US2631170A - Process for the preparation of fluorocarbons - Google Patents
Process for the preparation of fluorocarbons Download PDFInfo
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- US2631170A US2631170A US475852A US47585243A US2631170A US 2631170 A US2631170 A US 2631170A US 475852 A US475852 A US 475852A US 47585243 A US47585243 A US 47585243A US 2631170 A US2631170 A US 2631170A
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- fluorocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
Definitions
- This invention relates to the preparation of fiuorocarbons and more particularly to a method of preparing fiuorocarbons by the reaction between hydrocarbons and metal fluorides.
- One object of this invention resides in the provision of an improved process of producing fiuorocarbons in a relatively simple, economical and commercially feasible manner.
- a further object resides in the provision of such a method characterized by the fact that fiuorination of hydrocarbon compounds will take place in the absence of a catalytic agent.
- a still further object resides in the production of new and hitherto unknown fiuorocarbons.
- the invention contemplates the passage of a hydrocarbon vapor over, through, 01 in intimate association with a metal fiuorideof higher than normal fluorine constituency; as for example, cobalt trifiuoride (Jo-F3; silver difiuoride AgFz, or manganese trifiuoride MnFs.
- a metal fiuorideof higher than normal fluorine constituency as for example, cobalt trifiuoride (Jo-F3; silver difiuoride AgFz, or manganese trifiuoride MnFs.
- hydrocarbon as used hereinafter shall be construed to include all hydrocarbons, i. e., olefinic, paraffinic, aroma-tic, naphthenic, etc.
- Any desired hydrocarbon in vaporized form may be used, for example, heptane C'1H1s, hexane CsHm, cyclohexane Cal-I12, toluene CvHa, xylene CaH1o, mesitylene C9H12, octane, or any iso-octane CsHis.
- the single figure comprises a schematic flow sheet.
- Cobalt chloride hexahydrate CC12-6H2O is dehydrated in any suitable manner to the anhydrous form (C0012) and subjected to the action of anhydrous hydrogen fluoride, HF, forming the known cobalt difiuoride COFz according to the reaction:
- cobalt difiuoride may be converted to the trifiuoride by direct fiuorination, at any suitable elevated temperature above approximately 150 C. according to the reaction:
- Such a receptacle may take the form of a syum der having a series of electrical or other heating elements positioned thereabout. It has been discovered that it the temperature of such a recep'ta'cle is graduated progressively from the in let end to the outletthrough a range of approx: imately C. to 400 'C. a relatively higher yield of the desired fluorocarbon as will be discussed hereinafter, will result. t has also been found that the provision of suitable means for slowly rotating the cylinder axially win obviate channeling 'of the core upon the introduction of the organic compound. 7 I The cylinder may be partially or substantially entirely filled with Col and heated to the grade:- ated temperatures above. mentioned.
- CiHic is now passed into the chamber and reacts according to the following equation C'IHis-I32COF3 C7Fl6+ 16HF+ 32COFz
- a small culinary or an inert sweeping as such as nitrogen maybe introduced with the hydro carbon for the purpose or clearing the reaction chamber if desired.
- C7F1e and HF may be drawn from the reaction chamber together and subsequently separated in any desired manner as by fractional distillation, or condensing in a coo-ling chamber, following separation of the two liquid phases. Yields of fluorocarbons by the above method have exceeded seventy percent in quantity of the initial hydrocarbon input.
- the left hand vertical column indicates the ingredients, chemical and physical (i. e. agitation) embodied in the process.
- the center vertical column designated the reactions and the third vertical column the incidental resultants.
- the fiuorination of the lower metal fluoride and exposure of the higher fluoride to the hydrocarbon may be carried out in the same chamber in order to avoid shifting the fluoride, if a step by step process rather than the continuous chain process above described, is desired. In such case however, care must be taken thoroughly to cleanse the reaction vessel with an inert gas between operations.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
March 10, 1953 R. o. FOWLER 2,631,170
PROCESS FOR THE PREPARATION OF FLUOROCARBONS Filed Feb. 15, 1945 2 2 r 2 00 F F F (EXCESS) gii lonal L n a C0 F3 i HEAT E 00 F C H G7 H 32Gb F3 3200 F2 AGITATE 1 IG l6 HF HF 0 r HF INVENTOR. Robert D. Fowler Maw Patented Mar. 10, 1953 i itocsss ma irHE PREPARATION or FLUOROCARBONS Robert Dudley Fowler, Baltimore, Ma; assignor to the United States of America as represented by the United States Atomic Energy Commission Application February 13, 1943', Serial No; 475,852
. 3 Claims.
This invention relates to the preparation of fiuorocarbons and more particularly to a method of preparing fiuorocarbons by the reaction between hydrocarbons and metal fluorides.
