EP3947329A1 - Process for purifying 1-chloro-3,3,3-trifluoropropene - Google Patents

Process for purifying 1-chloro-3,3,3-trifluoropropene

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Publication number
EP3947329A1
EP3947329A1 EP20714236.5A EP20714236A EP3947329A1 EP 3947329 A1 EP3947329 A1 EP 3947329A1 EP 20714236 A EP20714236 A EP 20714236A EP 3947329 A1 EP3947329 A1 EP 3947329A1
Authority
EP
European Patent Office
Prior art keywords
trifluoropropene
chloro
ppm
less
equal
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.)
Pending
Application number
EP20714236.5A
Other languages
German (de)
French (fr)
Inventor
Emmanuel BOUSSARIE
Kevin HISLER
Anne Pigamo
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.)
Arkema France SA
Original Assignee
Arkema France SA
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 Arkema France SA filed Critical Arkema France SA
Publication of EP3947329A1 publication Critical patent/EP3947329A1/en
Pending legal-status Critical Current

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Classifications

    • 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
    • C07C17/093—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
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • 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
    • C07C17/395—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification of at least one compound

Definitions

  • TITLE Process for the purification of l-chloro-3,3,3-trifluoropropene
  • the present invention relates to a process for the purification of hydrochlorofluoroolefins.
  • the present invention relates to a process for the purification of 1-chloro-3,3,3-trifluoropropene.
  • the present invention also relates to a process for the production of 1-chloro-3,3,3-trifluoropropene.
  • HCFO-1233zd 3,3,3-trifluoro-1-chloropropene or l-chloro-3,3,3-trifluoropropene (HCFO-1233zd) exists in the form of two isomers: the cis isomer, namely Z-3.3 , 3-trifluoro-1-chloropropene (HCFO-1233zdZ), and the trans isomer, namely E-3,3,3-trifluoro-1-chloropropene (HCFO-1233zdE). They have different boiling points, respectively 18.5 ° C for the trans compound and 39.5 ° C for the cis compound.
  • Fluids based on E-3,3,3-trifluoro-1-chloropropene have found many applications in various industrial fields, in particular as heat transfer fluids, propellants, foaming agents, blowing agents, gaseous dielectrics, polymerization media or monomers, carrier fluids, abrasive agents, drying agents and fluids for power generation unit.
  • the manufacture of HCFO-1233zdE is accompanied by a multitude of by-products, having a boiling point close to HCFO-1233zdE. This leads to quite complex and expensive purification steps.
  • the difficulties encountered during the purification of HCFO-1233zdE generally involve a consequent loss of the desired product.
  • the by-products can form azeotropic compositions with HCFO-1233zdE, making separation by simple distillation very difficult or even impossible.
  • the purification steps include in particular a step of neutralization of the crude product at the outlet of the reactor to remove the residual traces of acids, i.e. HCl and HF. This neutralization step is generally carried out by means of a basic solution.
  • WO2015 / 167784 discloses a process for separating HCFO-1233zd and HF by a series of steps including, for example, a distillation to remove the HCl at the top of the distillation column, cooling of the stream at the bottom of column to obtain a mixture bi-phase, the separation of the two phases and the treatment of one of the latter with an adsorbent which can be a liquid adsorbent (water, NaOH or KOH).
  • an adsorbent which can be a liquid adsorbent (water, NaOH or KOH).
  • WO2016 / 148957 is a process for purifying HCFO-1233zdE comprising a washing stage, a condensation and phase separation stage and, finally, a drying stage.
  • a process for preparing HCFO-1233zd comprising a purification step such as washing with water or washing with a basic solution.
  • the treatment carried out to remove acidic impurities such as H F or HCl can contribute to the formation of certain impurities.
  • solution B is a basic solution.
  • Solution B aims to neutralize all or part of the acidic compound (s) of formula HX as defined above.
  • the Applicant has observed that the compound 1-chloro-1,3,3-trifluoropropene is formed in a non-negligible amount during the production and purification of 1-chloro-3,3,3-trifluoropropene, in particular during of the stage of neutralization of the acid compounds present in the reaction medium.
  • the applicant has surprisingly identified operating conditions making it possible to limit the formation of 1-chloro-1,3,3-trifluoropropene during the purification process, in particular during the neutralization step.
  • said conditions comprise the implementation of step a) with a solution B comprising an alkali metal hydroxide, preferably with a solution B comprising NaOH or KOH; in particular with a solution B comprising NaOH.
  • said solution B of step a) is an aqueous solution.
  • the alkali hydroxide content is from 2 to 40% by weight based on the total weight of said solution B.
  • step a) is carried out at a temperature of 10 ° C to 90 ° C.
  • step a) is carried out with a residence time of between 1 second and 5 minutes.
  • 1-chloro-3,3,3-trifluoropropene is in the trans form.
  • step a) makes it possible to obtain a gas stream C comprising 1-chloro-3,3,3-trifluoropropene, 1-chloro-1, 3,3-trifluoropropene and 1,1-dichloro -
  • l-chloro-l, 3,3-trifluoropropene is obtained by dehydrochlorination of l, l-dichloro-l, 3,3-trifluoropropane.
  • 1-Chloro-1,3,3-trifluoropropene is obtained by dehydrochlorination of 1,1-dichloro-1,3,3-trifluoropropane in a basic medium.
  • the present invention provides a process for the production of 1-chloro-
  • the present invention provides a composition comprising 1-chloro-
  • the molar content of 1-chloro-3,3,3-trifluoropropene in said composition is greater than 90%.
  • the molar content of 1-chloro-1,3-trifluoropropene is less than 100 ppm, preferably less than 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than 60 ppm, preferably less than 50 ppm.
  • the composition also comprises 1,1-dichloro-1,3,3-trifluoropropane.
  • the present invention provides a process for the preparation of 1-chloro-
  • the basic solution comprises an alkali metal or alkaline earth hydroxide, preferably the basic solution comprises NaOH or KOH.
  • the process is carried out at a temperature between 10 ° C and 150 ° C, preferably between 10 and 90 ° C.
  • the present invention relates to a process for neutralizing a composition A.
  • the present invention relates to a process for neutralizing said composition under conditions capable of limiting the formation of 1-chloro-1,3, 3-trifluoropropene during the neutralization of acidic compounds resulting from the production of 1-chloro-3,3,3-trifluoropropene.
  • said process comprises step a) of bringing said composition A into contact with a solution B under conditions capable of limiting the formation of 1-chloro-
  • solution B is a basic solution.
  • said conditions comprise step a) of bringing said composition A into contact with a solution B comprising an alkali hydroxide under conditions capable of limiting the formation of 1-chloro-1,3,3-trifluoropropene.
  • said conditions comprise the implementation of step a) with a solution B comprising NaOH or KOH as alkali hydroxide.
  • said conditions comprise the implementation of step a) with a solution B comprising NaOH as alkali hydroxide.
  • the content of alkali hydroxide is between 2 and 40% by weight based on the total weight of said solution B.
  • the content of alkali hydroxide is from 5 to 25% by weight based on weight. total of said solution B. More particularly, the content of alkali hydroxide is 10 to 25% by weight based on the total weight of said solution B.
  • the content of alkali hydroxide may be 15 to 25% by weight based on weight total of said solution B.
  • said solution B comprises NaOH in a mass content of 2 to 40% by weight based on the total weight of said solution B, advantageously of 5 to 25% by weight over based on the total weight of said solution B, in particular 10 to 25% by weight based on the total weight of said solution B.
  • the NaOH content may be 15 to 25% by weight based on the total weight of said solution B .
  • said solution B of step b) is an aqueous solution, in particular a basic aqueous solution.
  • said solution B is an aqueous solution, preferably basic, comprising an alkali hydroxide consisting of NaOH.
  • said solution B is an aqueous solution, preferably basic, comprising at least one alkali hydroxide consisting of NaOH; the mass content of NaOH in said solution being 2 to 40% by weight, in particular the mass content of NaOH in said solution is 5 to 25% by weight, more particularly 10 to 25% or 15 to 25% by weight weight based on the total weight of said solution B.
  • composition A may optionally comprise 1-chloro-1,3,3-trifluoropropene.
  • step a) makes it possible to obtain a gas stream C comprising 1-chloro-3,3,3-trifluoropropene, 1-chloro-1, 3,3-trifluoropropene and 1,1-dichloro - 1,3,3-trifluoropropane.
  • the molar content of 1-chloro-1,3-trifluoropropene in said stream C is less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less or equal to 80 ppm, in in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm.
  • the molar content of 1-chloro-3,3,3-trifluoropropene in said stream C is greater than 85%, advantageously greater than 87%, preferably greater than 90%, more preferably greater than 92%, in particular greater than 95%, more particularly greater than 97%, preferably greater than 99%.
  • said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 85% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm.
  • said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 87% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm.
  • said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 90% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal at 50 ppm.
  • said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 92% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal at 50 ppm.
  • said stream C may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 95% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm.
  • said stream C may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 97% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal at 50 ppm.
  • said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 99% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm. , advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less or equal to 50 ppm.
  • the molar content of 1,1-dichloro-1,3,3-trifluoropropane in said stream C may be between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
  • said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 85% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
  • said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 87% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
  • said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 90% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal at 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
  • said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 92% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal at 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
  • said stream C may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 95% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal at 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
  • said stream C may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 97% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal at 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
  • said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 99% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm.
  • ppm advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less or equal to 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
  • 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans -l-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1-chloro-3,3,3-trifluoropropene, preferably at least 95 mol% of trans-1-chloro- 3,3,3-trifluoropropene; the remainder being represented by the cis-1-chloro-3,3,3-trifluoropropene isomer.
  • 1-chloro-3,3,3-trifluoropropene is trans-1-chloro- 3,3,3-trifluoropropene.
  • Said solution B can optionally comprise reducing agents, such as sulphite or bisulphite salts.
  • said solution B can be an organic solution containing a solvent.
  • the solvent is defined as an inert organic compound in which 1-chloro-3,3,3-trifluoropropene is at least partially soluble.
  • the solvent is preferably selected from the group consisting of hydrocarbons, ethers, alcohols, alkyl halides, substituted or unsubstituted benzenes, alkyl nitrile, amides, sulfoxides, sulfones, phosphate esters and mixtures thereof.
  • the solvent is selected from ethers, alcohols, alkyl halides, substituted or unsubstituted benzenes, alkyl nitrile, amides, sulfoxides, sulfones, and mixtures thereof.
  • the ethers include acyclic alkyl ethers, cyclic ethers, perfluorinated ethers, glyme, diglyme, triglyme, tetraglyme, and mixtures thereof.
  • Acyclic alkyl ethers include dimethyl ether, ethyl ether, methyl ethyl ether, and mixtures thereof.
  • Cyclic ethers include 2-methyltetrahydrofuran, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, and mixtures thereof.
  • Perfluorinated ethers include perfluoro-N-methyl morpholine, perfluorotetrahydrofuran, and mixtures thereof.
  • Alcohols include alkyl alcohols, glycols, glycerol, and mixtures thereof.
  • Alcohol alkyls include methanol, ethanol, propanol, isopropanol, 2-methyl-2-propanol, cyclohexanol, and mixtures thereof.
  • Examples of glycol include ethylene glycol, propylene glycol, diethylene glycol, and mixtures thereof.
  • Substituted and unsubstituted benzenes include alkylbenzenes, halobenzenes, benzonitrile phenol, anisole, biphenyl, nitrobenzene and mixtures thereof.
  • Alkylbenzenes include toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, mesitylene, durene, 2-phenylhexane, and mixtures thereof.
  • Halobenzenes include fluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, and mixtures thereof.
  • Alkyl halides include dichloromethane, chloroform, carbon tetrachloride, chloroethane, 1,2-dichloroethane, and mixtures thereof.
  • Alkyl nitriles include acetonitrile, butyronitrile, methylglutaronitrile, adiponitrile, and mixtures thereof.
  • Amides include N, N-dimethyl formamide, N, N-dimethyl-acetamide, N-methyl-2-pyrrolidone, and mixtures thereof.
  • Sulfoxides include dimethyl sulfoxide.
  • Sulfones include sulfolane.
  • the solution B is an organic solution
  • the latter comprises at least one alkaline hydroxide consisting of NaOH, preferably in a content by mass of 2 to 40% based on the total weight of said solution B, in particular a content by mass of 5 to 20% by weight based on the total weight of said solution B.
  • step a) of the present process is carried out at a temperature of 10 ° C to 90 ° C, advantageously of 10 ° C to 80 ° C, preferably of 10 ° C. at 70 ° C, in particular from 10 ° C to 60 ° C.
  • step a) is carried out with a residence time of between 1 second and 5 minutes, in particular between 5 seconds and 5 minutes, more particularly between 10 seconds and 5 minutes, preferably between 15 seconds and 5 minutes.
  • a process for producing 1-chloro-3,3,3-trifluoropropene is provided.
  • Said process for the production of 1-chloro-3,3,3-trifluoropropene comprising the steps of: i) contacting, in a reactor, between hydrofluoric acid (HF) and a starting composition comprising at least one chlorinated compound selected from the group consisting of 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene and a mixture of the two, under conditions sufficient to obtain a stream D comprising 1-chloro-3,3,3 -trifluoropropene, 1,1-dichloro-1,3,3-trifluoropropane HF and / or HCl;
  • 3.3.3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1-chloro-3,3,3-trifluoropropene, so preferred at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene; the remainder being represented by the cis-1-chloro-3,3,3-trifluoropropene isomer.
  • 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
  • said step i) is carried out in a liquid phase, preferably low in HF.
  • said starting composition comprises at least 10% by weight of said at least one chlorinated compound based on the total weight of said starting composition.
  • said starting composition comprises at least 15% by weight of said at least one chlorinated compound, preferably at least 20% by weight of said at least one chlorinated compound, more preferably at least 25% by weight of said at least one chlorinated compound, in particular at least 30% by weight of said at least one chlorinated compound, more particularly at least 35% by weight of said at least one chlorinated compound, preferably at least 40% by weight of said at least one chlorinated compound, advantageously preferred at least 45% by weight of said at least one chlorinated compound, preferably at least 50% by weight of said at least one chlorinated compound, particularly preferably at least 55% by weight of said at least one chlorinated compound on the basis of weight total of said starting composition.
  • said starting composition comprises at least 60% by weight or at least 65% by weight or at least 70% by weight or at least 75% by weight or at least 80% by weight or at least 85% by weight or at least 90% by weight or at least 95% by weight or at least 99% by weight of said at least one chlorinated compound based on the total weight of said starting composition.
  • said at least one chlorinated compound is 1, 1,3,3-tetrachloropropene (1230za).
  • said method comprises a step i) of bringing into contact in a reactor between hydrofluoric acid (HF) and a starting composition comprising
  • HF hydrofluoric acid
  • 1.1.3.3-Tetrachloropropene (1230za) to produce a stream D comprising 1-chloro-3,3,3-trifluoropropene (1233zd), HF and HCl; said step i) is carried out in a liquid phase poor in HF as defined below.
  • the present process allows the production of 1-chloro-3,3,3-trifluoropropene as a mixture of the two isomers. cis and trans. The present process makes it possible to obtain mainly the trans-1-chloro- isomer.
  • said starting composition comprises at least 10% by weight of 1, 1,3,3-tetrachloropropene based on the total weight of said starting composition.
  • said starting composition comprises at least 15% by weight of 1,1,3,3-tetrachloropropene, preferably at least 20% by weight of 1,1,3,3-tetrachloropropene, more preferably at least 25% by weight. weight of 1,1,3,3-tetrachloropropene, in particular at least 30% by weight of
  • 1.1.3.3-tetrachloropropene more particularly at least 35% by weight of 1,1,3,3-tetrachloropropene, preferably at least 40% by weight of 1,1,3,3-tetrachloropropene, advantageously preferred over less 45% by weight of 1,1,3,3-tetrachloropropene, preferably at least 50% by weight of
  • said starting composition comprises at least 60% by weight or at least 65% by weight or at least 70% by weight or at least 75% by weight or at least 80% by weight or at least 85% by weight or at least 90% by weight or at least 95% by weight or at least 99% by weight of 1,1,3,3-tetrachloropropene based on the total weight of said starting composition.
  • said starting composition comprises less than 15% by weight of HF based on the total weight of said starting composition, advantageously less than 10% by weight of HF, preferably less than 8% by weight of HF, more preferably less than 6% by weight of HF, in particular less than 5% by weight of HF, more particularly less than 4% by weight of HF, preferably less than 2% by weight of HF on a weight basis total of said starting composition.
  • the starting composition is free of HF.
  • free means a content by weight of less than 500 ppm, preferably less than 100 ppm, in particular less than 10 ppm.
  • said liquid phase poor in HF is a liquid phase comprising less than 15% by weight of HF, advantageously less than 10% by weight of HF, preferably less than 8% by weight of HF, more preferably less than 6% by weight of HF, in particular less than 5% by weight of HF, more particularly less than 4% by weight of HF, preferably less than 2% by weight of HF based on the total weight of said liquid phase.
  • said liquid phase may comprise at least 10% by weight of compounds of formula (I) C3H n F m Cl p (I) in which n is an integer from 0 to 8, m is an integer from 0 to 8, and p is an integer from 0 to 8; preferably n is an integer from 0 to 8, m is an integer from 0 to 6 and p is an integer from 0 to 6.
  • compounds of formula (I) can be C366, C3H4Cl4 OR C3H3Cl5.
  • said liquid phase may comprise at least 10% by weight of compounds of formula (I) C3H n F m Cl p (I) in which n is an integer from 1 to 8, m is an integer from 0 to 4, and p is an integer from 0 to 4; preferably n is an integer from 1 to 4, m is an integer from 0 to 3 and p is an integer from 2 to 4.
  • the compounds of formula (I) can be compounds of the propane or propene type comprising one or more atoms chlorine and / or one or more fluorine atoms.
  • said liquid phase may comprise at least 10% by weight of compounds of formula (I) selected from the group consisting of C3H2Cl4, C3H2Cl3F, C3H2CI2F2, C3H3CI5, C3H3CI4F, C3H3Cl3F2 and C3H3CI2F3.
  • said liquid phase may comprise at least 10% by weight of compounds of formula (I) selected from the group consisting of C3H2Cl4, C3H2Cl3F and C3H2CI2F2.
  • Said liquid phase may comprise at least 15% by weight of compounds of formula (I) C3H n F m Cl p (I) in which n is an integer from 0 to 8, m is an integer from 0 to 8, and p is an integer from 0 to 8; preferably n is an integer from 0 to 8, m is an integer from 0 to 6 and p is an integer from 0 to 6.
  • said liquid phase can comprise at least 15% by weight of compounds of formula (I) C3H n F m Cl p (I) in which n is an integer from 1 to 8, m is an integer from 0 to 4, and p is an integer from 0 to 4; preferably n is an integer from 1 to 4, m is an integer from 0 to 3 and p is an integer from 2 to 4.
  • said liquid phase can comprise at least 15% by weight of compounds of formula (I) selected from the group consisting of C3H2CI4, C3H2CI3F, C3H2CI2F2, C3H3CI5, C3H3CI4F, C3H3CI3F2 and C3H3CI2F3.
