WO1999006342A1 - Preparation de 1,1,1,2,3,3,3-heptafluoropropane en phase vapeur - Google Patents

Preparation de 1,1,1,2,3,3,3-heptafluoropropane en phase vapeur Download PDF

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Publication number
WO1999006342A1
WO1999006342A1 PCT/GB1998/001951 GB9801951W WO9906342A1 WO 1999006342 A1 WO1999006342 A1 WO 1999006342A1 GB 9801951 W GB9801951 W GB 9801951W WO 9906342 A1 WO9906342 A1 WO 9906342A1
Authority
WO
WIPO (PCT)
Prior art keywords
hfp
hfc
hydrogen fluoride
carried out
reaction
Prior art date
Application number
PCT/GB1998/001951
Other languages
English (en)
Inventor
Paul Nicholas Ewing
Paul Hendry Stewart
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
Priority claimed from GBGB9716136.8A external-priority patent/GB9716136D0/en
Application filed by Imperial Chemical Industries Plc filed Critical Imperial Chemical Industries Plc
Priority to EP19980932350 priority Critical patent/EP1000002A1/fr
Priority to AU82289/98A priority patent/AU8228998A/en
Priority to JP2000505107A priority patent/JP2001512092A/ja
Publication of WO1999006342A1 publication Critical patent/WO1999006342A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • 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

