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
  • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
• • 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
  • C07C21/04—Chloro-alkenes
  • C07C21/073—Dichloro-alkenes
  • C07C21/08—Vinylidene chloride

Definitions

• composition comprising 1-chloro-2,2-difluoroethane and 1,1-dichloroethylene Technical Field
• the present invention relates to compositions comprising 1-chloro-2,2-difluoroethane.
• the invention relates to compositions comprising 1-chloro-2,2-difluoroethane and 1,1-dichloroethylene.
• the invention relates to azeotropic or quasi-azeotropic compositions comprising 1-chloro-2,2-difluoroethane and 1,1-dichloroethylene.
• Halocarbon based fluids have found numerous applications in various industrial fields, including heat transfer fluid, propellants, foaming agents, blowing agents, gaseous dielectrics, polymerization medium or monomer, carrier fluids, abrasives, drying agents and fluids for power generation unit.
• WO 2015/082812 discloses a process for producing 1-chloro-2,2-difluoroethane.
• azeotropic or quasi-azeotropic fluids lies in the absence of fractionation during evaporation processes and in that they act (almost) as a pure body. However, it is difficult to identify new fluids that meet these characteristics, since azeotropes are not predictable.
• the present invention provides an azeotropic or azeotropic composition comprising 1-chloro-2,2-difluoroethane and 1,1-dichloroethylene.
• said composition comprises from 1 to 99 mol% of 1-chloro-2,2-difluoroethane and from 99 to 1 mol% of 1,1-dichloroethylene, based on the total composition thereof expressed. in mole.
• the boiling temperature of said composition is between 30 ° C and 116 ° C.
• the pressure is between 1 and 11 bara.
• said composition comprises from 37 to 67 mol% of 1-chloro-2,2-difluoroethane and from 33 to 63 mol% of 1,1-dichloroethylene based on of the total composition thereof expressed in moles.
• the composition is azeotropic.
• said composition comprises trans-1,2-dichloroethylene.
• said composition consists of 1-chloro-2,2-difluoroethane and 1,1-dichloroethylene.
• said composition consists of 1-chloro-2,2-difluoroethane, 1,1-dichloroethylene and trans-1,2-dichloroethylene.
• the molar ratio between 1-chloro-2,2-difluoroethane and trans-1,2-dichloroethylene is between 3 and 30.
• the present invention provides a process for preparing a composition comprising 1-chloro-2,2-difluoroethane and 1,1-dichloroethylene comprising (i) at least one step in which the 1, 1,2-trichloroethane reacts with hydrofluoric acid in the gas phase optionally in the presence of an oxidizing agent, and in the presence or absence of a fluorination catalyst to give a stream comprising 1-chloro-2, 2-difluoroethane, hydrochloric acid, hydrofluoric acid and at least one compound (s) A chosen from 1,2-dichloroethylenes (cis and trans), 1 chloro, 2-fluoroethylenes (cis and trans), 1,2-dichloro-2-fluoroethane and unreacted 1,1,2-trichloroethane; (ii) at least one step of separating the compounds resulting from the reaction stage to give a first stream comprising hydrochloric acid and a second stream comprising hydrofluoric acid,
• step (iii) washing the organic phase PI obtained in step (iii) to form an organic phase B1 comprising 1-chloro-2,2-difluoroethane, at least one compound (s) A, 1,1,2-trichloroethane unreacted and 1,1-dichloroethylene; and a non-organic phase B2 comprising hydrofluoric acid;
• step b) optionally, drying the organic phase B 1 obtained in step a) to form an organic phase B 3 comprising 1-chloro-2,2-difluoroethane, at least one compound (s) A, 1,1,2-trichloroethane unreacted and 1,1-dichloroethylene; c) purifying, preferably by distillation, the organic phase B1 or the organic phase B3 to form a stream B4 comprising 1-chloro-2,2-difluoroethane and 1,1-dichloroethylene; and an organic phase B5 comprising unreacted 1,1,2-trichloroethane and at least one compound (s) A.
