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WO1997029065A1 - Procede de production d'une olefine comportant du fluor - Google Patents

Procede de production d'une olefine comportant du fluor Download PDF

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Publication number
WO1997029065A1
WO1997029065A1 PCT/GB1996/003178 GB9603178W WO9729065A1 WO 1997029065 A1 WO1997029065 A1 WO 1997029065A1 GB 9603178 W GB9603178 W GB 9603178W WO 9729065 A1 WO9729065 A1 WO 9729065A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction zone
reactant
hydrohalocarbon
range
steam
Prior art date
Application number
PCT/GB1996/003178
Other languages
English (en)
Inventor
Richard Llewellyn Powell
Andrew Paul Sharatt
Original Assignee
Imperial Chemical Industries Plc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Imperial Chemical Industries Plc filed Critical Imperial Chemical Industries Plc
Priority to AU11661/97A priority Critical patent/AU1166197A/en
Publication of WO1997029065A1 publication Critical patent/WO1997029065A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons

Definitions

  • the present invention relates to a non-catalytic process for the production of a fluorine containing olefin and more particularly to a non-catalytic process for the production of trifluoroethylene.
  • a non-catalytic process for the production of a fluorine containing olefin which process comprises passing a gaseous feed comprising steam and a saturated hydrohalocarbon reactant having a fluorine substituent and one or more further halogen substituents through a heated reaction zone.
  • a gaseous feed comprising steam and a saturated hydrohalocarbon reactant having a fluorine substituent and one or more further halogen substituents is passed through a heated reaction zone where the hydrohalocarbon reactant is subjected to elevated temperatures and undergoes a dehydrohalogenation reaction so as to yield the desired fluorine containing olefin.
  • the process is non-catalytic, by which we mean that no separate catalyst is placed in the heated reaction zone to catalyse the reaction process.
  • the process ofthe present invention may be used to prepare a variety of fluorine containing olefins, but is particularly concerned with the production of fluorine containing ethylenes and more specifically with the production of trifluoroethylene.
  • Fluorine containing ethylenes are prepared by subjecting a hydrohaloethane starting material containing a fluorine substituent and one or more further halogen substituents to the process ofthe present invention.
  • the one or more further halogen substituents contained in the hydrohaloethane may be fluorine, chlorine, bromine and/or iodine atoms, but will preferably be fluorine and/or chlorine atoms and more preferably will be exclusively fluorine atoms.
  • the hydrohaloethane starting material is preferably one of 1,1,1 ,2-tetrafluoroethane (hereinafter R- 134a) and 1 , 1 ,2,2-tetrafluoroethane (hereinafter R-134), and more preferably is R-134a.
  • the heated reaction zone may be provided by any suitably configured reactor vessel.
  • the heated reaction zone is provided by a tube reactor.
  • the reactor vessel should, of course, be made of a thermally conductive material which is stable, i.e. will not decompose or melt, at the elevated temperatures and under the chemical environment prevailing during operation ofthe process.
  • the reactor vessel may, for example, be made of carbon, graphite or a conductive metal or metal alloy such as nickel and its alloys.
  • the process ofthe present invention is carried out at elevated temperatures in a heated reaction zone.
  • the temperature in the heated reaction zone is not constant throughout and will be highest at the inlet end thereof and lowest at the outlet end.
  • the inlet end ofthe reaction zone is preferably maintained at a temperature in the range of from 800 to 1500°C, more preferably in the range of from 800 to 1200°C and particularly preferably in the range of from 900 to 1200°C.
  • the temperature in the heated reaction zone is not constant throughout and decreases on going from the inlet end to the outlet end thereof.
  • the temperature at the inlet end ofthe heated reaction zone will be of the order of 300 to 700°C higher than the temperature at the outlet end.
  • the residence time for the hydrohalocarbon reactant in the reaction zone is typically in the range of from 0.01 to 100 seconds, with residence times in the range of from 0.1 to 10 seconds being preferred.
  • residence times in the range of from 0.1 to 7 seconds are particularly preferred with residence times in the range of from 0.1 to 5 seconds being especially preferred.
  • residence time we mean the residence time as calculated at room temperatures and pressures (RTP) in accordance with the equation below.
  • volumetric fluid flow rate i.e. the volume of fluid being fed to the reaction zone per unit of time (ml/second)
  • the steam which is fed to the reaction zone is preferably superheated and more preferably is also heated to a temperature which is sufficient to allow its use as the primary or sole heating means for achieving and maintaining the desired reaction temperature in the reaction zone.