Definitions

  • the present invention relates to a process for the preparation of 1,1,1, 2,3,3, 3-heptafluoropropane from hexafluoropropene, particularly to the process therefor carried out in the vapour phase.
  • Hydrofluorocarbons referred to hereinafter for convenience as HFC 's, are widely used as replacements for chlorofluorocarbon compounds. Such uses include use in medical applications, for example as an aerosol propellant, use as a fire suppressant, use in refrigeration applications and in other applications.
  • 1,1,1,2,3,3,3-heptafluoropropane which will be referred to hereinafter for convenience as HFC 227ea, has zero ozone depletion potential and is particularly beneficial in medical propellant applications in the light of its combination of properties including low toxicity, non-flammability, solvent properties and boiling point.
  • HFC 227ea It is known in the art to produce HFC 227ea by the hydrofluorination of hexafluoropropene, optionally in the presence of a catalyst, in the liquid phase or vapour phase.
  • Hydrogen fluoride is known for use as a hydrofluorination agent in such a hydrofluorination reaction.
  • a variety of materials may be employed as catalyst in such a hydrofluorination reaction.
  • HFP liquid phase reaction of hexafluoropropene, hereinafter referred to for convenience as HFP, with hydrogen fluoride for the preparation of HFC 227ea
  • catalysts in the liquid phase reaction WO 97/11042 and EP 0,634,383 disclose the use of an organic amine complexed with hydrogen fluoride; WO 96/0243 discloses the use of certain antimony catalysts; and EP 0,634,384 discloses the use of a weak ion-exchange resin containing tertiary amine groups.
  • GB 902590 discloses the use of an activated carbon catalyst with an at least equimolar gaseous mixture of hydrogen fluoride and HFP, at atmospheric pressure and high temperature; for high yield, the HF.HFP molar ratio is preferably between 1.5:1 and 3:1.
  • the use of activated carbon as catalyst in the vapour phase reaction has the drawback that it rapidly becomes deactivated.
  • EP 0,562,509 describes a process for reactivating such a carbon catalyst by heating it at 450-900°C in a stream of inert gas or under reduced pressure.
  • US 4,158,023 describes the preparation of HFC 227ea as a non-isolated intermediate in the vapour-phase preparation of octafluoropropane from HFP. It discloses the use of a chromium oxyfluoride catalyst in the vapour phase reaction of HFP with hydrogen fluoride for the preparation of HFC 227ea, at 100-350°C, at generally normal pressure and with a low molar ratio of HF:HFP, namely from 1:1 to 3:1.
  • a process for the preparation of HFC 227ea by reacting hydrogen fluoride with HFP in the vapour phase over a fluorination catalyst characterised in that the molar ratio of HF:HFP is at least 3.5: 1.
  • the molar ratio of HF:HFP is preferably in the range 3.5:1 to 100:1, more preferably in the range 4:1 to 50:1.
  • a gaseous mixture of HFP and hydrogen fluoride is passed through a heatable reactor tube containing a hydrofluorination catalyst.
  • the reactor tube may be of conventional design made of appropriate material resistant to hydrogen fluoride.
  • fluorination catalysts which may be used in the process according to the present invention may be mentioned inter alia (i) fluorination catalysts based on metal oxides/halides or oxyhalides or mixed metal oxides/halides/oxyhalides, for example chromia or alumina; (ii) other metallic oxides/halides/oxyhalides supported on chromia or alumina, for example oxides of zinc, iron, magnesium or nickel; and (iii) metal oxides/halides/oxyhalides, or mixed metal oxides/halides/oxyhalides supported on carbon.
  • the fluorination catalyst is dried and subjected to a pretreatment, eg with hydrogen fluoride, prior to use.
  • fluorination catalysts are disclosed in our EP 0,502,605 and WO 93/25508, the disclosures in which are incorporated herein by way of reference.
  • the metal on which the fluorination catalyst used in the present invention is based is preferably a d- or p-block metal, oxide, fluoride or oxyfluoride thereof, and more preferably chromium, aluminium or a Group Villa metal.
  • the catalyst may be compressed into pellets and used in a fixed bed or, alternatively, catalysts of appropriate particle size may be used in a fluidised bed.
  • the reaction of HFP with hydrogen fluoride is not equilibrium limited, therefore it is possible to obtain very high conversions per pass, eg 50-100%.
  • the reaction of HFP with hydrogen fluoride is significantly exothermic.
  • the reaction can be carried out in a cooled reactor, eg a salt-cooled reactor, or in an adiabatic reactor under conditions which moderate the heat generated through formation of HFC 227ea.
  • the heat generated can be removed between reactors in a series thereof and/or by use of a diluent in the reaction mixture.
  • the reaction according to the present invention is preferably carried out in the presence of a diluent.
  • HFP is moderated and we have found that the reaction can be carried out in an adiabatic reactor or series of adiabatic reactors, that is a reactor to which none, or little thermal regulation, ie heating or cooling is required.
  • the diluent is preferably a HFC or hydrogen fluoride, more preferably a HFC. However, we do not exclude the possibility that it may be an alternative diluent, eg nitrogen, etc.
  • preferred HFC diluents may be mentioned inter alia 1,1,1,2-tetrafluoroethane, pentafluoroethane or preferably HFC 227ea.
  • HFC 227ea or hydrogen fluoride as diluent in the reaction facilitates separation of the products at the end of the reaction and allows the use of a simpler separation train and smaller plant.
  • the maximum acceptable exotherm across an adiabatic reactor is 50°C and the HF:HFP molar feed ratio is 10:1 we have found that for 50% HFP conversion, 70% HFP conversion and 100% HFP conversion using recycled HFC 227ea as diluent, the relative size of the reactor(s) compared with the use of excess hydrogen fluoride as diluent is about 30%, ie a reduction in reactor size of about 70%.
  • the presence of recycled HFC 227ea in the feed to the adiabatic reactor(s) does not adversely affect the conversion of HFP into HFC 227ea since, as mentioned above, the reaction of HFP with hydrogen fluoride is not equilibrium limited. It will be appreciated that use of a low cost adiabatic reactor provides significant capital cost advantage over a salt-cooled reactor employing an internal cooling surface.
  • the contact time is typically less than 5 minutes and preferably is 1-5 seconds.
  • the process according to the present invention is typically carried out in the temperature range 100-500°C.
  • the process according to the present invention is preferably carried out at superatmospheric pressure, for example 2-50 barg, more preferably 5-25 barg. It will be appreciated that where the process is carried out at superatmospheric pressure the productivity of the reactor is increased, smaller-scale plant can be used for the same throughput and less expensive refrigeration can be used in the primary separation stage following the reactor.
  • the product stream from the reactor in which HFP is reacted with hydrogen fluoride to prepare HFC 227ea typically contains HFC 227ea, hydrogen fluoride and hexafluoropropene.
  • the HFC 227ea may be isolated from unchanged starting materials and by-products using conventional procedures, for example distillation.
  • Example 1 The present invention is further illustrated by reference to the following Examples.
  • Example 1 The present invention is further illustrated by reference to the following Examples.
  • This Example illustrates the advantage of carrying out the reaction of HF with HFP at a high HF:HFP molar ratio, namely 10:1.
  • a mixed zinc/chromium oxide fluorination catalyst was charged to a reactor, dried under nitrogen at 200°C for 16 hours and treated with a vapour stream of hydrogen fluoride in nitrogen at 300-380°C for 16 hours.
  • the temperature in the reactor was adjusted to give the desired reaction temperature and vapour comprising HFP, hydrogen fluoride and nitrogen in the molar ratio shown in Table 1 was charged to the reactor under atmospheric pressure.
  • Example 1 In a Comparative Test, Example 1 was repeated except that a HF:HFP molar ratio of 1 : 1 was used instead of 10: 1.
  • CT2 is a Comparative Test.