  • said liquid phase may comprise at least 15% by weight of compounds of formula (I) selected from the group consisting of C3H2Cl4, C3H2Cl3F and C3H2CI2F2.
  • Said liquid phase may comprise at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80% or at least 90% by weight of compounds of formula (I) C3H n F m Cl p (I) where n is an integer from 0 to 8, m is an integer from 0 to 8, and p is an integer from 0 to 8; preferably n is an integer from 0 to 8, m is an integer from 0 to 6 and p is an integer from 0 to 6.
  • Said liquid phase can comprise at least 20%, at least 30%, at least 40%, at least. at least 50%, at least 60%, at least 70%, at least 80% or at least 90% by weight of compounds of formula (I) C3H n F m Cl p (I) in which n is an integer from 1 to 8, m is an integer of 0 to 4, and p is an integer of 0 to 4; preferably n is an integer from 1 to 4, m is an integer from 0 to 3 and p is an integer from 2 to 4.
  • said liquid phase can comprise at least 20%, at least 30%, at least 40 %, at least 50%, at least 60%, at least 70%, at least 80% or at least 90% by weight of compounds of formula (I) selected from the group consisting of C3H2Cl4, C3H2CI3F, C3H2CI2F2, C3H3CI5, C3H3CI4F, C3H3CI3F2 and C3H3CI2F3.
  • compounds of formula (I) selected from the group consisting of C3H2Cl4, C3H2CI3F, C3H2CI2F2, C3H3CI5, C3H3CI4F, C3H3CI3F2 and C3H3CI2F3.
  • said liquid phase may comprise at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80% or at least 90% by weight of compounds of formula (I) selected from the group consisting of C3H2Cl4, C3H2Cl3F and C3H2Cl2F2.
  • step i) is carried out in the absence of catalyst.
  • step i) can be carried out in the presence of a catalyst.
  • the catalyst may be a T1Cl4 or SbCl 5 type catalyst.
  • the catalyst can also be an ionic liquid.
  • Ionic liquids which may be suitable are derived from Lewis acids based on aluminum, titanium, niobium, tantalum, tin, antimony, nickel, zinc or iron.
  • the term “ionic liquids” is understood to mean nonaqueous salts of ionic character which are liquid at moderate temperatures (preferably below 120 ° C.). Ionic liquids preferably result from the reaction between an organic salt and an inorganic compound.
  • the ionic liquids are preferably obtained by reaction of at least one halogenated or oxyhalogenated Lewis acid based on aluminum, titanium, niobium, tantalum, tin, antimony, nickel, zinc or iron with a salt of general formula Y + A, in which A denotes a halide anion (bromide, iodide and, preferably chloride or fluoride) or hexafluoroantimonate (SbF 6 _ ) and Y + a quaternary ammonium cation, quaternary phosphonium or ternary sulfonium .
  • the halogenated Lewis acid based on aluminum, titanium, niobium, tantalum, antimony, nickel, zinc or iron can be a chlorinated, brominated, fluorinated or mixed derivative, for example a chlorofluorinated acid .
  • the chlorides, fluorides or chlorofluorides of the following formulas may be mentioned more particularly:
  • the following compounds are preferably used: T1CI 4 , TaCI 5 + TaF 5 , NbCI 5 + NbF 5 , SbCI 5 , SbFCU, SbF2Ü3, SbF3Ü2, SbF4Ü, SbF 5 and SbCI 5 + SbF 5 . More particularly preferred are antimonial compounds.
  • the Y + cation can correspond to one of the following general formulas: R 1 R 2 R 3 R 4 N + , R 1 R 2 R 3 R 4 P + , R 4 R 2 R 3 S + in which the symbols R 1 to R 4 , identical or different, each denote a hydrocarbyl, chlorohydrocarbyl, fluorohydrocarbyl, chlorofluorohydrocarbyle or fluorocarbyle group having from 1 to 10 carbon atoms, saturated or not, cyclic or not, or aromatic, l 'one or more of these groups may also contain one or more heteroatoms such as N, P, S or O.
  • ammonium, phosphonium or sulfonium cation Y + can also be part of a saturated or unsaturated, or aromatic heterocycle having 1 with 3 nitrogen, phosphorus or sulfur atoms, and meet one or other of the following general formulas:
  • R 1 and R 2 are as defined above.
  • a salt containing 2 or 3 ammonium, phosphonium or sulfonium sites in their formula may also be suitable.
  • Y + A salts there may be mentioned tetraalkyl ammonium chlorides and fluorides, tetraalkyl phosphonium chlorides and fluorides, and trialkyl sulfonium chlorides and fluorides, alkyl pyridinium chlorides and fluorides, chlorides, fluorides and bromides of dialkyl imidazolium, and trialkyl imidazolium chlorides and fluorides.
  • trimethyl sulfonium fluoride or chloride N-ethyl-pyridinium chloride or fluoride, N-butyl-pyridinium chloride or fluoride, 1-ethyl-3-methyl chloride or fluoride.
  • the ionic liquids can be prepared in a manner known per se by suitably mixing the halogenated or oxyhalogenated Lewis acid and the organic salt Y + A. We may refer in particular to the method described in document WO 01/81353. Alternatively, the catalyst can be triflic or trifluoroacetic acid as mentioned in document US Pat. No. 6,166,274.
  • stream D comprises co-products selected from the group consisting of 1, 3,3,3-tetrafluoropropene and 1,1,1,3 , 3-pentafluoropropane.
  • the content in stream D of co-products selected from the group consisting of 1, 3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane is less than 0.5% in mole.
  • the content of 1,3,3,3-tetrafluoropropene in said stream D is less than 0.5%, more preferably less than 0.4%, in particular less than 0.3% by mole.
  • the content of 1,1,1,3,3-pentafluoropropane in said stream D is less than 0.1%, more preferably less than 0.075%, in particular less than 0.05% by mole.
  • step i) is carried out at a temperature of 50 ° C to 150 ° C, preferably at a temperature of 75 ° C to 100 ° C.
  • step i) is carried out at a pressure of 5 to 20 bara, preferably at a pressure of 10 to 18 bara, in particular 12 to 18 bara.
  • the HF / [chlorinated compounds] molar ratio at the inlet of the reactor is between 5 and 10, more preferably between 5 and 7, in particular between 5 and 6.
  • said chlorinated compound of the composition of starting point is 1,1,3,3-tetrachloropropene (1230za)
  • the HF / 1230za molar ratio is between 5 and 10, more preferably between 5 and 7, in particular between 5 and 6.
  • the hydrofluoric acid and said starting composition can be introduced into the reactor via a static mixer.
  • the hydrofluoric acid is heated before its introduction into the reactor and thus before the implementation of step i).
  • the hydrofluoric acid is heated to a temperature of 100 ° C to 170 ° C, preferably 120 ° C to 170 ° C, in particular 125 ° C to 165 ° C, more particularly 125 ° C to 155 ° C.
  • the stream D obtained in step i) can be subjected to purification steps prior to the implementation of step ii).
  • the current D obtained in step i) can be used directly in step ii).
  • said production process may comprise a step i ′), subsequent to step i) and prior to step ii), comprising a step of treatment of current D to give a current DI comprising 1-chloro-3 , 3,3-trifluoropropene, HCl, HF and a stream D2 comprising at least 50% by weight of HF, for example preferably at least 70% by weight of HF.
  • the treatment step (i ′) is preferably a reflux column, advantageously carried out at a temperature of between 30 and 120 ° C. to give the stream D2 which is recycled to the reactor.
  • said process for the production of 1-chloro-3,3,3-trifluoropropene according to the present invention comprising the steps of:
  • the present production process can also comprise a step ii ′) subsequent to step i ′) and prior to step ii).
  • said step ii ′) is a step of recovering hydrochloric acid from stream DI to form a stream D3 of HCl and a stream D4 comprising 1-chloro-3,3,3-trifluoropropene, HCl, HF .
  • the recovery of HCl in step (ii ′) is preferably obtained using a distillation column fitted with a reboiler at the bottom and with a reflux system at the top.
  • the temperature at the bottom is advantageously between 20 ° C and 110 ° C.
  • the head temperature is advantageously between -50 ° C and 0 ° C.
  • the distillation of the HCl is typically carried out at a pressure of between 7 and 25 bars.
  • This recovery step makes it possible to obtain a stream D4 in which the quantity of HCl is greatly reduced relative to the quantity of HCl in the stream D
  • said process for the production of 1-chloro-3,3,3-trifluoropropene according to the present invention comprising the steps of:
  • stream D1 comprising 1-chloro-3,3,3-trifluoropropene, HCl, HF and stream D2 comprising at least 50% by weight of HF;
  • step iii ′) is a step of separating the stream D4 to form a stream D5 comprising at least 90% by weight, preferably at least 98% by weight and in particular at least 99% by weight of HF , and a stream D6 comprising 1-chloro-3,3,3-trifluoropropene, HCl and HF.
  • the separation step is preferably decantation, carried out at a temperature advantageously between -50 ° C and 50 ° C, preferably between -20 ° C and 10 ° C.
  • said process for the production of 1-chloro-3,3,3-trifluoropropene according to the present invention comprising the steps of:
  • HF hydrofluoric acid
  • stream D comprising 1-chloro-3,3,3-trifluoropropene, HCl, HF and stream D2 comprising at least 50% by weight of HF;
  • the present production process can also comprise a step iv ′) subsequent to step iii ′) and prior to step ii).
  • step iv ′) is a washing step with water. This step eliminates part of the HCl and HF included in the stream D6.
  • said process for the production of 1-chloro-3,3,3-trifluoropropene according to the present invention comprising the steps of:
  • HF hydrofluoric acid
  • iii ' separation of the stream D4 obtained in step ii') to form a stream D5 comprising at least 90% by weight and a stream D6 comprising 1-chloro-3,3,3-trifluoropropene, HCl and HF; iv ') washing said stream D6 obtained in step iii') with water to form a stream D7 comprising 1-chloro-3,3,3-trifluoropropene and an acidic aqueous solution D8;
  • step iii) consists of drying said gas stream C comprising 1-chloro-3,3,3-trifluoropropene to form a dried stream C2 comprising 1-chloro-3,3,3-trifluoropropene.
  • the drying step can be carried out using molecular sieve, zeolite, inorganic salts such as calcium sulfate or calcium chloride, silica gel, activated carbon. Examples of molecular sieves and zeolites are described in document WO2017 / 050686.
  • the drying step will be carried out using a molecular sieve, in particular using a 3A molecular sieve.
  • step iv) comprises one or more steps of distillation of said stream C2 obtained in step iii).
  • said process for the production of 1-chloro-3,3,3-trifluoropropene according to the present invention comprising the steps of:
  • HF hydrofluoric acid
  • stream D comprising 1-chloro-3,3,3-trifluoropropene, HCl, HF and stream D2 comprising at least 50% by weight of HF;
  • ii ' recovering hydrochloric acid from stream DI to form HCl stream D3 and stream D4 comprising 1-chloro-3,3,3-trifluoropropene, HCl, HF;
  • iii ' separation of the stream D4 obtained in step ii') to form a stream D5 comprising at least 90% by weight and a stream D6 comprising 1-chloro-3,3,3-trifluoropropene, HCl and HF; iv ') washing said stream D6 obtained in step iii') with water to form a stream D7 comprising 1-chloro-3,3,3-trifluoropropene and an acidic aqueous solution D8;
  • said production process according to the present invention is carried out continuously.
  • a composition comprising 1-chloro-3,3,3-trifluoropropene and 1-chloro-1,3,3-trifluoropropene.
  • the molar content of 1-chloro-1,3,3-trifluoropropene being less than 110 ppm in said composition.
  • the molar content of 1-chloro-3,3,3-trifluoropropene in said composition is greater than 85%.
  • 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro- 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene.
  • 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
  • said composition comprises a molar content of 1-chloro-3,3,3-trifluoropropene greater than 87% and a molar content of 1-chloro-1,3,3-trifluoropropene less than 110 ppm, advantageously less than 100 ppm, preferably less than 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than 60 ppm, preferably less than 50 ppm.
  • 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% of trans-1- chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% of trans-1-chloro-
  • 3.3.3-trifluoropropene the complement being represented by cis-1-chloro-3,3,3-trifluoropropene.
  • 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
  • said composition comprises a molar content of 1-chloro-3,3,3-trifluoropropene greater than 90% and a molar content of 1-chloro-1,3,3-trifluoropropene less than 110 ppm, advantageously less than 100 ppm, preferably less than 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than 60 ppm, preferably less than 50 ppm.
  • 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1-chloro -
  • 3.3.3-trifluoropropene preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro-3,3,3 - trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene.
  • 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
  • said composition comprises a molar content of 1-chloro-3,3,3-trifluoropropene greater than 92% and a molar content of 1-chloro-1,3,3-trifluoropropene less than 110 ppm, advantageously less than 100 ppm, preferably less than 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than 60 ppm, preferably less than 50 ppm.
  • 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro-
  • 3.3.3-trifluoropropene the complement being represented by cis-1-chloro-3,3,3-trifluoropropene.
  • 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
  • said composition comprises a molar content of 1-chloro-3,3,3-trifluoropropene greater than 95% and a molar content of 1-chloro-1,3,3-trifluoropropene less than 110 ppm, advantageously less than 100 ppm, preferably less than 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than 60 ppm, preferably less than 50 ppm.
  • 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1- chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro-
  • 3,3,3-trifluoropropene the complement being represented by cis-1-chloro-3,3,3-trifluoropropene.
  • 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
  • said composition comprises a molar content of 1-chloro-3,3,3-trifluoropropene greater than 97% and a molar content of 1-chloro-1,3,3-trifluoropropene less than 110 ppm, advantageously less than 100.
  • ppm preferably less than 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than 60 ppm, preferably less than 50 ppm.
  • 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro-
  • 3,3,3-trifluoropropene the complement being represented by cis-1-chloro-3,3,3-trifluoropropene.
  • 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
  • said composition comprises a molar content of 1-chloro-3,3,3-trifluoropropene greater than 99% and a molar content of 1-chloro-1,3,3-trifluoropropene less than 110 ppm, advantageously less than 100 ppm, preferably less than 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than 60 ppm, preferably less than 50 ppm.
  • 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro-
  • 3,3,3-trifluoropropene the complement being represented by cis-1-chloro-3,3,3-trifluoropropene.
  • 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
  • Said composition may also comprise 1,1-dichloro-1,3,3-trifluoropropane.
  • the molar content of 1,1-dichloro-1,3,3-trifluoropropane in said composition is between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
  • said composition may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 85% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less. or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
  • 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro- 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene.
  • 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
  • said composition may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 87% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
  • 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro- 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene.
  • 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
  • said composition may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 90% and a molar content of 1-chloro-1,3,3-trifluoropropene. less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm , preferably less than or equal to 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
  • 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro- 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene.
  • 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
  • said composition may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 92% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
  • 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro- 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene.
  • 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
  • said composition may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 95% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particularly between 50 and 100 ppm.
  • 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro- 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene.
  • 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
  • said composition may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 97% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
  • 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro- 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene.
  • 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
  • said composition may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 99% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal at 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
  • 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro- 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene.
  • 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
  • the examples are implemented in a reactor topped with a slaughter column (both being heat insulated).
  • a basic solution was introduced and a roundabout of this solution was carried out through a slaughter column packed with Raschig rings (about 185 ml / min).
  • the basic solution is brought to a temperature of 30 ° C. or 50 ° C. depending on the examples.
  • a composition comprising 95.8 mol% trans-l-chloro-3,3,3-trifluoropropene, 2.4 mol% of cis-1-chloro-3,3,3-trifluoropropene (i.e. a trans / cis molar ratio of 39.9), about 120 ppm of 1,1-dichloro-1,3,3-trifluoropropane and about 25 ppm of 1-chloro-1,3,3-trifluoropropene were then introduced into the reactor at a flow rate of 5 g / h. The contents of the constituents of the composition are expressed in moles.
  • Said composition can be obtained by implementing the process for producing 1-chloro-3,3,3-trifluoropropene as described in the present application.
  • the gas stream was collected to be dried over anhydrous CaCh and trapped using a liquid nitrogen trap.
  • the gas flow was analyzed by gas chromatography.
  • the amount of 1-chloro-1,3,3-trifluoropropene is determined after neutralization.
  • the use of a basic NaOH solution makes it possible to limit the formation of 1-chloro-1,3,3-trifluoropropene during the neutralization step; the HCFC-243fc content being slightly reduced.
  • the use of a basic KOH solution results in a higher content of HCFO-1233zb and a sharp decrease in the Tl HCFC-243fc content.
  • the trans-1-chloro-3,3,3-trifluoropropene thus obtained comprises less HCFO-1233zb capable of disturbing its effectiveness in the various fields of application.

Abstract

The present invention relates to a process for neutralizing a composition A comprising 1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-1,3,3-trifluoropropane and one or more acid compounds of formula HX with X = F or Cl; said process comprising the step a) of bringing said composition A into contact with a solution B under conditions capable of limiting the formation of 1-chloro-1,3,3-trifluoropropene.

Description

DESCRIPTION DESCRIPTION
TITRE : Procédé de purification du l-chloro-3,3,3-trifluoropropène TITLE: Process for the purification of l-chloro-3,3,3-trifluoropropene
Domaine technique de l'invention Technical field of the invention
La présente invention concerne un procédé de purification d'hydrochlorofluorooléfines. En particulier, la présente invention concerne un procédé de purification du l-chloro-3,3,3- trifluoropropène. La présente invention concerne également un procédé de production du 1- chloro-3,3,3-trifluoropropène. Arrière-plan technologique de l'invention The present invention relates to a process for the purification of hydrochlorofluoroolefins. In particular, the present invention relates to a process for the purification of 1-chloro-3,3,3-trifluoropropene. The present invention also relates to a process for the production of 1-chloro-3,3,3-trifluoropropene. Technological background of the invention
Le 3,3,3-trifluoro-l-chloropropène ou encore l-chloro-3,3,3-trifluoropropène (HCFO-1233zd) existe sous forme de deux isomères : l'isomère cis, à savoir le Z-3,3,3-trifluoro-l-chloropropène (HCFO-1233zdZ), et l'isomère trans, à savoir le E-3,3,3-trifluoro-l-chloropropène (HCFO- 1233zdE). Ils ont des points d'ébullition différents, respectivement de 18,5°C pour le composé trans et de 39,5°C pour le composé cis. 3,3,3-trifluoro-1-chloropropene or l-chloro-3,3,3-trifluoropropene (HCFO-1233zd) exists in the form of two isomers: the cis isomer, namely Z-3.3 , 3-trifluoro-1-chloropropene (HCFO-1233zdZ), and the trans isomer, namely E-3,3,3-trifluoro-1-chloropropene (HCFO-1233zdE). They have different boiling points, respectively 18.5 ° C for the trans compound and 39.5 ° C for the cis compound.
