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
• • 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

Definitions

• said composition A comprises at least 80% by weight of chlorotrifluoroethylene based on the total weight of said composition A, preferably at least 95% by weight of chlorotrifluoroethylene based on the total weight of said composition A, in in particular at least 90% by weight of chlorotrifluoroethylene based on the total weight of said composition A.
• said composition A also comprises trifluoroethylene, preferably in a mass content of less than 5% based on the total weight of said composition A.
• the catalyst comprises palladium supported on alpha alumina.
• said method comprises a step i') of activating the catalyst, implemented prior to step a), by bringing it into contact with a gas flow comprising a reducing agent, a inert gas or a mixture thereof.
• the temperature of the catalytic bed is increased from a temperature Tl to a temperature T2 greater than Tl with a temperature gradient less than 0.5°C/min; or the temperature of the catalytic bed is increased from a temperature Tl to a temperature T2 greater than Tl in steps.
• the present invention relates to a process for producing trifluoroethylene comprising a hydrogenolysis reaction step of chlorotrifluoroethylene (CTFE) with hydrogen in the gas phase and preferably in the presence of a catalyst.
• CTFE chlorotrifluoroethylene
• the process according to the invention described in the present application is carried out continuously.
• the hydrogen is in anhydrous form.
• the chlorotrifluoroethylene is in anhydrous form.
• anhydrous refers to a mass water content of less than 1000 ppm, advantageously 500 ppm, preferably less than 200 ppm, in particular less than 100 ppm based on the total weight of the compound considered.
• the catalyst is supported.
• the support is preferably selected from the group consisting of activated carbon, an aluminum-based support, calcium carbonate, and graphite.
• the support is based on aluminum.
• the support is alumina.
• the alumina may be alpha alumina.
• the alumina comprises at least 90% alpha alumina. It was observed that the conversion of the hydrogenolysis reaction was enhanced when the alumina is alpha alumina.
• the catalyst is more particularly palladium supported on alumina, advantageously palladium supported on an alumina comprising at least 90% alpha alumina, preferably palladium supported on alpha alumina.
• the inert gas can be nitrogen or argon; preferably nitrogen.
• Step i') may also include one or more stages between temperature Tl and Tla and/or between temperature Tla and T2.
• each stage between temperature Tl and temperature T2 can last between 5 min and 200 h, preferably between 10 min and 100 h, in particular between 15 min and 75 h, more particularly between 30 min and 50 h.
• each level between temperature Tl and temperature T2 can last between 5 min and 24 hours, preferably between 10 min and 20 hours, in particular between 15 min and 15 hours, more particularly between 30 min and 1 Oh.
• the plateau at temperature Tla can last between 5 min and 200 h, preferably between 10 min and 100 h, in particular between 15 min and 75 h, more particularly between 30 min and 50 h.
• the plateau at temperature Tla can last between 5 min and 24 hours, preferably between 10 min and 20 hours, in particular between 15 min and 15 hours, more particularly between 30 min and 1 Oh.
• the gas flow used during step i') may be different over time.
• the gas flow may comprise an inert gas between two bearings and for example comprise a reducing agent between two other bearings.
• the gas flow comprises an inert gas when step i') is carried out between the temperature Tl and Tla and the gas flow comprises a reducing agent, preferably hydrogen or Ci-Cio hydrohalocarbons such as defined above, when step i') is carried out between temperature Tla and T2.
• the gas flow used during step i') is modified during the stage implemented at the temperature Tla.
• the gas flow may comprise a reducing agent such as hydrogen or Ci-Cio hydrohalocarbons as defined above throughout step i'), optionally in mixture with an inert gas such as l 'nitrogen.
• a reducing agent such as hydrogen or Ci-Cio hydrohalocarbons as defined above, optionally in mixture with an inert gas such as nitrogen, during the rise in temperature between the temperature Tla of said bearing and the temperature T2 represents an additional advantage in terms of productivity.
• the temperature T2 is maintained for a certain period of time. During this level at temperature T2, the gas flow can be modified.
• the gas flow during the stage at temperature T2 may comprise hydrogen or a Ci-Cio hydrohalocarbon as defined above; in particular the gas flow during the stage at temperature T2 may comprise hydrogen, chlorotrifluoroethylene, trifluoroethane, trifluoroethylene, chlorotrifluoroethane or difluoroethane.
