (1959).
4) Davis, R. A., and Brcadworth, M. R. , U.S. Patent 3,002,934 (1961)
5) Farbwerke Hoechst A.-G., Fr. Patent 1,343,392 (1963).
6) Swamer, F. W., Fr. Patent 1,372,549 (1964).
24
-------
FLUOROCARBON PRODUCTION PROCESS NUMBER 5
Distillation from
Vapor Phase Fluorination
1. Function
To separate the products obtained from the vapor phase fluori-
nation process. The still may be made of steel, stainless
steel, or nickel clad steel.
2. Input Materials
The feed to this process consists of anhydrous hydrogen chlo-
ride, chlorofluorocarbons, fluorohydrocarbons, chlorocarbons,
and small quantities of anhydrous hydrogen fluoride. The
products may be separated by low temperature fractional dis-
tillation after separating out the anhydrous HC1. However,
certain fluorinated products may have a boiling point very
close to that of HC1. In this case, the HC1 and fluorocarbon
may be scrubbed with water, dissolving the HC1. One of the
by-products from this process is frequently a 3O% HC1 solution.
If conditions are adjusted during the fluorination step such
that no fluorocarbons are formed which have the same boiling
point as HC1, the HC1 may be first separated and the remain-
ing fluorocarbons separated as in the liquid phase fluorina-
tion process (see process 3).
3. Operating Parameters
If the process is operated such that the anhydrous HC1 is the
only highly volatile product, the operating conditions may be
the same as the distillation performed in process 2. However,
if a volatile fluorocarbon also is formed, then the HC1 may
be scrubbed with water and the volatile (insoluble) fluoro-
carbon recovered from the aqueous HC1. In this case, the
distillation may be accomplished under less pressure, i.e.,
up to atmospheric pressure.
25
-------
Thus, the pressure, temperature, and refrigeration
required for the distillation depend entirely upon the
product feed, the temperature, and the contact time for
fluorination.
4. Utilities
The quantity of refrigeration needed here is similar to that
in process 2, assuming similar input materials. Under the
proper conditions, water cooling would be adequate.
5. Waste Streams
No waste streams are involved in the above distillation. The
scrubbed HC1 may be removed to other plant uses as a 30% solu-
tion.
6. EPA Source Classification Code
3-01-011-02 BY-PRODUCT w/SCRUB
7. References
1) Stacey, M. , Tatlow, J. C. , and Sharpe, A. G. , Editors,
"Advances in Fluorine Chemistry," Vol. 3, Butterworths,
Washington, DC, 1963, pp 146-154.
2) Slesser, C., Editor, "Preparation, Properties, and Technology
of Fluorine and Organic Fluoro Compounds," McGraw-Hill Book
Company, Inc., New York, 1951, pp 427-454.
3) Ruh, R. P., and Davis, R. A., U.S. Patent 2,745,886 (1956).
26.
-------
FLUOROCARBON PRODUCTION PROCESS NUMBER 6
Separation, Neutralization, Drying of Products
from Vapor Phase Fluorination
1. Function
To separate, neutralize, and dry all desired products pre-
pared in the vapor phase process. Prior to this process, the
HC1 and low boiling products were removed via distillation
(see process J>). The remaining fluorocarbons, chlorofluoro-
carbons, and fluorohydrocarbons along with small quantities
of HP are separated by distillation, neutralized by scrubbing
with aqueous caustic to eliminate the HF, and dried with
molecular sieves, silica gel, etc. The still can be made
from steel, stainless steel, or similar materials.
2. Input Materials
The feed materials to this process vary considerably depending
on what products are being made. However, a typical example
may be seen below:
Assuming a production capacity of 10 million kg of product
per year, and assuming that nearly equal amounts of CC12F2
and CC13F are desired, the quantities of input materials are:
CC12F2 650 kg/hr
CC13F 490 kg/hr
HF 3 kg/hr
3. Operating Parameters
High efficiency distillation columns may be used to separate
the products from this process. They can be operated under
pressure, but usually are operated at atmospheric conditions.
However, for feeds such as CC12F2 and CClsF, the same operating
27
-------
conditions may be used as given in process J3.. For other
feeds, the distillation will be carried out at different
temperatures. The temperatures employed will be dependent
upon the boiling points of products being separated.
4. Utilities
Steam requirements for this process will vary considerably
depending upon what products are being separated. Assuming
the production of 65O kg/hr of CC12F2 and 49O kg/hr of
CC13F, an estimated 48,OOO kcal/hr of heat are required
for the distillation.
5. Waste Streams
A small amount of aqueous NaF - NaOH will be obtained from
the caustic scrubbing of the fluorocarbons. This may amount
to about 7 kg/hr for the production quantities given above.
This can be completely neutralized and disposed of by burial.
6- EPA Source Classification Code
None established.
7. References
1) Stacey, M., Tatlow, J. C., and Sharpe, A. G., Editors,
"Advances in Fluorine Chemistry," Vol. 3, Butterworths,
Washington, DC, 1963, pages 146-154.
2) Slesser, C., Editor, "Preparation, Properties, and Technology
of Fluorine and Organic Fluoro Compounds," McGraw-Hill Book
Company, Inc., New York, 1951, pages 427-454.
3) Ruh, R. P., and Davis, R. A., U.S. Patent 2,745,886 (1956).
28
-------
fMetalllcl
LFIuorldeJ
I
Refrig
Electrochemical
Fluorination 7
%
S3
VO
Sep.,Neut..Dry'g.
of Products from
Elec.Chem.FTuor. 8
FIGURE 4. FLOWSHEET FOR THE PRODUCTION OF FLUOROCARBONS BY
ELECTROCHEMICAL FLUORINATION
-------
FLUOROCARBON PRODUCTION PROCESS NUMBER 7
Electrochemical Fluorination
1. Function
To convert hydrocarbons and chlorocarbons into fluorocarbons.
Many organic compounds containing ether, carboxyl, amine, or
other groups can be fluorinated by this process without
destroying these groups. Other fluorination processes do
not permit this.
The electrochemical cell usually consists of a single compart-
ment cylindrical or rectangular metal vessel, commonly made
of iron, steel, or nickel. A condenser made of iron or copper
is attached to the cover, and is operated in a manner to
return the effluent hydrogen fluoride to the electrochemical
cell while allowing the products to exit the cell.
Products which boil at high temperatures are frequently drawn
off the bottom of the cell through a valve. (Most completely
fluorinated species are insoluble in liquid HF.)
2. Input Materials
Feed to the cell consists of a large variety of hydrocarbons,
chlorohydrocarbons, and organic materials containing func-
tional groups. Typical feeds and products are listed in
Table 3.
30
-------
Table 3. INPUT MATERIALS AND PRODUCTS FROM
ELECTROCHEMICAL FLUORINATION
Feed
Hexanes
CH3-0-CH3
CH3COF
CH3S02F
CH 2 C1 2
CHC1=CC12
(C,H9)3N
(CH3CO)20
Product
Perfluorohexanes
CHF2-0-CF3, CF3-OCF3, CHF2-0-CHF2
CF3COF
CF3S02F
CC12F2, CHC12F
CHC1F-CC12F
(C,F9)3N
CF3COF
In addition to the organic materials, anhydrous liquid hydro-
gen fluoride and usually a metallic fluoride, e.g., sodium
fluoride or lithium fluoride, are added.
3- Operating Parameters
During electrolysis, anhydrous HF is added periodically to
keep the cell full. The optimum cell potential is below
10 v and is usually around 5 v. Normally, direct current
is used, although alternating current is effective. The
current controls the amount of fluorination that takes
place in a given time. For any given cell the potential
applied and the substrate concentration are the variables
which determine current density. Current densities usually
range from 0.0008 to 0.02 amps/cm2. Current efficiencies
range from 60 to 90%.
The temperature at which electrochemical fluorinations are
carried out usually ranges from -10 to +40°C, but most fre-
quently it is aroung 0°C. Normally the fluorinations are
31
-------
performed at atmospheric pressures, but higher pressures are
required when the temperature is above 40°C.
Concentrations of the substrate may vary from 1 to 1570.
Normally the substrate is added continuously at the rate
it is fluorinated.
The optimum conditions for fluorination will usually be
chosen so that the best yields are obtained of the desired
products. Yields vary considerably and are low for many
compounds.
Cell sizes have been designed from 10 to 10,000 amps. With
all the ancillary equipment a cell 23 cm by 8.5 cm, and hold-
ing about 1 £. of solution, was rated at 20 amps. It measured
1.3 x 1.3 x 0.6 meters. The size of the cell will obviously
depend upon what quantities of product are desired.
4. Utilities
The major kind of energy required in this process is electri-
cal and the amount will depend upon the degree of fluorina-
tion, as well as the quantity of materials produced. From
0.4 to 0.6 g of fluorine are available per amp hr. Refriger-
ation is required for the condenser. The amount of cooling
required will depend to a large degree on the temperature at
which the cell is operated which, in turn, depends upon what
substrate is being fluorinated. Because of the high energy
demands, oh site power generation is usually from oil or gas
fired turbogenerators.
5. Waste Streams
There are almost no discharges to the air, water, or ground
in this process. Any HF which escapes from the condenser is
32
-------
absorbed by NaF. The NaF-HF may be heated to drive off the
HF and regenerate the NaF, or it may be disposed of by burial
6. EPA Source Classification Code
None established.
7. References
1) Stacey, M., Tatlow, J. C., and Sharpe, A. G., Editors,
"Advances in Fluorine Chemistry," Vol. 1, Butterworths,
Washington, DC, I960, pages 129-165.
