WO1996025377A1 - Procede de coproduction de difluoromethane et de 1,1,1,2-tetrafluoroethane - Google Patents
Procede de coproduction de difluoromethane et de 1,1,1,2-tetrafluoroethane Download PDFInfo
- Publication number
- WO1996025377A1 WO1996025377A1 PCT/FR1996/000070 FR9600070W WO9625377A1 WO 1996025377 A1 WO1996025377 A1 WO 1996025377A1 FR 9600070 W FR9600070 W FR 9600070W WO 9625377 A1 WO9625377 A1 WO 9625377A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- tetrafluoroethane
- difluoromethane
- hydrogen
- chlorodifluoromethane
- pressure
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons
Definitions
- the present invention relates to the simultaneous manufacture of difluoromethane (F32) and 1,1,1,2-tetrafluoroethane (F134a) by pyrolysis of chlorodifluoromethane in the presence of hydrogen, operating at a temperature above 500 ° C in the absence any catalyst or metallic surface. Depending on the operating conditions chosen, this process also makes it possible to manufacture a majority of either F134a or F32.
- 1,1,1,2-tetrafluoroethane (F134a) is already industrially manufactured to replace difluorodichloromethane (F12) in domestic refrigeration and automobile air conditioning in particular.
- Two channels are currently used commercially. They use processes which consist of: • either fluorinating trichlorethylene in two stages
- CCI 2 CCI 2 CF 3 'CCI 2 F " 2 CF 3 -CH 2 F CF3-CHCIF H 2
- Difluoromethane CH2F2 (F32) is a potentially very interesting compound, since in association with pentafluoroethane (F125) it gives an azeotropic mixture which is an excellent substitute for chlorodifluoromé ⁇ thane (F22) is scheduled between 2005 and 2015 due to its potential effect on the weakening of the stratospheric ozone layer.
- Chlorodifluoromethane is widely used as a refrigerant for commercial refrigeration and for air conditioning in large buildings. There are four ways to manufacture the F32 commercially: 1. Fluorination of methylene chloride CH2C-2 by HF in the liquid phase in the presence of an antimony-based catalyst.
- Chlorodifluoromethane (F22) is currently produced on a large scale for commercial refrigeration but also as a raw material for the production of PTFE. When the use of F22 as a refrigerating liquid is prohibited, it will be useful to be able to continue to enhance this compound in other applications.
- the present invention provides a particularly interesting means in this sense. It has in fact been found that chlorodifluoromethane (F22) can be selectively transformed into F134a and F32 by continuously pyrolyzing F22 at a temperature above 500 ° C. in the presence of hydrogen, but in the absence of metals in the reaction zone.
- the amount of hydrogen used is such that the H2 F22 molar ratio is between 2 and 50, and more particularly between 5 and 15.
- the working pressure can go up to 100 bars, but one generally operates at a pressure between 0.1 and 20 bar absolute, preferably between about 0.5 and 5 bar absolute and, more particularly, at pressure atmospheric than.
- the working temperature can be between 500 and 1000 ° C., but one preferentially operates between 650 and 800 ° C.
- the residence time can be between 0.1 and 100 seconds, but it is preferable to operate between 1 and 20 seconds.
- the residence time can be between 0.1 and 100 seconds, but it is preferable to operate between 1 and 20 seconds.
- the F134a formed is accompanied by a variable amount of F134 (HF2C-CHF2) which is easily isomerizable into F134a.
- All the examples are produced in a tubular quartz reactor 47 cm high and 2.3 cm in diameter, placed in an electric oven with a power of 1.5 kW.
- the working pressure is atmospheric pressure and the oven temperature is measured using a thermocouple.
- the reagents are introduced simultaneously continuously by means of calibrated rotameters allowing both to control the flow rates and therefore the molar ratios.
- the flow of reactants in the reactor can be diluted by a flow of inert gas such as helium or nitrogen.
- the entire gas stream leaving the reactor is acidic and is sent to a glass reactor containing aqueous sodium hydroxide to remove the co-produced hydrochloric acid.
- the outgoing gas stream is then dried on a molecular sieve, then condensed at low temperature (-78 ° C) in a stainless steel container fitted with valves allowing gas products to be stored at ordinary temperature.
- the analyzes of the gas mixtures obtained are made by gas chromatography coupled with mass spectrography so as to identify with certainty the products of the reaction.
- the conversion rate of F22 was 93% with selectivities for F32, F 134a and F 134 of 30%, 30% and 12% respectively.