  • the volume ratio ofthe steam to the hydrohalocarbon reactant in the gaseous feed entering the reaction zone is preferably in the range of from 1 : 1 to 20: 1, more preferably in the range of from 2: 1 to 15: 1 and particularly preferably in the range of from 5: 1 to 15:1.
  • the reaction pressure employed in the process ofthe present invention is not normally critical and may be atmospheric, sub-atmospheric, or super-atmospheric. However, operating pressures in the region of atmospheric pressure are preferred and, in general, operation at atmospheric pressure or substantially atmospheric pressure is particularly preferred.
  • the heating ofthe reactor vessel to generate the required temperature in the reaction zone may be accomplished by any suitable heating means.
  • heating may be achieved by electromagnetic induction or by means of a furnace disposed around the reactor vessel.
  • high temperature steam as the primary or sole source of heat for generating the desired temperature in the reaction zone.
  • steam is used to heat the reaction zone, it will typically need to be ofthe order of 200°C hotter than the temperature which you are aiming to achieve at the inlet end ofthe reaction zone.
  • supplementary heating means such as a furnace or an electromagnetic induction heater, may be used in addition to the steam to help maintain the desired reaction temperature.
  • the hydrohalocarbon reactant may be fed to the heated reaction zone at or around ambient temperature, but it is preferred to preheat the reactant prior to feeding it to the heated reaction zone.
  • the hydrohalocarbon reactant will be heated to a temperature in the range of from 300 to 700°C, more preferably in the range of from 500 to 600°C.
  • the hot gas stream emerging from the reactor vessel is normally quench cooled.
  • the crude material which is obtained from the present process may be treated and purified by conventional techniques (e.g. distillation) in order to isolate and collect the fluorine containing olefin. Any unreacted starting material collected from the process may be recycled to the inlet end ofthe reactor vessel and passed through the reaction zone once again in order to improve conversion.
  • conventional techniques e.g. distillation
  • TriFE trifluoroethylene
  • the reactor vessel comprised a piece of Inconel tubing of length 15 cms, internal diameter 0.3 cms and external diameter 0.6 cms.
  • the reactor tube was pre-conditioned prior to use by heating it to 1000 °C while passing a gaseous feed containing 90 % by volume of nitrogen and 10 % by volume of R- 134a through the tube. This procedure was continued until the conversion ofthe R-134a reached steady state.
  • the apparatus basically comprised the pre-conditioned reactor tube described above, a syringe pump containing a supply of water, a steam generator comprising a heated injection port, a pre-heater and a tube furnace disposed around the reactor tube.
  • the steam was generated by injecting water from the syringe pump into the heated injection port.
  • the steam so generated was first fed to the pre-heater, where its temperature was raised, and then to the reaction zone provided by the pre-conditioned reactor tube.
  • the R-134a reactant was injected into the steam flow at the entrance to the reaction zone.
  • the steam generator, pre-heater and tube furnace were switched on and the flows of steam and R-134a commenced.
  • the flows ofthe steam and R-134a were adjusted until the gaseous feed entering the reaction zone contained the desired amount of R- 134a, and the temperatures of the pre-heater and tube furnace were gradually raised in parallel up to 1000°C.
  • the temperature ofthe reactor tube wall at the inlet end ofthe reaction zone was 1000°C
  • samples ofthe gaseous product stream emerging from the reactor tube were collected and analysed by gas chromatography. The data obtained was used to calculate the conversion of R- 134a to products and the selectivity to TriFE.
  • the above described general procedure was used to prepare TriFE from R-134a.
  • the gaseous feed entering the reaction zone contained 91.0 % by volume of steam and 9.0 % by volume of R-134a.
  • the residence time for the R-134a in the reaction zone was 0.23 seconds.
  • the conversion of R- 134a to products was 10.4 % and the selectivity to TriFE formation was 79.3 %.
  • the above described general procedure was used to prepare TriFE from R-134a.
  • the gaseous feed entering the reaction zone contained 87.5 % by volume of steam and 12.5 % by volume of R- 134a.
  • the residence time for the R-134a in the reaction zone was 0.42 seconds.
  • the conversion of R- 134a to products was 29.5 % and the selectivity to TriFE formation was 74.6 %.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé non catalytique de production d'une oléfine comportant du fluor. Ce procédé comprend le passage, à travers une zone de réaction chauffée, de gaz d'alimentation comprenant de la vapeur d'eau et un réactif hydrohalocarbure saturé qui comporte un substituant fluor et un ou plusieurs autres substituants halogènes. Ce procédé peut être utilisé pour préparer du trifluoréthylène à partir de 1,1,1,2-tétrafluoroéthane.
PCT/GB1996/003178 1996-02-12 1996-12-20 Procede de production d'une olefine comportant du fluor WO1997029065A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU11661/97A AU1166197A (en) 1996-02-12 1996-12-20 Process for the production of a fluorine containing olefin

