GB1589924A - Manufacture of 1,1,1,2-tetrafluoroethane halogenated compounds - Google Patents
Manufacture of 1,1,1,2-tetrafluoroethane halogenated compounds Download PDFInfo
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- GB1589924A GB1589924A GB6687/77A GB668777A GB1589924A GB 1589924 A GB1589924 A GB 1589924A GB 6687/77 A GB6687/77 A GB 6687/77A GB 668777 A GB668777 A GB 668777A GB 1589924 A GB1589924 A GB 1589924A
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- tetrafluoroethane
- permanganate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
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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
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/395—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification of at least one compound
Description
(54) MANUFACTURE OF 1,1,1 ,2-TETRAFLUOROETHANE HALOGENATED
COMPOUNDS
(71) We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, Imperial Chemical
House, Millbank, London SW1P 3JF, a British Company, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
This invention relates to a process for the manufacture of 1,1,1,2-tetrafluoroethane and in particular to such a process wherein said tetrafluoroethane of a high degree of purity is obtained.
According to the present invention there is provided a process for the manufacture of 1,1,1,2-tetrafluoroethane which comprises reacting in the vapour phase at elevated temperature a haloethane of formula CX3CH2Y wherein each X, which is the same or different, is bromine, chlorine or fluorine and Y is either bromine or chlorine with hydrogen fluoride in the present of a catalyst which is chromium oxide or which is, at least in part, basic chromium fluoride, either catalyst being unsupported or supported on an alumina-free carrier.
In the haloethane starting material X may be chlorine only, fluorine only, bromine only or a combination of two or three of said halogens. Preferably X is chlorine and or fluorine and Y is chlorine. Preferably also at least one of the X substituents is fluorine. A very suitable haloethane is one having three fluorine atoms, more particularly, 1,1,1-trifluoro-2- chloroethane.
The chromium oxide catalyst may consist of chromium oxide alone. The chromium oxide may be activated by heating in an inert atmosphere. Again the catalyst may comprise a basic chromium fluoride in which chromium is associated with oxygen and fluorine atoms.
We find that by employing a chromium oxide catalyst prepared by heating a readilydecomposable salt of chromium e.g. chromic hydroxide in air or oxygen as described in our
UK Patent Specification 976883, in the present process that useful yields of the desired 1,1,1,2-tetrafluoroethane may be obtained.
It is particularly preferred in the present process to employ a chromium oxide catalyst which is obtained by treating a chromium hydroxide paste with steam as is more fully described and claimed in our UK Patent Specification 1,302,224. The catalyst may be compressed into pellets and used in a fixed bed. Alternatively the catalyst of appropriate particle size may be used in a fluidised bed. The pelleted or non pelleted catalyst may be given a prefluorination treatment by passing hydrogen fluoride over the catalyst at 250"C to 450"C for at least 30 minutes. In any even the catalyst may take up variable amounts of fluorine when used in the present process.
The amount of hydrogen fluoride employed in the process depends to a great extent on the haloethane starting material. At least the stoichiometric amount of hydrogen fluoride is usually employed per mole of haloethane starting material. We prefer to employ an excess of the stoichiometric amount but not greater than six times the stoichiometric amount of hydrogen fluoride in the present process. We prefer to employ at least two moles but not greater than six moles of hydrogen fluoride per mole of said organic starting material, e.g.
1,1 ,1-trifluoro-2-chloroethane.
Preferred temperatures in the present process are in the range 300"C to 400"C, for example 325"C to 3750C. Preferred contact times are in the range 2 to 60 seconds.
Atmospheric or superatmospheric pressures may be employed.
Unreacted organic starting material, hydrogen fluoride and by-products e.g. haloethanes
containing chlorine atoms in the CX3 group may be recycled to the process for further
reaction to give the desired compound.
In the present process, particularly when operating under preferred process conditions,
very high selectivities to the desired 1,1,1,2-tetrafluoroethane product are obtained.
When the Y substituent in the haloethane starting material is chlorine there may be
formed in addition to the desired product asym tetrafluoroethane (CF3 CH2F) a small
amount of 1,1-difluoro-2-chloroethylene (CF2=CHCl) as by-product. This occurs when the
organic starting material in the hydrofluorination reaction is 1,1,1-trifluoro-2-chloroethane.
