CA1117145A - Manufacture of halogenated compounds - Google Patents
Manufacture of halogenated compoundsInfo
- Publication number
- CA1117145A CA1117145A CA000311550A CA311550A CA1117145A CA 1117145 A CA1117145 A CA 1117145A CA 000311550 A CA000311550 A CA 000311550A CA 311550 A CA311550 A CA 311550A CA 1117145 A CA1117145 A CA 1117145A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- chromium
- hydrogen fluoride
- trifluoroethylene
- range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 150000001875 compounds Chemical class 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 11
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims abstract description 9
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 7
- 229910021563 chromium fluoride Inorganic materials 0.000 claims abstract description 3
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 15
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 3
- 238000003682 fluorination reaction Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000792 Monel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical class FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
1,1,1,2-tetrafluoroethane is manufactured by bringing trifluoroethylene into reaction with hydrogen fluoride in the vapour phase at elevated temperature in the presence of a chromium oxide or basic chromium fluoride hydrofluorination catalyst.
1,1,1,2-tetrafluoroethane is manufactured by bringing trifluoroethylene into reaction with hydrogen fluoride in the vapour phase at elevated temperature in the presence of a chromium oxide or basic chromium fluoride hydrofluorination catalyst.
Description
1. MD 29795 This invention relates to a process for the manufacture of 1,1,1,2-tetrafluoroethane.
According to the present invention there is provided a process for the manufacture of 1,1,1,2-tetrafluoroethane which comprises bringing intoreaction in the vapour phase at eleva~ed temperature trifluoroethylene with hydrogen fluoride in the presence of a hydrofluorination catalyst.
The catalyst may be supported or unsupported.
One very suitable catalyst is chromium oxide. The chromium o~ide catalyst may be activated by heating in an atmosphere such as nitrogen or air. Again the catalyst may comprise a basic chromium fluoride in which chromium is associated with oxygen and fluorine atoms. A particularly preferred catalyst is a chromium;oxide obtained by treating a chromium hydroxide paste with steam and calcined, suitably in air,as is more~ fully described and claimed in our UK Patent Specification 1 307 224. The catalyst of said UK Patent Specification may be given a pre-fluorination treatment~by passing hydrogen fluoride over the catalyst at 250C to 450C for at least 30 minutes~ The catalysts may be compressed into~
pellets and used in a fixed bed. Alternatively the catalyst of appropriate particle size may be used ~: .
i ' 11~7~l~5
According to the present invention there is provided a process for the manufacture of 1,1,1,2-tetrafluoroethane which comprises bringing intoreaction in the vapour phase at eleva~ed temperature trifluoroethylene with hydrogen fluoride in the presence of a hydrofluorination catalyst.
The catalyst may be supported or unsupported.
One very suitable catalyst is chromium oxide. The chromium o~ide catalyst may be activated by heating in an atmosphere such as nitrogen or air. Again the catalyst may comprise a basic chromium fluoride in which chromium is associated with oxygen and fluorine atoms. A particularly preferred catalyst is a chromium;oxide obtained by treating a chromium hydroxide paste with steam and calcined, suitably in air,as is more~ fully described and claimed in our UK Patent Specification 1 307 224. The catalyst of said UK Patent Specification may be given a pre-fluorination treatment~by passing hydrogen fluoride over the catalyst at 250C to 450C for at least 30 minutes~ The catalysts may be compressed into~
pellets and used in a fixed bed. Alternatively the catalyst of appropriate particle size may be used ~: .
i ' 11~7~l~5
2. MD 2g795 in a fluidised bed. In use the chromium oxide catalyst takes up variable amounts of fluorine and can be present in the form Oe complex mixtures of oxides oxyfluorides, hydroxy fluorides and fluorides of chromium.
Suitably 1 to 2 moles of hydrogen ~luoride is employed per mole of trifluoroethylene. Greater molar ratios of hydrogen fluoride to trifluoro-ethylene can be employed but too great a molar ratio is undesired as this makes the process less economic. It is preferred to employ a molar ratio of hydrogen fluoride to tri1uoroethylene in the range 1.4:1 to 1.8:1, for example 1.6:1.
Reaction temperatures are suitably in the range 200C to 500C, preferably 300C to 410C.