Abstract

La présente invention concerne un procédé de préparation de 1,1,1,2,3,3,3-heptafluoropropane (HFC 227ea) consistant à faire réagir un fluorure d'hydrogène avec un hexafluoropropane en phase vapeur sur un catalyseur de fluoration qui utilise un rapport molaire HP:HFP d'au moins 3,5:1. La réaction peut être réalisée dans des conditions adiabatiques avec un encrassement du catalyseur moindre. L'utilisation de HFC 227ea comme diluant permet d'utiliser une installation plus petite.
PCT/GB1998/001951 1997-07-31 1998-07-02 Preparation de 1,1,1,2,3,3,3-heptafluoropropane en phase vapeur WO1999006342A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP19980932350 EP1000002A1 (fr) 1997-07-31 1998-07-02 Preparation de 1,1,1,2,3,3,3-heptafluoropropane en phase vapeur
AU82289/98A AU8228998A (en) 1997-07-31 1998-07-02 Vapour phase preparation of 1,1,1,2,3,3,3-heptafluoropropane
JP2000505107A JP2001512092A (ja) 1997-07-31 1998-07-02 １，１，１，２，３，３，３−ヘプタフルオロプロパンの気相製造

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9716136.8 1997-07-31
GBGB9716136.8A GB9716136D0 (en) 1997-07-31 1997-07-31 Vapour phase separation
US6974297P 1997-12-16 1997-12-16
US60/069,742 1997-12-16

Publications (1)

Publication Number Publication Date
WO1999006342A1 true WO1999006342A1 (fr) 1999-02-11

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Application Number Title Priority Date Filing Date
PCT/GB1998/001951 WO1999006342A1 (fr) 1997-07-31 1998-07-02 Preparation de 1,1,1,2,3,3,3-heptafluoropropane en phase vapeur

Country Status (5)

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EP (1) EP1000002A1 (fr)
JP (1) JP2001512092A (fr)
CN (1) CN1271337A (fr)
AU (1) AU8228998A (fr)
WO (1) WO1999006342A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0967192A1 (fr) * 1998-06-19 1999-12-29 Ausimont S.p.A. Procédé de Préparation du 1,1,1,2,3,3,3-heptafluoropropane
WO2002018305A2 (fr) * 2000-08-30 2002-03-07 Showa Denko K. K. Production et utilisation d'octafluoropropane
JP2002069014A (ja) * 2000-08-30 2002-03-08 Showa Denko Kk オクタフルオロプロパンの製造方法及びその用途
EP1463696A2 (fr) * 2001-10-31 2004-10-06 E. I. du Pont de Nemours and Company Production en phase gazeuse de 1,1,1,2,3,3,3-heptafluoropropane a partir de fluorure d'hydrogene et d'hexafluoropropylene
CN102731245A (zh) * 2012-07-09 2012-10-17 临海市利民化工有限公司 一种七氟丙烷的生产方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3056269B1 (fr) * 2013-11-07 2019-04-24 China Petroleum & Chemical Corporation Catalyseur supporté, son procédé de préparation et son utilisation, et procédé de préparation d'isobutylène à partir d'un halométhane
CN112125777B (zh) 2020-08-27 2022-06-03 浙江衢化氟化学有限公司 一种联产氢氟烃的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2384734A1 (fr) * 1977-03-23 1978-10-20 Hoechst Ag Procede de preparation d'octafluoropropane
EP0502605A1 (fr) * 1991-03-07 1992-09-09 Imperial Chemical Industries Plc Procédé et catalyseur de fluoration
WO1993025508A1 (fr) * 1992-06-11 1993-12-23 Imperial Chemical Industries Plc Production d'hydrofluorocarbures
WO1995032935A1 (fr) * 1994-05-26 1995-12-07 E.I. Du Pont De Nemours And Company Production de 1,2-dihydro et 2,2-dihydro hexafluoropropanes et d'azeotropes de ces derniers a l'aide de fluorure d'hydrogene
EP0714873A1 (fr) * 1994-11-29 1996-06-05 Elf Atochem North America, Inc. Hydrofluoration adiabatique de chlorofluorohydrocarbures