It is desirable to reduce further even small amounts of said difluorochloroethylene but
this is extremely difficult to achieve by conventional methods, for example, by fractional
distillation.
We find that difluorochloroethylene contained in asym tetrafluoroethane may be reduced
in content by treating the impure asym tetrafluoroethane either with hydrogen fluoride in
the presence of catalysts used in the present process for manufacture of asym
tetrafluoroethane but at much lower temperatures or by intimately contacting said impure
asym tetrafluoroethane at much lower temperatures in the liquid phase with a metal
permanganate.
According to a further feature of the present invention we provide a process for the
manufacture of 1,1,1,2-tetrafluoroethane as hereinbefore described' wherein the Y
substituent in the haloethane starting material is chlorine and wherein the 1,1,1,2
tetrafluoroethane product containing 1,1-difluoro-2-chloro-ethylene as impurity is brought
together with hydrogen fluoride into contact with a catalyst which is chromium oxide or
which is at least in part basic chromium fluoride at a temperature in the range 100"C to 275"C whereby the said haloethylene content is reduced.
The impure asym tetrafluoroethane to be treated to remove the haloethylene impurity
may be the crude product which is associated with other haloethanes containing fluorine
including one or more of 1,1,1,2,2-pentafluoroethane (CF3 CHF2), 1,1,1,2-tetrafluoro-2
chloroethane (CF3 CHCIF), 1,1,1-trifluoroethane (CF3 CH3) and 1,1,1-trifluoro-2
chloroethane (CF3 CH2Cl).
Such a crude reaction product may be obtained by bringing 1,1,1-trifluoro-2
chloroethane into reaction with hydrogen fluoride at temperatures in the range 300"C to 400"C in the presence of a catalyst which is chromium oxide or which is at least in part basic
chromium fluoride as is previously described.
The manner of carrying out the process of this further feature of the invention is capable
of considerable variation. In one method the crude impure reaction product obtained by the
hydrofluorination of 1,1,1-trifluoro-2-chloroethane comprising asym tetrafluoroethane,
said other haloethanes containing fluorine and unreacted hydrogen fluoride leaving a
reactor are passed into a second reactor containing a catalyst which is chromium oxide or
which is at least a part basic chromium fluoride and maintained at 1000C to 2750C whereby
said impurity is almost completely removed. Such a crude reaction product will also be
associated with hydrogen chloride derived by reaction of hydrogen fluoride with organic
starting material, but such hydrogen chloride need not be removed before passing to the second reactor. In another variant the process is carried out in a single reactor having a first
reaction zone containing a catalyst which is a chromium oxide or which is at least in part basic chromium fluoride maintained at a temperature (higher than that of the second zone)
of 300"C to 400"C wherein the hydrofluorination of 1,1,1-trifluoro-2-chloroethane is
effected. The crude impure organic product together with unreacted hydrogen fluoride
(and hydrogen chloride) from the first reaction zone is fed to the second part of the reaction zone containing said chromium oxide or basic chromium fluoride catalyst maintained at a temperature of 100"C to 275"C whereby the amount of 1,1-difluoro-2-chloroethylene contaminant in the crude product is considerably reduced. Asym-tetrafluoroethane may be recovered from the reaction mixture leaving the reactor by conventional means, for example, by fractional distillation.
Preferred temperatures in the purification process are in the range 125"C to 2500C.
Contact times are usually in the range 2 to 20 seconds and preferably in the range 3 to 15 seconds. Atmospheric or super-atmospheric pressures may be employed.
According to a still further feature of the present invention we provide a process for the manufacture of 1,1,1,2-tetrafluoroethane as hereinbefore described wherein the Y substituent in the haloethane starting material is chlorine and wherein the 1,1,1,2tetrafluoroethane product containing 1,1-difluoro-2-chloroethylene as impurity is intimately contacted with a metal permanganate.
The permanganate treatment is usually carried out in a liquid medium. Preferably there are used aqueous, or non-aqueous solvents for the permanganate particularly organic solvents or mixtures thereof, which are not appreciably attacked by permanganate. It is particularly suitable to use the permanganate in the form of an aqueous solution.
The permanganate may be in particular an alkali metal or alkaline earth metal permanganate and the permanganate solution may be acid, neutral or alkaline. Of the latter a neutral or alkaline solution is preferred. If the solution is to be alkaline this may be achieved most conveniently by addition of an alkali metal hydroxide although other bases may be used if desired, for example alkaline earth metal hydroxides or ammonia.
