• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to the field of saturated fluorinated hydrocarbons. It relates more particularly to the manufacture of 1-chloro-2,2-difluoroethane from 1,1,2-trichloroethane and / or 1,2-dichloroethylene. The present invention provides a process for producing 1-chloro-2,2-difluoroethane from 1,1,2-trichloroethane and / or 1,2-dichloroethylene comprising (i) at least one step in which 1,1,2-trichloroethane and / or 1,2-dichloroethylene react or react with hydrofluoric acid in the gas phase in the presence of an oxidizing agent, a fluorination catalyst to give a flow comprising 1-chloro-2,2-difluoroethane, hydrochloric acid, hydrofluoric acid and at least one compound (s) C chosen from 1 chloro, 2-fluoroethylenes (cis and trans), 1 , 2-dichloro-2-fluoroethane and optionally unreacted 1,1,2-trichloroethane and / or 1,2-dichloroethylene.
    公开号:FR3014105A1
    申请号:FR1459421
    申请日:2014-10-02
    公开日:2015-06-05
    发明作者:Bertrand Collier；Philippe Bonnet；Dominique Garrait；Pierre-Marie Sedat
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the field of saturated fluorohydrocarbons. It more particularly relates to the manufacture of 1-chloro-2,2-difluoroethane from 1,1,2-trichloroethane. 1-Chloro-2,2-difluoroethane (HCFC-142) is not only known as an expander in the manufacture of foams, but also as a raw material in the manufacture of pharmaceutical or agrochemical compounds. It is known to prepare 1-chloro-2,2-difluoroethane by reacting 1,1,2-trichloroethane (HCC-140) with hydrofluoric acid in the liquid phase, at a temperature between 30 and 180 ° C and in the presence of a Lewis acid as catalyst (FR 2783821). The preparation of HCFC-142 can also be carried out in the gas phase at a temperature of between 120 and 400 ° C., in the presence of a supported chromium-based catalyst (FR 2783820 and EP 1008575).
    [0002] Moreover, the document WO 2013/053800 describes the preparation of the fluorination catalysts of HCC-140 and of 1,2-dichloroethylene (1130) with hydrofluoric acid, said catalysts being obtained by co-depositing ferric chloride and magnesium chloride on chromium oxide and alumina oxide or in the codepositing of chromium nitrate and nickel nitrate on activated charcoal or by doping alumina with zinc chloride. It can be seen from document WO 2013/053800 that all the tests were carried out for a very short time (maximum 6 hours) and that the fluorination of HCC-140 in most cases leads mainly to 1,2-dichloroethylene (unspecified isomers ).
    [0003] The Applicant has developed a method for producing 1-chloro-2,2-difluoroethane does not have the disadvantages of the prior art. The present invention provides a process for producing 1-chloro-2,2-difluoroethane from 1,1,2-trichloroethane and / or 1,2-dichloroethylene comprising (i) at least one step in which the 1,1,2-trichloroethane and / or 1,2-dichloroethylene reacts or reacts with hydrofluoric acid in the gas phase in the presence of an oxidizing agent, a fluorination catalyst to give a stream comprising from 1 to chloro-2,2-difluoroethane, hydrochloric acid, hydrofluoric acid and at least one C compound (s) chosen from 1 chloro, 2-fluoroethylenes (cis and trans), 1,2-dichloro-2-fluoroethane and optionally unreacted 1,1,2-trichloroethane and / or 1,2-dichloroethylene. The subject of the present invention is therefore a process for producing 1-chloro-2,2-difluoroethane from 1,1,2-trichloroethane comprising (i) at least one step in which the 1,1,2-trichloroethane comprises trichloroethane reacts with hydrofluoric acid in the gas phase in the presence of an oxidizing agent, a fluorination catalyst to give a stream comprising 1-chloro-2,2-difluoroethane, hydrochloric acid, hydrofluoric acid and at least one C compound (s) chosen from 1,2-dichloroethylenes (cis and trans), 1 chloro, 2-fluoroethylenes (cis and trans), 1,2-dichloro-2- fluoroethane and optionally unreacted 1,1,2-trichloroethane; (ii) at least one step of separating the compounds resulting from the reaction stage to give a stream A comprising hydrochloric acid and a stream B comprising hydrofluoric acid, 1-chloro-2,2-difluoroethane, at least one compound (s) C and optionally 1,1,2-trifluoroethane; (iii) at least one step of separating stream B to give an organic phase comprising 1-chloro-2,2-difluoroethane, at least one compound (s) C and optionally unreacted 1,1,2-trichloroethane and an inorganic phase comprising predominantly HF; (iv) at least one step of separating 1-chloro2,2-difluoroethane from the organic phase obtained in (iii); (v) optionally recycling to step (i) the organic phase after separation from step (iv); and (vi) optionally recycling to step (i) the non-organic phase from step (iii). After separation of 1-chloro-2,2-difluoroethane, the organic phase preferably comprises 1-chloro, 2-fluoroethylene, 1,2-dichloroethylenes (cis and trans) and 1,2-dichloro-2-fluoroethane .