Contact times are in the range 1 to 15 seconds.
Atmospheric or superatmospheric pressures may be employed.
In the present process particularly when operating under preferred process conditions very high conversions of trifluoroethylene to hydrofluorinated product and highly selective yields to 1,1,1,2-tetrafluoroethane are obtained. Conversions of up to 100% of fluorinated organic compounds with yields of greater than 9S% to 1,1,1,2-tetrafluoroethane can in fact be obtained in the present procesq.
The desired 1,1,1,2-tetrafluoroethane can be recovered using conventional techniques, for example, by washing the exit gases with water and aqueous sodium hydro;xide solution, drying and collecting the desired product by condensation.
Suitably 1 to 2 moles of hydrogen ~luoride is employed per mole of trifluoroethylene. Greater molar ratios of hydrogen fluoride to trifluoro-ethylene can be employed but too great a molar ratio is undesired as this makes the process less economic. It is preferred to employ a molar ratio of hydrogen fluoride to tri1uoroethylene in the range 1.4:1 to 1.8:1, for example 1.6:1.
Reaction temperatures are suitably in the range 200C to 500C, preferably 300C to 410C.
Contact times are in the range 1 to 15 seconds.
Atmospheric or superatmospheric pressures may be employed.
In the present process particularly when operating under preferred process conditions very high conversions of trifluoroethylene to hydrofluorinated product and highly selective yields to 1,1,1,2-tetrafluoroethane are obtained. Conversions of up to 100% of fluorinated organic compounds with yields of greater than 9S% to 1,1,1,2-tetrafluoroethane can in fact be obtained in the present procesq.
The desired 1,1,1,2-tetrafluoroethane can be recovered using conventional techniques, for example, by washing the exit gases with water and aqueous sodium hydro;xide solution, drying and collecting the desired product by condensation.
3. MD 29795 The trifluoroethylene starting material can be obtained by various methods. Thus it may b0 obtained by the reaction of hydrogen with trifluoro-chloroethylene in the vapour phase in the presence of a hydrogenation catalyst such as platinum or palladium. Another useful method is provided by bringing hydrogen into reaction with 1,1,2-trichloro 1,2,2-trifluoroethane in the presence of a hydrogenation catalyst such as palladium.
The ollowing Examples illustrate the invention.
Into a tubular nickel reactor 90 cms long and 2.5 cms internal diameter were placed 170 grams of a chromium oxide catalyst. The latter had been prepared by steam treatment of a chromium hydroxide paste at 95C for 18 hours and subsequently was calcined at 340C for 11 hours as described in our UK Patent Specification No 1307224. The catalyst was then pretreated with hydrogen fluoride at 350C for
The ollowing Examples illustrate the invention.
Into a tubular nickel reactor 90 cms long and 2.5 cms internal diameter were placed 170 grams of a chromium oxide catalyst. The latter had been prepared by steam treatment of a chromium hydroxide paste at 95C for 18 hours and subsequently was calcined at 340C for 11 hours as described in our UK Patent Specification No 1307224. The catalyst was then pretreated with hydrogen fluoride at 350C for
4 hours. The tubular reactor was heated by an electric furnace.
~ Iydrogen fluoride and trifluoroethylene in two different molar ratios were passed through the tube, the catalyst bed being maintained at 350C. The flow rates of organic material and hydrogen fluoride were 185 cc/min and 130 cc/min, respectively, for Run 1, 370 cc/min and 260 cc/min, respectively for Run 2, 440 cc/min and 286 cc/min, respectively, through half the catalytic bed length for Run 3.
The % v/v of organic materials in the exit gas was determined by gas/liquid chromatography.
The reaction conditions and composition of the product were as shown in Table I.
111',,'~.~5 4. MD 29795 TABLE I
Product Contact time ~ secs ) 14 L7 ~3 .
Molar Ratio of HF: CF2=CFH
1.43:1 1.43:1 l.5~:~
...
CF3CH2F 97 . 8 97 . 5 97 . 5 :~ , _ .
CF4 1.0 0. 2 0.04 ~,: . ~ . ._ C2F6 _ _ 0 . 04 ~ .