Useful results can be obtained when using from 0.1% up to 10% by weight in the aqueous phase of sodium hydroxide or potassium hydroxide. Lower rather than higher proportions than 10% by weight of NaOH or KOH are preferred and it is particularly preferred to employ concentrations from 0.5% to 2% by NaOH or KOH in the aqueous phase.
Sodium and potassium permanganates are particularly useful metal permanganates.
Useful results may be obtained with various concentrations of permanaganate in the aqueous phase. For example, good results are obtained when using 20 g/l to 60 g/l potassium permanganate in the aqueous phase.
The temperature used in the treatment with aqueous permanganate is usually in the range 10 C up to the boiling point of the mixture, for example 15"C to 40"C.
The contaminated asym tetrafluoroethane may be a crude product associated with the organic starting material and other haloethanes by-products containing fluorine as already described. However the crude product may be fractionally distilled to give a product consisting essentially of 1,1,1,2-tetrafluoroethane and 1,1-difluoro-2-chloroethylene impurity.
The times of treatment with aqueous permanganate may vary according to the process conditions. For example treatment times in the range 5 minutes to 90 minutes can be employed.
The relative proportions of aqueous solution of permanganate to crude asym tetrafluoroethane may be varied considerably and the optimum proportions will depend on such factors as thoroughness of mixing, the amount of the impurity, the temperature of treatment and composition of the product. Thus the proportion by volume of aqueous permanganate to crude organic material is usually in the range 1:0.1 to 1:10, for example 1:0.2 to 1:6.
After agitation of the organic material with aqueous permanganate the mixture is allowed to separate into two distinct layers and the purified lower asym tetrafluoroethane can be fractionally distilled.
1,1,1,2-tetrafluoroethane which has a low boiling point (-26.5"C) is useful as a refrigerant, for example, in food-freezing techniques. It is useful as an aerdsol propellant and as a foam blowing agent.
The following Examples illustrate the invention. All percentages are v/v unless otherwise stated.
Example 1
Into a tubular nickel reactor 90 cms long and 2.5 cms internal diameter were placed 150 grams of a chromium oxide catalyst. The latter had been prepared by steam treatment of a chromium hydroxide paste at 950C for 18 hours, and subsequently calcined at 340"C for 11 hours as described in our UK Patent Specification No. 1,307,224. The catalyst was then pretreated with hydrogen fluoride at 350"C for 4 hours.
The tubular reactor was heated by an electric furnace and the temperature inside the reactor was held at 3500C.
1827 grams of 1,1,1-tn.fluoro-2-chloroethane were passed together with an amount of hydrogen fluoride over the catalyst over a total period of 55 hours. The molar ratio of
HF:CF3CH2Cl was 4:1. The contact time was 7 seconds.
The products were collected, washed with water, scrubbed with 2.5% w/w aqueous KOH solution and dried.
The organic product thus obtained contained 18.2% 1,1,1,2-tetrafluoroethane, 1.65% of a mixture of pentafluoroethane with 1,1,1-trifluoroethane, 0.12% 1,1-difluoro-2chloroethylene and 80% 1,1,1-trifluoro-2-chloroethane which was available for recycling to the process. At the end of the run there was no evidence of deterioration of the activity of the catalyst. The carbon balance was 94%.
Example 2
The procedure of Example 1 was repeated except that the contact time was 14 seconds.
After 2 hours the exit gas stream was analysed and found to contain:
22.2% 1,1,1 ,2-tetrafluoroethane 1.94% of a mixture of pentafluoroethane with 1,1,1-trifluoroethane
0.13% 1, 1-difluoro-2-chloroethylene 75.7% 1,1,1-trifluoro-2-chloroethane
Example 3
The procedure of Example 1 was repeated except that the contact time was 28 seconds.