    [0004] According to one embodiment, before recycling in step (i), the non-organic phase is purified so that the HF content is greater than or equal to 90% by weight. Preferably, this purification comprises at least one distillation, advantageously carried out at a temperature of between -23 and 46 ° C. and an absolute pressure of between 0.3 and 3 bar.
    [0005] Preferably, the separation step (ii) comprises at least one distillation, advantageously carried out at a temperature of between -60 and 89 ° C. and an absolute pressure of between 3 and 11 bar. Preferably, the separation step (iii) comprises at least one settling step, advantageously carried out at a temperature of between -20 and 10 ° C. Preferably, the separation step (iv) comprises at least one distillation, advantageously carried out at a temperature of between 35 and 79 ° C. and an absolute pressure of between 1 and 4 bar. This separation step may be carried out by extractive azeotropic distillation, liquid / liquid extraction or membrane separation. The temperature of the reaction stage is preferably between 150 and 400 ° C., advantageously between 200 and 350 ° C. The pressure at which the fluorination reaction is carried out is preferably between 1 and 20 bar absolute, advantageously between 3 and 15 bar absolute. The amount of the hydrofluoric acid used in the reaction is preferably between 5 and 40 moles and advantageously between 10 and 30 moles per mole of HCC-140 and / or 1,2-dichloroethylene. The contact time defined as being the volume of catalyst / total volume gas flow at the temperature and pressure of the reaction is preferably between 2 and 100 seconds, advantageously between 2 and 50 seconds. The oxidizing agent pure or mixed with nitrogen may be selected from oxygen and chlorine. Chlorine is preferably chosen. The amount of oxidizing agent used is preferably between 0.01 to 0.2 mol% per mole of HCC-140 and / or 1,2-dichloroethylene. The catalyst used can be mass or supported. The catalyst may be based on a metal, in particular a transition metal or an oxide, halide or oxyhalide derivative of such a metal. By way of example, there may be mentioned FeCl 3, chromium oxyfluoride, NiCl 2, CrF 3 and mixtures thereof. As supported catalysts, mention may be made of those supported on carbon or on the basis of magnesium, such as magnesium derivatives, in particular halides such as MgF 2 or magnesium oxyhalides such as oxyfluorides or aluminum-based ones such as alumina. activated alumina or aluminum derivatives including halides, such as A1F3 or aluminum oxyhalides such as oxyfluoride. The catalyst may further comprise cocatalysts selected from Co, Zn, Mn, Mg, V, Mo, Te, Nb, Sb, Ta, P, Ni, Zr, Ti, Sn, Cu, Pd, Cd, Bi, rare earths or their mixtures. When the catalyst is based on chromium, Ni, Mg and Zn are advantageously chosen as cocatalyst. The atomic ratio cocatalyst / catalyst is preferably between 0.01 and 5. Chromium catalysts are particularly preferred. The catalyst used in the present invention can be prepared by coprecipitation of the corresponding salts optionally in the presence of a support. The catalyst can also be prepared by co-grinding the corresponding oxides. Prior to the fluorination reaction, the catalyst is subjected to an activation step with HF at a temperature of preferably between 100 and 450 ° C., advantageously between 200 and 300 ° C. for a duration of between 1 and 50 ° C. hours. In addition to the HF treatment, the activation can be carried out in the presence of the oxidizing agent. The activation steps can be carried out at atmospheric pressure or under pressure up to 20 bar. According to a preferred embodiment of the invention, the support can be prepared from high porosity alumina. In a first step, the alumina is converted into aluminum fluoride or a mixture of aluminum fluoride and alumina, by fluorination with air and hydrofluoric acid, the conversion rate of the alumina aluminum fluoride depending essentially on the temperature at which the fluorination of the