2) Simons, J. H., Editor, "Fluorine Chemistry," Vol. 1,
pages 414-420, Vol. 2., pages 340-341, Academic Press,
Inc. , New York QS50) .
3) Wolfe, J. K., U.S. Patent 2,806,817 (1957).
33
-------
FLUOROCARBON PRODUCTION PROCESS NUMBER 8
Separationf Neutralization. Drying of Products
from Electrochemical Fluorination
1. Function
To separate, neutralize, and dry all desired products .pre-
pared in the electrochemical fluorination process. Because
the products will contain compounds which vary considerably
in their degree of fluorination, their separation may at
times require high efficiency distillation columns.
2. Input Materials
All products and by-products from the electrochemical fluor-
ination (see process J7) are fed into this process. When
acid fluorides or anhydrides are the products, they are
scrubbed with sodium fluoride to eliminate any HF. Fluor-
inated hydrocarbons, ethers, amines, etc. are scrubbed
with water or aqueous caustic and the wet products are dried
with a desiccant.
3. Operating Parameters
The products are usually cooled, compressed, and distilled
under pressure; however, the degree of cooling and com-
pressing required will depend largely on the product ob-
tained since many of these are liquid under normal condi-
tions. Operating pressures may be as high as 20 kg/cm2 and
temperatures as low as -25°C.
4. Utilities
It is estimated that between 1 and 2O kcal/mole of heat
are required for the distillation of the products. If
refrigeration is used, 5-50 kcal/mole of heat need to be
withdrawn from the system.
34
-------
5. Waste Streams
A small amount (<10 g/kg product) of sodium fluoride-HF
or aqueous NaF/NaCl will be discharged to a waste pond.
Small amounts of fluorocarbons may be discharged to the
air in the pressurized distillation step.
6. EPA Source Classification Code
None established.
7. References
1) Stacey, M. , Tatlow, J. C. , and Sharpe, A. G. , Editors,
"Advances in Fluorine Chemistry," Vol. 1, Butterworths,
Washington, DC, pages 129-165 (1960).
2)' Simons, J. H., Editor, "Fluorine Chemistry," Vol. 1,
Academic Press, Inc., New York, 195O, pages 414-420,
Vol. 2, pages 34O-341.
3) Wolfe, J. K., U.S. Patent 2,806,817 (1957).
35
-------
Heat
Vaporizer,
Bromination
Reactor 9
Refrig.
Purif. , Scrubber,
Drier for Bromo-
fluoro Carbons 10
FIGURE 5. FLOWSHEET FOR THE PRODUCTION OF
BROMOFLUOROCARBONS
-------
FLUOROCARBON PRODUCTION . PROCESS NUMBER 9
Bromination of Fluorohydrocarbons
1. Function
To convert fluorohydrocarbons to bromofluorocarbons. In this
^ - \ •"•• • i
process CHC1F2 (FC-22) is converted into CBrClF0; CHF3 (FC-23)
is converted into CBrF3 ; and CH2F2 (FC-32) is converted into
CBr2F2. The process is accomplished in a pyrex glass reactor
through mixing and vaporizing the feed and reacting the
fluorohydrocarbons with the bromine vapor. Monel or nickel
tube reactors can be used in place of glass.
2. Input Materials
The fluorohydrocarbon is mixed with bromine vapors at a ratio
of from 25 to 45 percent by weight of the former to 75 to 55
percent by weight of the latter. Depending upon the conditions,
it is possible to prepare several different products. If the
main product desired is CBrClF2, a conversion of about 55% is
achievable. Thus, from 150 kg. of CHC1F2, 82 kg. of CBrClF2 is
prepared.
3. Operating Parameters
The temperatures at which the reaction is performed may vary
from 30O to 9OO°C. Normal operation is performed from 650° to
75O°C. Atmospheric pressure is used.
4. Utilities
Approximately 100 kcal. of heat are required per kg. of product.
5. Waste Streams
There should be no waste streams in this process other than
those occurring abnormally due to leaks or spills.
37
-------
6. EPA Source Classification Code
None established.
7. References
Barnhart, W. S., U.S. Patent 2,731,505 (1956)
-------
FLUOROCARBON PRODUCTION PROCESS NUMBER 10
Purification of Bromofluorocarbons
1. Function
The crude products from the bromination of the fluorohydro-
carbons (see process No. 9) are purified by scrubbing
out the by-product hydrogen bromide (HBr) and any unreacted
bromine. The scrubbed products, along with any unreacted
starting material, are subsequently dried with a desiccant.
2. Input Materials
Into this process are fed the following materials together
with their estimated quantities (per kg. of feed).
HBr 0.27 kgr
Br2 0.006
CBrClF2 0.55
CBr2F2 0.06
CHC1F2 0.12
HC1 O.OO4
The feed is scrubbed with water (or aqueous caustic) to re-
move the HBr and trace quantities of Br2 and HC1. The bromo-
fluorocarbons and starting material are passed through a des-
iccant (silica gel, molecular sieves, etc.) and the dried
products recovered. These may be used as a mixture or sep-
arated by distillation, if necessary.
3. Operating Parameters
The gases are scrubbed with ambient temperature water and
dried at atmospheric pressure. The dried gases are cooled
to about - 5°C, liquefied, and stored.
39
-------
4. Utilities
For a production plant having a capacity of 200 kg. per day,
it is estimated that 0.5 kg. of scrubbing water is required
and approximately 60 kcal. of heat need to be withdrawn from
i
the system per kg. of product.
5. Waste Streams
Since the aqueous HBr is too valuable to be discarded, it is
usually recycled to recover the bromine values or diverted to
other plant uses. Traces of HBr, HCl, and bromofluorocarbons
may escape due to pump leaks, etc., but in general no major
quantity of the products is lost to air, water, or ground.
6. EPA Source Classification Code
None established.
7. References
Barnhart, W. S., U.S. Patent 2,731,505 (1956).
40
-------
Heat
1
Pyrolysis
Reactor
Refrig.-
Crude
PyroTysis
Products
Pyrolysate
Scrubber,
Separator.Drier 12
FIGURE 6. FLOWSHEET FOR THE PYROLYSIS OF CHLORODIFLUOROMETHANE (FC-22)
-------
FLUOROCARBON PRODUCTION PROCESS NUMBER 11
Pyrolysis of Chlorodifluoromethane
1. Function
To prepare tetrafluoroethylene (CF2 = CF2) and hexafluoropropylene
(CF3-CF=CF2) from Chlorodifluoromethane (CHC1F2)(FC-22). Other
fluorochemicals obtained in small amounts from this process in-
clude difluoromethane (CH2F2), trifluoromethane (CHF3), chloro-
trifluoromethane , hexafluoroethane, octafluorocyclobutane, and
trifluoroethylene. These latter fluorochemicals, as well as HC1,
are by-products of the pyrolysis and are not made commercially
by this route.
Several equipment designs have been employed for the above process,
In general, the combustion chamber can be made of ceramic or high
temperature steel, and the reaction tube may be made of sintered
aluminum oxide or platinum.
2. Input Materials
Normally, Chlorodifluoromethane is the feed material to this proc-
ess. However, other feed materials such as tetrafluoromethane,
trifluoromethane, and octafluoropropane, may also be used in this
process to produce the same major products. In some reactor de-
signs, finely divided carbon is used as a quenching medium to
prevent further reaction of the tetrafluoroethylene.
3. Operating Parameters
The pyrolysis may be performed at 850-1300°C. The pyrolysis prod-
ucts are rapidly cooled to about 500°C to prevent further re-
action. Pressures of 0.1 to 0.5 kg/cm2 are frequently used with
preferred contact times of 0.1 to 0.001 seconds. Usually the
process is performed non-catalytically.
42
-------
4. Utilities
Heat for this pyrolytic process may be provided by electricity or
combustion gases. Electric arcs or oxyhydrogen torches have
also been used. The heat or power requirements are entirely
dependent upon the quantity and type of starting material fed
to the process. However, it is estimated that about 20 kcaL
of heat per mole of chlorodifluoromethane are required.
5. Waste Streams
Other than leaks or spills, there should be no waste streams
from the above process.
6. EPA Source Classification Code
None established.
7. References
1) Okamura, K., et al, U.S. Patent 3,221,070 (1965).
2) Benning, A. F., et al, U.S. Patent 2,406,794 (1946).
3) Dennison, J. T. et al, U.S. Patent 2,852,574 (1958).
4) Scherer, 0., et al, U.S. Patent 2,994,723 (1961).
5) Farlow, M. W., U.S. Patent 2,709,182 (1955).
6) Downing, F. B., et al, U.S. Patent 2,551,573 (1951).
43
-------
FLUOROCARBON PRODUCTION PROCESS NUMBER 12
Pyrolysate Scrubber, Separator, Drier
1. Function
To separate into pure components the pyrolysate from chloro-
difluoromethane (FC-22). The two major products, tetrafluoro-
ethylene (CF2=CF2) and hexafluoropropylene (CF3-CF=CF2) must
be highly pure before these monomers can be satisfactorily
homo- or copolymerized. Separation and purification is usu-
ally accomplished by a series of scrubbing, distillation, ad-
sorption and desorption steps under super-atmospheric pressures.
Stainless steel equipment is adequate for this process.
2. Input Materials
The feed into this process consists of all the products of the
pyrolysis from process 11. These usually consist of tetra-
fluoroethylene, hexafluoropropylene, hydrogen chloride, and the
unreacted starting material, chlorodifluoromethane. The follow-
ing may also be present in minor amounts: trifluoromethane,
chlorotrifluoromethane, hexafluoroethane, difluoromethane,
dichlorodifluoromethane, and octafluorocyclobutane. The con-
version of chlorodifluoromethane into tetrafluoroethylene is
dependent upon the pressure under which pyrolysis occurs.