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2384734A1 (fr) * 1977-03-23 1978-10-20 Hoechst Ag Procede de preparation d'octafluoropropane
EP0502605A1 (fr) * 1991-03-07 1992-09-09 Imperial Chemical Industries Plc Procédé et catalyseur de fluoration
WO1993025508A1 (fr) * 1992-06-11 1993-12-23 Imperial Chemical Industries Plc Production d'hydrofluorocarbures
WO1995032935A1 (fr) * 1994-05-26 1995-12-07 E.I. Du Pont De Nemours And Company Production de 1,2-dihydro et 2,2-dihydro hexafluoropropanes et d'azeotropes de ces derniers a l'aide de fluorure d'hydrogene
EP0714873A1 (fr) * 1994-11-29 1996-06-05 Elf Atochem North America, Inc. Hydrofluoration adiabatique de chlorofluorohydrocarbures

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0967192A1 (fr) * 1998-06-19 1999-12-29 Ausimont S.p.A. Procédé de Préparation du 1,1,1,2,3,3,3-heptafluoropropane
US6187975B1 (en) 1998-06-19 2001-02-13 Ausimont S.P.A. Preparation process of 227
KR100630399B1 (ko) * 1998-06-19 2006-09-29 오시몬트 에스.페.아. 227의 제조공정
US7102039B2 (en) 2000-08-30 2006-09-05 Showa Denko K.K. Production and use of octafluoropropane
WO2002018305A3 (fr) * 2000-08-30 2002-10-10 Showa Denko Kk Production et utilisation d'octafluoropropane
US6720464B2 (en) 2000-08-30 2004-04-13 Showa Denko K.K. Production and use of octafluoropropane
JP2002069014A (ja) * 2000-08-30 2002-03-08 Showa Denko Kk オクタフルオロプロパンの製造方法及びその用途
WO2002018305A2 (fr) * 2000-08-30 2002-03-07 Showa Denko K. K. Production et utilisation d'octafluoropropane
CN1314639C (zh) * 2000-08-30 2007-05-09 昭和电工株式会社 八氟丙烷的制备和用途
JP4539793B2 (ja) * 2000-08-30 2010-09-08 昭和電工株式会社 オクタフルオロプロパンの製造方法及びその用途
EP1463696A2 (fr) * 2001-10-31 2004-10-06 E. I. du Pont de Nemours and Company Production en phase gazeuse de 1,1,1,2,3,3,3-heptafluoropropane a partir de fluorure d'hydrogene et d'hexafluoropropylene
US6900362B2 (en) 2001-10-31 2005-05-31 E. I. Du Pont De Nemours And Company Vapor phase production of 1,1,1,2,3,3,3-heptafluoropropane from hydrogen fluoride and hexafluoropropylene
EP1463696A4 (fr) * 2001-10-31 2006-03-15 Du Pont Production en phase gazeuse de 1,1,1,2,3,3,3-heptafluoropropane a partir de fluorure d'hydrogene et d'hexafluoropropylene
CN102731245A (zh) * 2012-07-09 2012-10-17 临海市利民化工有限公司 一种七氟丙烷的生产方法

Also Published As

Publication number Publication date
CN1271337A (zh) 2000-10-25
JP2001512092A (ja) 2001-08-21
EP1000002A1 (fr) 2000-05-17
AU8228998A (en) 1999-02-22

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