alumina is carried out (generally between 200 ° C and 450 ° C, preferably between 250 ° C and 400 ° C). The support is then impregnated with aqueous solutions of chromium salts, nickel and possibly rare earth metal, or with aqueous solutions of chromic acid, nickel or zinc salt, and optionally salts or rare earth oxides and methanol (used as chromium reducer). As chromium, nickel or zinc salts and rare earth metals, it is possible to use chlorides, or other salts such as, for example, oxalates, formates, acetates, nitrates and sulphates or dichromate. nickel, and rare earth metals, provided that these salts are soluble in the amount of water that can be absorbed by the support. The catalyst can also be prepared by direct impregnation of alumina (which is generally activated) using the solutions of chromium, nickel or zinc compounds, and optionally rare earth metals, mentioned above. In this case, the transformation of at least a portion (for example 70% or more) of the alumina into aluminum fluoride or aluminum oxyfluoride is carried out during the activation step of the catalyst metal. The activated aluminas that can be used for catalyst preparation are well known, commercially available products. They are generally prepared by calcining alumina hydrates (aluminum hydroxides) at a temperature between 300 ° C and 800 ° C. Alumina (activated or not) can contain significant levels (up to 1000 ppm) of sodium without affecting the catalytic performance.
    [0006] Preferably, the catalyst is conditioned or activated, that is to say transformed into active constituents and stable (at the reaction conditions) by a prior operation called activation. This treatment can be carried out either "in situ" (in the fluorination reactor) or in a suitable apparatus designed to withstand the activation conditions.
    [0007] After impregnation of the support, the catalyst is dried at a temperature between 100 ° C and 350 ° C, preferably 220 ° C to 280 ° C in the presence of air or nitrogen. The dried catalyst is then activated in one or two stages with hydrofluoric acid, optionally in the presence of an oxidizing agent. The duration of this activation step by fluorination can be between 6 and 100 hours and the temperature between 200 and 400 ° C. The present invention also relates to a composition of the azeotropic or quazi-azeotropic type comprising 1-chloro-2,2-difluoroethane and trans 1,2-dichloroethylene.
    [0008] Preferably, the azeotropic or quasi-azeotropic composition comprises 80 to 95 mol% of 1-chloro-2,2-difluoroethane and 5 to 20 mol% of trans 1,2-dichloroethylene. Advantageously, the azeotropic or quasi-azeotropic composition has a boiling point of between 32 and 119 ° C. at a pressure of between 1 and 10 bar abs. The azeotropic composition can be obtained by extractive azeotropic distillation, liquid / liquid extraction or membrane separation. EXAMPLES Experimental Procedure: HCC-140 and / or optionally 1,2-dichloroethylene and HF are fed separately into a monotubular Inconel reactor, heated by means of a fluidized alumina bath. The pressure is regulated by means of a control valve located at the outlet of the reactor. The gases resulting from the reaction are analyzed by gas chromatography.
    [0009] The catalyst is first dried under a stream of nitrogen at 250 ° C., then the nitrogen is gradually replaced by HF to terminate the activation with pure HF (0.5 mol / h) at 350 ° C. during 8h. Example 1: The catalyst used is a chromium oxide (Cr 2 O 3). 35g are activated as described above. HCC-140 and HF are then fed with a molar ratio of 1: 8 (10 g / h HF), at 230 ° C., 11 bar abs, with a contact time of 65 seconds. The yield of F142 is 70% after 5 hours. After 30h, the yield is less than 30%.
    [0010] Example 2: The catalyst used is a chromium oxide (Cr 2 O 3) as in Example 1. 55 g are activated as described above. HCC-140, HF and chlorine are then fed with an HCC-140 / HF / chlorine molar ratio of 1: 9: 0.08 (17 g / h HF), at 230 ° C. abs bars, with a contact time of 54 s.