Normally, the pressure is kept at about 0.40 kg/cm2, whereupon
the conversion is about 30% and the yield of tetrafluoroethylene
is about 90%. Therefore the materials fed to this process based
on the kg of product obtained, are approximately
chlorodifluoromethane 3.5 kg.
tetrafluoroethylene 1.0 kg.
hexafluoropropylene 0.03 kg.
hydrogen chloride 0.7 kg.
minor products 0.02 kg.
-------
3- Operating Parameters
Pressure: 0.3-16 kg/cm2
Temperature: -20° to 0°C
The mixture of products obtained is extremely difficult to sep-
arate by distillation. Cold methanol dissolves all the products
except the tetrafluoroethylene and hexafluoropropylene. The
dissolved materials are later stripped from the methanol and
recycled or packaged.
4. Utilities
It is estimated that electrical power for compressors and refrig-
eration amounts to 5 kWh/kg of product. Heat input (steam) for
distillation processes is estimated to be about 5OO kcal/kg.
Water consumption is estimated to be about 50O 4./kg of product.
5. Waste Streams
Small quantities of tar may be formed in the process which are
discarded (ground burial). Due to the process pressures in-
volved, fluorocarbon vapor leaks may occur occasionally. The
aqueous hydrochloric acid resulting from the scrubbing of the
product may be transferred to other plant uses. Drying agents
(desiccants) may be regenerated or discarded.
6. EPA Source Classification Code
None established.
7. References
Okamura, K., et al, U.S. Patent 3,221,070
45
-------
Heat
Scrubber, Drier
Sep.Purif.of De-
ed! or in. Prods. 14
Reductive
hlorinator
FIGURE 7. FLOWSHEET FOR THE REDUCTIVE DECHLORINATION
OF 1,1,2-TRICHLOROTRIFLUOROETHANE
-------
FLUOROCARBON PRODUCTION PROCESS NUMBER 13
Reductive Dechlorination of 1. 1.2-Trichlorotrifluoroethane
1. Function
To prepare chlorotrifluoroethylene by reductive dechlorination
of 1,1,2-trichlorotrifluoroethane (FC-113) , according to the
following reaction: u
H2
CF2C1-GFC12 •+ CF2=CFC1 + 2HC1.
The vapor phase reaction is usually carried out at elevated temp-
eratures in the presence of hydrogen and a catalyst. In addition
to the desired product, two by-products predominate. The products
are later separated in a separate process (see process No. 14) .
The reaction may also be conducted using zinc in ethanol, accord-
ing to :
CCL2F-CC1F2 > CC1F=CF2 + ZnCl2
2. Input Materials
Based on 1 mole of product, the following feed rates are used:
1,1,2-trichlorotrifluoroethane - 1.3 moles /min.
Hydrogen gas - 2.3 moles/min.
3. Operating Parameters
Temperature: 490 - 580°C
Pressure: 1.O5 kg/cm2
Flow rate: 1,1,2-Trichlorotrifluoroethane - 15 moles/min.
Hydrogen - 3 moles/min.
Reactor size: 50 liters
Catalyst: Copper gauze, copper-cobalt on MgO, or MgF
4. Utilities
It is estimated that 15 kcal/mole of heat are required to carry
out this reaction. The energy may be supplied as gas or elec-
tricity.
47
-------
5. Waste Streams
The products from the above reactor are separated in the next
process. Other than leaks or spills, no waste streams should
be emitted from this closed system process. In the case of
reaction with zinc in ethanol, the ZnCl2 formed may present a
disposal problem.
6. EPA Source Classification Code
None established.
7. References
Mantell, R. M., U.S. Patent 2,697,124 (1954).
48
-------
FLUOROCARBON PRODUCTION PROCESS NUMBER 14
Separation and Purification of Products from Dechlorination of
1,1.2-Trichlorotrifluoroethane
1. Function
To separate chlorotrifluoroethylene, trifluoroethylene, vinyl-
idene fluoride and hydrogen chloride and purify the monomers.
A mixture of these materials along with the unreacted start-
ing material from the reductive dechlorination step (see proc-
ess 13). are fed into this process. The main product, chloro-
trifluoroethylene, is later used in homo- and copolymerizations.
The two by-products,trifluoroethylene and vinylidene fluoride,
are not made commercially by this process. (See processes 2jO
and 23). These materials are separated by fractional distil-
lation and the HC1 is usually scrubbed out with water. Stain-
less stell materials may be used.
2. Input Materials
The feed to this process is the same as the product from the
dechlorination process (see process 13), and consists of
chlorotrifluoroethylene, trifluoroethylene, vinylidene fluor-
ide and HC1, along with the unreacted 1,1,2-trichlorotri-
fluoroethane and hydrogen.
3. Operating Parameters
Temperature: 0 to -20°C
Pressure: 140 kg/cm2
Flow rate: approximately 15 moles/min.
4. Utilities
It is estimated that 15 kcal/mole of heat need to be withdrawn
from the system by refrigeration. Additionally, it is estimated
that 5 kWh of electricity are required for compression of the
gases. About 0.25 i. of water per mole of product is needed
for scrubbing.
49
-------
5. Waste Streams
For every mole of product, about 2 moles of HC1 are formed. When
dissolved in water, this aqueous acid can be transferred to other
plant uses.
6. EPA Source Classification Code
3-O1-O11-02 BYPRODUCT W/SCRUB
7. References
Mantell, R. M., U.S. Patent 2,697,124 (1954).
50
-------
Fluoro-
olefin
or
'
_^. Cool ing
JX^ water
IT A
Addition
Hater
coz
— ,
Heat
>
Dimerization
Reactor ] g
FIGURE 8. FLOWSHEET FOR THE REACTIONS OF FLUOROOLEFINS
-------
FLUOROCARBON PRODUCTION PROCESS NUMBER 15
Addition of Halogens to Perfluoroalkenes
1. Function
to prepare brdittlnated and chlorinated fluorocarbons by the chem-
ical addition of bromine or chlorine to a perfluoroolefin. These
exothermic reactions may be performed in the vapor phase or, alter-
natively, may be performed by bubbling the olefin into the liquid
halogen. The equation for the reaction is shown below.
R-CF=CF, + X_ > R-CF-CF,
22 xx2
where X=Br,Cl.
The reaction proceeds quite cleanly - with the formation of only
the product and with little or no by-products. A glass or monel
reactor is satisfactory.
2. Input Materials
A halogen and a perf luoroolef in are the only feed materials.
3. Operating Parameters
If the perfluoroolefin is bubbled through the liquid halogen,
the halogen must be cooled with water. The reaction normally
occurs at atmospheric pressure. No catalyst is required. If
reacted in the vapor phase, the product is passed through a
cooling condenser.
4. Utilities
Only cooling water is required. The amount of cooling is
dependent upon the rate of input. It is estimated to be from
160 to 240 kcal/kg. of product, depending upon which product
is made.
52
-------
5. Waste Streams
Traces of halogen gases may leave the reactor as an effluent.
These may be scrubbed with water, which is sent to a waste
disposal pond.
6. EPA Source Classification Code
None established.
7. References
1) Ruff, 0., and Bretschneider, 0., Chem. Abstr. 27, 2131 (1933)
2) Lacher, J. R., et al., J. Amer. Chem. Soc., 71, 1330 (1949).
3) Patrick, C. R., "Advances in Fluorine Chemistry," Vol. 2,
Stacey, M., Tatlow, J. C., and Sharpe, A. G., Editors,
Butterworths, Washington, DC, 1961
53
-------
FLUOROCARBON PRODUCTION PROCESS NUMBER 16
Dimerization of Fluoroolefins
1. Function
To prepare cyclic perfluoroalkanes by homodimerization of a per-
fluoroalkene. Tetrafluoroethylene is converted into perfluoro-
cyclobutane. This is an alternative process for the preparation
of perfluorocyclobutane (see process 11). This reaction is
amenable to homo- and codimerizations of other olefins as well.
2* Input Materials
For the preparation of octafluorocyclobutane, the material intro-
duced in this process is tetrafluoroethylene along with an inhib-
itor such as C02 (3).
3. Operating Parameters
The temperature is maintained at 150-200°C and the pressure is
usually 14-18 kg/cm2. Under normal operating conditions, the
cyclic dimer is formed, with the unreacted monomer tetrafluoro-
ethylene being recycled.
4. Utilities
It is estimated that approximately 2 kWh of electrical energy are
required for compressors. Approximately 10 kcal/kg of heat energy
are required.
5. Waste Streams
Other than leaks or spills, a small quantity of CO2 and fluoro-
carbons may be lost in this pressurized closed cycle process.
54
-------
6. EPA Source Classification Code
None established.
7. References
1) Banks, R. E., "Fluorocarbons and Their Derivatives," University
Chemistry Series, MacDonald Technical and Scientific, London,
1970, pp 7-69.
2) Wust, H. A., U.S. Patent 3,101,304 (1963).
3) Knunyants, I. L. , et al.. USSR Patent 173,733 (1965).
