WO2010013576A1 - Procédé de production de composé à base de propène fluoré - Google Patents

Procédé de production de composé à base de propène fluoré Download PDF

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Publication number
WO2010013576A1
WO2010013576A1 PCT/JP2009/062068 JP2009062068W WO2010013576A1 WO 2010013576 A1 WO2010013576 A1 WO 2010013576A1 JP 2009062068 W JP2009062068 W JP 2009062068W WO 2010013576 A1 WO2010013576 A1 WO 2010013576A1
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WO
WIPO (PCT)
Prior art keywords
formula
catalyst
compound represented
reaction
hydrogen
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PCT/JP2009/062068
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English (en)
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WO2010013576A8 (fr
Inventor
Masatoshi Nose
Atsushi Suzuki
Akinari Sugiyama
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Daikin Industries, Ltd.
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Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Publication of WO2010013576A1 publication Critical patent/WO2010013576A1/fr
Publication of WO2010013576A8 publication Critical patent/WO2010013576A8/fr

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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

Definitions

  • this process is not suitable for industrial production because of the high cost of zinc and large amounts of waste.
  • NPL 2 and NPL 3 disclose processes for producing HFC-1234yf.
  • PTL 6 discloses a process for carrying out HCl-elimination of CF 2 CICFCICH 3 (HCFC-243bc) ; however, the starting materials for this process are extremely difficult to obtain.
  • Patent Literature PTL 1 WO 2008/060614 A2
  • NPL 1 J. Chem. Soc, 1957, 2193-2197
  • NPL 3 J. Flu. Chem., 1997, 82, 171-174
  • CF 2 XCF CCl 2 wherein X is the same as the above, with hydrogen in the presence of a catalyst.
  • the present invention has been accomplished on the basis of this finding. More specifically, the present invention provides the following process for producing a fluorine-containing propene compound:
  • Item 2. The process according to Item 1, wherein the catalyst is a palladium-carbon catalyst.
  • Item 3. The process according to Item 2, wherein the palladium- carbon catalyst is poisoned with sulfur using 0.1 to 5 mol of poisoning agent per mol of the palladium in the catalyst.
  • Item 4. The process according to any one of Items 1 to 3, wherein the reduction reaction is carried out in the presence of a base, in water as a reaction medium.
  • Item 5 The process according to any one of Items 1 to 4, wherein the reaction temperature is -5 to 50 0 C.
  • a compound represented by the formula: CF 3 CF CCl 2 (CFC-1214ya)
  • Such starting compounds can be produced by known methods. For example, they can be easily obtained by an HF- elimination reaction of a compound represented by Formula (3) : CF 2 XCF 2 CHCl 2 wherein X is F, Cl, or H.
  • CF 3 CF 2 CHCl 2 (HCFC-225ca)
  • HF-elimination can be performed with KOH in the presence of a phase-transfer catalyst (e.g., Aliquat 336
  • the starting compounds can be produced by or based on the method described in the Bulletin de Ia Societe Chimique de France, (6), pp. 920-4, 1986.
  • a preferable catalyst for the hydrogen reduction reaction is, although not limited to, palladium. It is preferable to use a palladium catalyst as a palladium-carbon (Pd-C) catalyst in which palladium is supported on activated carbon.
  • the amount of the palladium is preferably 0.001 to 0.2 parts by weights, and more preferably about 0.005 to 0.1 parts by weight, per part by weight of the support.
  • the palladium catalyst can be poisoned by adding potassium sulfate (K 2 SO 4 ) , barium sulfate (BaSO 4 ) , sodium sulfate (Na 2 SO 4 ) , or other sulfur-containing compounds as a poisoning agent to an aqueous suspension of the palladium catalyst, followed by sufficient mixing.
  • the amount of the poisoning agent is preferably about 0.1 to 5 mol, and more preferably about 1 to 3 mol, per mol of the palladium in the catalyst.
  • the time required for the poisoning treatment is not limited, but is, for example, set about 5 to 60 minutes.
  • the poisoning treatment of the palladium catalyst can be performed in a reactor before introducing hydrogen for the hydrogenation reaction.
  • the poisoning treatment may be carried out by adding halogenated propene compound, which is the starting material, to water (reaction medium) together with a palladium catalyst and a poisoning agent, and sufficiently stirring the mixture; and then hydrogen is introduced to perform a hydrogenation reaction.
  • the amount of the catalyst is preferably about 0.001 to 0.01 parts by weight, and more preferably about 0.002 to 0.008 parts by weight, per part by weight of the compound represented by Formula (1) .
  • water can generally be used as a reaction medium for the hydrogen reduction reaction of the compound of Formula (1) .
  • the halogenated propene compound represented by Formula (1) and a catalyst may be mixed and uniformly suspended in water, which is used as a reaction medium, and the suspension may be brought into contact with hydrogen.
  • the amount of water used as a reaction medium is preferably about 1 to 10 parts by weight, and more preferably about 3 to 7 parts by weight, per part by weight of the compound represented by Formula (1) .
  • ethanol, methanol, propanol, and other hydrophilic solvents may be added as reaction mediums in an amount of about 0.1 to 5 parts by weight, per part by weight of the water.
