Classifications

• • 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
• • 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
  • C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/38—Separation; Purification; Stabilisation; Use of additives
  • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C19/00—Acyclic saturated compounds containing halogen atoms
  • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
  • C07C19/10—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine
  • C07C19/12—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine having two carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
  • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
  • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
  • C07B2200/09—Geometrical isomers

Definitions

• 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.
• HCFC-142 1-Chloro-2,2-difluoroethane 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.
• HCFC-140 1,1,2-trichloroethane
• FR 2783821 Lewis acid as catalyst
• 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 chromium-based or supported chromium-based catalyst (FR 2783820 and EP 1008575).
• 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 by co-depositing chromium nitrate and nickel nitrate on activated charcoal or by doping alumina with zinc chloride.
• the Applicant has developed a method of manufacturing 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 hydrogen fluoride in the gas phase and in the presence or absence of a fluorination catalyst to provide a flow comprising chloro-2,2-difluoroethane, hydrochloric acid, 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 reacts with hydrofluoric acid in the gas phase in the presence or absence of a fluorination catalyst to give a stream comprising 1-chloro-2,2-difluoroethane, hydrochloric acid, 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 from the reaction step to give a stream A comprising hydrochloric acid and a stream B comprising acid hydrofluoric acid, 1-chloro-2,2-difluoroethane,
• a catalyst is preferably used in step (i) and advantageously in the presence of an oxidizing agent.
• the organic phase preferably comprises 1-chloro, 2-fluoroethylene, 1,2-dichloroethylenes (cis and trans) and 1,2-dichloro-2- fluoroethane.
• the non-organic phase obtained in (iii) is purified so that the HF content is greater than or equal to 90% by weight.
• 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.
• the separation step (ii) comprises at least one distillation, advantageously carried out at a temperature of between -60 ° and 120 ° C. and more particularly between -60 and 89 ° C. and an absolute pressure of between 3 and 20 bar and advantageously between 3 and 11 bar.
• the separation step (iii) comprises at least one settling step, advantageously carried out at a temperature between -20 and 60 ° C and more particularly between -20 and 10 ° C.
• the separation step (iv) comprises at least one distillation, advantageously carried out at a temperature of between 10 and 115 ° C. and more particularly between 35 and 79 ° C. and an absolute pressure of between 0.3 and 4 bar, advantageously 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 30 bar absolute, advantageously between 3 and 20 bar absolute and more particularly between 3 and 15 bar.
• 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 temperature and pressure of the reaction may be between 2 and 200 seconds, 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 and 20 mol% per mol of F 140 or Fl 130, advantageously 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.
• a metal in particular a transition metal or an oxide, halide or oxyhalide derivative of such a metal.
• 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, especially halides, such as AlF 3 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.
• 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.
• 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.
• 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.
• the catalyst Prior to the fluorination reaction, the catalyst is subjected to an activation step with HF at a temperature preferably of between 100 and 450 ° C., advantageously of between 200 and 400 ° C. for a duration of between 1 and 50. hours.
• the activation can be carried out in the presence of the oxidizing agent.
• the activation steps may be carried out at atmospheric pressure or under pressure up to 20 bar.
• the support can be prepared from high porosity alumina.
• the alumina is transformed into aluminum fluoride or a mixture of aluminum fluoride and alumina, by fiuoration with air and hydrofluoric acid, the conversion rate of alumina to aluminum fluoride depends essentially on the temperature wherein 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).
• salts of chromium, nickel or zinc and of rare earth metals it is possible to use chlorides, or other salts such as, for example, oxalates, formates, acetates, nitrates and sulphates or nickel dichromate, 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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 F 142 is 70% after 5 hours. After 30h, the yield is less than 30%.
• the catalyst used is a chromium oxide (Cr 2 O 3 ) as in Example 1. 55g 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.
• the yield of F 142 is 60%> after 5 hours. After 100 h, the yield is 62%.
• 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 F 142 is 50%> stable over a 500h period.
• 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 F 142 is 70%> after 5 hours. After 30h, the yield is less than 30%.
• HCC-140 and HF are fed with an HCC-140 / HF molar ratio of 1:20 (30 g / h HF), at 225 ° C., 11 bar abs, with a contact time of 50 s.
• the yield of F 142 is 25% stable over a period of 500 hours.

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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 2013
  • 2013-12-04 FR FR1362095A patent/FR3014099B1/fr not_active Expired - Fee Related
• 2014
  • 2014-10-02 FR FR1459421A patent/FR3014105B1/fr not_active Expired - Fee Related
  • 2014-11-28 EP EP14821753.2A patent/EP3077351A1/de not_active Withdrawn
  • 2014-11-28 WO PCT/FR2014/053083 patent/WO2015082812A1/fr active Application Filing
  • 2014-11-28 JP JP2016536654A patent/JP6634373B2/ja not_active Expired - Fee Related
  • 2014-11-28 US US15/101,733 patent/US9981891B2/en not_active Expired - Fee Related
  • 2014-11-28 CA CA2931400A patent/CA2931400A1/fr not_active Abandoned
  • 2014-11-28 CN CN201480065920.XA patent/CN105793219B/zh not_active Expired - Fee Related

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