55
-------
Ul
I te«- V.UUI I
It fiT""r
Chloro-
fluoro-
olefin
Tri-
fluoro
Acetic Aci
FIGURE 9. FLOWSHEET FOR THE OXIDATION OF
CHLOROFLUOROOLEFINS
-------
FLUOROCARBON PRODUCTION PROCESS NUMBER 17
Oxidation of Chlorofluorooleflns
1. Function
To prepare trifluoroacetic acid via oxidation of a double bond
in olefins. This chemical reaction is a laboratory scale alter-
native to the commercial electrochemical process for making tri-
fluoroacetic acid. The product of oxidation may be extracted
and distilled, or the aqueous alkaline solution may be evaporated
to dryness, then acidified, to recover the desired product. Tri-
fluoroacetic acid may also be prepared from 1,1,2-trichlorotri-
fluoroethane (FC-113) by forming the isomer CF3CC12 which is then
hydrolyzed to CF3COC1 by fuming sulfuric acid and then further
hydrolyzed to the acid by water.
2. Input Materials
An alkaline oxidizing agent is usually used for the chemical ox-
idation. Frequently potassium permanganate along with a small
amount of sodium or potassium hydroxide are used. Potassium
dichromate has also been used. The fluoroolefin compound most
frequently used is:
Cl
CF3-C=C-CF3
Cl
although the octafluorobutene-2 has also been used. The yields
of trifluoroacetic acid are about 80-857o based on the moles of
trifluoromethyl compound fed. About two moles of KMnOi, are re-
quired per mole of product.
3. Operating Parameters
Normally the organic olefin is added portionwise to the oxidizing
agent in this batch process, but the reverse is also effective.
57
-------
The solution is maintained at 80-100°C during the oxidation which
occurs at atmospheric pressure. The feed rate is dependent upon
the rate of oxidation; normally from 1-10 moles/day are added.
A. Utilities
It is estimated that 30 kcal of heat are needed per mole of
product formed. About 500 £ of cooling water are required
per mole of product.
5. Waste Streams
The by-product, manganese dioxide (Mn02), can be recovered or
sent to ground burial. Aqueous potassium chloride may be sent
to a disposal pond. Waste from the acid hydrolysis of CF3CC13
would be mainly spent sulfuric acid, which could be neutralized
and sent to pond or sewer.
6. EPA Source Classification Code
None established.
7. References
1) Babcock, J. H., and Kischitz, A. D., U.S. Patent 2,414,706
(1947).
2) McBee, E. T., Wiseman, P. A., and Bachman, G. B., Ind. Eng.
Chem., 39, 415 (1947).
58
-------
Heat
"1
Catalytic
Hydrogenator
Ol
rRefrig
9
Fl uoro-
alcohol
FIGURE 10. FLOWSHEET FOR THE PRODUCTION OF
FLUOROALCOHOLS BY CATALYTIC HYDROGENATION
-------
FLUOROCARBON PRODUCTION PROCESS NUMBER 18
Production of Fluoroalcohols by Catalytic Hydrogenation
1. Function
To prepare fluorinated alcohols by the catalytic reduction of
ketones or fluorinated esters, according to following general
reaction:
S cat.
R-0-C-(CF2)nF + 2H2 -»• ROM + HOCH2-(CF2)nF
The pure fluorinated alcohol may be recovered by distillation.
The reduction is frequently carried out in a steel bomb. This
process finds use in the preparation of hexafluoro-2-propanol,
but, because of the relatively low yield, it is not normally
used for preparation of 2,2,2-trifluoroethanol.
2. Input Materials
In addition to the ketone or ester and hydrogen gas, a catalyst
is required. The composition of the catalyst may involve pal-
ladium, or platinum impregnated on alumina (1), or it may in-
volve a copper-chromium compound (2). Conversions and yields
vary with the pressure, temperature, catalyst, and compound used.
3. Operating Parameters
If the process is carried out in a pressure vessel (bomb), high
pressure (35O-70O kg/cm2) is required. If carried out under low
pressure (<5 kg/cm2), conversions usually are lower. Tempera-
tures may vary from 5O-3OO°C. The amount of catalyst may vary
from 0.5-300% based on the weight of the ketone or ester. In
one example, 10O cm3 of Ru-Al203 catalyst (0.5% Ru) was charged
into a 1.5 cm internal diameter fused alumina reactor 91 cm long
which was heated over 76 cm of length in an electric furnace.
The internal temperature was maintained at 265°C and a mixture
of 183 g of 2,2,2-trifluoroethyl trifluoroacetate and 46 i. of
hydrogen was passed through the reactor in a 5 hour period. The
residence time was approximately 15 seconds. The exit gases
60
-------
were cooled in a dry ice-trap and the condensate was later
fractionated into 45 g. of starting material and 40 g. of
2,2,2-trifluoroethanol representing a 21% conversion. The
yield for the conversion of hexafluoroacetone to hexafluoro-
2-propanol is >9O%.
4. Utilities
It is estimated that about 2O kcal of heat are required per
mole (100 g.) of product formed. Electrical heating is
usually used. Water (100 kg/kg) or refrigeration is required
for condensation of the product.
5. Waste Streams
Excess hydrogen can be vented to the atmosphere. The catalyst
will need replacement after a period of time due to handling
losses. It is estimated that this will involve not more than
1 g./kg of product.
6. EPA Source Classification Code
None assigned.
7. References
1) Anello, L. G., and Cunningham, W. J., U.S. Patent 3,356,746
(1967).
2) Case, L. C., and Yan, T-Y, U.S. Patent 3,314,987 (1967).
61
-------
to
SilverN
Perfluoro-'
Carboxylate
FIGURE 11. FLOWSHEET FOR THE PRODUCTION OF
PERFLUOROALKYL IODIDES
-------
FLUOROCARBON PRODUCTION PROCESS NUMBER 19
Preparation of Perfluoroalkyl Iodides
1. Function
To convert perfluoroearbbxylic acids to perfluoroalkyl iodides.
The batch reaction involves careful heating of the dry silver
salt of a perfluorocarboxylic acid with iodine vapors according
to the following general equation:
Rf-COOAg + I2 > RfI + C02 + Agl
Any mono- or difunctional perfluorocarboxylic acid can be con-
verted in this manner, including trifluoroacetic and perfluoro-
heptanoic acids. This Hunsdieker reaction is usually carried
out in glass equipment on a small scale; steel should also be
satisfactory.
2. Input Materials
Assuming a typical average yield of 90% of the perfluoroalkyl
iodide from the perfluorocarboxylic acid, input materials (per
mole of product) consist of:
1.11 moles silver perfluorocarboxylate
1.44 moles of iodine (30% excess)
0.10-0.20 moles phosphorus pentoxide (desiccant)
3. Operating Parameters
The reaction is carried out at atmospheric pressure and at
1OO-160°C. A 3-Z. flask with adequate air and water-cooled
condensers is adequate to prepare one mole of the perfluoroalkyl
iodide.
4. Utilities
It is estimated that about 2 kcal/mole of heat is required,
usually electrical energy, to carry out this process. About
63
-------
10O 1. of cooling water per mole of product is needed. An
additional 5 kcal/mole of heat needs to be withdrawn from
the product prior to packaging.
5. Waste Streams
A small amount of phosphoric acid (or anhydride) will be dis-
charged from this process; the quantity depends upon the dryness
of the feed. This can be sent to a waste pond. One mole of
silver iodide is formed per mole of product. This is recovered
and recycled after appropriate treatment. Carbon dioxide
(1 mole/mole) is also evolved in the process.
6. EPA Source Classification Code
None established.
7. References
1) Hudlicky, M., "Chemistry of Organic Fluorine Compounds,"
The Macmillan Co., New York, 1962.
2) Crawford, G. H. , and Simons, J. H. , J. Amer. Chem. Soc.,
7£, 5737 (1953).
3) Banks, R. E., "Fluorocarbons and their Derivatives," Second
Edition, MacDonald Technical and Scientific, London, 1970.
64
-------
Ul
("Metallic!
[Fluoride]
Dehydro-
Chlorinator
FIGURE 12. FLOWSHEET FOR THE PRODUCTION OF FLUOROCARBONS
FROM ACETYLENE
-------
FLUOROCARBON PRODUCTION PROCESS NUMBER 20
HF Addition to Acetylene
1. Function
To convert unsaturated hydrocarbons into fluorohydrocarbons by
the chemical addition of HF. In this process, with the addition
of HF, acetylene is converted to vinyl fluoride which is then
further reacted to 1,1-difluoroethane according to the following
reaction:
CH=CH + HF * CH2=CHF + HF -> CH3CHF2
The hydrofluorination reaction is usually carried out in a vertical
tubular reactor with HF and HC=CH feed inlets at the base and
product outlet at the top. The tube is filled with a powdered
catalyst. The reactor may be made of stainless steel, Monel,
or high nickel alloys.
2. Input Materials
A mole ratio of hydrogen fluoride to acetylene of between one
and five is usually used, and the reaction is carried out in
the vapor phase. Approximately one volume of powdered cat-
alyst is required per 100 volumes per minute of gas passing
through the reactor. About half of the product is vinyl fluo-
ride and the other half is mainly 1,1-difluoroethane (based on
acetylene).
3. Operating Parameters
The vaporized feed is fed into the reactor at from 10 to 40OO
ml. of acetylene per gram of catalyst per hour. Preferably
the feed rate is approximately 10O volumes/volume of catalyst
per hour. Several catalysts are capable of speeding up the
reaction—these are usually metal fluorides, e.g., aluminum
fluoride. The catalyst is normally impregnated powdered
alumina. The feed rate is highly dependent upon the activ-
66
-------
ity of the catalyst. The reaction is normally carried out
at a temperature of 250 to 400°C and at a pressure of one
atmosphere or higher. It is estimated that a reactor
10 x 50 cm will produce about 200 g of product/hr.
4. Utilities
Assuming a production rate of 20O g of product/hr., about 2O
kcal. of heat energy are needed to heat the reactor. This is
usually accomplished either by electric heaters or molten
salt baths.