Les fluides à base de E-3,3,3-trifluoro-l-chloropropène (HCFO-1233zdE) ont trouvé de nombreuses applications dans des domaines industriels variés, notamment en tant que fluides de transfert de chaleur, propulseurs, agents moussants, agents gonflants, diélectriques gazeux, milieux de polymérisation ou monomères, fluides supports, agents abrasifs, agents de séchage et fluides pour unité de production d'énergie. Fluids based on E-3,3,3-trifluoro-1-chloropropene (HCFO-1233zdE) have found many applications in various industrial fields, in particular as heat transfer fluids, propellants, foaming agents, blowing agents, gaseous dielectrics, polymerization media or monomers, carrier fluids, abrasive agents, drying agents and fluids for power generation unit.
La fabrication du HCFO-1233zdE s'accompagne d'une multitude de sous-produits, ayant un point d'ébullition proche du HCFO-1233zdE. Cela conduit à des étapes de purification assez complexes et coûteuses. Les difficultés rencontrées au cours de la purification du HCFO-1233zdE impliquent généralement une perte conséquente en produit recherché. De plus, les sous-produits peuvent former des compositions azéotropiques avec le HCFO-1233zdE, rendant très difficile voire impossible la séparation par distillation simple. Les étapes de purification incluent notamment une étape de neutralisation du produit brut en sortie du réacteur pour éliminer les traces résiduelles d'acides, i.e. HCl et HF. Cette étape de neutralisation s'effectue généralement par l'intermédiaire d'une solution basique. The manufacture of HCFO-1233zdE is accompanied by a multitude of by-products, having a boiling point close to HCFO-1233zdE. This leads to quite complex and expensive purification steps. The difficulties encountered during the purification of HCFO-1233zdE generally involve a consequent loss of the desired product. In addition, the by-products can form azeotropic compositions with HCFO-1233zdE, making separation by simple distillation very difficult or even impossible. The purification steps include in particular a step of neutralization of the crude product at the outlet of the reactor to remove the residual traces of acids, i.e. HCl and HF. This neutralization step is generally carried out by means of a basic solution.
On connaît notamment par WO2015/167784 un procédé de séparation du HCFO-1233zd et de l'HF par une série d'étapes incluant par exemple une distillation pour éliminer l'HCI en tête de colonne de distillation, le refroidissement du flux en pied de colonne pour obtenir un mélange bi-phasique, la séparation des deux phases et le traitement d'une de celle-ci par un adsorbant pouvant être un adsorbant liquide (eau, NaOH ou KOH). In particular, WO2015 / 167784 discloses a process for separating HCFO-1233zd and HF by a series of steps including, for example, a distillation to remove the HCl at the top of the distillation column, cooling of the stream at the bottom of column to obtain a mixture bi-phase, the separation of the two phases and the treatment of one of the latter with an adsorbent which can be a liquid adsorbent (water, NaOH or KOH).
On connaît aussi par WO2016/148957 un procédé de purification du HCFO-1233zdE comprenant une étape de lavage, une étape de condensation et de séparation de phase et, enfin une étape de séchage. On connaît également par W02014/010530, WO2014/189674, WO2014/099464 un procédé de préparation du HCFO-1233zd comprenant une étape de purification telle qu'un lavage à l'eau ou un lavage à l'aide d'une solution basique. Also known from WO2016 / 148957 is a process for purifying HCFO-1233zdE comprising a washing stage, a condensation and phase separation stage and, finally, a drying stage. Also known from WO2014 / 010530, WO2014 / 189674, WO2014 / 099464 is a process for preparing HCFO-1233zd comprising a purification step such as washing with water or washing with a basic solution.
Lors de la purification du FICFO-1233zd, le traitement mis en oeuvre pour éliminer des impuretés acides telles que H F ou HCl peut contribuer à la formation de certaines impuretés. During the purification of FICFO-1233zd, the treatment carried out to remove acidic impurities such as H F or HCl can contribute to the formation of certain impurities.
Ainsi, de nouvelles conditions de neutralisation des impuretés acides doivent être mises en oeuvre pour minimiser la dégradation du FICFO-1233zdE. Il existe un besoin pour un procédé efficace de purification du trans-l-chloro-3,3,3-trifluoropropène minimisant la production de sous-produits ou autres impuretés issues d'une réaction de déshydrochloration. Thus, new conditions for neutralizing the acid impurities must be implemented to minimize the degradation of FICFO-1233zdE. There is a need for an efficient process for purifying trans-1-chloro-3,3,3-trifluoropropene which minimizes the production of by-products or other impurities from a dehydrochlorination reaction.
Résumé de l'invention Summary of the invention
Selon un premier aspect, la présente invention fournit un procédé de neutralisation d'une composition A comprenant l-chloro-3,3,3-trifluoropropène, l,l-dichloro-l,3,3- trifluoropropane et un ou plusieurs composé(s) acide de formule HX avec X = F ou Cl ; ledit procédé comprenant l'étape a) de mise en contact de ladite composition A avec une solution B dans des conditions aptes à limiter la formation du l-chloro-l,3,3-trifluoropropène. According to a first aspect, the present invention provides a process for neutralizing a composition A comprising 1-chloro-3,3,3-trifluoropropene, l, l-dichloro-1,3,3-trifluoropropane and one or more compound ( s) acid of formula HX with X = F or Cl; said process comprising step a) of bringing said composition A into contact with a solution B under conditions capable of limiting the formation of 1-chloro-1,3,3-trifluoropropene.
De préférence, la solution B est une solution basique. La solution B vise à neutraliser tout ou partie du (des) composé(s) acide(s) de formule HX tel que définie ci-dessus. Preferably, solution B is a basic solution. Solution B aims to neutralize all or part of the acidic compound (s) of formula HX as defined above.
Le demandeur a observé que le composé l-chloro-l,3,3-trifluoropropène se formait en quantité non négligeable au cours de la production et de la purification du l-chloro-3,3,3- trifluoropropène, en particulier au cours de l'étape de neutralisation des composés acides présents dans le milieu réactionnel. Le demandeur a de manière surprenante identifié des conditions opératoires permettant de limiter la formation du l-chloro-l,3,3-trifluoropropène au cours du processus de purification, en particulier au cours de l'étape de neutralisation. The Applicant has observed that the compound 1-chloro-1,3,3-trifluoropropene is formed in a non-negligible amount during the production and purification of 1-chloro-3,3,3-trifluoropropene, in particular during of the stage of neutralization of the acid compounds present in the reaction medium. The applicant has surprisingly identified operating conditions making it possible to limit the formation of 1-chloro-1,3,3-trifluoropropene during the purification process, in particular during the neutralization step.
Selon un mode de réalisation préféré, lesdites conditions comprennent la mise en oeuvre de l'étape a) avec une solution B comprenant un hydroxyde alcalin, de préférence avec une solution B comprenant NaOH ou KOH ; en particulier avec une solution B comprenant NaOH. According to a preferred embodiment, said conditions comprise the implementation of step a) with a solution B comprising an alkali metal hydroxide, preferably with a solution B comprising NaOH or KOH; in particular with a solution B comprising NaOH.
Selon un mode de réalisation préféré, -ladite solution B de l'étape a) est une solution aqueuse. Selon un mode de réalisation préféré, la teneur en hydroxyde alcalin est de 2 à 40% en poids sur base du poids total de ladite solution B. According to a preferred embodiment, said solution B of step a) is an aqueous solution. According to a preferred embodiment, the alkali hydroxide content is from 2 to 40% by weight based on the total weight of said solution B.
Selon un mode de réalisation préféré, l'étape a) est mise en oeuvre à une température de 10°C à 90°C. According to a preferred embodiment, step a) is carried out at a temperature of 10 ° C to 90 ° C.
Selon un mode de réalisation préféré, l'étape a) est mise en oeuvre avec un temps de séjour compris entre 1 seconde et 5 minutes. According to a preferred embodiment, step a) is carried out with a residence time of between 1 second and 5 minutes.
Selon un mode de réalisation préféré, le l-chloro-3,3,3-trifluoropropène est sous la forme trans. Selon un mode de réalisation préféré, l'étape a) permet d'obtenir un courant gazeux C comprenant l-chloro-3,3,3-trifluoropropène, l-chloro-l,3,3-trifluoropropène et 1,1-dichloro- According to a preferred embodiment, 1-chloro-3,3,3-trifluoropropene is in the trans form. According to a preferred embodiment, step a) makes it possible to obtain a gas stream C comprising 1-chloro-3,3,3-trifluoropropene, 1-chloro-1, 3,3-trifluoropropene and 1,1-dichloro -
1.3.3-trifluoropropane. 1.3.3-trifluoropropane.
Selon un mode de réalisation préféré, le l-chloro-l,3,3-trifluoropropène est obtenu par déshydrochloration du l,l-dichloro-l,3,3-trifluoropropane. Le l-chloro-l,3,3-trifluoropropène est obtenu par déshydrochloration du l,l-dichloro-l,3,3-trifluoropropane en milieu basique. Selon un second aspect, la présente invention fournit un procédé de production du 1-chloro- According to a preferred embodiment, l-chloro-l, 3,3-trifluoropropene is obtained by dehydrochlorination of l, l-dichloro-l, 3,3-trifluoropropane. 1-Chloro-1,3,3-trifluoropropene is obtained by dehydrochlorination of 1,1-dichloro-1,3,3-trifluoropropane in a basic medium. In a second aspect, the present invention provides a process for the production of 1-chloro-
3.3.3-trifluoropropène comprenant les étapes de : 3.3.3-trifluoropropene comprising the steps of:
i) mise en contact, dans un réacteur, entre l'acide fluorhydrique (HF) et une composition de départ comprenant au moins un composé chloré sélectionné parmi le groupe consistant eni) bringing into contact, in a reactor, between hydrofluoric acid (HF) and a starting composition comprising at least one chlorinated compound selected from the group consisting of
1.1.3.3-tetrachloropropene, 1,3,3,3-tetrachloropropene et un mélange des deux, dans des conditions suffisantes pour obtenir un courant D comprenant l-chloro-3,3,3-trifluoropropène, l,l-dichloro-l,3,3-trifluoropropane HF et/ou HCl ; 1.1.3.3-tetrachloropropene, 1,3,3,3-tetrachloropropene and a mixture of the two, under conditions sufficient to obtain a stream D comprising l-chloro-3,3,3-trifluoropropene, l, l-dichloro-l , 3,3-trifluoropropane HF and / or HCl;
ii) mise en oeuvre du procédé de neutralisation selon la présente invention à partir du courant D obtenu à l'étape i). ii) implementation of the neutralization process according to the present invention from the stream D obtained in step i).
Selon un troisième aspect, la présente invention fournit une composition comprenant 1-chloro- According to a third aspect, the present invention provides a composition comprising 1-chloro-
3.3.3-trifluoropropène et l-chloro-l,3,3-trifluoropropène, la teneur molaire en l-chloro-1,3,3- trifluoropropène étant inférieure à 110 ppm dans ladite composition. 3.3.3-trifluoropropene and 1-chloro-1,3,3-trifluoropropene, the molar content of 1-chloro-1,3,3-trifluoropropene being less than 110 ppm in said composition.
Selon un mode de réalisation préféré, la teneur molaire en l-chloro-3,3,3-trifluoropropène dans ladite composition est supérieure à 90%. According to a preferred embodiment, the molar content of 1-chloro-3,3,3-trifluoropropene in said composition is greater than 90%.
Selon un mode de réalisation préféré, la teneur molaire en l-chloro-l,3,3-trifluoropropène est inférieure à 100 ppm, de préférence inférieure à 90 ppm, plus préférentiellement inférieure à 80 ppm, en particulier inférieure à 70 ppm, plus particulièrement inférieure à 60 ppm, de manière privilégiée inférieure à 50 ppm. According to a preferred embodiment, the molar content of 1-chloro-1,3-trifluoropropene is less than 100 ppm, preferably less than 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than 60 ppm, preferably less than 50 ppm.
Selon un mode de réalisation préféré, la composition comprend également l,l-dichloro-l,3,3- trifluoropropane. Selon un autre aspect, la présente invention fournit un procédé de préparation du 1-chloro-According to a preferred embodiment, the composition also comprises 1,1-dichloro-1,3,3-trifluoropropane. In another aspect, the present invention provides a process for the preparation of 1-chloro-
1.3.3-trifluoropropène par déshydrochloration du l,l-dichloro-l,3,3-trifluoropropane en présence d'une solution basique. 1.3.3-trifluoropropene by dehydrochlorination of l, l-dichloro-l, 3,3-trifluoropropane in the presence of a basic solution.
Selon un mode de réalisation préféré, la solution basique comprend un hydroxyde alcalin ou alcalino-terreux, de préférence la solution basique comprend NaOH ou KOH. According to a preferred embodiment, the basic solution comprises an alkali metal or alkaline earth hydroxide, preferably the basic solution comprises NaOH or KOH.
Selon un mode de réalisation préféré, le procédé est mis en oeuvre à une température comprise entre 10°C et 150°C, de préférence entre 10 et 90°C. According to a preferred embodiment, the process is carried out at a temperature between 10 ° C and 150 ° C, preferably between 10 and 90 ° C.
Description détaillée de la présente invention Detailed description of the present invention
Selon un premier aspect, la présente invention concerne un procédé de neutralisation d'une composition A. De préférence, la présente invention concerne un procédé de neutralisation de ladite composition dans des conditions aptes à limiter la formation de l-chloro-1,3,3- trifluoropropène au cours de la neutralisation des composés acides issus de la production du 1- chloro-3,3,3-trifluoropropène. De préférence, ladite composition A comprend l-chloro-3,3,3- trifluoropropène, l,l-dichloro-l,3,3-trifluoropropane et un composé acide de formule HX avec X = F ou Cl. De préférence, ledit procédé comprend l'étape a) de mise en contact de ladite composition A avec une solution B dans des conditions aptes à limiter la formation du 1-chloro- According to a first aspect, the present invention relates to a process for neutralizing a composition A. Preferably, the present invention relates to a process for neutralizing said composition under conditions capable of limiting the formation of 1-chloro-1,3, 3-trifluoropropene during the neutralization of acidic compounds resulting from the production of 1-chloro-3,3,3-trifluoropropene. Preferably, said composition A comprises 1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-1,3,3-trifluoropropane and an acidic compound of formula HX with X = F or Cl. Preferably, said process comprises step a) of bringing said composition A into contact with a solution B under conditions capable of limiting the formation of 1-chloro-
1.3.3-trifluoropropène. De préférence, la solution B est une solution basique. 1.3.3-trifluoropropene. Preferably, solution B is a basic solution.
De préférence, lesdites conditions comprennent l'étape a) de mise en contact de ladite composition A avec une solution B comprenant un hydroxyde alcalin dans des conditions aptes à limiter la formation du l-chloro-l,3,3-trifluoropropène. Preferably, said conditions comprise step a) of bringing said composition A into contact with a solution B comprising an alkali hydroxide under conditions capable of limiting the formation of 1-chloro-1,3,3-trifluoropropene.
Ainsi, la présente invention fournit un procédé de neutralisation d'une composition A comprenant l-chloro-3,3,3-trifluoropropène, l,l-dichloro-l,3,3-trifluoropropane et un composé acide de formule HX avec X = F ou Cl ; ledit procédé comprenant l'étape a) de mise en contact de ladite composition A avec une solution B comprenant un hydroxyde alcalin dans des conditions aptes à limiter la formation du l-chloro-l,3,3-trifluoropropène. Thus, the present invention provides a process for neutralizing a composition A comprising 1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-1,3,3-trifluoropropane and an acidic compound of formula HX with X = F or Cl; said process comprising step a) of bringing said composition A into contact with a solution B comprising an alkali metal hydroxide under conditions capable of limiting the formation of 1-chloro-1,3,3-trifluoropropene.
De préférence, lesdites conditions comprennent la mise en oeuvre de l'étape a) avec une solution B comprenant NaOH ou KOH comme hydroxyde alcalin. Preferably, said conditions comprise the implementation of step a) with a solution B comprising NaOH or KOH as alkali hydroxide.
Ainsi, la présente invention fournit un procédé de neutralisation d'une composition A comprenant l-chloro-3,3,3-trifluoropropène, l,l-dichloro-l,3,3-trifluoropropane et un composé acide de formule HX avec X = F ou Cl ; ledit procédé comprenant l'étape a) de mise en contact de ladite composition A avec une solution B comprenant NaOH ou KOH. En particulier, lesdites conditions comprennent la mise en oeuvre de l'étape a) avec une solution B comprenant NaOH comme hydroxyde alcalin. Thus, the present invention provides a process for neutralizing a composition A comprising 1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-1,3,3-trifluoropropane and an acidic compound of formula HX with X = F or Cl; said process comprising step a) of bringing said composition A into contact with a solution B comprising NaOH or KOH. In particular, said conditions comprise the implementation of step a) with a solution B comprising NaOH as alkali hydroxide.
Ainsi, la présente invention fournit un procédé de neutralisation d'une composition A comprenant l-chloro-3,3,3-trifluoropropène, l,l-dichloro-l,3,3-trifluoropropane et un composé acide de formule HX avec X = F ou Cl ; ledit procédé comprenant l'étape a) de mise en contact de ladite composition A avec une solution B comprenant NaOH. Thus, the present invention provides a process for neutralizing a composition A comprising 1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-1,3,3-trifluoropropane and an acidic compound of formula HX with X = F or Cl; said method comprising step a) of bringing said composition A into contact with a solution B comprising NaOH.
Selon un mode de réalisation préféré, la teneur en hydroxyde alcalin est entre 2 et 40% en poids sur base du poids total de ladite solution B. En particulier, la teneur en hydroxyde alcalin est de 5 à 25% en poids sur base du poids total de ladite solution B. Plus particulièrement, la teneur en hydroxyde alcalin est de 10 à 25% en poids sur base du poids total de ladite solution B. La teneur en hydroxyde alcalin peut être de 15 à 25% en poids sur base du poids total de ladite solution B. Ainsi, dans un mode de réalisation préféré, ladite solution B comprend NaOH dans une teneur massique de 2 à 40% en poids sur base du poids total de ladite solution B, avantageusement de 5 à 25% en poids sur base du poids total de ladite solution B, en particulier de 10 à 25% en poids sur base du poids total de ladite solution B. La teneur en NaOH peut être de 15 à 25% en poids sur base du poids total de ladite solution B. According to a preferred embodiment, the content of alkali hydroxide is between 2 and 40% by weight based on the total weight of said solution B. In particular, the content of alkali hydroxide is from 5 to 25% by weight based on weight. total of said solution B. More particularly, the content of alkali hydroxide is 10 to 25% by weight based on the total weight of said solution B. The content of alkali hydroxide may be 15 to 25% by weight based on weight total of said solution B. Thus, in a preferred embodiment, said solution B comprises NaOH in a mass content of 2 to 40% by weight based on the total weight of said solution B, advantageously of 5 to 25% by weight over based on the total weight of said solution B, in particular 10 to 25% by weight based on the total weight of said solution B. The NaOH content may be 15 to 25% by weight based on the total weight of said solution B .
De préférence, ladite solution B de l'étape b) est une solution aqueuse, en particulier une solution aqueuse basique. Preferably, said solution B of step b) is an aqueous solution, in particular a basic aqueous solution.