2H2 0. 2 0. 3 0.04 ~ ., __ .. __ C2F5H ~ 1 . 0 1 . 1 1 . 5 20 _ '~ U2 _ _ I o,j I ~.8 :' ~ .
:: .
~ Iydrogen fluoride and trifluoroethylene in two different molar ratios were passed through the tube, the catalyst bed being maintained at 350C. The flow rates of organic material and hydrogen fluoride were 185 cc/min and 130 cc/min, respectively, for Run 1, 370 cc/min and 260 cc/min, respectively for Run 2, 440 cc/min and 286 cc/min, respectively, through half the catalytic bed length for Run 3.
The % v/v of organic materials in the exit gas was determined by gas/liquid chromatography.
The reaction conditions and composition of the product were as shown in Table I.
111',,'~.~5 4. MD 29795 TABLE I
Product Contact time ~ secs ) 14 L7 ~3 .
Molar Ratio of HF: CF2=CFH
1.43:1 1.43:1 l.5~:~
...
CF3CH2F 97 . 8 97 . 5 97 . 5 :~ , _ .
CF4 1.0 0. 2 0.04 ~,: . ~ . ._ C2F6 _ _ 0 . 04 ~ .
2H2 0. 2 0. 3 0.04 ~ ., __ .. __ C2F5H ~ 1 . 0 1 . 1 1 . 5 20 _ '~ U2 _ _ I o,j I ~.8 :' ~ .
:: .
5. MD 29795 The apparatus and procedure were broadly similar to those of Example l. However the internal diameter of the reactor was larger (.3.8 cms) and the reactor was 5 constructed of 'Monel' ('Monel' is a Trade Mark).
The amount of catalyst was 1 kg. The flow rates of hydrogen fluoride and trifluoroethylene were 200 g hr l and 125 1 hr l (gas) tri1uoroethylene, respectively.
The molar ratio o~ HF:CF2=CFH was 1.9:1. The contact time was 4 seconds.
The exit gas was washed with water and aqueous - alkaline hydroxide solution, passed through a catchpot to collect water droplets, dried; the product was collected by condensation and was distilled.
The conversion to CF3CH2F was > 95%. The product contained only 0.5% of fluorinated methanes and fluorinated ethane.
.
' '
The amount of catalyst was 1 kg. The flow rates of hydrogen fluoride and trifluoroethylene were 200 g hr l and 125 1 hr l (gas) tri1uoroethylene, respectively.
The molar ratio o~ HF:CF2=CFH was 1.9:1. The contact time was 4 seconds.
The exit gas was washed with water and aqueous - alkaline hydroxide solution, passed through a catchpot to collect water droplets, dried; the product was collected by condensation and was distilled.
The conversion to CF3CH2F was > 95%. The product contained only 0.5% of fluorinated methanes and fluorinated ethane.
.
' '
Claims (7)
1. A process for the manufacture of 1,1,1,2-tetrafluoroethane which comprises bringing trifluoro-ethylene into reaction with hydrogen fluoride in the vapour phase at elevated temperature in the presence of a chromium oxide or basic chromium fluoride hydro-fluorination catalyst.
2. A process as claimed in Claim 1 in which the hydrofluorination catalyst is chromium oxide.
3. A process as claimed in Claim 2 in which the chromium oxide catalyst is one obtained by treating a chromium hydroxide paste in an atmosphere comprising from 10 to 100 percent by weight of steam at a temperature in the range from 50°C to 180°C for at least one hour and then calcining the product.
4. A process as claimed in Claim 1, 2 or 3 in which there is employed 1 to 2 moles hydrogen fluoride per mole of trifluoroethylene.
5. A process as claimed in Claim 1, 2 or 3 in which there is employed 1.4 moles to 1,8 moles hydrogen fluoride per mole of trifluoroethylene.
6. A process as claimed in Claim 1, 2 or 3 in which the reaction temperature is in the range 200°C
to 500°C.
to 500°C.