• the washing step a) is carried out with water and the non-organic phase B2 is an aqueous phase.
• step a) is carried out at a temperature of between 0 ° C. and 30 ° C. at a pressure of between 1 and 4 bara.
• the present invention relates to a composition
• a composition comprising 1-chloro-2,2-difluoroethane and 1,1-dichloroethylene.
• said composition is azeotropic or almost azeotropic.
• near-azeotropic has a broad meaning and is meant to include compositions that are strictly azeotropic and those that behave as an azeotropic mixture.
• Said composition may comprise from 1 to 99 mol% of 1-chloro-2,2-difluoroethane based on the total composition thereof expressed in moles.
• said composition may comprise 1 mol% of 1-chloro-2,2-difluoroethane, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%.
• Said composition may comprise from 1 to 99 mol% of 1,1-dichloroethylene based on the total composition expressed in moles.
• said composition may comprise 1 mol% of 1,1-dichloroethylene, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol% and 9 mol%.
• mol% 11 mol%, 12 mol%, 13 mol%, 14 mol%, 15 mol%, 16 mol%, 17 mol%, 18 mol%, 19 mol%, 20 mol%, 21 mol%, 22 mol% , 23 mol%, 24 mol%, 25 mol%, 26 mol%, 27 mol%, 28 mol%, 29 mol%, 30 mol%, 31 mol%, 32 mol%, 33 mol%, 34 mol%, mol%, 36 mol%, 37 mol%, 38 mol%, 39 mol%, 40 mol%, 41 mol%, 42 mol%, 43 mol%, 44 mol%, 45 mol%, 46 mol%, 47 mol% 48% molar, 49 mol%, 50 mol%, 51 mol%, 52 mol%, 53 mol%, 54 mol%, 55 mol%, 56 mol%, 57 mol%, 58 mol%, 59 mol%, mol%
• said composition may comprise 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%, 10 mol%, 11 mol% 12% molar, 13% molar, 14% molar, 15% molar, 16% molar, 17% molar, 18 mol%, 19 mol%, 20 mol%, 21 mol%, 22 mol%, 23 mol%, 24 mol%, 25 mol%, 26 mol%, 27 mol%, 28 mol%, 29 mol%, 30 mol%, 31 mol%, 32 mol%, 33 mol%, 34 mol%, 35 mol%, 36 mol%, 37 mol%, 38 mol%, 39 mol%, 40 mol%, 41 mol%, 42% molar, 43 mol%, 44 mol%, 45 mol%, 46 mol%, 47 mol%, 48 mol%, 49
• said composition may comprise from 2 to 98 mol% of 1-chloro-2,2-difluoroethane, from 3 to 97 mol%, from 4 to 96 mol%, from 5 to 95 mol%, from 6 to 94% molar, 7 to 93 mol%, 8 to 92 mol%, 9 to 91 mol%, 10 to 90 mol%, 11 to 89 mol%, 12 to 88 mol%, 13 to 87 mol% from 14 to 86 mol%, from 15 to 85 mol%, from 16 to 84 mol%, from 17 to 83 mol%, from 18 to 82 mol%, from 19 to 81 mol%, from 20 to 80 mol%, from 21 to 79 mol%, from 22 to 78 mol%, from 23 to 77 mol%, from 24 to 76 mol%, from 25 to 75 mol%, from 26 to 74 mol%, from 27 to 73 mol%, 28 to 72 mol%, 29 to 71
• said composition may comprise from 2 to 98 mol% of 1,1-dichloroethylene, from 3 to 97 mol%, from 4 to 96 mol%, from 5 to 95 mol%, from 6 to 94 mol%, from 7 to 10 mol%. at 93 mol%, 8 to 92 mol%, 9 to 91 mol%, 10 to 90 mol%, 11 to 89 mol%, 12 to 88 mol%, 13 to 87 mol%, 14 to 14 mol%, 86 mol%, 15 to 85 mol%, 16 to 84 mol%, 17 to 83 mol%, 18 to 82 mol%, 19 to 81 mol%, 20 to 80 mol%, 21 to 79 mol%.