After 2 hours the exit gas stream was analysed and found to contain:
25.2% 1,1,1 ,2-tetrafluoroethane 2.4% of a mixture of pentafluoroethane with 1,1,1-trifluoroethane
0.08% 1 ,1-difluoro-2-chloroethylene 72.3% 1,1, 1-trifluoro-2-chloroethane Example 4
The procedure of Example 1 was repeated except that the molar ratio of hydrogen fluoride to 1,1,1-trifluoro-2-chloroethane was 8.6:1. After 2 hours the exit gas stream was analysed and found to contain:
27.4% 1,1 ,1,2-tetrafluoroethane 1.4% of a mixture of pentafluoroethane with 1,1,1-trifluoroethane 0.05% 1 ,1-difluoro-2-chloroethylene 71.2% 1 ,1,1-trifluoro-2-chloroethane Example 5
Into a tubular nickel reactor 90 cms long and 2.5 cms internal diameter were placed 130 grams of a chromium oxide catalyst. The latter had been prepared by steam treatment of a chromium hydroxide paste at 95"C for 18 hours, and subsequently calcined at 3400C as described in our UK Patent Specification No. 1,307,224. The catalyst was then pretreated with hydrogen fluoride at 350"C for 4 hours. The tubular reactor was heated by an electric furnace and the temperature inside the reactor was maintained in the range 335"C to 3550C.
This reactor was connected to a second similar reactor containing the same amount of said catalyst but held at 1600C.
89 grams of 1,1,1-trifluoro-2-chloroethane were passed together with an amount of hydrogen fluoride over the fixed catalyst bed over a total period of 3 hours. The molar ratio of HF:CF3CH2Cl was 3:1. The contact time was 7 seconds. The exit gas leaving the reactor was analyzed by gas/liquid chromatography and was found to contain (O/o).
CF3 CH2F 12.63
CF2 = CHCl 0.53
CF3CHCIF 0.04
OTHERS 0.375
CF3CH3 0.17
CF3CHF2 0.02
CF3CH2Cl 86.23
Said exit gas containing hydrogen fluoride was passed to said second similar reactor the contact time being again 7 seconds. The exit gas leaving the second reactor was analysed by gas/liquid chromatography and was found to contain (%).
CF3CH2F 12.63
CF2 = CHCl 0.0007
CF3CHCIF 0.06
OTHERS 0.1
CF3 CH3 0.18
CF3 CHF2 0.0005
CF3CH2Cl 87.0
Example 6
A crude organic product containing 16% 1,1,1,2-tetrafluoroethane, 83% 1,1,1-trifluoro2-chloroethane, 0.8% pentafluoroethane and 1000 pp m of 1,1-difluoro-2-chloroethylene contaminant was obtained by a method substantially as described in Example 1.
Samples were taken of an aqueous solution of permanganate containing 10g NaOH2 60g
KMnO4 and 1500g water. These were placed together with said crude organic product in an autoclave in various ratios (v/v) and were vigorously stirred at different temperatures under autogeneous pressure. After the runs the mixtures were allowed to settle and the lower organic layer was recovered and analysed for remaining 1,1-difluoro-2-chloroethylene content. The results are indicated in the Table.
TABLE
KMnO4/Organics Temp Time Remaining CF2=CHCl
ratio "C Mins ppm v/v in organic
product
1:1 30"C 15 5 30"C 90 Not detectable
1:5 20"C 60 5
1:0.2 20"C 20 10
30 7 30"C 20 7.5
30 5
WHAT WE CLAIM IS:
1. A process for the manufactureof 1,1,1,2-tetrafluoroethane which comprises reacting in the vapour phase at elevated temperature a haloethane of formula CX3CH2Y wherein each X, which is the same or different, is bromine, chlorine or fluorine and Y is either bromine or chlorine with hydrogen fluoride in the presence of a catalyst which is chromium oxide or which is, at least in part, basic chromium fluoride, either catalyst being unsupported or supported on an alumina-free carrier.
2. A process as claimed in Claim 1 in which in the haloethane starting material X is chlorine and/or fluorine and Y is chlorine.
3. A process as claimed in Claim 2 in which at least one of the X substituents is fluorine.
4. A process as claimed in Claim 3 in which the haloethane is 1,1,1-trifluoro-2chloroethane.
5. A process as claimed in any one of the preceding claims wherein a chromium oxide catalyst is employed which is obtained by treating a chromium hydroxide paste with steam as claimed in UK Patent 1,302,224.
6. A process as claimed in any one of the preceding claims in which there is employed at least the stoichiometric amount of hydrogen fluoride required for conversion of the haloethane starting material to 1,1,1,2-tetrafluoroethane.
7. A process as claimed in Claim 6 in which there is employed at least two moles but not greater than six moles of hydrogen fluoride per mole of said organic starting material.
8. A process as claimed in any one of the preceding claims which is carried out at a reaction temperature in the range 300"C to 400"C.