• step i') can be carried out with a quantity of reducing agent greater than 0.01 per gram of catalyst, preferably greater than 0.05 per gram of catalyst.
• step i') can be carried out with a quantity of reducing agent of between 0.01 and 10 mol per gram of catalyst, preferably between 0.05 and 5 mol per gram of catalyst.
• This temperature T2' can be reached from a temperature Tl' using a low temperature gradient.
• the temperature of the catalytic bed is increased from a temperature Tl' to a temperature T2' greater than Tl', preferably the temperature of the catalytic bed is increased from a temperature Tl' to a temperature T2' greater than Tl' with a temperature gradient less than 0.5°C/min.
• the temperature gradient implemented makes it possible to avoid premature degradation of the catalyst and thus to allow better yield or better productivity of the hydrogenolysis reaction.
• the present invention comprises, as mentioned above, a reaction step of hydrogenolysis of a composition A comprising chlorotrifluoroethylene with hydrogen to produce a stream comprising trifluoroethylene.
• the hydrogenolysis step is carried out in the presence of a catalyst and in the gas phase.
• the hydrogenolysis step is carried out in the presence of a catalyst previously activated and in the gas phase.
• the hydrogenolysis step consists of simultaneously introducing hydrogen, CTFE and optionally an inert gas, such as nitrogen, in the gas phase and in the presence of said catalyst, preferably activated.
• the contact time calculated as the ratio between the volume, in liters, of catalyst and the total flow rate of the gas mixture, in normal liters per second, at the reactor inlet, is between 1 and 60 seconds, preferably between 5 and 45 seconds, particularly between 10 and 30 seconds, more particularly between 15 and 25 seconds.
• the total mass content of said at least one of the additional compounds Cl is less than 15% based on the total weight of said composition A.
• the total mass content of said at least one of the additional compounds Cl is less than 10%, more preferably less than 5%, in particular less than 2%, more particularly less than 1%.
• the total mass content of said at least one of the additional compounds Cl is greater than 1 ppm based on the total weight of said composition A.
• the total mass content of said at least one of the additional compounds Cl is greater than 5 ppm, more preferably greater than 10 ppm, in particular greater than 20 ppm, more particularly greater than 50 ppm, preferably greater than 100 ppm based on the total weight of said composition A.
• composition A comprises 1,1,1-trifluoroethane and the total mass content of 1,1,1-trifluoroethane is less than 5000 ppm, advantageously less than 2500 ppm, preferably less than 1000 ppm , more preferably less than 750 ppm based on the total weight of said composition A.
• the total mass content of 1,1,1-trifluoroethane is greater than 1 ppm, advantageously greater than 5 ppm, preferably greater than 10 ppm, more preferably greater than 20 ppm, in particular greater than 50 ppm, more particularly greater than 100 ppm based on the total weight of said composition A.
• composition A comprises 1,1,1,2-tetrafluoroethane and the total mass content of 1,1,1,2-tetrafluoroethane is less than 1000 ppm, advantageously less than 750 ppm, preferably less than 500 ppm, more preferably less than 250 ppm, in particular less than 100 ppm based on the total weight of said composition A.
• the total mass content of 1,1,1,2- tetrafluoroethane is greater than 1 ppm, advantageously greater than 5 ppm, preferably greater than 10 ppm, more preferably greater than 20 ppm based on the total weight of said composition A.
• composition A comprises hexafluorocyclobutene and the total mass content of hexafluorocyclobutene is less than 1%, advantageously less than 7500 ppm, preferably less than 5000 ppm, more preferably less than 2500 ppm, in particular less than 1000 ppm based on the total weight of said composition A.
• the total mass content of hexafluorocyclobutene is greater than 1 ppm, advantageously greater than 5 ppm, preferably greater than 10 ppm, more preferably greater than 20 pm, in particular greater than 50 ppm, more particularly greater than 100 ppm based on the total weight of said composition A.
• composition A comprises fluoroethane and the total mass content of fluoroethane is less than 100 ppm, advantageously less than 75 ppm, preferably less than 50 ppm, more preferably less than 25 ppm, in particular less than 10 ppm based on the total weight of said composition A.
• the total mass content of fluoroethane is greater than 0.1 ppm, advantageously greater than 0.5 ppm, preferably greater than 1 ppm on based on the total weight of said composition A.