5. Waste Streams
The products from the reactor consisting of vinyl fluoride,
1,1-difluoroethane, and HF, along with small quantities of
acetylene, are sent to the next process (process 21) for sep-
aration. Depending upon the conditions under which this
process is operated, the lifetime and activity of the cat-
alyst is such that replacement is eventually needed. This
solid waste can be disposed of by burial. The only other
waste which should occur is due to leaks and spills.
6. EPA Source Classification Code
None established.
7. References
1) Christoph, F. J., et al. , U.S. Patent 3,178,484 (1965).
2) Petit, R., et al., U.S. Patent 3,187,060 (1965).
3) Clark, J. W., U.S. Patent 2,626,963 (1953).
4) Swamer, F. W., U.S. Patent 2,830,101 (195S).
67
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FLUOROCARBON PRODUCTION PROCESS NUMBER 21
Separation and Purification of
Fluorohydrocarbons from HF Addition
1. Function
To separate the crude products and starting materials from
the HP-addition process. In this process, vinyl fluoride,
1,1-difluoroethane and small quantities of the starting ma-
terials, acetylene and hydrogen fluoride, are separated by
distillation under pressures higher than atmospheric. Mate-
rials of construction will be Monel or nickel-clad steel.
2. Input Materials
An estimated 30% of the material entering this process is
vinyl fluoride, another 35% is 1,1-difluoroethane, the re-
mainder being hydrogen fluoride (30%) and acetylene (2%).
3. Operating Parameters
The operation of this process is usually closely integrated
with the preceding process, and flow rates will be dependent
upon the rate of production from process 20.
The gaseous materials entering this process are cooled and
compressed. After cooling to about 0°C under pressures of
up to 20 kg/cm2, the products are separated by distillation.
The desired products may be passed through a scrubber and
drier, if necessary, before being sent to storage. The
hydrogen fluoride and acetylene are recycled as feed to
the HF-addition process (process 2O).
4. Utilities
At a production rate of 200 g of product/hr. , about 75 kcal/kg
68
-------
of heat need to be withdrawn from the system. The compressor
will require approximately 5 kWh/kg of product.
5. Waste Streams
Small quantities of fluorohydrocarbons may be lost due to leaks
and spills. If the vinyl fluoride is scrubbed with 5% caustic
(NaOH), small quantities of aqueous NaF may be sent to waste
water. The quantity of NaF formed is highly dependent upon the
efficiency of the process at a particular location.
6. EPA Source Classification Code
None established.
7. References
1) Houben-Weyl "Methoden der Organischen Chemie", Vol. 5,
Part 3, Georg Thieme Verlag, Stuttgart, 1962, pp 8-14.
2) Air Reduction Co., Inc., British Patent 790,824 (1958).
69
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FLUOROCARBON PRODUCTION PROCESS NUMBER 22
Chlorination of lrl-Difluoroethane
1. Function
To convert 1,1-difluoroethane into l-chloro-l,l-difluoroethane
according to the following reaction:
CHF2-CH3 + C12 > CC1P2-CH3 + HC1
The reaction may be performed in a stainless steel, nickel,
or Monel reactor, usually tubular.
2. Input Materials
The feed materials are 1,1-difluoroethane and chlorine usually
two moles of the former to about one of the latter. This is
arranged to ensure complete reaction of the chlorine. A free-
radical initiator (usually O.1-O.2% by weight, based on the
amount of difluoroethane) is added in the feed. The HC1 gas
evolved may be forwarded to other plant uses or may be scrubbed
out with water or aqueous sodium hydroxide.
3. Operating Parameters
The mixture of difluoroethane, chlorine and catalyst is pre-
heated to 75-lOO°C, at which time free radical initiation
begins. An exothermic reaction ensues and the rate of feed
is such that the subsequent reaction temperature is maintained
between ISO and 2OO°C. Pressures of about 27-38 kg/cm2 are
normally used. The preferred residence time is from 2 to 8
seconds. The catalyst normally used is azo-bis-isobutyroni-
trile; however, any catalyst capable of forming free radicals
above room temperature should function as an initiator.
4. Utilities
Although the chlorination reactor can be cooled externally by
70
-------
water, it normally is not. No other utilities are usually
involved.
5. Waste Streams
If aqueous caustic is used to scrub the HC1 by-product, the
waste stream will consist of aqueous NaCl. If the gaseous
by-product is desired in other plant uses, it can be trans-
ferred as such.
6. EPA Source Classification Code
None established
7. References
Wolf, H. 0., U.S. Patent 3,047,642 (1962).
71
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FLUOROCARBON PRODUCTION PROCESS NUMBER 23
Dehydrochlorination of 1-Chloro-l.l-Difluoroethane
1. Function
To prepare vinylidene fluoride (CF2=CH2) by the pyrolytic re-
moval of hydrogen chloride from l-chloro-l,l-difluoroethane
according to the following reaction:
CC1F2-CH3 > CF2=CH2 + HC1
This vapor phase reaction is usually carried out, in the
absence of a catalyst, in a stainless steel or nickel heated
tube.
2. Input Materials
Normally, l-chloro-l,l-difluoroethane is the only feed material
to this process. The process gives high conversions and essen-
tially quantitative yields, i.e., one mole of feed produces one
mole of product. Water, or aqueous caustic (NaOH) may be used
to scrub out the hydrogen chloride eliminated during the reaction.
This requires 1 mole of NaOH per mole of product.
3. Operating Parameters
The optimum temperatures for dehydrohalogenation are 7OO-850°C.
The reaction is normally performed at atmospheric pressure or
slightly lower, with reaction times of less than 1 second and
at space velocities of 100 to 500 per hour.
4. Utilities
This endotheraiic reaction requires about 20 kcal/mole of feed.
The reactor tube can be heated with gas or electricity. If
water is used to scrub the products, 1 liter of water is re-
quired for every 10 moles of product. Compression and refrig-
eration are needed to package the vinylidene fluoride. An
72
-------
estimated 1 kWh/mole is required.
5. Waste Streams
If water is used for scrubbing, the aqueous (35%) hydrochloric
acid can be transferred to other plant uses. If 10% aqueous
caustic is used, the aqueous salt (NaCl) solution could be
disposed of in a waste pond. One liter of salt solution will
be formed for every 2.5 liters of vinylidene fluoride formed.
6. EPA Source Classification Code
3-O1-O11-02 BYPRODUCT W/SCRUB
)
7. References
1) Scherer, 0., et al. U.S. Patent 3,183,277 (1965).
2) Feasley, C. F., et al. U.S. Patent 2,627,529 (1953).
3) Miller, C. B., U.S. Patent 2,628,989 (1953).
73
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Heafc
Cooling
water
Fluoro
aromatic
Compounds
Chloro-
aromatic
Compound
Aromatic
Fluorination
FIGURE 13. FLOWSHEET FOR THE PRODUCTION OF
FLUOROAROMATIC COMPOUNDS
-------
FLUOROCARBON PRODUCTION
PROCESS NUMBER 24
Production of Fluoroaromatic Compounds
1. Function
To prepare fluorine-substituted benzenes, pyridines, pyrimidines,
etc. , by the action of a metal fluoride on the corresponding
chlorine-substituted benzene, etc. This rather recently de-
veloped process is being used to make limited amounts of the
fluoroaromatic compounds. Certain fluoroaromatics can be
made in glass equipment in a solvent; others are more commonly
made neat (without solvent) in pressurized stainless steel or
Monel vessels. Aromatic fluorine compounds have historically
been prepared by diazotization of amines in HF alone or with
complexing agents such as BF3 to form diazonium salts which
decompose to aromatic fluorine compounds
2. Input Materials
The following are typical of input materials together with
products obtained in this batch process.
Table 4. TYPICAL FLUOROAROMATIC COMPOUNDS AND INPUT MATERIALS
Feed Material
2-Chloropyridine
2,6-Dichloropyridine
2,4,6-Trichloropyrimidine
Nitrobenzene
1,3,5-Trichlorobenzene
Product (% yield)
2-Fluoropyridine (74)
2,6-Difluoropyridine (8O)
2,4,6-Trifluoropyrimidine (90)
+Chlorodifluoropyrimidine (9)
+Dichlorofluoropyrimidine (0.9)
3-Fluoronitrobenzene
+2-Fluoroni trobenzene
44-Fluoronitrobenzene
3,5-Dichlorofluorobenzene (54.5)
3,5-Difluorochlorobenzene (47.7)
1,3,5-Trifluorobenzene (56.2)
75
-------
CsF or KF may be used as the fluorinating agent depending
upon the substrate being fluorinated. Usually an 8-10% excess
of the fluorinating agent is used.
3. Operating Parameters
When the process is performed in a solvent, the reaction is
carried out at about 100-200*0 at atmospheric pressure. When
performed neat, the temperatures are about 30O-40O°C and the
pressures 20-25 kg/cm2.
4. Utilities
It is estimated that the heat required per mole of product is
10 kcal. This may be in the form of electrical or gas heat.
About 10O 4» of cooling water will be required per mole of
product.
5. Waste Streams
For each mole of chlorine atoms replaced, there will be one
mole of KC1 formed. This can be discharged to a waste pond.
The solvent, when used, can be recycled or discharged to a
waste pond.
6. EPA Source Classification Code
None assigned.
7. References
1) Boudakian, M. M., J. Hetero. Chem., 5, 683 (1968).
2) Boudakian, M. M., U.S. Patent 3,296,269 (1967).
3) Boudakian, M. M., U.S. Patent 3,280,124 (1966).
4) Boudakian, M. M., and Kaufman, C. W., U.S. Patent 3,314,955 (1967!