One object of this invention resides in the provision of an improved process of producing fiuorocarbons in a relatively simple, economical and commercially feasible manner.
A further object resides in the provision of such a method characterized by the fact that fiuorination of hydrocarbon compounds will take place in the absence of a catalytic agent.
A still further object resides in the production of new and hitherto unknown fiuorocarbons.
Other objects will in part be obvious and in part be pointed out hereinafter. s
. In general, the invention contemplates the passage of a hydrocarbon vapor over, through, 01 in intimate association with a metal fiuorideof higher than normal fluorine constituency; as for example, cobalt trifiuoride (Jo-F3; silver difiuoride AgFz, or manganese trifiuoride MnFs.
The term hydrocarbon as used hereinafter shall be construed to include all hydrocarbons, i. e., olefinic, paraffinic, aroma-tic, naphthenic, etc.
Any desired hydrocarbon in vaporized form may be used, for example, heptane C'1H1s, hexane CsHm, cyclohexane Cal-I12, toluene CvHa, xylene CaH1o, mesitylene C9H12, octane, or any iso-octane CsHis.
Any suitable apparatus may be utilized for the carrying out of the process of this invention, a specific example of which will now be described in conjunction with the accompanying drawing wherein:
The single figure comprises a schematic flow sheet.
The specific embodiment now described contemplates the use of cobalt trifluoride, a product not at present commercially available :but which may be prepared as follows:
Cobalt chloride hexahydrate CC12-6H2O is dehydrated in any suitable manner to the anhydrous form (C0012) and subjected to the action of anhydrous hydrogen fluoride, HF, forming the known cobalt difiuoride COFz according to the reaction:
cobalt difiuoride may be converted to the trifiuoride by direct fiuorination, at any suitable elevated temperature above approximately 150 C. according to the reaction:
the anhydrous Com is now placed in a suitable receptacle. 7 V
Such a receptacle may take the form of a syum der having a series of electrical or other heating elements positioned thereabout. It has been discovered that it the temperature of such a recep'ta'cle is graduated progressively from the in let end to the outletthrough a range of approx: imately C. to 400 'C. a relatively higher yield of the desired fluorocarbon as will be discussed hereinafter, will result. t has also been found that the provision of suitable means for slowly rotating the cylinder axially win obviate channeling 'of the core upon the introduction of the organic compound. 7 I The cylinder may be partially or substantially entirely filled with Col and heated to the grade:- ated temperatures above. mentioned. it hydro carbon, CiHic is now passe into the chamber and reacts according to the following equation C'IHis-I32COF3 C7Fl6+ 16HF+ 32COFz A small culinary or an inert sweeping as such as nitrogen maybe introduced with the hydro carbon for the purpose or clearing the reaction chamber if desired.
Upon the completion of the reaction above mentioned C7F1e and HF may be drawn from the reaction chamber together and subsequently separated in any desired manner as by fractional distillation, or condensing in a coo-ling chamber, following separation of the two liquid phases. Yields of fluorocarbons by the above method have exceeded seventy percent in quantity of the initial hydrocarbon input.
Having reference now to the accompanying flow sheet the process will be readily understood. The left hand vertical column indicates the ingredients, chemical and physical (i. e. agitation) embodied in the process. The center vertical column designated the reactions and the third vertical column the incidental resultants.
It should here be pointed out that the COFz initially used suffers virtually no quantitative loss in the process and may be reutilized as frequently as feasible.
Additionally, if desired the fiuorination of the lower metal fluoride and exposure of the higher fluoride to the hydrocarbon may be carried out in the same chamber in order to avoid shifting the fluoride, if a step by step process rather than the continuous chain process above described, is desired. In such case however, care must be taken thoroughly to cleanse the reaction vessel with an inert gas between operations.
From the above it will be apparent that virtually any desired fluorocarbon may be produced by proper solution of ingredients to give a high yield of a resultant fluorocarbon. For example, exposure of COFa to an octane C8H18 or dodecahydrobiphenyl C12H22, will react according to the following equations:
As previously pointed out it will be understood that the use of other higher metal fluorides and other hydrocarbons will produce other fluorocarbons as may be desired.
Now from the foregoing, it will be seen that there is herein described a simple, economical and commercially practicable method for the production of fluorocarbons.
As many embodiments may be made of this inventive concept and as modifications may be made in the embodiments herein shown and described, it is to be understood that allmatter hereinbefore is to be interpreted merely as illus trative and not in a limiting sense.
I claim:
1. In the preparation of perfiuororganic compounds, the step of reacting a trifluoride selected from the group consisting of manganese trifiuoride and cobalt trifiuoride with a hydrocarbon vapor at a temperature between 150 C. and 400 C. until all of the hydrogen of said hydrocarbon has been replaced by fluorine.