    [0011] The yield of F142 is 60% after 5 hours. After 100h, the yield is 62%. EXAMPLE 3 The catalyst used is a chromium oxide (Cr 2 O 3) as in Example 1. 35g are activated as described above. HCC-140, HF and chlorine are then fed with an HCC-140 / HF / chlorine molar ratio of 1: 20: 0.08 (30g / h HF) at 225 ° C. abs bars, with a contact time of 4 s. The yield of F142 is 50% stable over a 500h period. Example 4: The catalyst used is a chromium oxide (Cr 2 O 3) supported on alumina. 27g are activated as described above. HCC-140 and HF are then fed with an HCC-140 / HF molar ratio of 1: 8 (10 g / h HF), at 235 ° C., 11 bar abs, with a contact time of 45 sec. The yield of F142 is 70% after 5 hours. After 30h, the yield is less than 30%. Example 1 2 3 4 Calcium oxide mass Cr Cr (mass) mass Cr oxide Cr oxide on alumina Amount (g) 35 55 35 27 Molar ratio HF / T112 8 9 20 8 HF (g / h) 10 17.5 30 10 Molar Ratio Chlorine / T112 0 0.08 0.08 0 T (° C) 230 230 225 235 P (bar abs) 11 11 3 11 tc (s) 65 54 4 45 Yield (%) after 5 hours 70 60 53 70 Yield (%) after 30h <30 61 <30 Yield (%) after 100h <10 62 Yield (%) after 500h 50 20
    权利要求:
    Claims (3)
    [0001]
    REVENDICATIONS1. Azeotropic or quasi-azeotropic composition comprising 1-chloro-2,2-difluoroethane and trans 1,2-dichloroethylene.
    [0002]
    2. Composition according to claim 1 comprising from 80 to 95 mol% of 1-chloro-2,2-difluoroethane and from 5 to 20 mol% of trans 1,2-dichloroethylene.
    [0003]
    3. Composition according to claim 1 or 2 characterized in that the boiling temperature is between 32 and 119 ° C at a pressure between 1 and 10 bar abs.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR2783820A1|1998-09-03|2000-03-31|Atochem Elf Sa|Process for the manufacture of 1-chloro-2,2-difluoroethane by a liquid phase reaction of hydrogen fluoride with 1,1,2-trichloroethane in the presence of a Lewis acid|
    EP1008575A1|1998-12-08|2000-06-14|Elf Atochem North America, Inc.|Preparation of 1-chloro-2,2-difluoroethane |
    WO2013053800A2|2011-10-12|2013-04-18|Bayer Intellectual Property Gmbh|Catalytic gas phase fluorination of 1,1,2-trichloroethane and/or 1,2-dichloroethene to produce 1-chloro-2,2-difluoroethane|
    JPS5233604B2|1973-05-08|1977-08-30|
    JPS5623407B2|1975-01-16|1981-05-30|
    WO1999007470A1|1997-08-08|1999-02-18|Alliedsignal Inc.|Fluorination catalysts and process for their preparation|
    JP2850907B2|1997-12-26|1999-01-27|ダイキン工業株式会社|Method for producing fluorinated compound|
    FR2783821B1|1998-09-03|2000-12-08|Atochem Elf Sa|PROCESS FOR PRODUCING DIFLUOROETHYLENE|
    US6063969A|1998-12-08|2000-05-16|Elf Atochem North America, Inc.|Preparation of 142|
    US7217678B2|2002-08-22|2007-05-15|E. I. Du Pont De Nemours And Company|Cobalt-substituted chromium oxide compositions, their preparation, and their use as catalysts and catalyst precursors|
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    JP2019532055A|2016-09-27|2019-11-07|アルケマ フランス|Composition comprising 1-chloro-2,2-difluoroethane|
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    法律状态:
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    2016-09-19| PLFP| Fee payment|Year of fee payment: 4 |
    2016-11-11| PLFP| Fee payment|Year of fee payment: 4 |
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    2019-11-14| PLFP| Fee payment|Year of fee payment: 7 |
    2021-09-10| ST| Notification of lapse|Effective date: 20210806 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1362095A|FR3014099B1|2013-12-04|2013-12-04|PROCESS FOR THE PRODUCTION OF 1-CHLORO-2,2-DIFLUOROETHANE|
    FR1459421A|FR3014105B1|2013-12-04|2014-10-02|PROCESS FOR THE PRODUCTION OF 1-CHLORO-2,2-DIFLUOROETHANE|FR1459421A| FR3014105B1|2013-12-04|2014-10-02|PROCESS FOR THE PRODUCTION OF 1-CHLORO-2,2-DIFLUOROETHANE|
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