7. A process as claimed in Claim 1, 2 or 3 in which the reaction temperature is in the range 300°C to 410°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB39088/77 | 1977-09-20 | ||
| GB3908877 | 1977-09-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1117145A true CA1117145A (en) | 1982-01-26 |
Family
ID=10407570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000311550A Expired CA1117145A (en) | 1977-09-20 | 1978-09-19 | Manufacture of halogenated compounds |
Country Status (14)
| Country | Link |
|---|---|
| JP (1) | JPS5452012A (en) |
| AR (1) | AR225276A1 (en) |
| AU (1) | AU519072B2 (en) |
| BE (1) | BE870530A (en) |
| BR (1) | BR7806150A (en) |
| CA (1) | CA1117145A (en) |
| DE (1) | DE2837515A1 (en) |
| ES (1) | ES473516A1 (en) |
| FR (1) | FR2403321A1 (en) |
| GB (1) | GB2004539B (en) |
| GR (1) | GR64019B (en) |
| IT (1) | IT1098853B (en) |
| NL (1) | NL7808881A (en) |
| ZA (1) | ZA784828B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5500400A (en) * | 1993-12-09 | 1996-03-19 | Korea Institute Of Science And Technology | Catalyst for producing 1,1,1,2-tetrafluoroethane and method for preparing the same |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2712732C2 (en) * | 1977-03-23 | 1986-03-13 | Hoechst Ag, 6230 Frankfurt | Process for the production of octafluoropropane |
| JPS5527139A (en) * | 1978-08-14 | 1980-02-27 | Daikin Ind Ltd | Preparation of tetrafluoroethane |
| DE3009760A1 (en) * | 1980-03-14 | 1981-09-24 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING HIGH PURITY PARTLY FLUORINATED AETHANES |
| FR2501062A1 (en) * | 1980-12-29 | 1982-09-10 | Ugine Kuhlmann | GAS PHASE FLUORURIZATION CATALYSTS OF ALIPHATIC CHLORINE DERIVATIVES, BASED ON CHROMIUM OXIDE MICROBALLS, AND FLUORURIZATION METHODS USING THE SAME CATALYSTS |
| DE3545625A1 (en) * | 1985-12-21 | 1987-06-25 | Dataprint Datendrucksysteme R | Water-free, liquid recording material |
| IT1230779B (en) * | 1989-07-12 | 1991-10-29 | Ausimont Srl | PROCEDURE FOR PREPARING 1,1,1,2 TETRAFLUOROETHANE. |
| BE1004450A3 (en) * | 1990-06-18 | 1992-11-24 | Solvay | METHOD FOR MANUFACTURING 1,1,1,2-tetrafluoroethane. |
| FR2694556B1 (en) * | 1992-08-05 | 1994-09-23 | Atochem Elf Sa | Process for the purification of 1,1,1,2-tetrafluoroethane. |
| US5750808A (en) * | 1995-07-11 | 1998-05-12 | E. I. Du Pont De Nemours And Company | Dehydrohalogenation processes |
| RU2243961C1 (en) * | 2003-08-18 | 2005-01-10 | Федеральное государственное унитарное предприятие Российский научный центр "Прикладная химия" | Method for preparing 1,1,1,2-tetrafluoroethane |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2669590A (en) * | 1951-08-03 | 1954-02-16 | Allied Chem & Dye Corp | Production of fluorine compounds |
| US2855427A (en) * | 1955-05-24 | 1958-10-07 | American Potash & Chem Corp | Continuous process for preparation of pure methyl borate |
| GB1307224A (en) * | 1969-06-27 | 1973-02-14 | Ici Ltd | Chromium oxide catalyst |
| JPS4872105A (en) * | 1971-12-29 | 1973-09-29 | ||
| DE3009760A1 (en) * | 1980-03-14 | 1981-09-24 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING HIGH PURITY PARTLY FLUORINATED AETHANES |
-
1978
- 1978-08-16 GB GB7833506A patent/GB2004539B/en not_active Expired
- 1978-08-23 GR GR57064A patent/GR64019B/en unknown
- 1978-08-24 ZA ZA00784828A patent/ZA784828B/en unknown
- 1978-08-28 DE DE19782837515 patent/DE2837515A1/en active Granted
- 1978-08-29 NL NL7808881A patent/NL7808881A/en not_active Application Discontinuation
- 1978-08-30 AU AU39367/78A patent/AU519072B2/en not_active Expired