2. In the preparation of perfluoro organic compounds, the step of reacting manganese trifiuoride with a hydrocarbon vapor at a temperature between 150 C. and 400 C. until all the hydrogen of said hydrocarbon has been replaced by fluorine.
3. In the preparation of perfiuoro organic compounds, the step of reacting cobalt trifiuoride with a hydrocarbon vapor at a temperature between 150 C. and 400 C. until all the hydrogen of said hydrocarbon has been replaced by fluroine.
ROBERT DUDLEY FOWLER.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number 7 Name Date 1,978,840 Henne Oct. 30, 1934 2,004,931 Daudt et al June 18, 1935 2,013,030 Calcott et al Sept. 3, 1935 2,090,772 Wiezevich Aug. 24, 1937 2,129,289 8011 Sept. 6, 1938 2,186,916 Wiezevich Jan. 9, 1940 2,307,773 Egloff Jan. 12, 1943 FOREIGN PATENTS Number Country Date 214,293 Great Britain Apr. 14, 1924 730,874 France Aug. 25, 1932 OTHER REFERENCES Mellor, Comprehensive Treatise on Inorganic and Theoretical Chemistry, vol. 14, pages 608-9.
Mellor, Comprehensive Treatise on Inorganic and Theoretical Chemistry, vol. 12, page 344.
Moissan, Comptes Rendus, vol. 130, page 627 (1900).
Ruff et al., Z. fiir Anorg. und Allg. Chemie, vol.183, p. 199 (1929).
Rufi et al., ibid., vol. 201, page 253 (1931).
Chemical Abstracts, vol. 26, page 1258 (1932). Abstract of article by End et al. in Z. fiir Anorg. und Allgem. Chemie, vol. 201, pages 245-58 (1931).
Ruff et al., Angewandte Chemie, vol. 47, page 480 (1934).
Rufi et al., Z. fiir Anorg. und Allg. Chemie, vol. 219, pp. 143-8 (1934).
Jockusch, Naturwissenschaften, vol. 22, page 561 (1934).
Simons et al., Jour. Am. Chem. Soc, vol. 59, p. 1407 (1937).
Chemical Abstracts," vol. 28, cols. 5770-1 (1934). Abstract of article by Ruff et al. in Angew. Chemie, vol. 47, p. 430 (1934).
Claims (1)
1. IN THE PREPARATION OF PERFLUOROGANIC COMPOUNDS, THE STEP OF REACTING A TRIFLUORIDE SELECTED FROM THE GROUP CONSISTING OF MANGANESE TRIFLUORIDE AND COBALT TRIFLUORIDE WITH A HYDROCARBON VAPOR AT A TEMPERATURE BETWEEN 150* C. AND 400* C. UNTIL ALL OF THE HYDROGEN OF SAID HYDROCARBON HAS BEEN REPLACED BY FLUORINE.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US475852A US2631170A (en) | 1943-02-13 | 1943-02-13 | Process for the preparation of fluorocarbons |
GB2027/44A GB791271A (en) | 1943-02-13 | 1944-02-03 | Process for the preparation of fluorocarbons |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US791271XA | 1943-02-13 | 1943-02-13 | |
US475852A US2631170A (en) | 1943-02-13 | 1943-02-13 | Process for the preparation of fluorocarbons |
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US2631170A true US2631170A (en) | 1953-03-10 |
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US475852A Expired - Lifetime US2631170A (en) | 1943-02-13 | 1943-02-13 | Process for the preparation of fluorocarbons |
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GB (1) | GB791271A (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4143079A (en) * | 1978-05-15 | 1979-03-06 | Suntech, Inc. | Novel process for production of perfluoro p-methane from pinene |
US4777304A (en) * | 1987-08-25 | 1988-10-11 | Air Products & Chemicals, Inc. | Perfluorinated butyl derivative compounds |
US4827053A (en) * | 1988-08-03 | 1989-05-02 | Air Products And Chemicals, Inc. | Perfluorinated Di-isopropylmethyl decalin |
US4849553A (en) * | 1988-08-03 | 1989-07-18 | Air Products And Chemicals, Inc. | Perfluorinated dibutyl derivatives compounds |
US4873315A (en) * | 1987-08-25 | 1989-10-10 | Air Products And Chemicals, Inc. | Perfluorinated propyl derivative compounds |
US4881682A (en) * | 1987-08-25 | 1989-11-21 | Air Products And Chemicals, Inc. | Vapor phase soldering with perfluorinated butyl derivative compounds |
US4956390A (en) * | 1987-08-25 | 1990-09-11 | Air Products And Chemicals, Inc. | Gas transport employing perfluorobutyldecalin |
US6252099B1 (en) | 1998-07-28 | 2001-06-26 | E. I. Du Pont De Nemours And Company | Fluorocarbon manufacturing process |