• said composition may comprise from 2 to 98 mol%, from 3 to 97 mol%, from 4 to 96 mol%, from 5 to 95 mol%, from 6 to 94 mol%, from 7 to 93 mol%, 8 to 92 mol%, 9 to 91 mol%, 10 to 90 mol%, 11 to 89 mol%, 12 to 88 mol%, 13 to 87 mol%, 14 to 90 mol%, at 86 mol%, from 15 to 85 mol%, from 16 to 84 mol%, from 17 to 83 mol%, from 18 to 82 mol%, from 19 to 81 mol%, from 20 to 80 mol%, from 21 to 79 mol%, 22 to 78 mol%, 23 to 77 mol%, 24 to 76 mol%, 25 to 75 mol%, 26 to 74 mol%, 27 to 73 mol%, 28 to 72 mol% mol%, 29 to 71 mol%
• the boiling temperature of said composition is between -50 ° C and 250 ° C, more preferably between -20 ° C and 185 ° C, in particular between 5 ° C and 145 ° C. More particularly, the boiling temperature of said composition is between 30 ° C and 116 ° C.
• the pressure is between 0.005 bar to 20 bar, more preferably from 0.3 bar to 15 bar abs. In particular, the pressure is between 1 and 11 bar abs.
• the boiling temperature of said composition is between -50 ° C. and 250 ° C., more preferably between -20 ° C. and 185 ° C., in particular between 5 ° C. and 145 ° C., more particularly between 30 ° C. C and 116 ° C at a pressure between 0.005 bar to 20 bar, more preferably from 0.3 bar to 15 bar, more particularly between 1 and 11 bar abs.
• said composition comprises from 37 to 67 mol% of 1-chloro-2,2-difluoroethane and from 33 to 63 mol% of 1,1-dichloroethylene based on the total composition thereof expressed. in mole.
• said composition comprises from 37 to 67 mol% of 1-chloro-2,2-difluoroethane and from 33 to 63 mol% of 1,1-dichloroethylene based on the total composition expressed thereof in mol, of which the boiling temperature of said composition is between 30 ° C and 116 ° C at a pressure of between 1 and 11 bara.
• said composition in the proportions and conditions expressed herein is azeotropic.
• said composition consists of 1-chloro-2,2-difluoroethane and 1,1-dichloroethylene, in the proportions detailed above.
• 1-Chloro-2,2-difluoroethane and 1,1-dichloroethylene can be separated by extractive distillation to form a high purity 1-chloro-2,2-difluoroethane composition.
• said composition may also comprise trans-1, 2-dichloroethylene.
• the composition comprises trans-1,1-dichloroethylene
• the molar ratio between 1-chloro-2,2-difluoroethane and trans-1,2-dichloroethylene may be between 3 and 30.
• a ternary composition comprising preferably, 1-chloro-2,2-difluoroethane, 1,1-dichloroethylene and trans-1,2-dichloroethylene is provided.
• the proportions, the boiling point and the pressure are as detailed above.
• said composition comprises, preferably consists of: From 2 to 98 mol% of 1-chloro-2,2-difluoroethane, from 3 to 97 mol%, from 4 to 96 mol%, from 5 to 95 mol%, from 6 to 94 mol%, from 7 to 93 mol% mol%, 8 to 92 mol%, 9 to 91 mol%, 10 to 90 mol%, 11 to 89 mol%, 12 to 88 mol%, 13 to 87 mol%, 14 to 86% molar, 15 to 85 mol%, 16 to 84 mol%, 17 to 83 mol%, 18 to 82 mol%, 19 to 81 mol%, 20 to 80 mol%, 21 to 79 mol% from 22 to 78 mol%, from 23 to 77 mol%, from 24 to 76 mol%, from 25 to 75 mol%, from 26 to 74 mol%, from 27 to 73 mol%, from 28 to 72 mol%
• Trans-1, 2-dichloroethylene the molar ratio between 1-chloro-2,2-difluoroethane and trans-1,2-dichloroethylene may be between 3 and 30;
• the boiling temperature of said composition comprising 1-chloro-2,2-difluoroethane, 1,1-dichloroethylene and trans-1,2-dichloroethylene is between -50 ° C and 250 ° C, more preferably between -20 ° C C and 185 ° C, in particular between 5 ° C and 145 ° C, more particularly between 30 ° C and 116 ° C at a pressure between 0.005 bar to 20 bar, more preferably from 0.3 bar to 15 bar, more especially between 1 and 11 bar abs.