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9602805.5A GB9602805D0 (en) 1996-02-12 1996-02-12 Production process
GB9602805.5 1996-02-12

Publications (1)

Publication Number Publication Date
WO1997029065A1 true WO1997029065A1 (fr) 1997-08-14

Family

ID=10788532

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1996/003178 WO1997029065A1 (fr) 1996-02-12 1996-12-20 Procede de production d'une olefine comportant du fluor

Country Status (3)

Country Link
AU (1) AU1166197A (fr)
GB (1) GB9602805D0 (fr)
WO (1) WO1997029065A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7897823B2 (en) * 2004-10-29 2011-03-01 E. I. Du Pont De Nemours And Company Process for production of azeotrope compositions comprising hydrofluoroolefin and hydrogen fluoride and uses of said azeotrope compositions in separation processes
WO2011157907A1 (fr) 2010-06-15 2011-12-22 Arkema France Procédé de préparation de trifluoroéthylène
WO2015115549A1 (fr) * 2014-01-30 2015-08-06 旭硝子株式会社 Procédé de production de trifluoroéthylène

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2106382A1 (fr) * 1970-09-08 1972-05-05 Bayer Ag
FR2710054A1 (fr) * 1993-09-16 1995-03-24 Atochem Elf Sa Procédé de préparation du trifluoroéthylène.
RU2043328C1 (ru) * 1993-01-11 1995-09-10 Российский научный центр "Прикладная химия" Способ получения мономеров
WO1996005157A1 (fr) * 1994-08-08 1996-02-22 Imperial Chemical Industries Plc Procede de production d'olefines contenant du fluor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2106382A1 (fr) * 1970-09-08 1972-05-05 Bayer Ag
RU2043328C1 (ru) * 1993-01-11 1995-09-10 Российский научный центр "Прикладная химия" Способ получения мономеров
FR2710054A1 (fr) * 1993-09-16 1995-03-24 Atochem Elf Sa Procédé de préparation du trifluoroéthylène.
WO1996005157A1 (fr) * 1994-08-08 1996-02-22 Imperial Chemical Industries Plc Procede de production d'olefines contenant du fluor

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 9621, Derwent World Patents Index; Class A41, AN 96-207690, XP002025983 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7897823B2 (en) * 2004-10-29 2011-03-01 E. I. Du Pont De Nemours And Company Process for production of azeotrope compositions comprising hydrofluoroolefin and hydrogen fluoride and uses of said azeotrope compositions in separation processes
WO2011157907A1 (fr) 2010-06-15 2011-12-22 Arkema France Procédé de préparation de trifluoroéthylène
WO2015115549A1 (fr) * 2014-01-30 2015-08-06 旭硝子株式会社 Procédé de production de trifluoroéthylène
US10093600B2 (en) 2014-01-30 2018-10-09 AGC Inc. Method for producing trifluoroethylene

Also Published As

Publication number Publication date
AU1166197A (en) 1997-08-28
GB9602805D0 (en) 1996-04-10

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