• composition A comprises 2-chloro-l,l,l-trifluoroethane and the total mass content of 2-chloro-l,l,l-trifluoroethane is less than 1%, advantageously less than 7500 ppm, preferably less than 5000 ppm, more preferably less than 2500 ppm, in particular less than 1000 ppm based on the total weight of said composition A.
• composition A comprises 1,2-dichlorohexafluorocyclobutane.
• 1,2-Dichlorohexafluorocyclobutane can exist as two diastereoisomers.
• the term "1,2-dichlorohexafluorocyclobutane" refers to both diastereoisomers.
• the total mass content of 1,2-dichlorohexafluorocyclobutane is less than 15%, advantageously less than 10%, preferably less than 5%, in particular less than 1% based on the total weight of said composition A.
• the total mass content of 1,2-dichlorohexafluorocyclobutane is less than 5000 ppm, advantageously less than 1000 ppm, preferably less than 500 ppm, more preferably less than 250 ppm, in particular less than 100 ppm based on the total weight of said composition A.
• the total mass content of 1,2-dichlorohexafluorocyclobutane is greater than 1 ppm, advantageously greater than 5 ppm, preferably greater than 10 ppm, more preferably greater than 20 ppm based on the total weight of said composition A.
• said composition A comprises at least 80% by weight of chlorotrifluoroethylene based on the total weight of said composition A, advantageously at least 82% by weight, preferably at least 84% by weight, more preferably at least 86% by weight, in particular at least 88% by weight, more particularly at least 90%, preferably at least 92% by weight of chlorotrifluoroethylene based on the total weight of said composition A.
• Said composition A may also comprise trifluoroethylene, preferably in a mass content of less than 5%, preferably less than 4.5%, in particular less than 4% based on the total weight of said composition A.
• Said composition A may optionally comprise at least one of the additional compounds C2 selected from the group consisting of 1,1,2-trifluoroethane, l-chloro-1,1,2-trifluoroethane, l-chloro-2,2-difluoroethylene , E/Z-1-chloro-1,2-difluoroethylene, 1-chloro-1,2,2-trifluoroethane.
• the mass content of said at least one of the additional compounds C2 may be less than 5% based on the total weight of said composition A, advantageously less than 4%, preferably less than 3%, more preferably less than 2%, in particular less than 1% based on the total weight of said composition A.
• Reaction flow processing Stream B from step a) can be treated to recover a stream of purified trifluoroethylene (HFO-1123).
• Said current B may comprise, in addition to trifluoroethylene, HF, HCl, unreacted hydrogen, unreacted chlorotrifluoroethylene, optionally one or more of the additional compounds Cl or C2.
• Stream B from step a) is recovered at the reactor outlet in gaseous form.
• the product stream is first treated to eliminate HCl and HF.
• the product stream is passed through water in a wash column followed by washing with a dilute base such as NaOH or KOH.
• the remainder of the gas mixture consisting of the unconverted reagents (H2 and CTFE), the dilution nitrogen (if present), the trifluoroethylene and the additional compounds mentioned above is directed to a dryer in order to eliminate traces of washing water. Drying can be carried out using products such as calcium sodium or magnesium sulfate, calcium chloride, potassium carbonate, silica gel (silica gel) or zeolites.
• a molecular sieve such as siliporite is used for drying.
• the gas mixture thus dried is subjected to a step of separation of hydrogen and inerts from the rest of the other products present in the gas mixture by absorption/desorption in the presence of an alcohol comprising 1 to 4 carbon atoms and preferably ethanol, at atmospheric pressure and at a temperature below room temperature, preferably below 10°C and even more preferably at a temperature of -25°C, for absorption.
• the absorption of organics is carried out in a counter-current column with ethanol cooled to -25°C. The ethanol flow rate is adjusted according to the flow rate of organics to be absorbed.
• step iii) can be implemented by a membrane separation process. According to step iv), the organics thus obtained are distilled to form and recover a stream DI comprising trifluoroethylene and a stream D2 comprising chlorotrifluoroethylene and optionally one or more of the additional compounds Cl or C2. Current D2 can be recycled in step a).
• Said current DI may comprise at least 95% trifluoroethylene, advantageously at least 96%, preferably at least 97%, in particular at least 98%, more particularly at least 99% by weight based on the total weight of said current B.
• the present invention provides compositions comprising chlorotrifluoroethylene.