  • a base is added to water containing the halogenated propene compound represented by Formula (1) and a catalyst in order to neutralize HCl generated by the reaction.
  • Any bases can be used as long as they can neutralize HCl.
  • Preferable examples include KOH, NaOH, CH 3 CO 2 Na, etc.
  • the amount of the base used is preferably about 2 to 2.4 mol, and more preferably about 2 to 2.2 mol, per mol of the compound represented by Formula (1) .
  • the process of the present invention can usually be carried out in batch mode.
  • the hydrogenation reaction of the halogenated propene compound represented by Formula (1) can be performed in such a manner that the halogenated propene compound of Formula (1) , a base, and a catalyst are uniformly dispersed in water; the mixture is put in a reactor; hydrogen is introduced into the reactor; and the mixture is stirred.
  • the amount of hydrogen used is preferably about 2 to 2.4 mol, and more preferably about 2.1 to 2.3 mol, per mol of the halogenated propene compound represented by Formula (1) .
  • the pressure in the reactor is not limited, usually the partial pressure of hydrogen is preferably about 0.05 to 1.0 MPa-G, and more preferably about 0.1 to 0.8 MPa-G.
  • the reaction temperature is preferably about -5 to 5O 0 C, and more preferably about 0 to 20°C. Temperatures outside this range are not preferable. At reaction temperatures below -5 0 C, an aqueous solution cannot be stirred because the solution is solidified. On the other hand, at temperatures above 50 0 C, the reduction reaction excessively proceeds, raising the production of by-products .
  • reaction time varies depending on the reaction conditions, it is usually about 12 to 48 hours.
  • the progress of the reaction can be monitored by taking a gas sample from the reaction system and analyzing the components of the gas phase using gas chromatography.
  • the fluorine-containing propene compound of Formula (2) obtained by the process of the present invention can be used in various applications.
  • 2,3, 3,3-tetrafluoropropene (HFC-1234yf) which has a low warming potential and a low ozone depletion potential, is useful as, for example, a constituent for a mixed refrigerant that functions as an alternative to chlorofluorocarbon.
  • the process has some advantages including the use of an inexpensive reagent, moderate reaction conditions, and a high yield of target compounds. These advantages make the process of the present invention suitable for industrial production.
  • Example 1 Pd-C catalyst (0.0681 g; type-K; produced by NE-
  • the reactor Under ice-cooling, the reactor was purged with nitrogen, followed by pressure reduction using a vacuum pump. Then, a hydrogen cylinder (filled with hydrogen gas (47 L, 14.7 MPa)) was connected to the reactor.
  • the reaction mixture was stirred at 500 rpm, and held at 1 to 2°C using ice water.
  • the pressure at this time was -0.02 MPa-G.
  • hydrogen was supplied from the hydrogen cylinder connected to the reactor until the internal pressure of the autoclave became 0.8 MPa-G.
  • the internal pressure decreased to around 0.2 MPa-G and hydrogen was again supplied in the same manner.
  • This process was repeated for 17 hours until a total of 0.1185 mol (2653 cc) of hydrogen was supplied.
  • a gas sample was taken at times, and the composition of the gas phase was analyzed using gas chromatography. The reaction was carried out for a total of 21 hours.
  • the internal pressure of the reactor at this time was 0.14 MPa-G.
  • the gas component was removed from the reactor at a temperature of 1 to 2°C. Subsequently, the reactor was heated to an internal temperature of 4O 0 C, and all the organic compounds were taken out. Since the boiling point of the main product (HFC-1234yf) was -28.3°C, the product was collected using a freezing mixture made of dry ice and acetone. The collected product weighed 6.33 g. The collected product was analyzed using gas chromatography; the CFC-1214ya conversion was 97.9%, the HFC-1234yf selectivity was 75.6%, and the isolation yield was 74.0%.
  • the reactor Under ice-cooling, the reactor was purged with nitrogen, followed by pressure reduction using a vacuum pump. Then, a hydrogen cylinder (filled with hydrogen gas (47 L, 14.7 MPa)) was connected to the reactor.
  • the reaction mixture was stirred at 500 rpm, and held at 1 to 2°C using ice water.
  • the pressure at this time was -0.04 MPa-G.
  • hydrogen was supplied from the hydrogen cylinder connected to the reactor until the internal pressure of the autoclave became 0.8 MPa-G.
  • the internal pressure decreased to around 0.3 MPa-G and hydrogen was again supplied in the same manner.
  • This process was repeated for 34 hours until a total of 0.1144 mol (2562 cc) of hydrogen was supplied.
  • a gas sample was taken at times, and the composition of the gas phase was analyzed using gas chromatography. The reaction was carried out for a total of 43 hours.
  • the internal pressure of the reactor at this time was 0.19 MPa-G.
  • the gas component was removed from the reactor at a temperature of 1 to 2 0 C. Subsequently, the reactor was heated to an internal temperature of 8O 0 C, and all the organic compounds were taken out.
  • the product was collected using a freezing mixture made of dry ice and acetone. The collected product weighed 6.67 g. The collected product was analyzed using gas chromatography; the CFC-1213ya conversion was 94.4%, the HCFC-1233yf selectivity was 67.3%, and the isolation yield was 63.5%.

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

Abstract

Cette invention concerne un procédé de production d’un composé à base de propène fluoré de formule (2) : CF2191XCF=CH2, X étant F, Cl ou H, le procédé comprenant la réduction d’un composé de formule (1) : CF2XCF=CCl2, X étant le même que précédemment, avec hydrogène en présence d’un catalyseur. Le procédé selon l’invention convient pour la production industrielle et garantit une production simple et efficace simple du composé à base de propène fluoré de formule (2) : CF2XCF=CH2, X étant F, Cl ou H.
PCT/JP2009/062068 2008-07-30 2009-06-25 Procédé de production de composé à base de propène fluoré WO2010013576A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US8471208P 2008-07-30 2008-07-30
US61/084,712 2008-07-30

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WO2010013576A1 true WO2010013576A1 (fr) 2010-02-04
WO2010013576A8 WO2010013576A8 (fr) 2010-04-29

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011162341A1 (fr) * 2010-06-23 2011-12-29 旭硝子株式会社 Procédé de fabrication de 2,3,3,3-tétrafluoropropène
WO2011162336A1 (fr) * 2010-06-23 2011-12-29 旭硝子株式会社 Procédé de fabrication de 1,1-dichloro-2,3,3,3-tétra-fluoropropène et de 2,3,3,3-tétrafluoropropène
EP2586759A1 (fr) * 2010-06-23 2013-05-01 Asahi Glass Company, Limited Procédé de fabrication de 2,3,3,3-tétrafluoropropène
US9637429B2 (en) 2014-04-16 2017-05-02 The Chemours Company Fc, Llc Conversion of chlorofluororopanes and chlorofluropropenes to more desirable fluoropropanes and fluororopenes
CN107759440A (zh) * 2017-11-07 2018-03-06 中国民航大学 一种将含氟烯烃双键上的氟置换成氢的方法
CN109563010A (zh) * 2016-08-09 2019-04-02 Ａｇｃ株式会社 1-氯-2,3,3,3-四氟丙烯的制造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008060614A2 (fr) * 2006-11-15 2008-05-22 E. I. Du Pont De Nemours And Company Procédé de production de 2,3,3,3-tétrafluoropropène
WO2008079265A1 (fr) * 2006-12-20 2008-07-03 E. I. Du Pont De Nemours And Company Procédé de synthèse et de séparation d'hydrofluoro-oléfines

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008060614A2 (fr) * 2006-11-15 2008-05-22 E. I. Du Pont De Nemours And Company Procédé de production de 2,3,3,3-tétrafluoropropène
WO2008079265A1 (fr) * 2006-12-20 2008-07-03 E. I. Du Pont De Nemours And Company Procédé de synthèse et de séparation d'hydrofluoro-oléfines

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5713016B2 (ja) * 2010-06-23 2015-05-07 旭硝子株式会社 １，１−ジクロロ−２，３，３，３−テトラフルオロプロペンおよび２，３，３，３−テトラフルオロプロペンの製造方法
EP2586759A1 (fr) * 2010-06-23 2013-05-01 Asahi Glass Company, Limited Procédé de fabrication de 2,3,3,3-tétrafluoropropène
WO2011162341A1 (fr) * 2010-06-23 2011-12-29 旭硝子株式会社 Procédé de fabrication de 2,3,3,3-tétrafluoropropène
CN102958879A (zh) * 2010-06-23 2013-03-06 旭硝子株式会社 2,3,3,3-四氟丙烯的制造方法
WO2011162336A1 (fr) * 2010-06-23 2011-12-29 旭硝子株式会社 Procédé de fabrication de 1,1-dichloro-2,3,3,3-tétra-fluoropropène et de 2,3,3,3-tétrafluoropropène
US8530711B2 (en) 2010-06-23 2013-09-10 Asahi Glass Company, Limited Process for producing 2,3,3,3-tetrafluoropropene
US8642820B2 (en) 2010-06-23 2014-02-04 Asahi Glass Company, Limited Process for producing 1,1-dichloro-2,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene
EP2586759A4 (fr) * 2010-06-23 2014-04-16 Asahi Glass Co Ltd Procédé de fabrication de 2,3,3,3-tétrafluoropropène
CN102958879B (zh) * 2010-06-23 2014-12-10 旭硝子株式会社 2,3,3,3-四氟丙烯的制造方法
JP5713020B2 (ja) * 2010-06-23 2015-05-07 旭硝子株式会社 ２，３，３，３−テトラフルオロプロペンの製造方法
CN102947257A (zh) * 2010-06-23 2013-02-27 旭硝子株式会社 1,1-二氯-2,3,3,3-四氟丙烯及2,3,3,3-四氟丙烯的制造方法
US9637429B2 (en) 2014-04-16 2017-05-02 The Chemours Company Fc, Llc Conversion of chlorofluororopanes and chlorofluropropenes to more desirable fluoropropanes and fluororopenes
US9822047B2 (en) 2014-04-16 2017-11-21 The Chemours Company Fc, Llc Conversion of chlorofluororopanes and chlorofluropropenes to more desirable fluoropropanes and fluororopenes
US10351495B2 (en) 2014-04-16 2019-07-16 The Chemours Company Fc, Llc Conversion of chlorofluororopanes and chlorofluropropenes to more desirable fluoropropanes and fluororopenes
US10584082B2 (en) 2014-04-16 2020-03-10 The Chemours Company Fc, Llc Conversion of chlorofluororopanes and chlorofluropropenes to more desirable fluoropropanes and fluororopenes
US10815173B2 (en) 2014-04-16 2020-10-27 The Chemours Company Fc, Llc Compositions comprising fluoropropenes and fluoropropanes and methods for preparing the compositions
US11332424B2 (en) 2014-04-16 2022-05-17 The Chemours Company Fc, Llc Conversion of chlorofluororopanes and chlorofluropropenes to more desirable fluoropropanes and fluororopenes
US12060309B2 (en) 2014-04-16 2024-08-13 The Chemours Company Fc, Llc Conversion of chlorofluororopanes and chlorofluropropenes to more desirable fluoropropanes and fluororopenes and compositions thereof
CN109563010A (zh) * 2016-08-09 2019-04-02 Ａｇｃ株式会社 1-氯-2,3,3,3-四氟丙烯的制造方法
CN107759440A (zh) * 2017-11-07 2018-03-06 中国民航大学 一种将含氟烯烃双键上的氟置换成氢的方法
CN107759440B (zh) * 2017-11-07 2020-07-03 中国民航大学 一种将含氟烯烃双键上的氟置换成氢的方法

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