Avantageusement, ladite solution B est une solution aqueuse, de préférence basique, comprenant un hydroxyde alcalin consistant en NaOH. De préférence, ladite solution B est une solution aqueuse, de préférence basique, comprenant au moins un hydroxyde alcalin consistant en NaOH ; la teneur massique en NaOH dans ladite solution étant de 2 à 40% en poids, en particulier la teneur massique en NaOH dans ladite solution est de 5 à 25% en poids, plus particulièrement de 10 à 25% ou de 15 à 25% en poids sur base du poids total de ladite solution B. Advantageously, said solution B is an aqueous solution, preferably basic, comprising an alkali hydroxide consisting of NaOH. Preferably, said solution B is an aqueous solution, preferably basic, comprising at least one alkali hydroxide consisting of NaOH; the mass content of NaOH in said solution being 2 to 40% by weight, in particular the mass content of NaOH in said solution is 5 to 25% by weight, more particularly 10 to 25% or 15 to 25% by weight weight based on the total weight of said solution B.
Ladite composition A peut éventuellement comprendre du l-chloro-l,3,3-trifluoropropène. Selon un mode de réalisation préféré, l'étape a) permet d'obtenir un courant gazeux C comprenant l-chloro-3,3,3-trifluoropropène, l-chloro-l,3,3-trifluoropropène et 1,1-dichloro- 1,3,3-trifluoropropane. Said composition A may optionally comprise 1-chloro-1,3,3-trifluoropropene. According to a preferred embodiment, step a) makes it possible to obtain a gas stream C comprising 1-chloro-3,3,3-trifluoropropene, 1-chloro-1, 3,3-trifluoropropene and 1,1-dichloro - 1,3,3-trifluoropropane.
De préférence, la teneur molaire en l-chloro-l,3,3-trifluoropropène dans ledit courant C est inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm. Preferably, the molar content of 1-chloro-1,3-trifluoropropene in said stream C is less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less or equal to 80 ppm, in in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm.
De préférence, la teneur molaire en l-chloro-3,3,3-trifluoropropène dans ledit courant C est supérieure à 85%, avantageusement supérieure à 87%, de préférence supérieure à 90%, plus préférentiellement supérieure à 92%, en particulier supérieure à 95%, plus particulièrement supérieure à 97%, de manière privilégiée supérieure à 99%. Preferably, the molar content of 1-chloro-3,3,3-trifluoropropene in said stream C is greater than 85%, advantageously greater than 87%, preferably greater than 90%, more preferably greater than 92%, in particular greater than 95%, more particularly greater than 97%, preferably greater than 99%.
Ainsi, ledit courant C peut comprendre une teneur molaire en l-chloro-3,3,3-trifluoropropène supérieure à 85% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure à 80 ppm, en particulier inférieure à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm. Thus, said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 85% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm.
Avantageusement, ledit courant C peut comprendre une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 87% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm. Advantageously, said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 87% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm.
De préférence, ledit courant C peut comprendre une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 90% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm. Preferably, said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 90% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal at 50 ppm.
Plus préférentiellement, ledit courant C peut comprendre une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 92% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm. More preferably, said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 92% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal at 50 ppm.
En particulier, ledit courant C peut comprendre une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 95% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm. In particular, said stream C may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 95% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm.
Plus particulièrement, ledit courant C peut comprendre une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 97% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm. More particularly, said stream C may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 97% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal at 50 ppm.
De manière privilégiée, ledit courant C peut comprendre une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 99% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm. Preferably, said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 99% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm. , advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less or equal to 50 ppm.
La teneur molaire en l,l-dichloro-l,3,3-trifluoropropane dans ledit courant C peut être comprise entre 10 et 200 ppm, de préférence entre 20 et 150 ppm, en particulier entre 50 et 100 ppm. The molar content of 1,1-dichloro-1,3,3-trifluoropropane in said stream C may be between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
Ainsi, ledit courant C peut comprendre une teneur molaire en l-chloro-3,3,3-trifluoropropène supérieure à 85% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure à 80 ppm, en particulier inférieure à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm ; et une teneur molaire en l,l-dichloro-l,3,3-trifluoropropane comprise entre 10 et 200 ppm, de préférence entre 20 et 150 ppm, en particulier entre 50 et 100 ppm. Thus, said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 85% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
Avantageusement, ledit courant C peut comprendre une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 87% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm ; et une teneur molaire en l,l-dichloro-l,3,3- trifluoropropane comprise entre 10 et 200 ppm, de préférence entre 20 et 150 ppm, en particulier entre 50 et 100 ppm. De préférence, ledit courant C peut comprendre une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 90% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm ; et une teneur molaire en l,l-dichloro-l,3,3- trifluoropropane comprise entre 10 et 200 ppm, de préférence entre 20 et 150 ppm, en particulier entre 50 et 100 ppm. Advantageously, said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 87% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm. Preferably, said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 90% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal at 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
Plus préférentiellement, ledit courant C peut comprendre une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 92% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm ; et une teneur molaire en l,l-dichloro-l,3,3- trifluoropropane comprise entre 10 et 200 ppm, de préférence entre 20 et 150 ppm, en particulier entre 50 et 100 ppm. More preferably, said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 92% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal at 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
En particulier, ledit courant C peut comprendre une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 95% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm ; et une teneur molaire en l,l-dichloro-l,3,3- trifluoropropane comprise entre 10 et 200 ppm, de préférence entre 20 et 150 ppm, en particulier entre 50 et 100 ppm. In particular, said stream C may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 95% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal at 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
Plus particulièrement, ledit courant C peut comprendre une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 97% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm ; et une teneur molaire en l,l-dichloro-l,3,3- trifluoropropane comprise entre 10 et 200 ppm, de préférence entre 20 et 150 ppm, en particulier entre 50 et 100 ppm. De manière privilégiée, ledit courant C peut comprendre une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 99% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm ; et une teneur molaire en l,l-dichloro-l,3,3- trifluoropropane comprise entre 10 et 200 ppm, de préférence entre 20 et 150 ppm, en particulier entre 50 et 100 ppm. More particularly, said stream C may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 97% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal at 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm. Preferably, said stream C can comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 99% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm. , advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less or equal to 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
En particulier, dans l'un quelconque desdits courants C définis ci-dessus ou dans l'une quelconque des compositions A telles que définies ci-dessus, l-chloro-3,3,3-trifluoropropène représente au moins 90 mol% de trans-l-chloro-3,3,3-trifluoropropène, plus particulièrement au moins 92 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière privilégiée au moins 95 mol% de trans-l-chloro-3,3,3-trifluoropropène ; le complément étant représenté par l'isomère cis-l-chloro-3,3,3-trifluoropropène. De préférence, dans l'un quelconque desdits courants C définis ci-dessus ou dans l'une quelconque des compositions A telles que définies ci-dessus, 1- chloro-3,3,3-trifluoropropène est le trans-l-chloro-3,3,3-trifluoropropène. In particular, in any one of said streams C defined above or in any one of the compositions A as defined above, 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans -l-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1-chloro-3,3,3-trifluoropropene, preferably at least 95 mol% of trans-1-chloro- 3,3,3-trifluoropropene; the remainder being represented by the cis-1-chloro-3,3,3-trifluoropropene isomer. Preferably, in any one of said streams C defined above or in any of the compositions A as defined above, 1-chloro-3,3,3-trifluoropropene is trans-1-chloro- 3,3,3-trifluoropropene.
Ladite solution B peut optionnellement comprendre des agents réducteurs, tels que des sels de sulfite ou de bisulfite. Said solution B can optionally comprise reducing agents, such as sulphite or bisulphite salts.
Alternativement, ladite solution B peut être une solution organique contenant un solvant. Le solvant est défini comme un composé organique inerte dans lequel le l-chloro-3,3,3- trifluoropropène est au moins partiellement soluble. Le solvant est de préférence sélectionné parmi le groupe consistant en hydrocarbures, éthers, alcools, halogénures d'alkyles, benzènes substitués ou non, nitrile d'alkyle, amides, sulfoxydes, sulfones, esters de phosphate et les mélanges de ceux-ci. De préférence, le solvant est sélectionné parmi éthers, alcools, halogénures d'alkyles, benzènes substitués ou non, nitrile d'alkyle, amides, sulfoxydes, sulfones, et les mélanges de ceux-ci. Les éthers incluent les éthers d'alkyle acyclique, les éthers cycliques, les éthers perfluorés, glyme, diglyme, triglyme, tetraglyme et les mélanges de ceux-ci. Les éthers d'alkyle acyclique incluent l'éther diméthylique, l'éther éthylique, l'éther de méthyle éthyle et les mélanges de ceux-ci. Les éthers cycliques incluent le 2-methyltetrahydrofurane, tetrahydrofurane, tétrahydropyrane, 1,4-dioxane et les mélanges de ceux-ci. Les éthers perfluorés incluent perfluoro-N-méthyl morpholine, perfluorotétrahydrofurane, et les mélanges de ceux-ci. Les alcools incluent les alcools d'alkyle, les glycols, glycérol, et les mélanges de ceux- ci. Les alkykes d'alcool incluent méthanol, éthanol, propanol, isopropanol, 2-méthyl-2-propanol, cyclohexanol, et les mélanges de ceux-ci. Les exemples de glycol incluent l'éthylène glycol, propylène glycol, diéthylène glycol et les mélanges de ceux-ci. Les benzènes substitués ou non incluent les alkylbenzènes, halobenzènes, benzonitrile phénol, anisole, biphényle, nitrobenzène et les mélanges de ceux-ci. Les alkylbenzènes incluent toluène, éthylbenzène, o-xylène, m- xylène, p-xylène, mésitylène, durène, 2-phénylhexane et les mélanges de ceux-ci. Les halobenzènes incluent fluorobenzène, chlorobenzène, 1,2-dichlorobenzène, 1,4- dichlorobenzène, et les mélanges de ceux-ci. Les halogénures d'alkyles incluent dichlorométhane, chloroforme, tétrachlorure de carbone, chloroéthane, 1,2-dichloroéthane et les mélanges de ceux-ci. Les nitrile d'alkyles incluent acétonitrile, butyronitrile, méthylglutaronitrile, adiponitrile et les mélanges de ceux-ci. Les amides incluent N,N-diméthyl formamide, N,N-diméthyl-acétamide, N-méthyl-2-pyrrolidone et les mélanges ceux-ci. Les sulfoxides incluent le diméthyle sulfoxyde. Les sulfones incluent le sulfolane. Alternatively, said solution B can be an organic solution containing a solvent. The solvent is defined as an inert organic compound in which 1-chloro-3,3,3-trifluoropropene is at least partially soluble. The solvent is preferably selected from the group consisting of hydrocarbons, ethers, alcohols, alkyl halides, substituted or unsubstituted benzenes, alkyl nitrile, amides, sulfoxides, sulfones, phosphate esters and mixtures thereof. Preferably, the solvent is selected from ethers, alcohols, alkyl halides, substituted or unsubstituted benzenes, alkyl nitrile, amides, sulfoxides, sulfones, and mixtures thereof. The ethers include acyclic alkyl ethers, cyclic ethers, perfluorinated ethers, glyme, diglyme, triglyme, tetraglyme, and mixtures thereof. Acyclic alkyl ethers include dimethyl ether, ethyl ether, methyl ethyl ether, and mixtures thereof. Cyclic ethers include 2-methyltetrahydrofuran, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, and mixtures thereof. Perfluorinated ethers include perfluoro-N-methyl morpholine, perfluorotetrahydrofuran, and mixtures thereof. Alcohols include alkyl alcohols, glycols, glycerol, and mixtures thereof. Alcohol alkyls include methanol, ethanol, propanol, isopropanol, 2-methyl-2-propanol, cyclohexanol, and mixtures thereof. Examples of glycol include ethylene glycol, propylene glycol, diethylene glycol, and mixtures thereof. Substituted and unsubstituted benzenes include alkylbenzenes, halobenzenes, benzonitrile phenol, anisole, biphenyl, nitrobenzene and mixtures thereof. Alkylbenzenes include toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, mesitylene, durene, 2-phenylhexane, and mixtures thereof. Halobenzenes include fluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, and mixtures thereof. Alkyl halides include dichloromethane, chloroform, carbon tetrachloride, chloroethane, 1,2-dichloroethane, and mixtures thereof. Alkyl nitriles include acetonitrile, butyronitrile, methylglutaronitrile, adiponitrile, and mixtures thereof. Amides include N, N-dimethyl formamide, N, N-dimethyl-acetamide, N-methyl-2-pyrrolidone, and mixtures thereof. Sulfoxides include dimethyl sulfoxide. Sulfones include sulfolane.
Lorsque ladite solution B est une solution organique, celle-ci comprend au moins un hydroxyde alcalin consistant en NaOH, de préférence, dans une teneur massique de 2 à 40% sur base du poids total de ladite solution B, en particulier une teneur massique de 5 à 20% en poids sur base du poids total de ladite solution B. When said solution B is an organic solution, the latter comprises at least one alkaline hydroxide consisting of NaOH, preferably in a content by mass of 2 to 40% based on the total weight of said solution B, in particular a content by mass of 5 to 20% by weight based on the total weight of said solution B.
De préférence, quelle que soit la solution B, l'étape a) du présent procédé est mis en oeuvre à une température de 10°C à 90°C, avantageusement de 10°C à 80°C, de préférence de 10°C à 70°C, en particulier de 10°C à 60°C. Preferably, whatever the solution B, step a) of the present process is carried out at a temperature of 10 ° C to 90 ° C, advantageously of 10 ° C to 80 ° C, preferably of 10 ° C. at 70 ° C, in particular from 10 ° C to 60 ° C.
De préférence, l'étape a) est mise en oeuvre avec un temps de séjour compris entre 1 seconde et 5 minutes, en particulier entre 5 secondes et 5 minutes, plus particulièrement entre 10 secondes et 5 minutes, de manière privilégiée entre 15 secondes et 5 minutes. Preferably, step a) is carried out with a residence time of between 1 second and 5 minutes, in particular between 5 seconds and 5 minutes, more particularly between 10 seconds and 5 minutes, preferably between 15 seconds and 5 minutes.
Selon un second aspect de la présente invention, un procédé de production du l-chloro-3,3,3- trifluoropropène est fourni. According to a second aspect of the present invention, a process for producing 1-chloro-3,3,3-trifluoropropene is provided.
Ledit procédé de production du l-chloro-3,3,3-trifluoropropène comprenant les étapes de : i) mise en contact, dans un réacteur, entre l'acide fluorhydrique (HF) et une composition de départ comprenant au moins un composé chloré sélectionné parmi le groupe consistant en 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene et un mélange des deux, dans des conditions suffisantes pour obtenir un courant D comprenant l-chloro-3,3,3-trifluoropropène, l,l-dichloro-l,3,3-trifluoropropane HF et/ou HCl ; Said process for the production of 1-chloro-3,3,3-trifluoropropene comprising the steps of: i) contacting, in a reactor, between hydrofluoric acid (HF) and a starting composition comprising at least one chlorinated compound selected from the group consisting of 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene and a mixture of the two, under conditions sufficient to obtain a stream D comprising 1-chloro-3,3,3 -trifluoropropene, 1,1-dichloro-1,3,3-trifluoropropane HF and / or HCl;
ii) mise en oeuvre du procédé de neutralisation selon la présente invention à partir du courant D obtenu à l'étape i). En particulier, dans ce procédé de production tel que décrit ci-dessus et ci-dessous, 1-chloro-ii) implementation of the neutralization process according to the present invention from the stream D obtained in step i). In particular, in this production process as described above and below, 1-chloro-
3.3.3-trifluoropropène représente au moins 90 mol% de trans-l-chloro-3,3,3-trifluoropropène, plus particulièrement au moins 92 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière privilégiée au moins 95 mol% de trans-l-chloro-3,3,3-trifluoropropène ; le complément étant représenté par l'isomère cis-l-chloro-3,3,3-trifluoropropène. De préférence, dans ce procédé de production tel que décrit ci-dessus et ci-dessous, l-chloro-3,3,3-trifluoropropène est le trans- l-chloro-3,3,3-trifluoropropène. 3.3.3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1-chloro-3,3,3-trifluoropropene, so preferred at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene; the remainder being represented by the cis-1-chloro-3,3,3-trifluoropropene isomer. Preferably, in this production process as described above and below, 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
De préférence, ladite étape i) est mise en oeuvre dans une phase liquide, de préférence pauvre en HF. Preferably, said step i) is carried out in a liquid phase, preferably low in HF.
Selon un mode de réalisation préféré, ladite composition de départ comprend au moins 10% en poids dudit au moins un composé chloré sur base du poids total de ladite composition de départ. Avantageusement, ladite composition de départ comprend au moins 15% en poids dudit au moins un composé chloré, de préférence au moins 20% en poids dudit au moins un composé chloré, plus préférentiellement au moins 25% en poids dudit au moins un composé chloré, en particulier au moins 30% en poids dudit au moins un composé chloré, plus particulièrement au moins 35% en poids dudit au moins un composé chloré, de manière privilégiée au moins 40% en poids dudit au moins un composé chloré, de manière avantageusement privilégiée au moins 45% en poids dudit au moins un composé chloré, de manière préférentiellement privilégiée au moins 50% en poids dudit au moins un composé chloré, de manière particulièrement privilégiée au moins 55% en poids dudit au moins un composé chloré sur base du poids total de ladite composition de départ. According to a preferred embodiment, said starting composition comprises at least 10% by weight of said at least one chlorinated compound based on the total weight of said starting composition. Advantageously, said starting composition comprises at least 15% by weight of said at least one chlorinated compound, preferably at least 20% by weight of said at least one chlorinated compound, more preferably at least 25% by weight of said at least one chlorinated compound, in particular at least 30% by weight of said at least one chlorinated compound, more particularly at least 35% by weight of said at least one chlorinated compound, preferably at least 40% by weight of said at least one chlorinated compound, advantageously preferred at least 45% by weight of said at least one chlorinated compound, preferably at least 50% by weight of said at least one chlorinated compound, particularly preferably at least 55% by weight of said at least one chlorinated compound on the basis of weight total of said starting composition.
De préférence, ladite composition de départ comprend au moins 60% en poids ou au moins 65% en poids ou au moins 70% en poids ou au moins 75 % en poids ou au moins 80% en poids ou au moins 85% en poids ou au moins 90% en poids ou au moins 95% en poids ou au moins 99% en poids dudit au moins un composé chloré sur base du poids total de ladite composition de départ. Selon un mode de réalisation préféré, ledit au moins un composé chloré est le 1, 1,3,3- tétrachloropropène (1230za). Ainsi, ledit procédé comprend une étape i) de mise en contact dans un réacteur entre l'acide fluorhydrique (HF) et une composition de départ comprenant Preferably, said starting composition comprises at least 60% by weight or at least 65% by weight or at least 70% by weight or at least 75% by weight or at least 80% by weight or at least 85% by weight or at least 90% by weight or at least 95% by weight or at least 99% by weight of said at least one chlorinated compound based on the total weight of said starting composition. According to a preferred embodiment, said at least one chlorinated compound is 1, 1,3,3-tetrachloropropene (1230za). Thus, said method comprises a step i) of bringing into contact in a reactor between hydrofluoric acid (HF) and a starting composition comprising
1.1.3.3-tétrachloropropène (1230za) pour produire un courant D comprenant le l-chloro-3,3,3- trifluoropropène (1233zd), HF et HCl ; ladite étape i) est mise en oeuvre dans une phase liquide pauvre en HF telle que définie ci-dessous. De préférence, le présent procédé permet la production de l-chloro-3,3,3-trifluoropropène sous la forme d'un mélange des deux isomères cis et trans. Le présent procédé permet d'obtenir majoritairement l'isomère trans-l-chloro-1.1.3.3-Tetrachloropropene (1230za) to produce a stream D comprising 1-chloro-3,3,3-trifluoropropene (1233zd), HF and HCl; said step i) is carried out in a liquid phase poor in HF as defined below. Preferably, the present process allows the production of 1-chloro-3,3,3-trifluoropropene as a mixture of the two isomers. cis and trans. The present process makes it possible to obtain mainly the trans-1-chloro- isomer.
3.3.3-trifluoropropène, de préférence au moins 90% en mole de l'isomère trans. 3.3.3-trifluoropropene, preferably at least 90 mol% of the trans isomer.
Ainsi, ladite composition de départ comprend au moins 10% en poids de 1, 1,3,3- tétrachloropropène sur base du poids total de ladite composition de départ. Avantageusement, ladite composition de départ comprend au moins 15% en poids de 1,1,3,3-tétrachloropropène, de préférence au moins 20% en poids de 1,1,3,3-tétrachloropropène, plus préférentiellement au moins 25% en poids de 1,1,3,3-tétrachloropropène, en particulier au moins 30% en poids de Thus, said starting composition comprises at least 10% by weight of 1, 1,3,3-tetrachloropropene based on the total weight of said starting composition. Advantageously, said starting composition comprises at least 15% by weight of 1,1,3,3-tetrachloropropene, preferably at least 20% by weight of 1,1,3,3-tetrachloropropene, more preferably at least 25% by weight. weight of 1,1,3,3-tetrachloropropene, in particular at least 30% by weight of
1.1.3.3-tétrachloropropène, plus particulièrement au moins 35% en poids de 1,1,3,3- tétrachloropropène, de manière privilégiée au moins 40% en poids de 1,1,3,3- tétrachloropropène, de manière avantageusement privilégiée au moins 45% en poids de 1,1,3,3- tétrachloropropène, de manière préférentiellement privilégiée au moins 50% en poids de1.1.3.3-tetrachloropropene, more particularly at least 35% by weight of 1,1,3,3-tetrachloropropene, preferably at least 40% by weight of 1,1,3,3-tetrachloropropene, advantageously preferred over less 45% by weight of 1,1,3,3-tetrachloropropene, preferably at least 50% by weight of
1.1.3.3-tétrachloropropène, de manière particulièrement privilégiée au moins 55% en poids de1.1.3.3-tetrachloropropene, particularly preferably at least 55% by weight of
1.1.3.3-tétrachloropropène sur base du poids total de ladite composition de départ. 1.1.3.3-tetrachloropropene based on the total weight of said starting composition.
De préférence, ladite composition de départ comprend au moins 60% en poids ou au moins 65% en poids ou au moins 70% en poids ou au moins 75 % en poids ou au moins 80% en poids ou au moins 85% en poids ou au moins 90% en poids ou au moins 95% en poids ou au moins 99% en poids de 1,1,3,3-tétrachloropropène sur base du poids total de ladite composition de départ. Selon un mode de réalisation préféré, ladite composition de départ comprend moins de 15% en poids de HF sur base du poids total de ladite composition de départ, avantageusement moins de 10% en poids de HF, de préférence moins de 8% en poids de HF, plus préférentiellement moins de 6% en poids de HF, en particulier moins de 5% en poids de HF, plus particulièrement moins de 4% en poids de HF, de manière privilégiée moins de 2% en poids de HF sur base du poids total de ladite composition de départ. Dans le présent procédé, de préférence, la composition de départ est dépourvue de HF. Le terme « dépourvu » signifie une teneur pondérale inférieure à 500 ppm, de préférence inférieure à 100 ppm, en particulier inférieure à 10 ppm. Preferably, said starting composition comprises at least 60% by weight or at least 65% by weight or at least 70% by weight or at least 75% by weight or at least 80% by weight or at least 85% by weight or at least 90% by weight or at least 95% by weight or at least 99% by weight of 1,1,3,3-tetrachloropropene based on the total weight of said starting composition. According to a preferred embodiment, said starting composition comprises less than 15% by weight of HF based on the total weight of said starting composition, advantageously less than 10% by weight of HF, preferably less than 8% by weight of HF, more preferably less than 6% by weight of HF, in particular less than 5% by weight of HF, more particularly less than 4% by weight of HF, preferably less than 2% by weight of HF on a weight basis total of said starting composition. In the present process, preferably, the starting composition is free of HF. The term “free” means a content by weight of less than 500 ppm, preferably less than 100 ppm, in particular less than 10 ppm.
De préférence, ladite phase liquide pauvre en HF est une phase liquide comprenant moins de 15% en poids de HF, avantageusement moins de 10% en poids de HF, de préférence moins de 8% en poids de HF, plus préférentiellement moins de 6% en poids de HF, en particulier moins de 5% en poids de HF, plus particulièrement moins de 4% en poids de HF, de manière privilégiée moins de 2% en poids de HF sur base du poids total de ladite phase liquide. Preferably, said liquid phase poor in HF is a liquid phase comprising less than 15% by weight of HF, advantageously less than 10% by weight of HF, preferably less than 8% by weight of HF, more preferably less than 6% by weight of HF, in particular less than 5% by weight of HF, more particularly less than 4% by weight of HF, preferably less than 2% by weight of HF based on the total weight of said liquid phase.
Au cours de la mise en oeuvre de l'étape i), ladite phase liquide peut comprendre au moins 10% en poids de composés de formule (I) C3HnFmClp (I) dans laquelle n est un entier de 0 à 8, m est un entier de 0 à 8, et p est un entier de 0 à 8 ; de préférence n est un entier de 0 à 8, m est un entier de 0 à 6 et p est un entier de 0 à 6. Par exemple, des composés de formule (I) peuvent être C3Ü6, C3H4CI4 OU C3H3CI5. De préférence, au cours de la mise en oeuvre de l'étape i), ladite phase liquide peut comprendre au moins 10% en poids de composés de formule (I) C3HnFmClp (I) dans laquelle n est un entier de 1 à 8, m est un entier de 0 à 4, et p est un entier de 0 à 4 ; de préférence n est un entier de 1 à 4, m est un entier de 0 à 3 et p est un entier de 2 à 4. Les composés de formule (I) peuvent être des composés de type propane ou propène comprenant un ou plusieurs atomes de chlore et/ou un ou plusieurs atomes de fluor. De préférence, ladite phase liquide peut comprendre au moins 10% en poids de composés de formule (I) sélectionnée parmi le groupe consistant en C3H2CI4, C3H2CI3F, C3H2CI2F2, C3H3CI5, C3H3CI4F, C3H3CI3F2 et C3H3CI2F3. En particulier, ladite phase liquide peut comprendre au moins 10% en poids de composés de formule (I) sélectionnée parmi le groupe consistant en C3H2CI4, C3H2CI3F et C3H2CI2F2. Ladite phase liquide peut comprendre au moins 15% en poids de composés de formule (I) C3HnFmClp (I) dans laquelle n est un entier de 0 à 8, m est un entier de 0 à 8, et p est un entier de 0 à 8 ; de préférence n est un entier de 0 à 8, m est un entier de 0 à 6 et p est un entier de 0 à 6. En particulier, au cours de la mise en oeuvre de l'étape i), ladite phase liquide peut comprendre au moins 15% en poids de composés de formule (I) C3HnFmClp (I) dans laquelle n est un entier de 1 à 8, m est un entier de 0 à 4, et p est un entier de 0 à 4; de préférence n est un entier de 1 à 4, m est un entier de 0 à 3 et p est un entier de 2 à 4. De préférence, ladite phase liquide peut comprendre au moins 15% en poids de composés de formule (I) sélectionnée parmi le groupe consistant en C3H2CI4, C3H2CI3F, C3H2CI2F2, C3H3CI5, C3H3CI4F, C3H3CI3F2 et C3H3CI2F3. En particulier, ladite phase liquide peut comprendre au moins 15% en poids de composés de formule (I) sélectionnée parmi le groupe consistant en C3H2CI4, C3H2CI3F et C3H2CI2F2. Ladite phase liquide peut comprendre au moins 20%, au moins 30%, au moins 40%, au moins 50%, au moins 60%, au moins 70%, au moins 80% ou au moins 90% en poids de composés de formule (I) C3HnFmClp (I) dans laquelle n est un entier de 0 à 8, m est un entier de 0 à 8, et p est un entier de 0 à 8 ; de préférence n est un entier de 0 à 8, m est un entier de 0 à 6 et p est un entier de 0 à 6. Ladite phase liquide peut comprendre au moins 20%, au moins 30%, au moins 40%, au moins 50%, au moins 60%, au moins 70%, au moins 80% ou au moins 90% en poids de composés de formule (I) C3HnFmClp (I) dans laquelle n est un entier de 1 à 8, m est un entier de 0 à 4, et p est un entier de 0 à 4; de préférence n est un entier de 1 à 4, m est un entier de 0 à 3 et p est un entier de 2 à 4. De préférence, ladite phase liquide peut comprendre au moins 20%, au moins 30%, au moins 40%, au moins 50%, au moins 60%, au moins 70%, au moins 80% ou au moins 90% en poids de composés de formule (I) sélectionnée parmi le groupe consistant en C3H2CI4, C3H2CI3F, C3H2CI2F2, C3H3CI5, C3H3CI4F, C3H3CI3F2 et C3H3CI2F3. En particulier, ladite phase liquide peut comprendre au moins 20%, au moins 30%, au moins 40%, au moins 50%, au moins 60%, au moins 70%, au moins 80% ou au moins 90% en poids de composés de formule (I) sélectionnée parmi le groupe consistant en C3H2CI4, C3H2CI3F et C3H2CI2F2. During the implementation of step i), said liquid phase may comprise at least 10% by weight of compounds of formula (I) C3H n F m Cl p (I) in which n is an integer from 0 to 8, m is an integer from 0 to 8, and p is an integer from 0 to 8; preferably n is an integer from 0 to 8, m is an integer from 0 to 6 and p is an integer from 0 to 6. For example, compounds of formula (I) can be C366, C3H4Cl4 OR C3H3Cl5. Preferably, during the implementation of step i), said liquid phase may comprise at least 10% by weight of compounds of formula (I) C3H n F m Cl p (I) in which n is an integer from 1 to 8, m is an integer from 0 to 4, and p is an integer from 0 to 4; preferably n is an integer from 1 to 4, m is an integer from 0 to 3 and p is an integer from 2 to 4. The compounds of formula (I) can be compounds of the propane or propene type comprising one or more atoms chlorine and / or one or more fluorine atoms. Preferably, said liquid phase may comprise at least 10% by weight of compounds of formula (I) selected from the group consisting of C3H2Cl4, C3H2Cl3F, C3H2CI2F2, C3H3CI5, C3H3CI4F, C3H3Cl3F2 and C3H3CI2F3. In particular, said liquid phase may comprise at least 10% by weight of compounds of formula (I) selected from the group consisting of C3H2Cl4, C3H2Cl3F and C3H2CI2F2. Said liquid phase may comprise at least 15% by weight of compounds of formula (I) C3H n F m Cl p (I) in which n is an integer from 0 to 8, m is an integer from 0 to 8, and p is an integer from 0 to 8; preferably n is an integer from 0 to 8, m is an integer from 0 to 6 and p is an integer from 0 to 6. In particular, during the implementation of step i), said liquid phase can comprise at least 15% by weight of compounds of formula (I) C3H n F m Cl p (I) in which n is an integer from 1 to 8, m is an integer from 0 to 4, and p is an integer from 0 to 4; preferably n is an integer from 1 to 4, m is an integer from 0 to 3 and p is an integer from 2 to 4. Preferably, said liquid phase can comprise at least 15% by weight of compounds of formula (I) selected from the group consisting of C3H2CI4, C3H2CI3F, C3H2CI2F2, C3H3CI5, C3H3CI4F, C3H3CI3F2 and C3H3CI2F3. In particular, said liquid phase may comprise at least 15% by weight of compounds of formula (I) selected from the group consisting of C3H2Cl4, C3H2Cl3F and C3H2CI2F2. Said liquid phase may comprise at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80% or at least 90% by weight of compounds of formula (I) C3H n F m Cl p (I) where n is an integer from 0 to 8, m is an integer from 0 to 8, and p is an integer from 0 to 8; preferably n is an integer from 0 to 8, m is an integer from 0 to 6 and p is an integer from 0 to 6. Said liquid phase can comprise at least 20%, at least 30%, at least 40%, at least. at least 50%, at least 60%, at least 70%, at least 80% or at least 90% by weight of compounds of formula (I) C3H n F m Cl p (I) in which n is an integer from 1 to 8, m is an integer of 0 to 4, and p is an integer of 0 to 4; preferably n is an integer from 1 to 4, m is an integer from 0 to 3 and p is an integer from 2 to 4. Preferably, said liquid phase can comprise at least 20%, at least 30%, at least 40 %, at least 50%, at least 60%, at least 70%, at least 80% or at least 90% by weight of compounds of formula (I) selected from the group consisting of C3H2Cl4, C3H2CI3F, C3H2CI2F2, C3H3CI5, C3H3CI4F, C3H3CI3F2 and C3H3CI2F3. In particular, said liquid phase may comprise at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80% or at least 90% by weight of compounds of formula (I) selected from the group consisting of C3H2Cl4, C3H2Cl3F and C3H2Cl2F2.
De préférence, l'étape i) est mise en oeuvre en l'absence de catalyseur. Preferably, step i) is carried out in the absence of catalyst.
Alternativement, l'étape i) peut être mise en oeuvre en présence d'un catalyseur. Le catalyseur peut être un catalyseur de type T1CI4 ou SbCI5. Le catalyseur peut être également un liquide ionique. Les liquides ioniques pouvant convenir sont dérivés d'acides de Lewis à base d'aluminium, de titane, de niobium, de tantale, d'étain, d'antimoine, de nickel, de zinc ou de fer. On entend par liquides ioniques des sels non aqueux à caractère ionique qui sont liquides à des températures modérées (de préférence en-dessous de 120°C). Les liquides ioniques résultent de préférence de la réaction entre un sel organique et un composé inorganique. Les liquides ioniques sont de préférence obtenus par réaction d'au moins un acide de Lewis halogéné ou oxyhalogéné à base d'aluminium, de titane, de niobium, de tantale, d'étain, d'antimoine, de nickel, de zinc ou de fer avec un sel de formule générale Y+A , dans laquelle A désigne un anion halogénure (bromure, iodure et, de préférence chlorure ou fluorure) ou hexafluoroantimoniate (SbF6 _) et Y+ un cation ammonium quaternaire, phosphonium quaternaire ou sulfonium ternaire. L'acide de Lewis halogéné à base d'aluminium, de titane, de niobium, de tantale, d'antimoine, de nickel, de zinc ou de fer peut être un dérivé chloré, bromé, fluoré ou mixte, par exemple un acide chlorofluoré. Peuvent être mentionnés plus particulièrement les chlorures, fluorures ou chlorofluorures des formules suivantes : Alternatively, step i) can be carried out in the presence of a catalyst. The catalyst may be a T1Cl4 or SbCl 5 type catalyst. The catalyst can also be an ionic liquid. Ionic liquids which may be suitable are derived from Lewis acids based on aluminum, titanium, niobium, tantalum, tin, antimony, nickel, zinc or iron. The term “ionic liquids” is understood to mean nonaqueous salts of ionic character which are liquid at moderate temperatures (preferably below 120 ° C.). Ionic liquids preferably result from the reaction between an organic salt and an inorganic compound. The ionic liquids are preferably obtained by reaction of at least one halogenated or oxyhalogenated Lewis acid based on aluminum, titanium, niobium, tantalum, tin, antimony, nickel, zinc or iron with a salt of general formula Y + A, in which A denotes a halide anion (bromide, iodide and, preferably chloride or fluoride) or hexafluoroantimonate (SbF 6 _ ) and Y + a quaternary ammonium cation, quaternary phosphonium or ternary sulfonium . The halogenated Lewis acid based on aluminum, titanium, niobium, tantalum, antimony, nickel, zinc or iron can be a chlorinated, brominated, fluorinated or mixed derivative, for example a chlorofluorinated acid . The chlorides, fluorides or chlorofluorides of the following formulas may be mentioned more particularly:
TiClxFy avec x+y = 4 et 0 <= x <= 4 TiClxFy with x + y = 4 and 0 <= x <= 4
TaClxFy avec x+y = 5 et 0 <= x <= 5 TaClxFy with x + y = 5 and 0 <= x <= 5
NbClxFy avec x+y = 5 et 0 <= x <= 5 NbClxFy with x + y = 5 and 0 <= x <= 5
SnClxFy avec x+y = 4 et 1 <= x <= 4 SnClxFy with x + y = 4 and 1 <= x <= 4
SbClxFy avec x+y = 5 et 0 <= x <= 5 SbClxFy with x + y = 5 and 0 <= x <= 5
AlCIxFy avec x+y =3 et 0 <= x <= 3 AlCIxFy with x + y = 3 and 0 <= x <= 3
NiClxFy avec x+y = 2 et 0 <= x <= 2 NiClxFy with x + y = 2 and 0 <= x <= 2
FeClxFy avec x+y = 3 et 0 <= x <= 3 FeClxFy with x + y = 3 and 0 <= x <= 3
Comme exemples de tels composés, on peut mentionner les composés suivants : T1CI4, T1F4, TaCI5, TaF5, NbCI5, NbF5, SbCI5, SbCUF, SbÜ3F2, SbC^Fs, SbCIF4, SbF5 et leurs mélanges. Sont préferentiellement utilisés les composés suivants : T1CI4, TaCI5+TaF5, NbCI5+NbF5, SbCI5, SbFCU, SbF2Ü3, SbF3Ü2, SbF4Ü, SbF5 et SbCI5+SbF5. Sont plus particulièrement préférés les composés antimoniés. Comme exemples d'acides de Lewis oxyhalogénés, utilisables selon l'invention, on peut mentionner T1OCI2, TiC^et SbOCIxFy (x+y=3). Dans le sel Y+A , le cation Y+ peut répondre à l'une des formules générales suivantes: R1R2R3R4N+, R1R2R3R4P+, R4R2R3S+ dans lesquelles les symboles R1 a R4, identiques ou différents, désignent chacun un groupement hydrocarbyle, chlorohydrocarbyle, fluorohydrocarbyle, chlorofluorohydrocarbyle ou fluorocarbyle ayant de 1 a 10 atomes de carbone, saturé ou non, cyclique ou non, ou aromatique, l'un ou plusieurs de ces groupements pouvant également contenir un ou plusieurs hétéroatomes tels que N, P, S ou O. Le cation ammonium, phosphonium ou sulfonium Y+ peut également faire partie d'un hétérocycle saturé ou non, ou aromatique ayant de 1 à 3 atomes d'azote, de phosphore ou de soufre, et répondre à l'une ou l'autre des formules générales suivantes : As examples of such compounds, the following compounds may be mentioned: T1Cl 4 , T1F 4 , TaCl 5 , TaF 5 , NbCl 5 , NbF 5 , SbCI 5 , SbCUF, Sb03F2, SbC ^ Fs, SbCIF 4 , SbF 5 and mixtures thereof . The following compounds are preferably used: T1CI 4 , TaCI 5 + TaF 5 , NbCI 5 + NbF 5 , SbCI 5 , SbFCU, SbF2Ü3, SbF3Ü2, SbF4Ü, SbF 5 and SbCI 5 + SbF 5 . More particularly preferred are antimonial compounds. As examples of oxyhalogenated Lewis acids which can be used according to the invention, mention may be made of T1OCI2, TiCl2 and SbOCI x F y (x + y = 3). In the Y + A salt, the Y + cation can correspond to one of the following general formulas: R 1 R 2 R 3 R 4 N + , R 1 R 2 R 3 R 4 P + , R 4 R 2 R 3 S + in which the symbols R 1 to R 4 , identical or different, each denote a hydrocarbyl, chlorohydrocarbyl, fluorohydrocarbyl, chlorofluorohydrocarbyle or fluorocarbyle group having from 1 to 10 carbon atoms, saturated or not, cyclic or not, or aromatic, l 'one or more of these groups may also contain one or more heteroatoms such as N, P, S or O. The ammonium, phosphonium or sulfonium cation Y + can also be part of a saturated or unsaturated, or aromatic heterocycle having 1 with 3 nitrogen, phosphorus or sulfur atoms, and meet one or other of the following general formulas:
[Chem 1] [Chem 1]
dans lesquelles R1 et R2 sont tels que définis précédemment. Un sel contenant 2 ou 3 sites ammonium, phosphonium ou sulfonium dans leur formule peut également convenir. Comme exemples de sels Y+A on peut mentionner les chlorures et fluorures de tétraalkyl ammonium, les chlorures et fluorures de tétraalkyl phosphonium, et chlorures et fluorures de trialkyl sulfonium, les chlorures et fluorures d'alkyl pyridinium, les chlorures, fluorures et bromures de dialkyl imidazolium, et les chlorures et fluorures de trialkyl imidazolium. Sont plus particulièrement appréciés le fluorure ou le chlorure de trimethyl sulfonium, le chlorure ou le fluorure de N-ethyl-pyridinium, le chlorure ou le fluorure de N-butyl-pyridinium, le chlorure ou le fluorure de l-ethyl-3-methyl-imidazolium, et le chlorure ou fluorure de l-butyl-3-methyl- imidazolium. Les liquides ioniques peuvent être préparés de façon connue en soi en mélangeant de manière appropriée l'acide de Lewis halogéné ou oxyhalogéné et le sel organique Y+A . On peut se reporter notamment à la méthode décrite dans le document WO 01/81353. Alternativement, le catalyseur peut être l'acide triflique ou trifluoroacétique tel que mentionné dans le document US 6,166,274. in which R 1 and R 2 are as defined above. A salt containing 2 or 3 ammonium, phosphonium or sulfonium sites in their formula may also be suitable. As examples of Y + A salts, there may be mentioned tetraalkyl ammonium chlorides and fluorides, tetraalkyl phosphonium chlorides and fluorides, and trialkyl sulfonium chlorides and fluorides, alkyl pyridinium chlorides and fluorides, chlorides, fluorides and bromides of dialkyl imidazolium, and trialkyl imidazolium chlorides and fluorides. More particularly preferred are trimethyl sulfonium fluoride or chloride, N-ethyl-pyridinium chloride or fluoride, N-butyl-pyridinium chloride or fluoride, 1-ethyl-3-methyl chloride or fluoride. -imidazolium, and 1-butyl-3-methyl-imidazolium chloride or fluoride. The ionic liquids can be prepared in a manner known per se by suitably mixing the halogenated or oxyhalogenated Lewis acid and the organic salt Y + A. We may refer in particular to the method described in document WO 01/81353. Alternatively, the catalyst can be triflic or trifluoroacetic acid as mentioned in document US Pat. No. 6,166,274.
Selon un mode de réalisation préféré, outre le l-chloro-3,3,3-trifluoropropène, le courant D comprend des coproduits sélectionnés parmi le groupe consistant en 1, 3,3,3- tétrafluoropropène et 1,1,1,3,3-pentafluoropropane. Selon un mode de réalisation préféré, la teneur dans la courant D en coproduits sélectionnés parmi le groupe consistant en 1, 3,3,3- tétrafluoropropène et 1,1,1,3,3-pentafluoropropane est inférieure à 0,5 % en mole. De préférence, la teneur en 1,3,3,3-tétrafluoropropène dans ledit courant D est inférieure à 0,5%, plus préférentiellement inférieure à 0,4%, en particulier inférieure à 0,3% en mole. De préférence, la teneur en 1,1,1,3,3-pentafluoropropane dans ledit courant D est inférieure à 0,1%, plus préférentiellement inférieure à 0,075%, en particulier inférieure à 0,05% en mole. According to a preferred embodiment, besides 1-chloro-3,3,3-trifluoropropene, stream D comprises co-products selected from the group consisting of 1, 3,3,3-tetrafluoropropene and 1,1,1,3 , 3-pentafluoropropane. According to a preferred embodiment, the content in stream D of co-products selected from the group consisting of 1, 3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane is less than 0.5% in mole. Preferably, the content of 1,3,3,3-tetrafluoropropene in said stream D is less than 0.5%, more preferably less than 0.4%, in particular less than 0.3% by mole. Preferably, the content of 1,1,1,3,3-pentafluoropropane in said stream D is less than 0.1%, more preferably less than 0.075%, in particular less than 0.05% by mole.
De préférence, l'étape i) est mise en oeuvre à une température de 50°C à 150°C, de préférence à une température de 75°C à 100°C. Preferably, step i) is carried out at a temperature of 50 ° C to 150 ° C, preferably at a temperature of 75 ° C to 100 ° C.
De préférence, l'étape i) est mise en oeuvre à une pression de 5 à 20 bara, de préférence à une pression de 10 à 18 bara, en particulier de 12 à 18 bara. Preferably, step i) is carried out at a pressure of 5 to 20 bara, preferably at a pressure of 10 to 18 bara, in particular 12 to 18 bara.
De préférence, le ratio molaire HF/[composés chlorés] à l'entrée du réacteur est compris entre 5 et 10, plus préférentiellement entre 5 et 7, en particulier entre 5 et 6. En particulier, lorsque ledit composé chloré de la composition de départ est 1,1,3,3-tétrachloropropène (1230za), le ratio molaire HF/1230za est compris entre 5 et 10, plus préférentiellement entre 5 et 7, en particulier entre 5 et 6. Preferably, the HF / [chlorinated compounds] molar ratio at the inlet of the reactor is between 5 and 10, more preferably between 5 and 7, in particular between 5 and 6. In particular, when said chlorinated compound of the composition of starting point is 1,1,3,3-tetrachloropropene (1230za), the HF / 1230za molar ratio is between 5 and 10, more preferably between 5 and 7, in particular between 5 and 6.
L'acide fluorhydrique et ladite composition de départ peuvent être introduits dans le réacteur par l'intermédiaire d'un mélangeur statique. De préférence, l'acide fluorhydrique est chauffé avant son introduction dans le réacteur et ainsi avant la mise en oeuvre de l'étape i). De préférence, l'acide fluorhydrique est chauffé à une température de 100°C à 170°C, de préférence de 120°C à 170°C, en particulier de 125°C à 165°C, plus particulièrement de 125°C à 155°C. Selon un mode de réalisation particulier, le courant D obtenu à l'étape i) peut être soumis à des étapes de purification préalablement à la mise en oeuvre de l'étape ii). Alternativement, le courant D obtenu à l'étape i) peut être utilisé directement à l'étape ii). The hydrofluoric acid and said starting composition can be introduced into the reactor via a static mixer. Preferably, the hydrofluoric acid is heated before its introduction into the reactor and thus before the implementation of step i). Preferably, the hydrofluoric acid is heated to a temperature of 100 ° C to 170 ° C, preferably 120 ° C to 170 ° C, in particular 125 ° C to 165 ° C, more particularly 125 ° C to 155 ° C. According to a particular embodiment, the stream D obtained in step i) can be subjected to purification steps prior to the implementation of step ii). Alternatively, the current D obtained in step i) can be used directly in step ii).
Ainsi, ledit procédé de production peut comprendre une étape i'), subséquente à l'étape i) et préalable à l'étape ii), comprenant une étape de traitement du courant D pour donner un courant DI comprenant le l-chloro-3,3,3-trifluoropropène, HCI, H F et un courant D2 comprenant au moins 50% en poids d' HF, par exemple de préférence au moins 70% en poids d'HF. L'étape de traitement (i') est de préférence une colonne de reflux, mise en oeuvre avantageusement à une température comprise entre 30 et 120°C pour donner le courant D2 qui est recyclé au réacteur. Thus, said production process may comprise a step i ′), subsequent to step i) and prior to step ii), comprising a step of treatment of current D to give a current DI comprising 1-chloro-3 , 3,3-trifluoropropene, HCl, HF and a stream D2 comprising at least 50% by weight of HF, for example preferably at least 70% by weight of HF. The treatment step (i ′) is preferably a reflux column, advantageously carried out at a temperature of between 30 and 120 ° C. to give the stream D2 which is recycled to the reactor.
Selon un mode de réalisation particulier, ledit procédé de production du l-chloro-3,3,3- trifluoropropène selon la présente invention comprenant les étapes de : According to a particular embodiment, said process for the production of 1-chloro-3,3,3-trifluoropropene according to the present invention comprising the steps of:
i) mise en contact, dans un réacteur, entre l'acide fluorhydrique (HF) et une composition de départ comprenant au moins un composé chloré sélectionné parmi le groupe consistant eni) bringing into contact, in a reactor, between hydrofluoric acid (HF) and a starting composition comprising at least one chlorinated compound selected from the group consisting of
1.1.3.3-tetrachloropropene, 1,3,3,3-tetrachloropropene et un mélange des deux, pour obtenir un courant D comprenant l-chloro-3,3,3-trifluoropropène, H F et HCl ; 1.1.3.3-tetrachloropropene, 1,3,3,3-tetrachloropropene and a mixture of the two, to obtain a stream D comprising 1-chloro-3,3,3-trifluoropropene, H F and HCl;
i') une étape de traitement du courant D pour donner un courant DI comprenant le 1-chloro-i ') a step of processing the current D to give a current DI comprising 1-chloro-
3.3.3-trifluoropropène, HCl, HF et un courant D2 comprenant au moins 50% en poids d'HF ; ii) mise en oeuvre du procédé de neutralisation selon la présente invention à partir du courant DI obtenu à l'étape i'). 3.3.3-trifluoropropene, HCl, HF and a stream D2 comprising at least 50% by weight of HF; ii) implementation of the neutralization process according to the present invention from the current DI obtained in step i ′).
Le présent procédé de production peut également comprendre une étape ii') subséquente à l'étape i') et préalable à l'étape ii). De préférence, ladite étape ii') est une étape de récupération de l'acide chlorhydrique du courant DI pour former un courant D3 d'HCI et un courant D4 comprenant le l-chloro-3,3,3-trifluoropropène, HCl, HF. La récupération d'HCI à l'étape (ii') est de préférence obtenue à l'aide d'une colonne de distillation munie d'un rebouilleur en pied et d'un système de reflux en tête. La température en pied est avantageusement comprise entre 20°C et 110°C. La température en tête est avantageusement comprise entre -50°C et 0°C. La distillation de l'HCI est typiquement effectuée à une pression comprise entre 7 et 25 bars. Cette étape de récupération permet d'obtenir un courant D4 dans lequel la quantité d'HCI est fortement diminuée par rapport à la quantité d'HCI dans le courant Dl. The present production process can also comprise a step ii ′) subsequent to step i ′) and prior to step ii). Preferably, said step ii ′) is a step of recovering hydrochloric acid from stream DI to form a stream D3 of HCl and a stream D4 comprising 1-chloro-3,3,3-trifluoropropene, HCl, HF . The recovery of HCl in step (ii ′) is preferably obtained using a distillation column fitted with a reboiler at the bottom and with a reflux system at the top. The temperature at the bottom is advantageously between 20 ° C and 110 ° C. The head temperature is advantageously between -50 ° C and 0 ° C. The distillation of the HCl is typically carried out at a pressure of between 7 and 25 bars. This recovery step makes it possible to obtain a stream D4 in which the quantity of HCl is greatly reduced relative to the quantity of HCl in the stream D1.
Ainsi, selon un mode de réalisation particulier, ledit procédé de production du l-chloro-3,3,3- trifluoropropène selon la présente invention comprenant les étapes de : Thus, according to a particular embodiment, said process for the production of 1-chloro-3,3,3-trifluoropropene according to the present invention comprising the steps of:
i) mise en contact, dans un réacteur, entre l'acide fluorhydrique (HF) et une composition de départ comprenant au moins un composé chloré sélectionné parmi le groupe consistant eni) bringing into contact, in a reactor, between hydrofluoric acid (HF) and a starting composition comprising at least one chlorinated compound selected from the group consisting of
1.1.3.3-tetrachloropropene, 1,3,3,3-tetrachloropropene et un mélange des deux, pour obtenir un courant D comprenant l-chloro-3,3,3-trifluoropropène, HF et HCl ; 1.1.3.3-tetrachloropropene, 1,3,3,3-tetrachloropropene and a mixture of the two, to obtain a stream D comprising 1-chloro-3,3,3-trifluoropropene, HF and HCl;
i') traitement du courant D pour donner un courant Dl comprenant le l-chloro-3,3,3- trifluoropropène, HCl, HF et un courant D2 comprenant au moins 50% en poids d'HF ; i ') treating stream D to give stream D1 comprising 1-chloro-3,3,3-trifluoropropene, HCl, HF and stream D2 comprising at least 50% by weight of HF;
ii') récupération de l'acide chlorhydrique du courant Dl pour former un courant D3 d'HCI et un courant D4 comprenant le l-chloro-3,3,3-trifluoropropène, HCl, HF ; ii) mise en œuvre du procédé de neutralisation selon la présente invention à partir du courant D4 obtenu à l'étape ii') pour former le courant gazeux C. ii ') recovering hydrochloric acid from stream D1 to form HCl stream D3 and stream D4 comprising 1-chloro-3,3,3-trifluoropropene, HCl, HF; ii) implementation of the neutralization process according to the present invention from the stream D4 obtained in step ii ′) to form the gas stream C.
Le présent procédé de production peut également comprendre une étape iii') subséquente à l'étape ii') et préalable à l'étape ii). De préférence, l'étape iii') est une étape de séparation du courant D4 pour former un courant D5 comprenant au moins 90% en poids, de préférence au moins 98% en poids et en particulier au moins 99% en poids d'HF, et un courant D6 comprenant l-chloro-3,3,3-trifluoropropène, HCl et HF. L'étape de séparation est de préférence une décantation, mise en œuvre à une température avantageusement comprise entre -50°C et 50°C, de préférence entre -20°C et 10°C. The present production process can also comprise a step iii ′) subsequent to step ii ′) and prior to step ii). Preferably, step iii ′) is a step of separating the stream D4 to form a stream D5 comprising at least 90% by weight, preferably at least 98% by weight and in particular at least 99% by weight of HF , and a stream D6 comprising 1-chloro-3,3,3-trifluoropropene, HCl and HF. The separation step is preferably decantation, carried out at a temperature advantageously between -50 ° C and 50 ° C, preferably between -20 ° C and 10 ° C.
Ainsi, selon un mode de réalisation particulier, ledit procédé de production du l-chloro-3,3,3- trifluoropropène selon la présente invention comprenant les étapes de : Thus, according to a particular embodiment, said process for the production of 1-chloro-3,3,3-trifluoropropene according to the present invention comprising the steps of:
i) mise en contact, dans un réacteur, entre l'acide fluorhydrique (HF) et une composition de départ comprenant au moins un composé chloré sélectionné parmi le groupe consistant en 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene et un mélange des deux, pour obtenir un courant D comprenant l-chloro-3,3,3-trifluoropropène, HF et HCl ; i) contacting, in a reactor, between hydrofluoric acid (HF) and a starting composition comprising at least one chlorinated compound selected from the group consisting of 1,1,3,3-tetrachloropropene, 1,3,3 , 3-tetrachloropropene and a mixture of the two, to obtain a stream D comprising 1-chloro-3,3,3-trifluoropropene, HF and HCl;
i') traitement du courant D pour donner un courant DI comprenant le l-chloro-3,3,3- trifluoropropène, HCl, HF et un courant D2 comprenant au moins 50% en poids d'HF ; i ') treating stream D to give stream DI comprising 1-chloro-3,3,3-trifluoropropene, HCl, HF and stream D2 comprising at least 50% by weight of HF;
ii') récupération de l'acide chlorhydrique du courant DI pour former un courant D3 d'HCI et un courant D4 comprenant le l-chloro-3,3,3-trifluoropropène, HCl, HF ; ii ') recovering hydrochloric acid from stream DI to form HCl stream D3 and stream D4 comprising 1-chloro-3,3,3-trifluoropropene, HCl, HF;
iii') séparation du courant D4 obtenu à l'étape ii') pour former un courant D5 comprenant au moins 90% en poids et un courant D6 comprenant l-chloro-3,3,3-trifluoropropène, HCl et HF ; ii) mise en œuvre du procédé de neutralisation selon la présente invention à partir du courant D6 obtenu à l'étape iii') pour former le courant gazeux C. iii ') separation of the stream D4 obtained in step ii') to form a stream D5 comprising at least 90% by weight and a stream D6 comprising 1-chloro-3,3,3-trifluoropropene, HCl and HF; ii) implementation of the neutralization process according to the present invention from the stream D6 obtained in step iii ′) to form the gas stream C.
Le présent procédé de production peut également comprendre une étape iv') subséquente à l'étape iii') et préalable à l'étape ii). De préférence, l'étape iv') est une étape de lavage à l'eau. Cette étape permet éliminer une partie du HCl et du HF compris dans le courant D6. The present production process can also comprise a step iv ′) subsequent to step iii ′) and prior to step ii). Preferably, step iv ′) is a washing step with water. This step eliminates part of the HCl and HF included in the stream D6.
Ainsi, selon un mode de réalisation particulier, ledit procédé de production du l-chloro-3,3,3- trifluoropropène selon la présente invention comprenant les étapes de : Thus, according to a particular embodiment, said process for the production of 1-chloro-3,3,3-trifluoropropene according to the present invention comprising the steps of:
i) mise en contact, dans un réacteur, entre l'acide fluorhydrique (HF) et une composition de départ comprenant au moins un composé chloré sélectionné parmi le groupe consistant en 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene et un mélange des deux, pour obtenir un courant D comprenant l-chloro-3,3,3-trifluoropropène, HF et HCl ; i') traitement du courant D pour donner un courant DI comprenant le l-chloro-3,3,3- trifluoropropène, HCl, HF et un courant D2 comprenant au moins 50% en poids d'HF ; i) contacting, in a reactor, between hydrofluoric acid (HF) and a starting composition comprising at least one chlorinated compound selected from the group consisting of 1,1,3,3-tetrachloropropene, 1,3,3 , 3-tetrachloropropene and a mixture of the two, to obtain a stream D comprising 1-chloro-3,3,3-trifluoropropene, HF and HCl; i ') treating stream D to give stream DI comprising 1-chloro-3,3,3-trifluoropropene, HCl, HF and stream D2 comprising at least 50% by weight of HF;
ii') récupération de l'acide chlorhydrique du courant DI pour former un courant D3 d'HCI et un courant D4 comprenant le l-chloro-3,3,3-trifluoropropène, HCl, HF ; ii ') recovering hydrochloric acid from stream DI to form HCl stream D3 and stream D4 comprising 1-chloro-3,3,3-trifluoropropene, HCl, HF;
iii') séparation du courant D4 obtenu à l'étape ii') pour former un courant D5 comprenant au moins 90% en poids et un courant D6 comprenant l-chloro-3,3,3-trifluoropropène, HCl et HF ; iv') lavage dudit courant D6 obtenu à l'étape iii') avec de l'eau pour former un courant D7 comprenant l-chloro-3,3,3-trifluoropropène et une solution aqueuse acide D8 ; iii ') separation of the stream D4 obtained in step ii') to form a stream D5 comprising at least 90% by weight and a stream D6 comprising 1-chloro-3,3,3-trifluoropropene, HCl and HF; iv ') washing said stream D6 obtained in step iii') with water to form a stream D7 comprising 1-chloro-3,3,3-trifluoropropene and an acidic aqueous solution D8;
ii) mise en oeuvre du procédé de neutralisation selon la présente invention à partir du courant D7 obtenu à l'étape iv') pour former le courant gazeux C. ii) implementation of the neutralization process according to the present invention from the stream D7 obtained in step iv ′) to form the gas stream C.
Le présent procédé de production peut également comprendre une étape iii) subséquente à l'étape ii). De préférence, l'étape iii) consiste en un séchage dudit courant gazeux C comprenant l-chloro-3,3,3-trifluoropropène pour former un courant séché C2 comprenant l-chloro-3,3,3- trifluoropropène. L'étape de séchage peut être effectuée à l'aide de tamis moléculaire, de zéolithe, de sels inorganiques tels que le sulfate de calcium ou le chlorure de calcium, de gel de silice, de charbon actif. Des exemples de tamis moléculaires et de zéolithes sont décrits dans le document W02017/050686. Des exemples de sels inorganiques, de tamis moléculaires, de gel de silice et de charbon actif sont également décrits dans W02017/031406. Des exemples de tamis moléculaires, de charbon actif et de gel de silice sont également décrits dans WO2016/148957. De préférence, l'étape de séchage s'effectuera à l'aide de tamis moléculaire, en particulier à l'aide d'un tamis moléculaire 3A. The present production process can also comprise a step iii) subsequent to step ii). Preferably, step iii) consists of drying said gas stream C comprising 1-chloro-3,3,3-trifluoropropene to form a dried stream C2 comprising 1-chloro-3,3,3-trifluoropropene. The drying step can be carried out using molecular sieve, zeolite, inorganic salts such as calcium sulfate or calcium chloride, silica gel, activated carbon. Examples of molecular sieves and zeolites are described in document WO2017 / 050686. Examples of inorganic salts, molecular sieves, silica gel and activated carbon are also described in WO2017 / 031406. Examples of molecular sieves, activated carbon and silica gel are also described in WO2016 / 148957. Preferably, the drying step will be carried out using a molecular sieve, in particular using a 3A molecular sieve.
Le présent procédé de production peut également comprendre une étape iv) subséquente à l'étape iii). De préférence, l'étape iv) comprend une ou plusieurs étapes de distillation dudit courant C2 obtenu à l'étape iii). The present production process can also comprise a step iv) subsequent to step iii). Preferably, step iv) comprises one or more steps of distillation of said stream C2 obtained in step iii).
Ainsi, selon un mode de réalisation particulier, ledit procédé de production du l-chloro-3,3,3- trifluoropropène selon la présente invention comprenant les étapes de : Thus, according to a particular embodiment, said process for the production of 1-chloro-3,3,3-trifluoropropene according to the present invention comprising the steps of:
i) mise en contact, dans un réacteur, entre l'acide fluorhydrique (HF) et une composition de départ comprenant au moins un composé chloré sélectionné parmi le groupe consistant en 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene et un mélange des deux, pour obtenir un courant D comprenant l-chloro-3,3,3-trifluoropropène, HF et HCl ; i) contacting, in a reactor, between hydrofluoric acid (HF) and a starting composition comprising at least one chlorinated compound selected from the group consisting of 1,1,3,3-tetrachloropropene, 1,3,3 , 3-tetrachloropropene and a mixture of the two, to obtain a stream D comprising 1-chloro-3,3,3-trifluoropropene, HF and HCl;
i') traitement du courant D pour donner un courant DI comprenant le l-chloro-3,3,3- trifluoropropène, HCl, HF et un courant D2 comprenant au moins 50% en poids d'HF ; ii') récupération de l'acide chlorhydrique du courant DI pour former un courant D3 d'HCI et un courant D4 comprenant le l-chloro-3,3,3-trifluoropropène, HCl, HF ; i ') treating stream D to give stream DI comprising 1-chloro-3,3,3-trifluoropropene, HCl, HF and stream D2 comprising at least 50% by weight of HF; ii ') recovering hydrochloric acid from stream DI to form HCl stream D3 and stream D4 comprising 1-chloro-3,3,3-trifluoropropene, HCl, HF;
iii') séparation du courant D4 obtenu à l'étape ii') pour former un courant D5 comprenant au moins 90% en poids et un courant D6 comprenant l-chloro-3,3,3-trifluoropropène, HCl et HF ; iv') lavage dudit courant D6 obtenu à l'étape iii') avec de l'eau pour former un courant D7 comprenant l-chloro-3,3,3-trifluoropropène et une solution aqueuse acide D8 ; iii ') separation of the stream D4 obtained in step ii') to form a stream D5 comprising at least 90% by weight and a stream D6 comprising 1-chloro-3,3,3-trifluoropropene, HCl and HF; iv ') washing said stream D6 obtained in step iii') with water to form a stream D7 comprising 1-chloro-3,3,3-trifluoropropene and an acidic aqueous solution D8;
ii) mise en oeuvre du procédé de neutralisation selon la présente invention à partir du courant D7 obtenu à l'étape iv') pour former le courant gazeux C ; ii) implementation of the neutralization process according to the present invention from the stream D7 obtained in step iv ′) to form the gas stream C;
iii) séchage dudit courant gazeux C comprenant l-chloro-3,3,3-trifluoropropène pour former un courant séché C2 comprenant l-chloro-3,3,3-trifluoropropène ; et iii) drying said gas stream C comprising 1-chloro-3,3,3-trifluoropropene to form a dried stream C2 comprising 1-chloro-3,3,3-trifluoropropene; and
iv) distillation dudit courant C2 à l'aide d'une ou plusieurs colonnes de distillation pour former un courant C3 comprenant l-chloro-3,3,3-trifluoropropène. iv) distillation of said stream C2 using one or more distillation columns to form a stream C3 comprising 1-chloro-3,3,3-trifluoropropene.
De préférence, ledit procédé de production selon la présente invention est mis en oeuvre en continu. Preferably, said production process according to the present invention is carried out continuously.
Selon un autre aspect de la présente invention, une composition est fournie. Ladite composition comprenant l-chloro-3,3,3-trifluoropropène et l-chloro-l,3,3-trifluoropropène. De préférence, la teneur molaire en l-chloro-l,3,3-trifluoropropène étant inférieure à 110 ppm dans ladite composition. De préférence, la teneur molaire en l-chloro-3,3,3-trifluoropropène dans ladite composition est supérieure à 85%. De préférence, dans ladite composition, l-chloro-3,3,3- trifluoropropène représente au moins 90 mol% de trans-l-chloro-3,3,3-trifluoropropène, plus particulièrement au moins 92 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière privilégiée au moins 95 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière plus privilégiée au moins 98 mol% de trans-l-chloro-3,3,3-trifluoropropène ; le complément étant représenté par cis-l-chloro-3,3,3-trifluoropropène. De préférence, dans ladite composition, 1- chloro-3,3,3-trifluoropropène est le trans-l-chloro-3,3,3-trifluoropropène. According to another aspect of the present invention, a composition is provided. Said composition comprising 1-chloro-3,3,3-trifluoropropene and 1-chloro-1,3,3-trifluoropropene. Preferably, the molar content of 1-chloro-1,3,3-trifluoropropene being less than 110 ppm in said composition. Preferably, the molar content of 1-chloro-3,3,3-trifluoropropene in said composition is greater than 85%. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro- 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
Ainsi, avantageusement, ladite composition comprend une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 87% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure à 110 ppm, avantageusement inférieure à 100 ppm, de préférence inférieure à 90 ppm, plus préférentiellement inférieure à 80 ppm, en particulier inférieure à 70 ppm, plus particulièrement inférieure à 60 ppm, de manière privilégiée inférieure à 50 ppm. De préférence, dans ladite composition, l-chloro-3,3,3-trifluoropropène représente au moins 90 mol% de trans-l-chloro-3,3,3-trifluoropropène, plus particulièrement au moins 92 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière privilégiée au moins 95 mol% de trans-1- chloro-3,3,3-trifluoropropène, de manière plus privilégiée au moins 98 mol% de trans-l-chloro-Thus, advantageously, said composition comprises a molar content of 1-chloro-3,3,3-trifluoropropene greater than 87% and a molar content of 1-chloro-1,3,3-trifluoropropene less than 110 ppm, advantageously less than 100 ppm, preferably less than 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than 60 ppm, preferably less than 50 ppm. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% of trans-1- chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% of trans-1-chloro-
3.3.3-trifluoropropène ; le complément étant représenté par cis-l-chloro-3,3,3- trifluoropropène. De préférence, dans ladite composition, l-chloro-3,3,3-trifluoropropène est le trans-l-chloro-3,3,3-trifluoropropène. 3.3.3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
De préférence, ladite composition comprend une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 90% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure à 110 ppm, avantageusement inférieure à 100 ppm, de préférence inférieure à 90 ppm, plus préférentiellement inférieure à 80 ppm, en particulier inférieure à 70 ppm, plus particulièrement inférieure à 60 ppm, de manière privilégiée inférieure à 50 ppm. De préférence dans ladite composition l-chloro-3,3,3-trifluoropropène représente au moins 90 mol% de trans- l-chloro-3,3,3-trifluoropropène, plus particulièrement au moins 92 mol% de trans-l-chloro- Preferably, said composition comprises a molar content of 1-chloro-3,3,3-trifluoropropene greater than 90% and a molar content of 1-chloro-1,3,3-trifluoropropene less than 110 ppm, advantageously less than 100 ppm, preferably less than 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than 60 ppm, preferably less than 50 ppm. Preferably in said composition 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1-chloro -
3.3.3-trifluoropropène, de manière privilégiée au moins 95 mol% de trans-l-chloro-3,3,3- trifluoropropène, de manière plus privilégiée au moins 98 mol% de trans-l-chloro-3,3,3- trifluoropropène ; le complément étant représenté par cis-l-chloro-3,3,3-trifluoropropène. De préférence, dans ladite composition, l-chloro-3,3,3-trifluoropropène est le trans-l-chloro-3,3,3- trifluoropropène. 3.3.3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro-3,3,3 - trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
Plus préférentiellement, ladite composition comprend une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 92% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure à 110 ppm, avantageusement inférieure à 100 ppm, de préférence inférieure à 90 ppm, plus préférentiellement inférieure à 80 ppm, en particulier inférieure à 70 ppm, plus particulièrement inférieure à 60 ppm, de manière privilégiée inférieure à 50 ppm. De préférence, dans ladite composition, l-chloro-3,3,3-trifluoropropène représente au moins 90 mol% de trans-l-chloro-3,3,3-trifluoropropène, plus particulièrement au moins 92 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière privilégiée au moins 95 mol% de trans-1- chloro-3,3,3-trifluoropropène, de manière plus privilégiée au moins 98 mol% de trans-l-chloro- More preferably, said composition comprises a molar content of 1-chloro-3,3,3-trifluoropropene greater than 92% and a molar content of 1-chloro-1,3,3-trifluoropropene less than 110 ppm, advantageously less than 100 ppm, preferably less than 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than 60 ppm, preferably less than 50 ppm. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro-
3.3.3-trifluoropropène ; le complément étant représenté par cis-l-chloro-3,3,3- trifluoropropène. De préférence, dans ladite composition, l-chloro-3,3,3-trifluoropropène est le trans-l-chloro-3,3,3-trifluoropropène. 3.3.3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
En particulier, ladite composition comprend une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 95% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure à 110 ppm, avantageusement inférieure à 100 ppm, de préférence inférieure à 90 ppm, plus préférentiellement inférieure à 80 ppm, en particulier inférieure à 70 ppm, plus particulièrement inférieure à 60 ppm, de manière privilégiée inférieure à 50 ppm. De préférence, dans ladite composition, l-chloro-3,3,3-trifluoropropène représente au moins 90 mol% de trans-l-chloro-3,3,3-trifluoropropène, plus particulièrement au moins 92 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière privilégiée au moins 95 mol% de trans-1- chloro-3,3,3-trifluoropropène, de manière plus privilégiée au moins 98 mol% de trans-l-chloro-In particular, said composition comprises a molar content of 1-chloro-3,3,3-trifluoropropene greater than 95% and a molar content of 1-chloro-1,3,3-trifluoropropene less than 110 ppm, advantageously less than 100 ppm, preferably less than 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than 60 ppm, preferably less than 50 ppm. Of preferably, in said composition, 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1- chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro-
3,3,3-trifluoropropène ; le complément étant représenté par cis-l-chloro-3,3,3- trifluoropropène. De préférence, dans ladite composition, l-chloro-3,3,3-trifluoropropène est le trans-l-chloro-3,3,3-trifluoropropène. 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
Plus particulièrement, ladite composition comprend une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 97% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure à 110 ppm, avantageusement inférieure à 100 ppm, de préférence inférieure à 90 ppm, plus préférentiellement inférieure à 80 ppm, en particulier inférieure à 70 ppm, plus particulièrement inférieure à 60 ppm, de manière privilégiée inférieure à 50 ppm. De préférence, dans ladite composition, l-chloro-3,3,3-trifluoropropène représente au moins 90 mol% de trans-l-chloro-3,3,3-trifluoropropène, plus particulièrement au moins 92 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière privilégiée au moins 95 mol% de trans-1- chloro-3,3,3-trifluoropropène, de manière plus privilégiée au moins 98 mol% de trans-l-chloro- More particularly, said composition comprises a molar content of 1-chloro-3,3,3-trifluoropropene greater than 97% and a molar content of 1-chloro-1,3,3-trifluoropropene less than 110 ppm, advantageously less than 100. ppm, preferably less than 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than 60 ppm, preferably less than 50 ppm. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro-
3,3,3-trifluoropropène ; le complément étant représenté par cis-l-chloro-3,3,3- trifluoropropène. De préférence, dans ladite composition, l-chloro-3,3,3-trifluoropropène est le trans-l-chloro-3,3,3-trifluoropropène. 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
De manière privilégiée, ladite composition comprend une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 99% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure à 110 ppm, avantageusement inférieure à 100 ppm, de préférence inférieure à 90 ppm, plus préférentiellement inférieure à 80 ppm, en particulier inférieure à 70 ppm, plus particulièrement inférieure à 60 ppm, de manière privilégiée inférieure à 50 ppm. De préférence, dans ladite composition, l-chloro-3,3,3-trifluoropropène représente au moins 90 mol% de trans-l-chloro-3,3,3-trifluoropropène, plus particulièrement au moins 92 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière privilégiée au moins 95 mol% de trans-1- chloro-3,3,3-trifluoropropène, de manière plus privilégiée au moins 98 mol% de trans-l-chloro- Preferably, said composition comprises a molar content of 1-chloro-3,3,3-trifluoropropene greater than 99% and a molar content of 1-chloro-1,3,3-trifluoropropene less than 110 ppm, advantageously less than 100 ppm, preferably less than 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than 60 ppm, preferably less than 50 ppm. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro-
3,3,3-trifluoropropène ; le complément étant représenté par cis-l-chloro-3,3,3- trifluoropropène. De préférence, dans ladite composition, l-chloro-3,3,3-trifluoropropène est le trans-l-chloro-3,3,3-trifluoropropène. Ladite composition peut également comprendre l,l-dichloro-l,3,3-trifluoropropane. La teneur molaire en l,l-dichloro-l,3,3-trifluoropropane dans ladite composition est comprise entre 10 et 200 ppm, de préférence entre 20 et 150 ppm, en particulier entre 50 et 100 ppm. 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene. Said composition may also comprise 1,1-dichloro-1,3,3-trifluoropropane. The molar content of 1,1-dichloro-1,3,3-trifluoropropane in said composition is between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm.
Ainsi, ladite composition peut comprendre une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 85% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure à 80 ppm, en particulier inférieure à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm ; et une teneur molaire en l,l-dichloro-l,3,3-trifluoropropane comprise entre 10 et 200 ppm, de préférence entre 20 et 150 ppm, en particulier entre 50 et 100 ppm. De préférence, dans ladite composition, l-chloro-3,3,3-trifluoropropène représente au moins 90 mol% de trans-l-chloro-3,3,3-trifluoropropène, plus particulièrement au moins 92 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière privilégiée au moins 95 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière plus privilégiée au moins 98 mol% de trans- l-chloro-3,3,3-trifluoropropène ; le complément étant représenté par cis-l-chloro-3,3,3- trifluoropropène. De préférence, dans ladite composition, l-chloro-3,3,3-trifluoropropène est le trans-l-chloro-3,3,3-trifluoropropène. Thus, said composition may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 85% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less. or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro- 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
Avantageusement, ladite composition peut comprendre une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 87% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm ; et une teneur molaire en l,l-dichloro-l,3,3- trifluoropropane comprise entre 10 et 200 ppm, de préférence entre 20 et 150 ppm, en particulier entre 50 et 100 ppm. De préférence, dans ladite composition, l-chloro-3,3,3- trifluoropropène représente au moins 90 mol% de trans-l-chloro-3,3,3-trifluoropropène, plus particulièrement au moins 92 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière privilégiée au moins 95 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière plus privilégiée au moins 98 mol% de trans-l-chloro-3,3,3-trifluoropropène ; le complément étant représenté par cis-l-chloro-3,3,3-trifluoropropène. De préférence, dans ladite composition, 1- chloro-3,3,3-trifluoropropène est le trans-l-chloro-3,3,3-trifluoropropène. Advantageously, said composition may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 87% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro- 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
De préférence, ladite composition peut comprendre une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 90% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm ; et une teneur molaire en l,l-dichloro-l,3,3- trifluoropropane comprise entre 10 et 200 ppm, de préférence entre 20 et 150 ppm, en particulier entre 50 et 100 ppm. De préférence, dans ladite composition, l-chloro-3,3,3- trifluoropropène représente au moins 90 mol% de trans-l-chloro-3,3,3-trifluoropropène, plus particulièrement au moins 92 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière privilégiée au moins 95 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière plus privilégiée au moins 98 mol% de trans-l-chloro-3,3,3-trifluoropropène ; le complément étant représenté par cis-l-chloro-3,3,3-trifluoropropène. De préférence, dans ladite composition, 1- chloro-3,3,3-trifluoropropène est le trans-l-chloro-3,3,3-trifluoropropène. Preferably, said composition may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 90% and a molar content of 1-chloro-1,3,3-trifluoropropene. less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm , preferably less than or equal to 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro- 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
Plus préférentiellement, ladite composition peut comprendre une teneur molaire en 1-chloro- 3,3,3-trifluoropropène supérieure à 92% et une teneur molaire en l-chloro-1,3,3- trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm ; et une teneur molaire en 1,1- dichloro-l,3,3-trifluoropropane comprise entre 10 et 200 ppm, de préférence entre 20 et 150 ppm, en particulier entre 50 et 100 ppm. De préférence, dans ladite composition, l-chloro-3,3,3- trifluoropropène représente au moins 90 mol% de trans-l-chloro-3,3,3-trifluoropropène, plus particulièrement au moins 92 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière privilégiée au moins 95 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière plus privilégiée au moins 98 mol% de trans-l-chloro-3,3,3-trifluoropropène ; le complément étant représenté par cis-l-chloro-3,3,3-trifluoropropène. De préférence, dans ladite composition, 1- chloro-3,3,3-trifluoropropène est le trans-l-chloro-3,3,3-trifluoropropène. More preferably, said composition may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 92% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro- 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
En particulier, ladite composition peut comprendre une teneur molaire en l-chloro-3,3,3- trifluoropropène supérieure à 95% et une teneur molaire en l-chloro-l,3,3-trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm ; et une teneur molaire en l,l-dichloro-l,3,3- trifluoropropane comprise entre 10 et 200 ppm, de préférence entre 20 et 150 ppm, en particulier entre 50 et 100 ppm. De préférence, dans ladite composition, l-chloro-3,3,3- trifluoropropène représente au moins 90 mol% de trans-l-chloro-3,3,3-trifluoropropène, plus particulièrement au moins 92 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière privilégiée au moins 95 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière plus privilégiée au moins 98 mol% de trans-l-chloro-3,3,3-trifluoropropène ; le complément étant représenté par cis-l-chloro-3,3,3-trifluoropropène. De préférence, dans ladite composition, 1- chloro-3,3,3-trifluoropropène est le trans-l-chloro-3,3,3-trifluoropropène. In particular, said composition may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 95% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particularly between 50 and 100 ppm. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro- 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
Plus particulièrement, ladite composition peut comprendre une teneur molaire en 1-chloro- 3,3,3-trifluoropropène supérieure à 97% et une teneur molaire en l-chloro-1,3,3- trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm ; et une teneur molaire en 1,1- dichloro-l,3,3-trifluoropropane comprise entre 10 et 200 ppm, de préférence entre 20 et 150 ppm, en particulier entre 50 et 100 ppm. De préférence, dans ladite composition, l-chloro-3,3,3- trifluoropropène représente au moins 90 mol% de trans-l-chloro-3,3,3-trifluoropropène, plus particulièrement au moins 92 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière privilégiée au moins 95 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière plus privilégiée au moins 98 mol% de trans-l-chloro-3,3,3-trifluoropropène ; le complément étant représenté par cis-l-chloro-3,3,3-trifluoropropène. De préférence, dans ladite composition, 1- chloro-3,3,3-trifluoropropène est le trans-l-chloro-3,3,3-trifluoropropène. More particularly, said composition may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 97% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal to 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro- 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
De manière privilégiée, ladite composition peut comprendre une teneur molaire en 1-chloro- 3,3,3-trifluoropropène supérieure à 99% et une teneur molaire en l-chloro-1,3,3- trifluoropropène inférieure ou égale à 110 ppm, avantageusement inférieure ou égale à 100 ppm, de préférence inférieure ou égale à 90 ppm, plus préférentiellement inférieure ou égale à 80 ppm, en particulier inférieure ou égale à 70 ppm, plus particulièrement inférieure ou égale à 60 ppm, de manière privilégiée inférieure ou égale à 50 ppm ; et une teneur molaire en 1,1- dichloro-l,3,3-trifluoropropane comprise entre 10 et 200 ppm, de préférence entre 20 et 150 ppm, en particulier entre 50 et 100 ppm. De préférence, dans ladite composition, l-chloro-3,3,3- trifluoropropène représente au moins 90 mol% de trans-l-chloro-3,3,3-trifluoropropène, plus particulièrement au moins 92 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière privilégiée au moins 95 mol% de trans-l-chloro-3,3,3-trifluoropropène, de manière plus privilégiée au moins 98 mol% de trans-l-chloro-3,3,3-trifluoropropène ; le complément étant représenté par cis-l-chloro-3,3,3-trifluoropropène. De préférence, dans ladite composition, 1- chloro-3,3,3-trifluoropropène est le trans-l-chloro-3,3,3-trifluoropropène. Preferably, said composition may comprise a molar content of 1-chloro-3,3,3-trifluoropropene greater than 99% and a molar content of 1-chloro-1,3,3-trifluoropropene less than or equal to 110 ppm, advantageously less than or equal to 100 ppm, preferably less than or equal to 90 ppm, more preferably less than or equal to 80 ppm, in particular less than or equal to 70 ppm, more particularly less than or equal to 60 ppm, preferably less than or equal at 50 ppm; and a molar content of 1,1-dichloro-1,3,3-trifluoropropane of between 10 and 200 ppm, preferably between 20 and 150 ppm, in particular between 50 and 100 ppm. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene represents at least 90 mol% of trans-1-chloro-3,3,3-trifluoropropene, more particularly at least 92 mol% of trans-1 -chloro-3,3,3-trifluoropropene, preferably at least 95 mol% trans-1-chloro-3,3,3-trifluoropropene, more preferably at least 98 mol% trans-1-chloro- 3,3,3-trifluoropropene; the complement being represented by cis-1-chloro-3,3,3-trifluoropropene. Preferably, in said composition, 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene.
Exemples Examples
Les exemples sont mis en oeuvre dans un réacteur surmonté d'une colonne d'abattage (tous les deux étant calorifugés). La colonne d'abattage (diamètre intérieur = 24 mm, hauteur = 300 mm) est garnie avec des anneaux de Raschig (diamètre intérieur 3 mm, diamètre extérieur = 5 mm, longueur = 5 mm, fraction de vie dans la colonne garnie = 63%). On a introduit une solution basique et un tourne-en-rond de cette solution est mise en oeuvre à travers une colonne d'abattage garnie avec des anneaux de Raschig (environ 185 ml/min). La solution basique est portée à une température de 30°C ou 50°C suivant les exemples. Une composition comprenant 95,8 mol% trans-l-chloro-3,3,3-trifluoropropène, 2,4 mol% de cis-l-chloro-3,3,3- trifluoropropène (soit un ratio molaire trans/cis de 39,9), environ 120 ppm de 1,1-dichloro- 1,3,3-trifluoropropane et environ 25 ppm de l-chloro-l,3,3-trifluoropropène a ensuite été introduite dans le réacteur à un débit de 5 g/h. Les teneurs des constituants de la composition sont exprimées en mole. Ladite composition peut être obtenue en mettant en oeuvre le procédé de production du l-chloro-3,3,3-trifluoropropène tel que décrit dans la présente demande. Le flux gazeux a été récupéré pour être séché sur du CaCh anhydre et piégé à l'aide d'un piège à l'azote liquide. Le flux gazeux a été analysé par chromatographie phase gazeuse. On détermine la quantité de l-chloro-l,3,3-trifluoropropène après neutralisation. The examples are implemented in a reactor topped with a slaughter column (both being heat insulated). The slaughter column (internal diameter = 24 mm, height = 300 mm) is packed with Raschig rings (internal diameter 3 mm, external diameter = 5 mm, length = 5 mm, fraction of life in the packed column = 63 %). A basic solution was introduced and a roundabout of this solution was carried out through a slaughter column packed with Raschig rings (about 185 ml / min). The basic solution is brought to a temperature of 30 ° C. or 50 ° C. depending on the examples. A composition comprising 95.8 mol% trans-l-chloro-3,3,3-trifluoropropene, 2.4 mol% of cis-1-chloro-3,3,3-trifluoropropene (i.e. a trans / cis molar ratio of 39.9), about 120 ppm of 1,1-dichloro-1,3,3-trifluoropropane and about 25 ppm of 1-chloro-1,3,3-trifluoropropene were then introduced into the reactor at a flow rate of 5 g / h. The contents of the constituents of the composition are expressed in moles. Said composition can be obtained by implementing the process for producing 1-chloro-3,3,3-trifluoropropene as described in the present application. The gas stream was collected to be dried over anhydrous CaCh and trapped using a liquid nitrogen trap. The gas flow was analyzed by gas chromatography. The amount of 1-chloro-1,3,3-trifluoropropene is determined after neutralization.
Les solutions basiques testées (teneur exprimée en poids) et les résultats sont repris ci-dessous dans le tableau 1. The basic solutions tested (content expressed by weight) and the results are given below in Table 1.
[Tableau 1] [Table 1]
Comme démontré par les exemples ci-dessus, l'utilisation d'une solution basique de NaOH permet de limiter la formation de l-chloro-l,3,3-trifluoropropène lors de l'étape de neutralisation ; la teneur en HCFC-243fc étant légèrement diminuée. L'utilisation d'une solution basique de KOH aboutit à une teneur plus forte en HCFO-1233zb et une forte diminution de la Tl teneur en HCFC-243fc. Le trans-l-chloro-3,3,3-trifluoropropène ainsi obtenu comprend moins de HCFO-1233zb susceptible de perturber son efficacité dans les différents domaines d'applications. En outre, il est plus aisé de séparer le l,l-dichloro-l,3,3-trifluoropropane du trans-l-chloro-3,3,3-trifluoropropène que de séparer le l-chloro-l,3,3-trifluoropropène du trans-l-chloro-3,3,3-trifluoropropène. Le présent procédé représente donc un avantage important dans un procédé de production et de purification du trans-l-chloro-3,3,3- trifluoropropène. As demonstrated by the examples above, the use of a basic NaOH solution makes it possible to limit the formation of 1-chloro-1,3,3-trifluoropropene during the neutralization step; the HCFC-243fc content being slightly reduced. The use of a basic KOH solution results in a higher content of HCFO-1233zb and a sharp decrease in the Tl HCFC-243fc content. The trans-1-chloro-3,3,3-trifluoropropene thus obtained comprises less HCFO-1233zb capable of disturbing its effectiveness in the various fields of application. In addition, it is easier to separate l, l-dichloro-l, 3,3-trifluoropropane from trans-l-chloro-3,3,3-trifluoropropene than to separate l-chloro-1,3,3 -trifluoropropene from trans-1-chloro-3,3,3-trifluoropropene. The present process therefore represents a significant advantage in a process for the production and purification of trans-1-chloro-3,3,3-trifluoropropene.

Claims

REVENDICATIONS
1. Procédé de neutralisation d'une composition A comprenant l-chloro-3,3,3- trifluoropropène, l,l-dichloro-l,3,3-trifluoropropane et un ou plusieurs composé(s) acide de formule HX avec X = F ou Cl ; ledit procédé comprenant l'étape a) de mise en contact de ladite composition A avec une solution B dans des conditions aptes à limiter la formation du l-chloro-l,3,3-trifluoropropène. 1. Process for neutralizing a composition A comprising l-chloro-3,3,3-trifluoropropene, l, l-dichloro-l, 3,3-trifluoropropane and one or more acidic compound (s) of formula HX with X = F or Cl; said process comprising step a) of bringing said composition A into contact with a solution B under conditions capable of limiting the formation of 1-chloro-1,3,3-trifluoropropene.
2. Procédé selon la revendication précédente caractérisé en ce que lesdites conditions comprennent la mise en oeuvre de l'étape a) avec une solution B basique, avantageusement une solution B comprenant un hydroxyde alcalin, de préférence avec une solution B comprenant NaOH ou KOH, en particulier avec une solution B comprenant NaOH. 2. Method according to the preceding claim characterized in that said conditions comprise the implementation of step a) with a basic solution B, advantageously a solution B comprising an alkaline hydroxide, preferably with a solution B comprising NaOH or KOH, in particular with a solution B comprising NaOH.
3. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que ladite solution B de l'étape a) est une solution aqueuse. 3. Method according to any one of the preceding claims, characterized in that said solution B of step a) is an aqueous solution.
4. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que la teneur en hydroxyde alcalin est de 2 à 40% en poids sur base du poids total de ladite solution B. 4. Method according to any one of the preceding claims characterized in that the alkali hydroxide content is from 2 to 40% by weight based on the total weight of said solution B.
5. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que l'étape a) est mise en oeuvre à une température de 10°C à 90°C. 5. Method according to any one of the preceding claims, characterized in that step a) is carried out at a temperature of 10 ° C to 90 ° C.
6. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que l'étape a) est mise en oeuvre avec un temps de séjour compris entre 1 seconde et 5 minutes. 6. Method according to any one of the preceding claims, characterized in that step a) is carried out with a residence time of between 1 second and 5 minutes.
7. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que le l-chloro-3,3,3-trifluoropropène est sous la forme trans. 7. Method according to any one of the preceding claims, characterized in that the 1-chloro-3,3,3-trifluoropropene is in the trans form.
8. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que l'étape a) permet d'obtenir un courant gazeux C comprenant l-chloro-3,3,3- trifluoropropène, l-chloro-l,3,3-trifluoropropène et l,l-dichloro-l,3,3- trifluoropropane. 8. Method according to any one of the preceding claims, characterized in that step a) makes it possible to obtain a gas stream C comprising 1-chloro-3,3,3- trifluoropropene, 1-chloro-1,3,3-trifluoropropene and 1,1-dichloro-1,3,3-trifluoropropane.
9. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que le l-chloro-l,3,3-trifluoropropène est obtenu par déshydrochloration du 1,1-dichloro- 1,3,3-trifluoropropane. 9. Process according to any one of the preceding claims, characterized in that the 1-chloro-1,3,3-trifluoropropene is obtained by dehydrochlorination of 1,1-dichloro-1,3,3-trifluoropropane.
10. Procédé de production du l-chloro-3,3,3-trifluoropropène comprenant les étapes de : i) mise en contact, dans un réacteur, entre l'acide fluorhydrique (HF) et une composition de départ comprenant au moins un composé chloré sélectionné parmi le groupe consistant en 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene et un mélange des deux, dans des conditions suffisantes pour obtenir un courant D comprenant 1- chloro-3,3,3-trifluoropropène, l,l-dichloro-l,3,3-trifluoropropane HF et/ou HCl ; ii) mise en oeuvre du procédé selon l'une quelconque des revendications précédentes 1 à 9 à partir du courant D obtenu à l'étape i). 10. A process for the production of 1-chloro-3,3,3-trifluoropropene comprising the steps of: i) contacting, in a reactor, between hydrofluoric acid (HF) and a starting composition comprising at least one compound chlorinated selected from the group consisting of 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene and a mixture of the two, under conditions sufficient to obtain a stream D comprising 1-chloro-3,3, 3-trifluoropropene, 1,1-dichloro-1,3,3-trifluoropropane HF and / or HCl; ii) implementation of the method according to any one of the preceding claims 1 to 9 from the stream D obtained in step i).
11. Composition comprenant l-chloro-3,3,3-trifluoropropène et l-chloro-1,3,3- trifluoropropène, la teneur molaire en l-chloro-l,3,3-trifluoropropène étant inférieure à 110 ppm dans ladite composition. 11. Composition comprising 1-chloro-3,3,3-trifluoropropene and 1-chloro-1,3,3-trifluoropropene, the molar content of 1-chloro-1,3,3-trifluoropropene being less than 110 ppm in said. composition.
12. Composition selon la revendication précédente caractérisée en ce que la teneur molaire en l-chloro-3,3,3-trifluoropropène dans ladite composition est supérieure à 90%. 12. Composition according to the preceding claim, characterized in that the molar content of 1-chloro-3,3,3-trifluoropropene in said composition is greater than 90%.
13. Composition selon l'une quelconque des revendications précédentes 11 ou 12 caractérisée en ce que la teneur molaire en l-chloro-l,3,3-trifluoropropène est inférieure à 100 ppm, de préférence inférieure à 90 ppm, plus préférentiellement inférieure à 80 ppm, en particulier inférieure à 70 ppm, plus particulièrement inférieure à 60 ppm, de manière privilégiée inférieure à 50 ppm. 13. Composition according to any one of the preceding claims 11 or 12, characterized in that the molar content of 1-chloro-1,3-trifluoropropene is less than 100 ppm, preferably less than 90 ppm, more preferably less than 80 ppm, in particular less than 70 ppm, more particularly less than 60 ppm, preferably less than 50 ppm.
14. Composition selon l'une quelconque des revendications précédentes 11 à 13 caractérisée en ce qu'elle comprend également l,l-dichloro-l,3,3-trifluoropropane. 14. Composition according to any one of the preceding claims 11 to 13, characterized in that it also comprises l, l-dichloro-l, 3,3-trifluoropropane.
15. Procédé de préparation du l-chloro-l,3,3-trifluoropropène par déshydrochloration du l,l-dichloro-l,3,3-trifluoropropane en présence d'une solution basique. 15. Process for the preparation of l-chloro-l, 3,3-trifluoropropene by dehydrochlorination of l, l-dichloro-l, 3,3-trifluoropropane in the presence of a basic solution.
16. Procédé selon la revendication précédente caractérisé en ce que la solution basique comprend un hydroxyde alcalin ou alcalino-terreux, de préférence la solution basique comprend NaOH ou KOH. 16. Method according to the preceding claim, characterized in that the basic solution comprises an alkaline or alkaline-earth hydroxide, preferably the basic solution comprises NaOH or KOH.
17. Procédé selon l'une quelconque des revendications précédentes 15 ou 16 caractérisé en ce qu'il est mis en oeuvre à une température comprise entre 10°C et 150°C, de préférence entre 10 et 90°C. 17. Process according to any one of the preceding claims 15 or 16, characterized in that it is carried out at a temperature of between 10 ° C and 150 ° C, preferably between 10 and 90 ° C.
EP20714236.5A 2019-04-03 2020-04-01 Process for purifying 1-chloro-3,3,3-trifluoropropene Pending EP3947329A1 (en)

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FR1903539A FR3094714B1 (en) 2019-04-03 2019-04-03 Process for the purification of 1-chloro-3,3,3-trifluoropropene
PCT/EP2020/059233 WO2020201342A1 (en) 2019-04-03 2020-04-01 Process for purifying 1-chloro-3,3,3-trifluoropropene

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