- 1978-08-31 AR AR273526A patent/AR225276A1/en active
- 1978-09-15 BE BE190528A patent/BE870530A/en not_active IP Right Cessation
- 1978-09-18 JP JP11371378A patent/JPS5452012A/en active Granted
- 1978-09-18 IT IT27797/78A patent/IT1098853B/en active
- 1978-09-19 FR FR7826787A patent/FR2403321A1/en active Granted
- 1978-09-19 BR BR7806150A patent/BR7806150A/en unknown
- 1978-09-19 CA CA000311550A patent/CA1117145A/en not_active Expired
- 1978-09-20 ES ES473516A patent/ES473516A1/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5500400A (en) * | 1993-12-09 | 1996-03-19 | Korea Institute Of Science And Technology | Catalyst for producing 1,1,1,2-tetrafluoroethane and method for preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| GR64019B (en) | 1980-01-18 |
| AR225276A1 (en) | 1982-03-15 |
| DE2837515C2 (en) | 1989-06-29 |
| DE2837515A1 (en) | 1979-03-29 |
| AU3936778A (en) | 1980-03-06 |
| IT1098853B (en) | 1985-09-18 |
| GB2004539B (en) | 1982-02-10 |
| BR7806150A (en) | 1979-04-17 |
| FR2403321A1 (en) | 1979-04-13 |
| JPS5452012A (en) | 1979-04-24 |
| JPS6223728B2 (en) | 1987-05-25 |
| BE870530A (en) | 1979-03-15 |
| ZA784828B (en) | 1979-08-29 |
| NL7808881A (en) | 1979-03-22 |
| AU519072B2 (en) | 1981-11-05 |
| ES473516A1 (en) | 1979-05-01 |
| IT7827797A0 (en) | 1978-09-18 |
| FR2403321B1 (en) | 1984-01-20 |
| GB2004539A (en) | 1979-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3258500A (en) | Process for fluorinating halohydro-carbons | |
| US3087975A (en) | Process for making halogenated organic compounds | |
| JP4629062B2 (en) | Treatment of chromium oxide and catalytic production of vinyl fluoride | |
| CA1117145A (en) | Manufacture of halogenated compounds | |
| RU1838288C (en) | Method of 1,1,2,2-tetrafluoroethane synthesis | |
| EP0775100B1 (en) | Process for the production of trifluoroethylene | |
| JPH0267235A (en) | Production of 1, 1, 1, 2-tetrafluoroethane | |
| EP1017656B1 (en) | Method for producing perhalogenated cyclopentene | |
| JPH04226927A (en) | Method for producing 1,1,1,2-tetrafluorochloroethane and pentafluoroethane | |
| EP0365296B1 (en) | Manufacture of 1,1,1,2-tetrafluoroethane | |
| RU1817763C (en) | Process for preparing 1,1,1-trifluorodichloroethane and/or 1,1,1,2-tetrafluorochloroethane | |
| CA1119202A (en) | Manufacture of halogenated compounds | |
| JPH01268651A (en) | Gaseous phase fluorination | |
| US5345014A (en) | Process for preparing pentafluoroethane by dismutation of tetrafluorochloroethane | |
| US2576823A (en) | Fluorination with granular crf3 catalyst | |
| JPS5821900B2 (en) | Hexafluoropropanone-2 | |
| GB1589924A (en) | Manufacture of 1,1,1,2-tetrafluoroethane halogenated compounds | |
| US5444171A (en) | Method for purification of 1,1,1,2-tetrafluoroethane | |
| JP2759196B2 (en) | Method for producing 1,1,1-trifluoro-2-chloroethane | |
| US6297411B1 (en) | Mixed fluorination catalyst | |
| CA1095937A (en) | Preparation of 1-chloro-2-trifluoromethyl-3,3,3- trifluoropropene from isobutylene | |
| US3154592A (en) | Catalytic pyrolysis of fluoroform to form higher fluorocarbons | |
| JPH0368526A (en) | Preparation of mixture containing 1-chloro-1- fluoroethylene and vinylidene fluoride by gas-phase contacting disproportionate reaction of 1-chloro-1, 1-difluoroethane | |
| US4155881A (en) | Activation of chromic fluoride catalyst with hydrogen chloride and chlorine | |
| EP0408004A1 (en) | Process for preparing 1,2-dichloro-1,1,2-trifluoroethane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |