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WO1998040335A1 - Procede pour produire du 1,1,1,3,3-pentafluoropropane - Google Patents

Procede pour produire du 1,1,1,3,3-pentafluoropropane Download PDF

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Publication number
WO1998040335A1
WO1998040335A1 PCT/JP1998/000932 JP9800932W WO9840335A1 WO 1998040335 A1 WO1998040335 A1 WO 1998040335A1 JP 9800932 W JP9800932 W JP 9800932W WO 9840335 A1 WO9840335 A1 WO 9840335A1
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WO
WIPO (PCT)
Prior art keywords
pentafluoropropane
producing
propene
chlorine
tetrahalogenopropane
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP1998/000932
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English (en)
Japanese (ja)
Inventor
Tatsuo Nakada
Akinori Yamamoto
Noriaki Shibata
Takashi Shibanuma
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Original Assignee
Daikin Industries Ltd
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 Daikin Industries Ltd filed Critical Daikin Industries Ltd
Publication of WO1998040335A1 publication Critical patent/WO1998040335A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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

Definitions

  • the present invention is a useful compound that can be used as a refrigerant, a blowing agent, and a cleaning agent as a substitute for CFC (fluorocarbon fluorcarbon) and HCFC (hydrochlorofluorocarbon) used as a cleaning agent. It relates to a method for producing 1,3,3-pentafluoropropane (HFC-245ia).
  • Conventional technology
  • the reaction is generally performed using pentavalent antimony as a catalyst, but in order to keep the selectivity high and to increase the productivity, the reaction is performed in an HF solvent (that is, in the liquid phase). It is necessary to perform the reaction, and the material of the reactor that can be used under these reaction conditions is limited, and generally expensive materials are required.
  • a synthesis method by reduction of 1,1,1,3,3-pentachloro-1,2,3-dichloropropane obtained by fluorination of hexaclopropene is also known, but this method involves synthesis of raw materials, And two-step reaction of reduction are required, and the process is complicated.
  • An object of the present invention is to easily and economically produce 1,1,1,3,3-pentafluoropropane (HFC-245fa) from raw materials that can be obtained or synthesized at low cost.
  • the present inventors have conducted intensive studies on an efficient and efficient production process of 1,1,1,3,3-pentafluoropropane in order to solve the above-mentioned problems.
  • the inventors have found that the desired product can be easily (in one step) derived by chlorinating propane with chlorine and hydrogen fluoride (HF) in the presence of a specific catalyst, and have completed the present invention. It is.
  • the present invention provides 1,1,1,3,3-pentafluoropropane by reacting tetrahalogenopropane as a raw material and reacting it with chlorine and hydrofluoric acid in the presence of a catalyst, in particular, It relates to a method for producing 1,1,1,3,3-pentafluoromouth propane (HFC-245fa).
  • 1,1,3,3-tetrahalogenopropane, 1,1,1,3-tetraha- ⁇ -genopropane or the like be used as a raw material of tetrahalogenopropane.
  • 1,1,3,3-tetrahalogenopropane for example, 1,1,3,3-tetrachloropropane
  • the salt to trihalomethane such as chloroform, dichlorofluoromethane, chlorodifluoromethane, etc. It can be synthesized by adding fujidani vinyl.
  • 1,1,1,3-tetrahalogenobutane for example, 1,1,1,3-tetrachloropropane
  • tetrahalogenomethane such as carbon tetrachloride, trichlorofluoromethane, dichlorodifluoromethane, etc.
  • tetrahalogenopropanes can be converted to propane having a large amount of fluorine by fluorine and then subjected to chlorine fluorination, thereby leading to 1,1,1,1,3,3-pentafluoropropane.
  • 1,1,1,3-tetrachloropropane when 1,1,1,3-tetrachloropropane is fluorinated under appropriate conditions, it can be converted to 1,1,1 trifluoro-3-chloropropane, which can be chlorinated.
  • the raw material may be fluorinated to give 1,1,1,3,3-tetrafluoropropane or 1,1,1,1,3-tetrafluoropropane and then chlorinated.
  • the raw material thus obtained is preferably passed through a gaseous phase together with chlorine and HF to carry out chlorine fluorination.
  • activated carbon As the catalyst that can be used here, activated carbon, an activated carbon in which a metal is supported, or a metal oxide is suitably used.
  • the metal supported on the activated carbon one or more metals selected from the group consisting of chromium, iron, zinc, cobalt, nickel, palladium, and copper are selected. It is preferable from the aspect of the rate. These may be supported in the form of hydrochloric or nitrate salts. Before the reaction, heat treatment, fluorination treatment with HF, or the like may be performed. When nitrate is used, it changes to the corresponding oxide by heat treatment.
  • metal oxide alone as a catalyst.
  • metal oxides include one or more oxides selected from the group consisting of oxides of chromium, iron, zinc, copper, nickel, aluminum, magnesium, calcium, and barium. However, it is preferable in terms of the selectivity of the target.
  • chlorine be introduced in an amount of about 0.3 to 1.2 times the molar amount of the introduced raw material.
  • the theoretically necessary amount of HF is 1 to 5 times the molar amount of the raw material to be introduced, it is preferable to use about 0.5 to 5 times the HF with respect to this necessary amount.
  • the reaction may be performed in a substoichiometric amount.
  • the upper limit is also not particularly limited, but from the viewpoint of the efficiency of the reactor, the reaction is not carried out with HF being at least 5 times the theoretical amount. More preferably, 1 to 3 times the amount of HF is used.
  • the product in order to increase the selectivity of the target substance, the product is further fluorinated to obtain 1,1,1,3,3-pentanofluoropropane following the chlorine fluorination described above. It can also be manufactured.
  • this product examples include 1,1,1-trifluoro-3-co-opening ⁇ -2-propene, 1,1-difluoro-1,3-diclo ⁇ -2-propene, and 1-fluoro-1,4-propene.
  • Olefins such as 1,3-trichloro-2-propene and 1,1-difluoro-3,3-dichloro-2-propene are exemplified. You. By fluorinating these, 1,1,1,3,3-pentafluoropropane can be produced.
  • non-halogenated products such as 1,1,1,1-trifluoro-2-propene and 1,1, difluoro-3-chloro-2-propene, which are co-produced, are again It may be recycled by subjecting it to the above chlorine fluorination step.
  • the fluorination can be performed by reacting with HF in the presence of a catalyst.
  • a catalyst One or two selected from the group consisting of antimony halide, niobium genide and tantalum halide
  • antimony halide, niobium genide and tantalum halide can be mentioned, or the fluorination reaction can be carried out in the gas phase by using a chromium, aluminum, iron or nickel nitride or halide as a catalyst.
  • 1,1,1,3,3-pentafluoropropane is obtained by using tetraha ⁇ -genopropane as a raw material and reacting it with chlorine and hydrofluoric acid in the presence of a catalyst.
  • the desired product can be easily derived by subjecting easily obtainable or synthesizable tetrahalogenopropane to chlorine fluorination with chlorine and fluorine (HF) in the presence of a specific catalyst.
  • 1,1,3,3-tetrachloropropane can be obtained from Shiridani vinyl and black mouth form with a conversion of 63% and a selectivity of 93%.
  • a reaction tube having a diameter of 20 mm was filled with 25 g of activated carbon supporting iron chloride, and the temperature was adjusted to 300C.
  • 20 cc of chlorine and 200 cc of HF were introduced into the reaction tube, and the 1,1,3,3-tetrachlorobutane synthesized as described above was vaporized and introduced at 20 cc.
  • the reaction gas was washed with an aqueous solution of a hydroxylic lime and a sulfuric acid lime, then dried by passing through a chloridized calcium tower, and subjected to GLC analysis.
  • the analysis results are as follows Atsuta.
  • a reaction tube having a diameter of 2 Omm was filled with 25 g of activated carbon supporting iron chloride.
  • 20 cc of chlorine and 200 cc of HF were introduced into the reaction tube, and the 1,1,1,3-tetrachlorobutane synthesized as described above was vaporized and introduced at 20 cc.
  • the reaction gas was washed with an aqueous solution of a hydroxylic lime and a sulfuric acid lime, then dried by passing through a chloridized calcium tower, and subjected to GLC analysis.
  • the analysis results are as follows.
  • the reaction was carried out in the same manner as in Example 1, except that the metal salt supported on the activated carbon was changed to chromium nitrate.
  • the analysis results of the reaction product were as follows, and it was found that the desired product was obtained.
  • the reaction was carried out in the same manner as in Example 1, except that the metal salt supported on the activated carbon was changed to zinc chloride.
  • the analysis results of the reaction product are as follows, and it was found that the desired product was obtained.
  • the reaction was carried out in the same manner as in Example 1, except that the metal salt supported on the activated carbon was changed to cobalt chloride.
  • the analysis results of the reaction product were as follows, and it was found that the desired product was obtained.
  • the reaction was carried out in the same manner as in Example 1, except that the metal salt supported on the activated carbon was changed to nickel chloride.
  • the analysis results of the reaction product were as follows, and it was found that the desired product was obtained.
  • the reaction was carried out in the same manner as in Example 1, except that the metal salt supported on the activated carbon was changed to copper nitrate.
  • the analysis results of the reaction product are as follows, and it was found that the desired product was obtained.
  • the reaction was carried out in the same manner as in Example 1, except that the catalyst was changed to chromium oxide.
  • the analysis results of the reaction product are as follows, and it was found that the desired product was obtained.o
  • the reaction was carried out in the same manner as in Example 1, except that the catalyst was changed to iron oxide.
  • the analysis results of the reaction product were as follows, and it was found that the desired product was obtained.
  • 1,1,3,3-tetrachloropropane obtained in the same manner as in Example 1 was fluorinated in HF using SbF 5 as a catalyst to obtain 1,1,3,3-tetrafluoropropane.
  • a reaction tube having a diameter of 2 Omm was filled with 25 g of activated carbon supporting iron chloride, and the content was adjusted to 300. While introducing 20 cc of chlorine and 200 cc of HF, 1,1,3,3-tetrafluoropropane synthesized as described above was vaporized and introduced at 20 cc.
  • the reaction gas was washed with an aqueous solution of a hydroxylic lime and a sulfuric acid lime, then dried by passing through a chloridized calcium tower, and subjected to GLC analysis.
  • the analysis results are as follows.
  • 1,1,1-Trifluoropropane is brominated to form 1,1,1-Trifluoro 3-propidoprono. I got it.
  • a reaction tube having a diameter of 2 Omm was filled with 25 g of activated carbon supporting iron chloride, and this was made 300.
  • 1,1,1''fluoro-bromo-3-bromopropane synthesized as described above was vaporized and introduced into 20 cc.
  • the reaction gas was washed with an aqueous solution of a hydroxylic lime and a sulfuric acid lime, then dried by passing through a chloridized calcium tower, and subjected to GLC analysis.
  • the analysis results are as follows 7 0
  • 1,1,3,3-Tetrachlorobroja was prepared in the same manner as described in Example 1. I got it.
  • a reaction tube having a diameter of 20 mm was filled with 25 g of activated carbon supporting iron chloride, and the temperature was raised to 300 ° C. 20 cc of chlorine and 200 cc of HF were introduced, and the 1,1,3,3-tetrachloropropane synthesized as described above was vaporized. Introduced 20 cc.
  • the reaction gas was washed with an aqueous solution of a hydroxylic lime and a sulfuric acid lime, then dried by passing through a chloridized calcium tower, and subjected to GLC analysis.
  • the analysis results are as follows.
  • 1,1,1,3,3-pentafluoropropane can be obtained almost quantitatively and efficiently.
  • the by-produced tetrafluoropopene was able to be derived into the desired pen-fluorinated ⁇ -propane by recycling to the above liquid phase fluorination step. By this recycling, the selectivity of the target pentafluoropropane was improved to 99.3%.
  • Example 12 gas-phase fluorination was performed instead of liquid-phase fluorination.
  • a reaction tube having a diameter of 20 mm was filled with 25 g of Futsudani chrome, and this was set to 300.
  • reaction gas was washed with aqueous hydroxide and aqueous sodium sulfite, then dried by passing through a chloride tower, and subjected to GLC analysis.
  • the analysis results are as follows:
  • 1,1,1,3,3-pentafluoropropane can be obtained efficiently.
  • the by-produced tetrafluoropropane could be derived to the desired pentafluoropropane by recycling to the above-mentioned self-phase fluoridation process. Through this recycling, the desired pentafu Lulopropane selectivity increased to 95%.
  • Example 12 1,1-difluoro-3-chloro-2-propene produced as a by-product was recycled to the above-mentioned chlorine fluorination step. According to GLC analysis results, the selectivity of 1,3,3-Penyu fluo- ⁇ -pan was 86%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Abstract

On prend comme matériau de départ un tétrahalogénopropane et on le soumet à une chlorofluoration en le faisant réagir de préférence avec du chlore et de l'acide fluorhydrique en présence d'un catalyseur, de façon à obtenir du 1,1,1,3,3-pentafluoropropane. Il est possible de produire ainsi facilement du 1,1,1,3,3-pentafluoropropane à partir d'un matériau disponible ou pouvant être synthétisé à peu de frais.
PCT/JP1998/000932 1997-03-12 1998-03-05 Procede pour produire du 1,1,1,3,3-pentafluoropropane Ceased WO1998040335A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP9/57561 1997-03-12
JP5756197 1997-03-12
JP13489797A JPH10309464A (ja) 1997-03-12 1997-05-26 １，１，１，３，３−ペンタフルオロプロパンの製造方法
JP9/134897 1997-05-26

Publications (1)

Publication Number Publication Date
WO1998040335A1 true WO1998040335A1 (fr) 1998-09-17

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PCT/JP1998/000932 Ceased WO1998040335A1 (fr) 1997-03-12 1998-03-05 Procede pour produire du 1,1,1,3,3-pentafluoropropane

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JP (1) JPH10309464A (fr)
WO (1) WO1998040335A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CU22932A1 (es) * 2000-01-18 2004-02-20 Ct De Bioactivos Quimicos Procedimiento para la obtención del 2-bromo-5-(2-bromo-2-nitrovinil)-furano
US7279451B2 (en) * 2002-10-25 2007-10-09 Honeywell International Inc. Compositions containing fluorine substituted olefins
ES2542306T5 (es) 2006-10-31 2022-03-30 Chemours Co Fc Llc Procedimientos para la producción de fluoropropanos y halopropenos
EP2091896A1 (fr) 2006-10-31 2009-08-26 E.I. Du Pont De Nemours And Company Procédés de production de fluoropropanes et d'halogénopropènes
FR2933691B1 (fr) * 2008-07-10 2012-11-09 Arkema France Hydro(chloro)fluoroolefines et leur procede de preparation
CN110520401B (zh) * 2017-06-30 2022-05-10 中央硝子株式会社 1,3-二氯-3,3-二氟丙烯的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09241188A (ja) * 1996-03-05 1997-09-16 Central Glass Co Ltd １，１，１，３，３−ペンタフルオロプロパンの製造方法
JPH09268140A (ja) * 1996-04-03 1997-10-14 Central Glass Co Ltd １，１，１，３，３−ペンタフルオロプロパンの製造法
JPH1087532A (ja) * 1996-07-25 1998-04-07 Cerestar Holding Bv アラビニトールの製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09241188A (ja) * 1996-03-05 1997-09-16 Central Glass Co Ltd １，１，１，３，３−ペンタフルオロプロパンの製造方法
JPH09268140A (ja) * 1996-04-03 1997-10-14 Central Glass Co Ltd １，１，１，３，３−ペンタフルオロプロパンの製造法
JPH1087532A (ja) * 1996-07-25 1998-04-07 Cerestar Holding Bv アラビニトールの製造方法

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