9. A process as claimed in Claim 8 in which the reaction temperature is in the range 325"C to 375"C.
10. A process for the manufacture of 1,1,1,2-tetra-fluoroethane as claimed in any one of the preceding claims wherein the Y substituent in the haloethane starting material is chlorine and wherein the 1,1,1,2-tetrafluoroethane product containing 1,1,-difluoro-2chloroethylene as impurity is brought together with hydrogen fluoride into contact with a catalyst which is chromium oxide or which is at least in part basic chromium fluoride at a temperature in the range 100"C to 275"C whereby said haloethylene content is reduced.
11. A process as claimed in Claim 10 wherein the organic starting material is
1,1,1-trifluoro-2-chloroethane and in which the resulting crude impure asym tetrafluoroethane is associated with other haloethanes containing fluorine including one or more of pentafluoroethane 1,1,1 ,2-tetrafluoro-2-chloroethane, 1,1, 1-trifluoroethane and 1,1,1trifluoro-2-chloroethane .
12. A process as claimed in Claim 10 which the crude impure product comprising asym tetrafluoroethane, said other haloethanes containing fluorine and unreacted hydrogen fluoride leaving the reactor are passed into a second reactor containing a catalyst which is
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (33)
1. A process for the manufactureof 1,1,1,2-tetrafluoroethane which comprises reacting in the vapour phase at elevated temperature a haloethane of formula CX3CH2Y wherein each X, which is the same or different, is bromine, chlorine or fluorine and Y is either bromine or chlorine with hydrogen fluoride in the presence of a catalyst which is chromium oxide or which is, at least in part, basic chromium fluoride, either catalyst being unsupported or supported on an alumina-free carrier.
2. A process as claimed in Claim 1 in which in the haloethane starting material X is chlorine and/or fluorine and Y is chlorine.
3. A process as claimed in Claim 2 in which at least one of the X substituents is fluorine.
4. A process as claimed in Claim 3 in which the haloethane is 1,1,1-trifluoro-2chloroethane.
5. A process as claimed in any one of the preceding claims wherein a chromium oxide catalyst is employed which is obtained by treating a chromium hydroxide paste with steam as claimed in UK Patent 1,302,224.
6. A process as claimed in any one of the preceding claims in which there is employed at least the stoichiometric amount of hydrogen fluoride required for conversion of the haloethane starting material to 1,1,1,2-tetrafluoroethane.
7. A process as claimed in Claim 6 in which there is employed at least two moles but not greater than six moles of hydrogen fluoride per mole of said organic starting material.
8. A process as claimed in any one of the preceding claims which is carried out at a reaction temperature in the range 300"C to 400"C.
9. A process as claimed in Claim 8 in which the reaction temperature is in the range 325"C to 375"C.
10. A process for the manufacture of 1,1,1,2-tetra-fluoroethane as claimed in any one of the preceding claims wherein the Y substituent in the haloethane starting material is chlorine and wherein the 1,1,1,2-tetrafluoroethane product containing 1,1,-difluoro-2chloroethylene as impurity is brought together with hydrogen fluoride into contact with a catalyst which is chromium oxide or which is at least in part basic chromium fluoride at a temperature in the range 100"C to 275"C whereby said haloethylene content is reduced.
11. A process as claimed in Claim 10 wherein the organic starting material is
1,1,1-trifluoro-2-chloroethane and in which the resulting crude impure asym tetrafluoroethane is associated with other haloethanes containing fluorine including one or more of pentafluoroethane 1,1,1 ,2-tetrafluoro-2-chloroethane, 1,1, 1-trifluoroethane and 1,1,1trifluoro-2-chloroethane .
12. A process as claimed in Claim 10 which the crude impure product comprising asym tetrafluoroethane, said other haloethanes containing fluorine and unreacted hydrogen fluoride leaving the reactor are passed into a second reactor containing a catalyst which is
chromium oxide or which is at least in part basic chromium fluoride and maintained at a temperature in the range 100"C to 2750C.
13. A process as claimed in Claim 10 carried out in a single reactor having a first reaction zone containing a catalyst which is chromium oxide or, at least in part, basic chromium fluoride maintained at a temperature of 300"C to 4000C to produce said crude impure organic product comprising asym tetrafluoroethane, other haloethanes and unreacted hydrogen fluoride which is fed to a second part of the reaction zone containing said chromium oxide or basic chromium fluoride catalyst maintained at a temperature in the range 100"C to 275"C whereby the amount of 1,1-difluoro-2-chloroethylene contaminant is reduced.
14. A process as claimed in any one of the preceding Claims 10 to 13 in which the purification of the asym-tetrafluoroethane is carried out at a temperature in the range 125"C to 250"C.
15. A process for the manufacture of 1,1,1,2-tetrafluoroethane as claimed in any one of the preceding Claims 1 to 9 wherein the Y substituent in the haloethane starting material is chlorine and wherein 1,1,1,2-tetrafluoroethane product containing 1,1-difluoro-2chloroethylene as impurity is intimately contacted with a metal permanganate.
16. A process as claimed in Claim 15 in which the impure asym tetrafluoroethane is intimately contacted with the permanganate in a liquid medium.
17. A process as claimed in Claim 16 in which the impure asym tetrafluoroethane is intimately brought in contact with an aqueous solution of a permanganate.
18. A process as claimed in Claim 17 in which the metal permanganate is an alkali metal or alkaline earth metal permanganate.
19. A process as claimed in Claim 18 in which the solution of the permanganate is neutral or alkaline.
20. A process as claimed in Claim 19 in which the solution is made alkaline by addition of an alkali metal hydroxide.
21. A process as claimed in Claim 20 in which from 0.1% to 10% by weight of sodium hydroxide is present in the aqueous phase.
22. A process as claimed in Claim 21 in which from 0.5% to 2% by weight NaOH is present in the aqueous phase.
23. A process as claimed in any one of the preceding Claims 16 to 22 in which the metal permanganate is sodium or potassium permanganate.
24. A process as claimed in Claim 23 in which the concentration of potassium permanganate in the aqueous phase is 20 g/litre to 60 g/litre.
25. A process as claimed in any one of the preceding Claims 17 to 24 in which the treatment with the aqueous solution is carried out at a temperature in the range 10 C up to the boiling point of the mixture.
26. A process as claimed in Claim 25 in which the treatment with the aqueous solution is carried out at a temperature in the range 15"C to 40"C.
27. A process as claimed in any one of the preceding Claims 15 to 26 in which the impure 1,1,1,2-tetrafluoroethane is a crude product associated with the organic starting material and other haloethane by-products containing fluorine.
28. A process as claimed in any one of the preceding Claims 15 to 26 wherein the impure 1,1,1,2-tetrafluoroethane associated with organic starting material and other haloethane by-products containing fluorine is fractionally distilled to give an impure product consisting essentially of 1,1,1 ,2-tetrafluoroethane and 1,1 -difluoro-2- chloroethylene which product is then subjected to the treatment with metal permanganate.
29. A process as claimed in Claim 27 or Claim 28 wherein the proportion by volume of aqueous permanganate to the said crude or impure product is in the range 1:0.1 to 1:10.
30. A process as claimed in Claim 29 wherein the proportion by volume of aqueous permanganate to said crude or impure product is in the range 1:0.2 to 1:6.
31. A process for the manufacture of 1,1,1,2-tetrafluoroethane substantially as hereinbefore described with reference to any one of the Examples.
32. A process for the manufacture of 1,1,1,2-tetrafluoroethane substantially as described herein.
33. 1,1,1,2-tetrafluoroethane whenever manufactured by a process as claimed in any of the preceding claims.
Priority Applications (16)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB6687/77A GB1589924A (en) | 1977-02-17 | 1977-02-17 | Manufacture of 1,1,1,2-tetrafluoroethane halogenated compounds |
| ZA00780702A ZA78702B (en) | 1977-02-17 | 1978-02-06 | Manufacture of halogenated compounds |
| AU33118/78A AU518050B2 (en) | 1977-02-17 | 1978-02-08 | Manufacture of 1,1,1,2-tetrafluoro ethane & method of reducing amount of 1,1,difluord-chldro ethlene impurity |
| BE185127A BE863913A (en) | 1977-02-17 | 1978-02-13 | PRODUCTION OF HALOGEN COMPOUNDS |
| IT20257/78A IT1095355B (en) | 1977-02-17 | 1978-02-13 | PROCESS FOR THE PREPARATION OF HALOGEN COMPOUNDS |
| GR55436A GR65299B (en) | 1977-02-17 | 1978-02-13 | Manufacture of halogenated compounds |
| AR271120A AR216937A1 (en) | 1977-02-17 | 1978-02-16 | PROCEDURE FOR THE PREPARATION OF 1,1,1,2-TETRAFLUORETHANE |
| BR7800944A BR7800944A (en) | 1977-02-17 | 1978-02-16 | MANUFACTURING PROCESS 1,1,1,2-TETRAFLUOR-ETHANE |
| NL7801741A NL7801741A (en) | 1977-02-17 | 1978-02-16 | PROCESS FOR PREPARING HALOGENATED COMPOUNDS. |
| JP1669178A JPS53105404A (en) | 1977-02-17 | 1978-02-17 | Process for preparing 1*1*1*22tetrafluoroethane |
| ES467081A ES467081A1 (en) | 1977-02-17 | 1978-02-17 | Process for preparing 1*1*1*22tetrafluoroethane |
| DE19782806865 DE2806865A1 (en) | 1977-02-17 | 1978-02-17 | Process for the preparation of 1,1,1,2-TETRAFLUOROAETHANE |
| FR7804638A FR2381006A1 (en) | 1977-02-17 | 1978-02-17 | Highly pure tetra:fluoroethane prodn. - from halo-ethane(s) and hydrogen fluoride using chromium oxide contg. catalysts |
| CA000297242A CA1119202A (en) | 1977-02-17 | 1978-02-17 | Manufacture of halogenated compounds |
| CA378,715A CA1124265A (en) | 1977-02-17 | 1981-05-29 | Manufacture of halogenated compounds |
| CA378,716A CA1124264A (en) | 1977-02-17 | 1981-05-29 | Manufacture of halogenated compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB6687/77A GB1589924A (en) | 1977-02-17 | 1977-02-17 | Manufacture of 1,1,1,2-tetrafluoroethane halogenated compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1589924A true GB1589924A (en) | 1981-05-20 |
Family
ID=9818983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB6687/77A Expired GB1589924A (en) | 1977-02-17 | 1977-02-17 | Manufacture of 1,1,1,2-tetrafluoroethane halogenated compounds |
Country Status (3)
| Country | Link |
|---|---|
| BE (1) | BE863913A (en) |
| GB (1) | GB1589924A (en) |
| ZA (1) | ZA78702B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3543244A1 (en) * | 1984-12-10 | 1986-06-19 | Quadrex Hps Inc | METHOD AND APPARATUS FOR CLEANING CLOTHING AND TEXTILES that are contaminated with fissile, chemical and / or biological substances |
| EP0502605A1 (en) * | 1991-03-07 | 1992-09-09 | Imperial Chemical Industries Plc | Fluorination catalyst and process |
| US5334786A (en) * | 1990-03-13 | 1994-08-02 | Daikin Industries, Ltd. | Process for preparing 1,1,1,2-tetrafluoroethane |
| US5382722A (en) * | 1990-03-29 | 1995-01-17 | Imperial Chemical Industries Plc | Chemical process for the manufacture of 1,1,1,2-tetrafluoroethane |
| CN1049419C (en) * | 1992-02-26 | 2000-02-16 | 帝国化学工业公司 | A process for the production of a fluorinated hydrocarbon |
| CN1051252C (en) * | 1992-09-17 | 2000-04-12 | 帝国化学工业公司 | Catalyst production |
| US6300531B1 (en) | 1991-05-24 | 2001-10-09 | Daikin Industries, Ltd. | Fluorination catalyst and process for fluorinating halogenated hydrocarbon |
| US6337299B1 (en) | 1991-05-24 | 2002-01-08 | Daikin Industries Ltd. | Fluorination catalyst and process for fluorinating halogenated hydrocarbon |
| US6891074B2 (en) | 2000-09-02 | 2005-05-10 | Ineos Fluor Holdings Limited | Production of hydrofluoroalkanes |
| WO2006009949A2 (en) * | 2004-06-21 | 2006-01-26 | Exxonmobile Chemical Patents Inc. | Low fouling and high activity polymerization process |