• Said composition comprises at least 80% by weight of chlorotrifluoroethylene and at least one of the additional compounds chosen from the group consisting of 1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane, hexafluorocyclobutene, fluoroethane, 2- chloro-1,1,l-trifluoroethane, 1,2-dichlorohexafluorocyclobutane; the total mass content of said at least one of the additional compounds is less than 15% based on the total weight of said composition.
• the composition comprises hexafluorocyclobutene and the total mass content of hexafluorocyclobutene is less than 1%, advantageously less than 7500 ppm, preferably less than 5000 ppm, more preferably less than 2500 ppm, in particular less than 1000 ppm based on the total weight of said composition.
• the total mass content of hexafluorocyclobutene is greater than 1 ppm, advantageously greater than 5 ppm, preferably greater than 10 ppm, more preferably greater than 20 pm, in particular greater than 50 ppm, more particularly greater than 100 ppm based on the total weight of said composition.
• the composition comprises 1,2-dichloro-hexafluorocyclobutane and the total mass content of 1,2-dichlorohexafluorocyclobutane is less than 15%, advantageously less than 10%, preferably less than 5%, in particular less than 1% based on the total weight of said composition.
• the total mass content of 1,2-dichlorohexafluorocyclobutane is less than 5000 ppm, advantageously less than 1000 ppm, preferably less than 500 ppm, more preferably less than 250 ppm, in particular less than 100 ppm on based on the total weight of said composition.
• the total mass content of 1,2-dichlorohexafluorocyclobutane is greater than 1 ppm, advantageously greater than 5 ppm, preferably greater than 10 ppm, more preferably greater than 20 ppm based on the total weight of said composition.
• test benches are used in parallel, each comprising a reactor prepared as described above.
• the four benches were supplied with 1 mol/h of starting composition and 1 mol/h of hydrogen in anhydrous form.
• the temperature of the reactor jacket is 25°C.
• the contact time calculated as the ratio between the volume in liters of catalyst and the sum of the flow rates of the reagents in normal liters per second, was of the order of 22 seconds. Tests are carried out using different starting compositions. Comparative Example 1 was used using chlorotrifluoroethylene.
• Example 2 according to the invention was implemented from chlorotrifluoroethylene used in the comparative example in which the following compounds were added to obtain a composition A with the proportions mentioned for each of the constituents: 1,1,1-trifluoroethane (519 ppm), 1,1, 1,2-tetrafluoroethane (39 ppm), hexafluorocyclobutene (880 ppm) , fluoroethane (5 ppm), 2-chloro-1,1,1-trifluoroethane (600 ppm), 1,2-dichlorohexafluorocyclobutane (68 ppm) and trifluoroethylene (2.9%) and the complement in chlorotrifluoroethylene.
• 1,1,1-trifluoroethane 519 ppm
• 1,1, 1,2-tetrafluoroethane 39 ppm
• hexafluorocyclobutene 880 ppm
• fluoroethane 5 ppm
• Example 3 according to the invention was implemented from the chlorotrifluoroethylene used in the comparative example to which the following compounds were added to obtain a composition A with the proportions mentioned for each of the constituents: 1,1,1- trifluoroethane (453 ppm), 1,1,1,2-tetrafluoroethane (56 ppm), hexafluorocyclobutene (754 ppm), 2-chloro-l,l,l-trifluoroethane (455 ppm) and 1,2-dichlorohexafluorocyclobutane (54 ppm ) and the complement in chlorotrifluoroethylene.
• Example 4 according to the invention was implemented from the chlorotrifluoroethylene used in the comparative example to which the following compounds were added to obtain a composition A with the proportions mentioned for each of the constituents: 1,1,1- trifluoroethane (450 ppm), 1,1,1,2-tetrafluoroethane (52 ppm) and 2-chloro-l,l,l-trifluoroethane (467 ppm) and the balance in chlorotrifluoroethylene.
• 1,1,1- trifluoroethane 450 ppm
• 1,1,1,2-tetrafluoroethane 52 ppm
• 2-chloro-l,l,l-trifluoroethane 467 ppm

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• 2022
  • 2022-05-03 FR FR2204198A patent/FR3135266B1/fr active Active
• 2023
  • 2023-05-03 WO PCT/EP2023/061695 patent/WO2023213893A1/fr not_active Ceased
  • 2023-05-03 JP JP2024564888A patent/JP2025515083A/ja active Pending
  • 2023-05-03 US US18/861,873 patent/US20250282700A1/en active Pending
  • 2023-05-03 CN CN202380037663.8A patent/CN119137088A/zh active Pending
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