- the conversion rate of F22 was 92% with selectivities for F32, F134a and F134 of 34%, 33% and 18% respectively.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69602015T DE69602015T2 (de) | 1995-02-17 | 1996-01-16 | Verfahren zur coproduktion von difluormethan und 1,1,1,2-tetrafluorethan |
EP96901400A EP0809620B1 (fr) | 1995-02-17 | 1996-01-16 | Procede de coproduction de difluoromethane et de 1,1,1,2-tetrafluoroethane |
JP8524699A JPH11500429A (ja) | 1995-02-17 | 1996-01-16 | ジフルオロメタンおよび1,1,1,2−テトラフルオロエタンの同時製造方法 |
US08/875,656 US5750810A (en) | 1995-02-17 | 1996-01-16 | Method for coproducing difluoromethane and 1,1,1,2-tetrafluoroethane |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9501859A FR2730729B1 (fr) | 1995-02-17 | 1995-02-17 | Procede de coproduction de difluoromethane et de 1,1,1,2-tetrafluoroethane |
FR95/01859 | 1995-02-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996025377A1 true WO1996025377A1 (fr) | 1996-08-22 |
Family
ID=9476262
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1996/000070 WO1996025377A1 (fr) | 1995-02-17 | 1996-01-16 | Procede de coproduction de difluoromethane et de 1,1,1,2-tetrafluoroethane |
Country Status (8)
Country | Link |
---|---|
US (1) | US5750810A (fr) |
EP (1) | EP0809620B1 (fr) |
JP (1) | JPH11500429A (fr) |
CN (1) | CN1067042C (fr) |
DE (1) | DE69602015T2 (fr) |
ES (1) | ES2130789T3 (fr) |
FR (1) | FR2730729B1 (fr) |
WO (1) | WO1996025377A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8481778B2 (en) | 2007-08-16 | 2013-07-09 | Solvay (Societe Anonyme) | Process for the preparation of esters of 4-fluorosubstituted 3-oxo-alcanoic acids |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001005221A1 (fr) * | 1999-07-20 | 2001-01-25 | Ges. Für Erwerb Und Verwertung Von Schutzrechten-Gvs Mbh | Nouveau procede permettant la production et la selection de plantes de lin transgeniques |
US7396965B2 (en) * | 2005-05-12 | 2008-07-08 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
CN106565409B (zh) * | 2016-10-26 | 2019-03-22 | 北京理工大学 | 二氟甲烷热解制备含氟化合物ch2f-r(r=h或-cf3)的方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1991009000A1 (fr) * | 1989-12-15 | 1991-06-27 | Great Lakes Chemical Corporation | Procede de production du bromodifluoromethane |
EP0508660A1 (fr) * | 1991-04-11 | 1992-10-14 | Imperial Chemical Industries Plc | Préparation de difluorométhane |
WO1995024369A1 (fr) * | 1994-03-11 | 1995-09-14 | E.I. Du Pont De Nemours And Company | Procede de conversion de chlorodifluoromethane et ou de dichlorodifluoromethane |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2067370A1 (fr) * | 1989-10-10 | 1991-04-11 | Fernando F. Kielhorn | Hydrogenolyse d'hydrocarbures |
DK0518506T3 (da) * | 1991-06-14 | 1998-03-30 | Ici Plc | Fremstilling af bis-(fluomethyl)-ether og difluormethan |
-
1995
- 1995-02-17 FR FR9501859A patent/FR2730729B1/fr not_active Expired - Fee Related
-
1996
- 1996-01-16 CN CN96191962A patent/CN1067042C/zh not_active Expired - Fee Related
- 1996-01-16 JP JP8524699A patent/JPH11500429A/ja active Pending
- 1996-01-16 US US08/875,656 patent/US5750810A/en not_active Expired - Fee Related
- 1996-01-16 DE DE69602015T patent/DE69602015T2/de not_active Expired - Fee Related
- 1996-01-16 ES ES96901400T patent/ES2130789T3/es not_active Expired - Lifetime
- 1996-01-16 WO PCT/FR1996/000070 patent/WO1996025377A1/fr active IP Right Grant
- 1996-01-16 EP EP96901400A patent/EP0809620B1/fr not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1991009000A1 (fr) * | 1989-12-15 | 1991-06-27 | Great Lakes Chemical Corporation | Procede de production du bromodifluoromethane |
EP0508660A1 (fr) * | 1991-04-11 | 1992-10-14 | Imperial Chemical Industries Plc | Préparation de difluorométhane |
WO1995024369A1 (fr) * | 1994-03-11 | 1995-09-14 | E.I. Du Pont De Nemours And Company | Procede de conversion de chlorodifluoromethane et ou de dichlorodifluoromethane |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8481778B2 (en) | 2007-08-16 | 2013-07-09 | Solvay (Societe Anonyme) | Process for the preparation of esters of 4-fluorosubstituted 3-oxo-alcanoic acids |
Also Published As
Publication number | Publication date |
---|---|
FR2730729B1 (fr) | 1997-04-30 |
DE69602015D1 (de) | 1999-05-12 |
FR2730729A1 (fr) | 1996-08-23 |
EP0809620B1 (fr) | 1999-04-07 |
DE69602015T2 (de) | 1999-10-07 |
ES2130789T3 (es) | 1999-07-01 |
CN1174543A (zh) | 1998-02-25 |
CN1067042C (zh) | 2001-06-13 |
JPH11500429A (ja) | 1999-01-12 |
EP0809620A1 (fr) | 1997-12-03 |
US5750810A (en) | 1998-05-12 |
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