• a process for preparing a composition comprising 1-chloro-2,2-difluoroethane and 1,1-dichloroethylene is provided.
• the process comprises (i) at least one step in which 1,1,2-trichloroethane reacts with hydrogen fluoride gas phase optionally in the presence of an oxidizing agent, and in the presence or absence of a fluorination catalyst to give a stream comprising 1-chloro-2,2-difluoroethane, hydrochloric acid, hydrofluoric acid and at least one compound (s) A chosen from 1,2-dichloroethylenes (cis and trans) 1-chloro, 2-fluoroethylenes (cis and trans), 1,2-dichloro-2-fluoroethane and unreacted 1,1,2-trichloroethane; (ii) at least one step of separating the compounds resulting from the reaction stage to give a first stream comprising hydrochloric acid and a second stream comprising hydrofluoric acid, 1-chloro-2,2-difluoroethane, at least one compound (s) A and unreacted 1,1,2-trifluoroethane; (iii) at least one
• step (iii) washing the organic phase PI obtained in step (iii) to form an organic phase B1 comprising 1-chloro-2,2-difluoroethane, at least one compound (s) A, 1,1,2-trichloroethane unreacted and 1,1-dichloroethylene; and a non-organic phase B2 comprising hydrofluoric acid;
• step b) optionally, drying the organic phase B 1 obtained in step a) to form an organic phase B 3 comprising 1-chloro-2,2-difluoroethane, at least one compound (s) A, 1,1,2-trichloroethane unreacted and 1,1-dichloroethylene;
• a catalyst is preferably used in step (i) and advantageously in the presence of an oxidizing agent.
• 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 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.
• 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 F140, advantageously between 0.01 and 0.2 mol% per mole of HCC-140.
• 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 including halides, such as Al F3 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 THF 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 can be carried out at atmospheric pressure or under pressure up to 20 bar abs.
• the support can be prepared from high porosity alumina.
• 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).
• 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 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 abs and advantageously between 3 and 11 bar abs.
• the organic phase obtained in step (iii) also comprises at least one of the compounds A selected from the group consisting of cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, cis-1-chloro-2-fluoroethylene, 1,2-dichloro-1-fluorethane and trans-1-chloro-2-fluoroethylene.
• the non-organic phase obtained in (iii) preferably contains the majority of the HF initially present in the second stream with respect to the organic phase also obtained in step (iii) ).
• the organic phase obtained in (iii) may contain hydrofluoric acid.
• the amount of hydrofluoric acid in the organic phase is less than the amount of hydrofluoric acid in the inorganic phase.
• the molar ratio of the hydrofluoric acid present in the organic phase to the hydrofluoric acid present in the non-organic phase is less than 1: 10, preferably less than 1: 50, in particular 1: 100.
• 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 washing step a) is carried out with water and the non-organic phase B2 is an aqueous phase.
• the washing step a) allows the formation of 1,1-dichloroethylene.
• the latter is recovered in the organic phase B1.
• the step a) is carried out at a temperature of between 0 ° C. and 30 ° C. at a pressure of between 1 and 4 bar abs.
• the organic phase B1 may contain H 2 O, preferably in a small proportion.