WO2001096265A1 (en) * | 2000-06-12 | 2001-12-20 | E. I. Du Pont Nemours And Company | Fluorocarbon manufacturing process |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0791201B2 (en) * | 1990-08-28 | 1995-10-04 | 工業技術院長 | Method for producing trifluorohydrocarbon compound |
KR100353491B1 (en) * | 2000-02-22 | 2002-09-19 | 울산화학주식회사 | Manufacturing method for perfluoroethane |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB214293A (en) * | 1922-12-14 | 1924-04-14 | Henry Thomas Tizard | Improvements in and relating to the halogenation of hydrocarbons and their derivatives |
FR730874A (en) * | 1930-07-23 | 1932-08-25 | Du Pont | Improvements in the manufacture of acyclic fluorinated hydrocarbons |
US1978840A (en) * | 1931-01-30 | 1934-10-30 | Gen Motors Corp | Method of manufacturing halofluoro hydrocarbons |
US2004931A (en) * | 1931-03-20 | 1935-06-18 | Kinetic Chemicals Inc | Fluorination of carbon compounds |
US2013030A (en) * | 1932-09-10 | 1935-09-03 | Du Pont | Production of organic fluorine compounds |
US2090772A (en) * | 1933-03-17 | 1937-08-24 | Standard Oil Dev Co | Fluorinated solvents and process for making the same |
US2129289A (en) * | 1934-04-21 | 1938-09-06 | Ig Farbenindustrie Ag | Manufacture of new fluorine compounds |
US2186916A (en) * | 1934-01-11 | 1940-01-09 | Standard Oil Dev Co | Fluorinated compound and method of producing same |
US2307773A (en) * | 1940-11-18 | 1943-01-12 | Universal Oil Prod Co | Treatment of hydrocarbons |
-
1943
- 1943-02-13 US US475852A patent/US2631170A/en not_active Expired - Lifetime
-
1944
- 1944-02-03 GB GB2027/44A patent/GB791271A/en not_active Expired
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB214293A (en) * | 1922-12-14 | 1924-04-14 | Henry Thomas Tizard | Improvements in and relating to the halogenation of hydrocarbons and their derivatives |
FR730874A (en) * | 1930-07-23 | 1932-08-25 | Du Pont | Improvements in the manufacture of acyclic fluorinated hydrocarbons |
US1978840A (en) * | 1931-01-30 | 1934-10-30 | Gen Motors Corp | Method of manufacturing halofluoro hydrocarbons |
US2004931A (en) * | 1931-03-20 | 1935-06-18 | Kinetic Chemicals Inc | Fluorination of carbon compounds |
US2013030A (en) * | 1932-09-10 | 1935-09-03 | Du Pont | Production of organic fluorine compounds |
US2090772A (en) * | 1933-03-17 | 1937-08-24 | Standard Oil Dev Co | Fluorinated solvents and process for making the same |
US2186916A (en) * | 1934-01-11 | 1940-01-09 | Standard Oil Dev Co | Fluorinated compound and method of producing same |
US2129289A (en) * | 1934-04-21 | 1938-09-06 | Ig Farbenindustrie Ag | Manufacture of new fluorine compounds |
US2307773A (en) * | 1940-11-18 | 1943-01-12 | Universal Oil Prod Co | Treatment of hydrocarbons |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4143079A (en) * | 1978-05-15 | 1979-03-06 | Suntech, Inc. | Novel process for production of perfluoro p-methane from pinene |
US4777304A (en) * | 1987-08-25 | 1988-10-11 | Air Products & Chemicals, Inc. | Perfluorinated butyl derivative compounds |
US4873315A (en) * | 1987-08-25 | 1989-10-10 | Air Products And Chemicals, Inc. | Perfluorinated propyl derivative compounds |
US4881682A (en) * | 1987-08-25 | 1989-11-21 | Air Products And Chemicals, Inc. | Vapor phase soldering with perfluorinated butyl derivative compounds |
US4956390A (en) * | 1987-08-25 | 1990-09-11 | Air Products And Chemicals, Inc. | Gas transport employing perfluorobutyldecalin |
US4827053A (en) * | 1988-08-03 | 1989-05-02 | Air Products And Chemicals, Inc. | Perfluorinated Di-isopropylmethyl decalin |
US4849553A (en) * | 1988-08-03 | 1989-07-18 | Air Products And Chemicals, Inc. | Perfluorinated dibutyl derivatives compounds |
US6252099B1 (en) | 1998-07-28 | 2001-06-26 | E. I. Du Pont De Nemours And Company | Fluorocarbon manufacturing process |
WO2001096265A1 (en) * | 2000-06-12 | 2001-12-20 | E. I. Du Pont Nemours And Company | Fluorocarbon manufacturing process |
Also Published As
Publication number | Publication date |
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GB791271A (en) | 1958-02-26 |
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