5) Shiley, R. H., Dickerson, D. R., and Finger, G. C., J.
Fluorine Chem., 2, 19 (1972); I, 415 (1971); 4, 111 (1974);
3, 113 (1973).
76
-------
6) Pavlath, A.E. and Leffler, A.L., "Aromatic Fluorine
Compounds", ACS monograph No. 155, Reinhold, New York,
1962.
HF PRODUCTION PROCESSES
Hydrogen fluoride, important as the principal fluorinating agent,
is obtained by treating acid grade fluorspar (CaF2) with sulfuric
acid. The impure fluorspar is mined and beneficiated to obtain
material of adequate purity for use in producing fluorocarbons.
Process flowsheets and process descriptions for this segment of
the industry follow. Table 5 lists the processes involved in the
production of HF.
77
-------
Table 5. PROCESSES FOR HF PRODUCTION
25. Mining of Fluorspar
26. Fluorspar Beneficiation
27. Agglomeration of Fluorspar
28. Hydrogen Fluoride Generation
29. Hydrogen Fluoride Purification
78
-------
Heat
Mining
Ferrosilicon
Flotation
Agents
FIGURE 14. FLOWSHEET FOR THE PRODUCTION OF FLUORSPAR
-------
HF PRODUCTION PROCESS NUMBER 25
Mining of Fluorspar
1. Function
To obtain the mineral from the solid ore deposits found in
beds or veins in the earth. The mining is done by metal
mining practices, usually by top-slicing, cut-and-fill, and
shrinkage and open stoppage. Bedded deposits are usually
worked by the room-and-pillar system. Mining is done by
shafts, drifts, and open cuts.
2. Input Materials
Essentially none are required other than the utilities and
services required to support the personnel and equipment.
3. Operating Parameters
Mines range in size from small operations with mostly hand
operated equipment to large operations using extensively
mechanized equipment.
4. Utilities
Large quantities of air are required to support personnel
and mechanized equipment. Small quantities of electricity
are used for motors, lights, etc., but no large quantities
are required in mining fluorspar. Amounts of water used
will vary considerably from mine to mine, depending upon
the operations involved.
5. Waste Streams
Airborne fugitive dust of the same composition as the ore
being mined is emitted in mining. Water from subsurface
mining operations is usually contaminated with finely
crushed rock as well as with oil, hydraulic fluid, gasoline,
and other materials commonly used in underground operations.
80
-------
6. EPA Source Classification
None established.
7. Bibliography
1) Kirk-Othmer, Encyclopedia of Chemical Technology,
John Wiley & Sons, Inc., New York, 1966.
2) Malhotra, Ramesh, Illinois Minerals Note 58, Illinois
State Geological Survey, Urbana, Illinois, Oct. 1974.
81
-------
HF PRODUCTION PROCESS NUMBER 26
Fluorspar Beneficiation
1. Function
To remove rocks and clays from the desired ore so that the
crude ore may be purified. This is usually accomplished
by one or more of the following procedures, depending upon
the purity of the mined fluorspar.
(a) Washing. The raw ore is subjected to water sprays
as it travels up the log pulper, to remove the
associated clays.
(b) Heavy Media Separation. The ore minerals are sep-
arated from waste in a cone containing a suspension
of finely ground ferrosilicon. The ratio of ferro-
silicon to water is adjusted to give the suspension
a specific gravity of about 2.6 at the top of the
cone and about 2.9 at the bottom. Crude ore is
introduced at the top of the cone. Heavy minerals,
such as fluorspar and metal sulfides, and sink are
recovered at the bottom of the cone. Light minerals
float and are carried away with the overflow. Ferro-
silicon is recovered magnetically and returned to the
process.
(c) Crushing and Screening. The ore is fed through a
crushing system for reduction to the desired fine-
ness. Metallurgical grades require sizes between
0.95 and 3.8 cm. If the raw ore is of metallurgical
grade, it is crushed and screened to the proper size
with no previous refinement. To produce acid grade
fluorspar, the crushed ore is fed to a ball mill
which reduces the size to between 35 and 200 mesh.
(d) Flotation. Further purification is achieved by
82
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treating the ore minerals in flotation units by use
of agitated water baths to which are added frothing
agents and flotation reagents to selectively coat
the minerals. The sequence of reagents and flota-
tion procedures varies according to the composition
of the ore and preferences of the mill operator.
Typical reagents are xanthates, acids, or sulfates.
(e) Filter and Drier. The "pulp" from the flotation
cells usually contains from 20 to 40 percent solids.
The concentration is increased to about 6O% solids
in a thickener and the resultant mixture filtered.
The filter cake is further dried to less than 0.5
percent water in a rotary drier at about 25O°C.
(f) Grinding. The fluorspar is ground to a minus 325
mesh after which it is transported to storage bins
or enclosed hopper cars.
2. Input Materials
The primary feed to this process is the raw ore as mined
from the ground. Water is required in washing the crude
ore, in heavy media separation, and in the flotation
steps. The quantity of water required will depend upon
how many of these steps are used in the beneficiation
process. It also will depend upon the purity of the
fluorspar as mined. Small quantities of flotation agents
are also required.
3. Operating Parameters
The bulk of the operations is carried out at ambient
temperature and pressure. However, steam is required
to keep the flotation cells at about 38°C.
4. Utilities
Small quantities of steam are required as indicated above.
83
-------
Quantities of electricity are required to operate the var-
ious motors, pumps, etc. It is estimated that from 10 to
50 kWh of electrical energy is required per metric ton of
product. Oil or gas fired driers are required. This is
estimated to require 5O,OOO kcal per metric ton. An esti-
mated 8,000 - 10,000 liters of water are required per
metric ton of fluorspar.
5. Waste Streams
Aqueous effluents from washing and separation contain
suspended solids which are usually sent to settling ponds.
Tailings from the flotation operation contain both solids
and the flotation agents. The latter materials are not
necessarily toxic but cause excessive growth of algae and
bacteria. Air emissions in the form of dust may occur;
however, these are usually kept to a minimum since the ore
is usually maintained in a wet condition. Drying and
grinding of the purified ore present particle emission
problems as well as aqueous and flotation agent emissions.
6. EPA Source Classification Code
None established.
7. References
1) Kirk-Othmer, Encyclopedia of Chemical Technology,
New York, John Wiley & Sons, Inc., 1966.
2) West, L. and R. R. Walden, Milling Kentucky Fluorspar
Tailings, Mining Engineering, 542-544, May 1954.
3) Maier, F. J. and E. Bellack, Fluorspar for Fluorida-
tion, Journal of the American Water Works Association,
January 1957.
34
-------
HF PRODUCTION PROCESS NUMBER 27
Agglomeration of Fluorspar
1. Function
To recover fine grained flotation concentrates of metal-
lurgical quality and to convert them into weatherproof
dust-free pellets. The dry powder is mixed with a bind-
er solution, pelletized, and dried. The pellets with-
stand outdoor exposure, including freezing and thawing
and show less dusting than natural gravel spar when ex-
posed to thermal shock in the steel furnace.
2. Input Materials
Feed to this process consists of metallurgical grade
fluorspar fines in dry form along with a binder solution
of sodium silicate and an undisclosed additive. The
mass is pelletized in a 2.44-meter diameter rotating disc-
type pelletizer, and the "green" pellets are fed into a
long Porbeck baking oven where they are dried.
3. Operating Parameters
The "green" pellets are subjected to temperatures of 370-
40O°C for 20-30 minutes.
4. Utilities
An estimated 25,OOO kcal of heat (oil or gas fired) per
metric ton of finished metallurgical grade pellets is
required. Approximately 5-10 kWh of electricity are re-
quired/metric ton.
5. Waste Streams
The main emission source in this operation is from the
baking oven and consists of vapors from the binder
solution.
85
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6. EPA Source Classification
None established
7. References
1) Hall, W. E., and Heyl, A. V., Economic Geology, 63,
[6], 655 (1968).
2) Maier, F. J., and Bellack, E., Fluorspar for Fluori-
dation. Journal of the American Water Works Associ-
ation, 49, 41 (1957).
86
-------
00
Heat—-i
HF Generator
(kiln) 28
HF
Purifier 2g
FIGURE 15. FLOWSHEET FOR THE PRODUCTION OF HYDROGEN FLUORIDE
-------
HF PRODUCTION PROCESS NUMBER 28
Hydrogen Fluoride Generation
1. Function
To convert the mineral fluorspar (CaF2) into hydrogen fluoride
(HF). Finely ground acid grade fluorspar (? 97% CaF2) is
treated with concentrated sulfuric acid in a heated rotating
steel kiln. The product is formed according to the following
reaction:
CaF2 + H2S04 > CaS04 + 2 HF
The anhydrous HF product is collected as a gas and later dis-
tilled to remove a small variety of foreign substances, e.g.,
compounds of silicon and sulfur (see process 29).
2. Input Materials
In the manufacture of hydrogen fluoride, about 2.4 metric
tons of finely ground acid grade fluorspar and 2.7 metric
tons of commercial 96-98% sulfuric acid (5-10% excess) are
used per metric ton of HF produced. Small quantities of
oleum are used to keep the concentration of H2S04 at the
96-98% level.
3. Operating Parameters
Since the reaction between sulfuric acid and fluorspar is
endothermic, heat is usually supplied externally by direct
fire to the rotary kiln. The reaction temperature is kept
at 200to250°C. Under these conditions, the reaction time
is 30 to 60 minutes. A kiln 2 m x 4 m should produce about
20O kg. of hydrogen fluoride per hour. The overall yield
of HF is about 90% based on fluorspar; and 80% based on
H2S04.