• the content of H2O in the organic phase B1 is less than 5% by weight based on the total weight of the organic phase B1, more preferably less than 3% by weight, in particular less than 1% by weight.
• the organic phase B1 may comprise 1-chloro-2,2-difluoroethane, at least one compound (s) A, unreacted 1,1,2-trichloroethane, 1,1-dichloroethylene and H 2 O.
• the drying step b) of the organic phase B1 can be carried out at a temperature of between 0 ° C. and 30 ° C. at a pressure of between 1 and 4 bar abs.
• the drying step b) makes it possible to reduce the water content in the organic phase B1 to form a phase organic B3 comprising 1-chloro-2,2-difluoroethane, at least one compound (s) A, 1,1,2-trichloroethane unreacted and 1,1-dichloroethylene.
• the organic phase B3 comprises less than 1000 ppm of h 2 O, more preferably less than 100 ppm of h 2 O, in particular less than 10 ppm of h 2 O.
• the drying may be carried out on molecular sieves .
• the drying can be carried out in the presence of zeolite or absorbents known to those skilled in the art.
• Step c) of purification is preferably a distillation.
• the distillation of the organic phase B1 or B3 can be carried out at a temperature of 10 to 100 ° C, preferably of 20 to 90 ° C, more preferably of 30 to 80 ° C, and at an absolute pressure of 0, 3 to 8 bar abs, preferably from 0.5 to 6 bar abs, more preferably from 1 to 4 bar.
• the purification step c) preferably allows the formation of an azeotropic or quasi-azeotropic composition comprising 1-chloro-2,2-difluoroethane and 1,1-dichloroethylene as described above.
• said at least one compound (s) A comprises trans-1,2-dichloroethylene and at least one other compound A selected from the group consisting of cis-1,2-dichloroethylene, cis-1-chloro-2- fluoroethylene, 1,2-dichloro-1-fluorethane and trans-1-chloro-2-fluoroethylene.
• trans-1,2-dichloroethylene is preferably contained in stream B4, the latter thus comprising 1-chloro-2,2-difluoroethane, 1,1 -dichloroethylene and trans-1,2-dichloroethylene.
• the organic phase B5 preferably comprises unreacted 1,1,2-trichloroethane and said at least one other compound A selected from the group consisting of cis-1,2-dichloroethylene, cis-1-chloro, and 2-fluoroethylene, 1,2-dichloro-1-fluorethane and trans-1-chloro-2-fluoroethylene.
• the method also comprises a recycling step in step (i) of the organic phase B5.
• the method also comprises a step of recycling in step (i) the non-organic phase P2 resulting from step (iii).
• the non-organic phase P2 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 abs.
• HCC-140 and / or optionally 1,2-dichloroethylene and THF 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.
• 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 F142 is 60% after 5 hours. After 100 h, the yield is 62%.
• the mixture obtained is treated to separate the hydrofluoric acid from the other compounds.
• the organic phase obtained comprises 1-chloro-2,2-difluoroethane, trans-1,2-dichloroethylene and unreacted 1,1,2-trichloroethane.
• This phase is washed with water at a temperature between 0 and 30 ° C at a pressure between 1 and 4 bar abs.
• the aqueous phase contains residual hydrofluoric acid not removed in the previous step.
• the organic phase comprises 1-chloro-2,2-difluoroethane, trans-1,2-dichloroethylene, 1,1-dichloroethylene and unreacted 1,1,2-trichloroethane.
• the organic phase is then dried and distilled as detailed in the present application to form a composition comprising 1-chloro-2,2-difluoroethane, trans-1,2-dichloroethylene and 1,1-dichloroethylene.

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• 2016
  • 2016-10-12 FR FR1659845A patent/FR3057263B1/fr not_active Expired - Fee Related
• 2017
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  • 2017-10-09 JP JP2019519737A patent/JP2019530716A/ja active Pending
  • 2017-10-09 EP EP17793704.2A patent/EP3526184A1/de not_active Withdrawn
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