| US9771309B2 (en) | 2005-04-08 | 2017-09-26 | Mexichem Amanco Holding S.A. De C.V. | Chromia based fluorination catalyst |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1230779B (en) * | 1989-07-12 | 1991-10-29 | Ausimont Srl | PROCEDURE FOR PREPARING 1,1,1,2 TETRAFLUOROETHANE. |
-
1977
- 1977-02-17 GB GB6687/77A patent/GB1589924A/en not_active Expired
-
1978
- 1978-02-06 ZA ZA00780702A patent/ZA78702B/en unknown
- 1978-02-13 BE BE185127A patent/BE863913A/en unknown
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3543244A1 (en) * | 1984-12-10 | 1986-06-19 | Quadrex Hps Inc | METHOD AND APPARATUS FOR CLEANING CLOTHING AND TEXTILES that are contaminated with fissile, chemical and / or biological substances |
| GB2174720A (en) * | 1984-12-10 | 1986-11-12 | Quadrex Hps Inc | Method of and apparatus for cleaning garments and soft goods contaminated with nuclear, chemical and/or biological contaminants |
| US5475166A (en) * | 1990-03-13 | 1995-12-12 | Daikin Industries, Ltd. | Process for preparing 1,1,1,2-tetrafluoroethane |
| US5395998A (en) * | 1990-03-13 | 1995-03-07 | Daikin Industries, Ltd. | Process for preparing 1,1,1-trifluorochloroethane and 1,1,1,2-tetrafluoroethane |
| US5334786A (en) * | 1990-03-13 | 1994-08-02 | Daikin Industries, Ltd. | Process for preparing 1,1,1,2-tetrafluoroethane |
| US5382722A (en) * | 1990-03-29 | 1995-01-17 | Imperial Chemical Industries Plc | Chemical process for the manufacture of 1,1,1,2-tetrafluoroethane |
| US5281568A (en) * | 1991-03-07 | 1994-01-25 | Imperial Chemical Industries Plc | Process for the production of a chromium-containing fluorination catalyst |
| EP0666105A2 (en) * | 1991-03-07 | 1995-08-09 | Imperial Chemical Industries Plc | Fluorination catalyst and process |
| EP0666105A3 (en) * | 1991-03-07 | 1995-09-06 | Ici Plc | |
| US5449656A (en) * | 1991-03-07 | 1995-09-12 | Imperial Chemical Industries Plc | Fluorination catalyst and process |
| EP0502605A1 (en) * | 1991-03-07 | 1992-09-09 | Imperial Chemical Industries Plc | Fluorination catalyst and process |
| US5623092A (en) * | 1991-03-07 | 1997-04-22 | Imperial Chemical Industries Plc | Fluorination catalyst and process |
| EP1350564A1 (en) * | 1991-03-07 | 2003-10-08 | Ineos Fluor Holdings Limited | Fluorination catalyst and process |
| US6300531B1 (en) | 1991-05-24 | 2001-10-09 | Daikin Industries, Ltd. | Fluorination catalyst and process for fluorinating halogenated hydrocarbon |
| US6337299B1 (en) | 1991-05-24 | 2002-01-08 | Daikin Industries Ltd. | Fluorination catalyst and process for fluorinating halogenated hydrocarbon |
| CN1049419C (en) * | 1992-02-26 | 2000-02-16 | 帝国化学工业公司 | A process for the production of a fluorinated hydrocarbon |
| CN1051252C (en) * | 1992-09-17 | 2000-04-12 | 帝国化学工业公司 | Catalyst production |
| US6891074B2 (en) | 2000-09-02 | 2005-05-10 | Ineos Fluor Holdings Limited | Production of hydrofluoroalkanes |
| WO2006009949A2 (en) * | 2004-06-21 | 2006-01-26 | Exxonmobile Chemical Patents Inc. | Low fouling and high activity polymerization process |
| WO2006009949A3 (en) * | 2004-06-21 | 2007-09-07 | Exxonmobil Chem Patents Inc | Low fouling and high activity polymerization process |
| US7423103B2 (en) | 2004-06-21 | 2008-09-09 | Exxonmobil Chemical Patents Inc. | Low fouling and high activity polymerization process |
| US9771309B2 (en) | 2005-04-08 | 2017-09-26 | Mexichem Amanco Holding S.A. De C.V. | Chromia based fluorination catalyst |
| US10189757B2 (en) | 2005-04-08 | 2019-01-29 | Mexichem Amanco Holding S.A. De C.V. | Chromia based fluorination catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| BE863913A (en) | 1978-08-14 |
| ZA78702B (en) | 1979-01-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PCNP | Patent ceased through non-payment of renewal fee |