88
-------
4. Utilities
Assuming a production rate of 2OO kg. of HF per hour, an
estimated 12O,OOO kcal./hr. of heat are required.
5. Waste Streams
The by-product from the HF production is calcium sulfate
(CaS04). This is removed from the rotating kiln, at the
end opposite the feed, via an air-lock screw drive and
fed into water. This by-product can be neutralized with
lime and is frequently discarded (ground burial) although
it can be sold as gypsum or used in the manufacture of
cements. Assuming a production rate of 200 kg./hr. of HF,
about 775 kg./hr. of CaS04 are produced.
6. EPA Source Classification Code
3-01-012-O2 ROTRYKILN W/OSCRUB
7. References
1) Bradbury, J. C. , Finger, G. C., and Major, R. L.,
Fluorspar in Illinois, Illinois State Geological
Survey Circular 420, 1968, Urbana, Illinois.
2) Encyclopedia of Technology, Kirk-Othmer 2nd Edition,
Vol. 9, Interscience Publishers, New York, 1966
pp 610-625.
89
-------
HF PRODUCTION PROCESS NUMBER 29
Hydrogen Fluoride Purification
1. Function
In this process crude HF is purified by a series of sorption,
desorption and distillation steps which utilize sulfuric
acid (H0SO J . The volatile impurities are separated by these
Jt 4
steps and the impure HF is recovered from the H2S04 as >99%
pure HF. The towers and distillation apparatus needed to
accomplish this can be made of steel.
2. Input Materials
The feed materials to this process are composed primarily of
hydrogen fluoride, with small quantities of S02, SiF4, CO2,
H2S04, and H20. The feed entering this process from the kiln
(process 28) is composed of about 95% HF, 4% air and 1% of the
above impurities. Further downstream weak sulfuric acid is fed
countercurrent to the main flow and acts as an absorbent for
the hydrogen fluoride.
3. Operating Parameters
The product from the kiln is fed into this process at about
15O°C where it is cooled with condensers to liquefy the HF.
The cooled gases are passed into the H2SO4 scrubber and the
HF and H2O are absorbed into this solvent. The H0SO con-
• 24
taining the HF is subjected to warming for removal by dis-
tillation of the >99% pure KF; the water remains behind
with the H2S04.
4. Utilities
Since the product gases entering this process are at temper-
atures of about 150°C, they need only be cooled to condense
90
-------
the hydrogen fluoride (b.p. 19°C). Cooling water must remove
about 375,000 kcal. of heat per metric ton of hydrogen fluo-
ride produced.
5. Waste Streams
Gaseous HF and SiF4 are scrubbed out of the vent gases with
water to form H2SiF4, which is marketed as a 3O-35% solution.
A gaseous effluent of S02 and C02 is vented to the air. The
amounts of these gases which are vented will vary with the
purity of the fluorspar used in process 28, but probably
amount to less than 1O kg per metric ton of HF produced.
6. EPA Source Classification
3-01-012-01 ROTRYKILN W/SCRUB
7. References
1) Finger, G. C., Risser, H. E., and Bradbury, J, C.,
"Illinois Fluorspar," Illinois State Geological
Survey Circular 296, 1960.
2) Kirk-Othmer, Encyclopedia of Chemical Technology,
2nd Edition, Vol. 9, Interscience Publishers, New York,
1966, pp 61O-625.
91
-------
APPENDIX A
RAW MATERIALS
93
-------
Table A-l. LIST OF RAW MATERIALS
acetic anhydride
acetyl fluoride
acetylene
antimony pentachloride
antimony trichloride
aromatic chlorocarbons, unspecified
bromine
carbon dioxide
carbon tetrabromide
carbon tetrachloride
chlorine
chloroform
dimethyl ether
ferrosilicon
fluorspar, 2= 97% CaF2
flotation agents, unspecified
hexanes
hexachloroacetone
hexachlorobutadiene
hydrocarbons, unspecified
hydrogen
hydrogen fluoride
iodine
methylene chloride
methyl sulfonyl fluoride
phosphorus pentoxide
potassium bifluoride
potassium fluoride
potassium permanganate
pyridine compounds, unspecified
pyrimidine compounds, unspecified
sodium fluoride
sodium hydroxide
sodium silicate
sulfuric acid
tetrachloroethylene
trichloroethylene
tri-n-butylamine
- 94
-------
APPENDIX B
PRODUCTS AND BY-PRODUCTS
95
-------
Table B-l. LIST OF PRODUCTS AND BY-PRODUCTS
bromotrifluoromethane
calcium sulfate
carbon dioxide
l-chloro-l,l-difluoroethane
chlorodifluoromethane
chloropentafluoroethane
chlorotrifluoroethylene
chlorotrifluoromethane
decafluorobutane
dibromodifluoromethane
1,2-dibromohexafluoropropane
1,2-dibromotetrafluoroethane
1,2-dichloro-1,1-difluoroethane
1,2-dichloro-1,2-difluoroe thane
l,l-dichloro-2,2-difluoroethylene
1,2-dichloro-1,2-difluoroethylene
dichlorodifluoromethane
1,2-dichlorofluoroethane
dichlorofluoromethane
1,2-dichlorohexafluoropropane
1,2-dichlorotetrafluoroethane
1,1-difluoroethane
1,1-difluoroethylene
difluoromethane
difluoromethyl trifluoromethyl ether
fluoroethylene
fluorinated aromatic compounds, unspecified
fluorinated heterocyclic compounds, unspecified
fluosilicic acid
hexafluoroacetone
hexafluoroacetone, sesquihydrate
hexafluoroacetylacetone
hexafluorobutyne-2
hexafluorocyclobutene
hexafluoroe thane
96
-------
Table B-l (Continued). LIST OF PRODUCTS AND BY-PRODUCTS
hexafluoroisopropanol
hexafluoropropylene
hydrogen bromide
hydrogen chloride, anhydrous
hydrochloric acid
1-iodoperfluorohexane
manganese dioxide
octafluorobutene-2
octafluorocyclobutane
octafluoropropane
pentafluoroethane
phosphoric acid
silicon tetrafluoride
silver iodide
sodium fluoride
sulfur dioxide
1,1,1,2-tetrachloro-2,2-difluoroethane
1,1,2,2-tetrachloro-l,2-difluoroethane
1,1,1,3-te trachlorotetraf luoropropane
1,1,2,2-tetrafluoroethane
tetrafluoroethylene
tetrafluorome thane
trichlorofluoromethane
2,2,3-trichloroheptafluorobutane
1,1,2-trichloro-1,2,2-trifluoroethane
1,1,1-trichloro-2,2,2-trifluoroethane
1,1,1-trichloropentafluoropropane
trifluoroacetic acid
trifluoroacetic anhydride
1,1,1-trifluoroethane
1,2,2-trifluoroethane
trifluoroethanol
trifluoroethylene
trifluoroethyl vinyl ether
trifluoromethane
bis(trifluoromethy1) ether
trifluoromethyl iodide
97
-------
APPENDIX C
PRODUCERS AND PRODUCTS
99
-------
Table C-l. COMPANY/PRODUCT LIST
Bromotrifluoromethane (CBrF3)
Du Pont
l-Chloro-l,l-difluoroethane (CC1F2-CH3)
Allied
Du Pont
Pennwalt
Chlorodifluoromethane (CHC1F2) (FC-22)
Allied
Du Pont
Pennwalt
Union Carbide
Kaiser
Racon
Chioropentafluorbethane (CC1F2-CF3) (FC-115)
Allied
Du Pont
Chlorotrifluoroethylene (CC1F=CF2)
Allied
Hooker
3 M
Chlorotrifluoromethane (CC1F3) (FC-13)
Allied
Du Pont
Pennwalt
Decafluorobutane (C4F10)
Phillips!
Dibromodifluoromethane (CBr_F2)
Du Pont
PCR2
1,2-Dibromohexafluoropropane (CBrF2-CBrF-CF3)
Du Pont3
100
-------
Table C-l (Continued). COMPANY/PRODUCT LIST
1,2-Dibromotetrafluoroethane (CBrF2-CBrF2)
Du Pont
1,2-Dichloro-l,1-difluoroethane (CC1F2-CH2C1)
Phillips l
1,2-Dichloro-l,2-difluoroethane (CHC1F-CHC1F)
Phillips1
PCR
l,l-Dichloro-2,2-difluoroethylene (CC12=CF2)
Allied
PCR
1,2-Dichloro-l,2-difluoroethylene (CC1F=CC1F)
Allied
PCR
Dichlorodifluoromethane (CC12F2) (FC-12)
Allied
Du Pont
Kaiser
Pennwalt
Racon
Union Carbide
1,2-Dichlorofluoroethane (CHC1F-CH2C1)
Phillips1
Dichlorofluoromethane (CHC12F) (FC-21)
Allied
Du Pont
1,2-Dichlorohexafluoropropane (CC1F2-CC1F-CF3)
Du Pont3
1Q1
-------
Table C-l (Continued). COMPANY/PRODUCT LIST
1,2-Dichlorotetrafluoroethane (CC1F2-CC1F2) (FC-114)
Allied
Du Pont
Union Carbide4
Pennwalt1*
1,1-Difluoroethane (CHF2-CH3)
Allied
Du Pont
1,1-Difluoroethylene (CF2=CH2) (Vinylidene fluoride)
Allied
Du Pont
Difluoromethyl trifluoromethyl ether (CHF2-0-CF3)
Phillips1
Fluoroethylene (CHF=CH2) (Vinyl fluoride)
Du Pont
Fluorinated Aromatic Chemicals (unspecified)
Olin
Fluorinated Heterocyclic Chemicals (unspecified)
Olin
Hexafluoroacetone (CF3-CO-CF3)
Allied5
Du Pont
Matheson5
PCR5
Phillips1
102.
-------
Table C-l (Continued). COMPANY/PRODUCT LIST
Hexafluoroacetone, sesquihydrate (CF3-CO-CF3 • 1% H20)
Du Pont
Hexafluoroacetylacetone (CF3-CO-CH2-CO-CF3)
PCR
Hexafluorobutyne-2 (CF3-C=C-CF3)
PCR
Hexaf luorocyclobutene ( [pjj)
PCR
Hexafluoroethane (CF3-CF3) (FC-116)
Du Pont
Hexafluoroisopropanol (CF3-CHOH-CF3)
Du Pont
Hexafluoropropylene (CF3-CF-CF2)
Du Pont
PCR5
1- lodoperfluorohexane (CF2I-CF 2-CF2-CF2-CF2-CF 3)
Du Pont
Thiokol
Octafluorobutene-2 (CF 3-CF=CF-CF 3)
Halocarbon 5
Octafluoroeyclobutane ( {?]) (FC-C318)
Du Pont3
Phillips1
103
-------
Table C-l (Continued). COMPANY/PRODUCT LIST
Octafluoropropane (CF3-CF2-CF3)
Phillips1
Pentafluoroethane (CHF2-CF3)
PCR
Phillips1
1,1,1,2-Tetrachloro-2,2-difluoroethane (CC13-CC1F2)
Allied5
Du Pont5
l,l,2,2-Tetrachloro-l,2-difluoroethane (CC12F-CC12F) (FC-112)
Allied5
Du Pont5
Union Carbide1*
1,1,1,3-Tetrachlorotetrafluoropropane (CC13-CF2-CC1F2)
Du Pont3
1,1,2,1-Tetrafluoroethane (CHF2-CHF2)
Phillips1
Tetrafluoroethylene (CF2=CF2)
Du Pont
Pennwalt5
Thiokol5
Tetrafluoromethane (CFO (FC-14)
Du Pont
Trichlorofluoromethane (CC13F) (FC-11)
Allied
Du Pont
Pennwalt
Union Carbide
1Q4
-------
Table C-l (Continued). COMPANY/PRODUCT LIST
2,2,3-Trichloroheptafluorobutane (CF3-CC12-CC1F-CF3)
Halocarbon Products5
1,1,2-Trichloro-l,2,2-trifluoroethane (CC12F-CC1F2) (FC-113)
Allied
Du Pont
Kaiser
Pennwalt
Racon
Union Carbide
1,1,l-Trichloro-2,2,2-trifluoroethane (CC13CF3)
Allied6
Du Pont6
PCR"
1,1,1-Trichloropentafluoropropane (CC13-CF2-CF3)
Du Pont3
Trifluoroacetic Acid (CF3COOH)
Halocarbon Products
Phillips1
Trifluoroacetic Anhydride (CF3CO-0-CO-CF3)
Halocarbon Products
1,1,1-Trifluoroethane (CF3-CH3)
Phillips1
1,2,2-Trifluoroethane (CH2F-CHF2)
Phillips1
1Q5
-------
Table C-l (Continued). COMPANY/PRODUCT LIST
Trifluoroethanol (CF3CH2OH)
Halocarbon Products
Trifluoroethylene (CHF=CF2)
PCR
Trifluoroethyl vinyl ether (CF3-CH2-0-CH=CH2)
Airco, Inc.
Trifluoromethane (CHF3) (FC-23)
Allied
Du Pont
bis(Trifluoromethyl) ether (CF3-0-CF3)
Phillips1
Trifluoromethyl iodide (CF3I)
PCR
1) Pilot plant only - now discontinued.
2) Possible distributor only.
3) Not currently in production - telecon.
4) Probable producer not listed in 1976 DCP.
5) Possibly not in current production.
6) Not made as a pure product.
106
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Table C-2. PRODUCERS OF FLUOROCARBONS
Company Annual Capacity (millions of kg)
E. I. du Pont de Nemours & Co.
Organic Chemicals Department
Freon Products Division
Antioch, California
Deepwater, New Jersey
East Chicago, Indiana > 230
Louisville, Kentucky
Montague, Michigan
Allied Chemical Corporation
Specialty Chemicals Division
Baton Rouge, Louisiana
Danville, Illinois
Elizabeth, New Jersey
El Segundo, California -
Union Carbide Corporation
Chemicals and Plastics Dlv.
Institute & South Charleston,
West Virginia 70
Pennwalt Corporation
Chemical Division
Calvert City, Kentucky •! 53
Thorofare, New Jersey J
Kaiser Aluminum & Chemical Corp.
Kaiser Chemicals Division
Gramercy, Louisiana 23
Racon Incorporated
Wichita, Kansas 9
107
-------
Table C-3. SPECIALITY FLUOROCHEMICALS LIST
Airco, Inc.
Ohio Medicap Products Division
Cleveland, Ohio
Halocarbon Products Corporation
82 Burlews Court
Hackensack, New Jersey 07601
Hooker Chemical Corporation
Specialty Chemicals Division
Niagara Falls, New York 14302
Matheson Gas Products
Post Office Box E.
Lyndhurst, New Jersey 07071
3 M Company
Commercial Chemicals Division
3 M Center
Saint Paul, Minnesota, 55101
01in Corporation
12O Long Ridge Road
Stamford, Connecticut 06904
* Phillips Petroleum Company
Chemical Dept./Commercial Development Division
Bartlesville, Oklahoma 74004
PCR, Inc.
Gainesville, Florida
Thiokol Chemical Corporation
P. 0. Box 1296
Trenton, New Jersey 08607
^Produced on a pilot plant basis only - subsequently dis-
continued
108
-------
Table C-4. PRODUCERS OF HYDROGEN FLUORIDE
Company
Allied Chemical Corporation
Industrial Chemicals Division
Baton Rouge, Louisiana
Geismar, Louisiana
Nitro, West Virginia
North Claymont, Delaware
Pittsburg, California
Annual Capacity (metric tons)
98,000
E. I. du Pont de Nemours & Co., Inc.
Biochemicals Department
LaPorte, Texas
91,000
Aluminum Company of America
Point Comfort, Texas
50,000
Kaiser Aluminum & Chemical Corporation
Kaiser Chemicals Division
Grammercy, Louisiana
45,000
Pennwalt Corporation
Chemical Division
Calvert City, Kentucky
23,OOO
Stauffer Chemical Company
Industrial Chemical Division
Greens Bayou, Texas
16,OOO
Kewanee Oil Company
Harshaw Chemical Company, Division
Industrial Chemicals Department
Cleveland, Ohio
16,OOO
109
-------
Table C-4 (Continued). PRODUCERS OF HYDROGEN FLUORIDE
Olin Corporation
Industrial Products and Services Division
Joliet, Illinois 12,OOO
Essex Chemical Corporation
Chemicals Division
Pausboro, New Jersey 10,000
Lehigh Valley Chemical Company
Glendon, Pennsylvania 4,000
Total 361,000
Source: Chemical Marketing Reporter 7/15/73 p. 1.
110
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TECHNICAL REPORT DATA
(Please read luatniciions on the reverse before completing)
RfcPORT NO.
EPA-600/2-77-023P
2.
1. TITLE AND SUBTITLE
Industrial Process Profiles for Environmental Use:
Chapter l6. The Fluorocarbon - Hydrogen Floride
Industry
3. RECIPIENT'S ACCESSION-NO.
5. REPORT DATE
February 1977
6. PERFORMING ORGANIZATION CODE
•». AUTHOR(S)
H. E. Doorenbus (Dow Chemical)
Terry Parsons, Editor
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
8500 Shoal Creek Boulevard
P.O. Bo:-: 99^8
Austin. Texas 78766
10. PROGRAM ELEMENT NO.
1AB015
11. CONTRACT/GRANT NO.
68-02-1319, Task'
12, SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. ENVIRONMENTAL PROTECTION AGENCY
Cincinnati, Ohio 1*5268
13. TYPE OF REPORT AND PERIOD COVERED
_Ini1I al: 8/75-11/76
TiT'SPONSORING AGENCY CODE
EPA/600/12
16. SUPPLEMENTARY NOTES
16. ABSTRACT
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 materials of the fluorocarbon-hydrogen fluoride industry consist pri-
marily of chemically and thermally stable organofluoro compounds which generally
have nontoxic and nonflammable qualities. The industry is discussed in two segments:
(l) Fluorocarbon Production and (2) Hydrogen Fluoride Production. One chemical
tree, fourteen process flow sheets and twenty-nine process descriptions have been
prepared to characterize the industry. Within each process description available
data have been presented on input materials, operating parameters, utility require-
ments and waste streams. Data related to the subject matter, including company,
product and raw material dataware included as appendices.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Pollution
Fluorocarbon
Hydrogen Fluoride
Organofluro Compounds
Fluorocarbon Production
Hydrogen Fluoride Production
Process Description
1«. DISTRIBUTION GT ATtMLN C
Release to Public
b.lDENTIFIERS/OPEN ENDED TERMS
Air Pollution Control
Water Pollution Control
Solid Waste Control
Stationary Sources
Fluoride Compound Industry
19. SECURITY CLASS (IliisHepon)
Unclassified
aoTsfccurirf Y "CLASS (Tins pan'-')
Unclassified
COSATI I-'ield.'Group
07B
07C
13B
21. NO..OF PAGES
119
'21. PRICE
EPA Form 2220-1 (9-73)
11.1
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