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
  • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
  • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions

Definitions

• the present invention relates to a novel process for the synthesis of 1-chloro-3,3,3-trifluoropropene.
• 1-Chloro-3,3,3-trifluoropropene (HCFO-1233zd), and in particular trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zdE), is a hydrochlorofluoroolefin with thermodynamic and thermophysical properties. very favorable for use as a heat transfer fluid, particularly in cooling, air conditioning, power generation (including Rankine cycles) and heat pump applications, or for use in manufacturing of foam.
• this product is particularly advantageous since it also has a low global warming potential (GWP) and a low ozone depletion potential (ODP).
• GWP global warming potential
• ODP low ozone depletion potential
• WO 2005/108332 describes a process for the preparation of 1,3,3,3-tetrafluoropropene (HFO-1234ze) by the dehydrohalogenation of a compound of formula (I) CF3-CH2-CHFX, X being F, Cl, Br or I.
• This document also describes a process for preparing 1,1,3,3,3-tetrafluoropropene by pyrolysis.
• the invention firstly relates to a process for the preparation of 1-chloro-3,3,3-trifluoropropene comprising:
• the 1-chloro-3,3,3-trifluoropropene is trans-1-chloro-3,3,3-trifluoropropene, cis-1-chloro-3,3,3-trifluoropropene or a mixture of these.
• the dehydrobromination is carried out in the liquid phase.
• the dehydrobromination in the liquid phase is carried out in the presence of a base, preferably an alkali or alkaline earth hydroxide, in particular potassium hydroxide, an alkali carbonate or alkaline earth metal, a tertiary amine, a secondary amine, particularly triethylamine, or a combination thereof.
• a base preferably an alkali or alkaline earth hydroxide, in particular potassium hydroxide, an alkali carbonate or alkaline earth metal, a tertiary amine, a secondary amine, particularly triethylamine, or a combination thereof.
• the dehydrobromation in the liquid phase is carried out in the presence of a catalyst, preferably the catalyst being selected from tetraalkylammonium halides, in particular tetrabutylammonium bromide, solid metal catalysts impregnated on a support, and a combination thereof.
• a catalyst preferably the catalyst being selected from tetraalkylammonium halides, in particular tetrabutylammonium bromide, solid metal catalysts impregnated on a support, and a combination thereof.
• the dehydrobromation in the liquid phase is carried out without a catalyst.
• the dehydrobromination is carried out in the gas phase.
• the dehydrobromination in the gaseous phase is carried out in the presence of a catalyst, preferably the catalyst being chosen from active activated carbons or not, the alkaline or alkaline earth salts impregnated on an inorganic support such as alumina, magnesium oxide, and a combination thereof.
• the dehydrobromination in the gas phase is carried out without a catalyst.
• the compound of formula (I) is formed by the addition reaction of bromotrifluoromethane on vinyl chloride.
• the addition reaction is carried out in the liquid phase.
• the addition reaction in liquid phase is carried out in the presence of a catalyst, preferably the catalyst being selected from copper-based catalysts, palladium catalysts, iron-based catalysts and a combination thereof.
• the catalyst in the liquid phase, comprises a ligand, preferably chosen from an amine and an acetylacetone.
• the catalyst in the liquid phase, is the catalyst Pd [P (C6H5) 3] 4.
• the addition reaction in liquid phase is carried out at a temperature of 0 ° C to 300 ° C, preferably from 20 ° C to 250 ° C and even more preferably from 150 ° C to 250 ° C ° C.
• the addition reaction is carried out in the gas phase.
• the gas phase addition reaction is carried out in the presence of a catalyst, preferably the catalyst being chosen from solid catalysts of the metal salt type impregnated on an inorganic support such as alumina, and magnesium oxide.
• a catalyst being chosen from solid catalysts of the metal salt type impregnated on an inorganic support such as alumina, and magnesium oxide.
• the gas phase addition reaction is carried out at a temperature of 50 ° C to 300 ° C, preferably 100 ° C to 200 ° C.
• the process further comprises isolating the compound of formula (I) obtained by the addition reaction before dehydrobromination, preferably by distillation.
• the invention also relates to a composition comprising 1-chloro-3,3,3-trifluoropropene and the compound of formula (I):
• the compound of formula (I) being preferably present in a molar proportion of less than 5%.
• the invention also relates to a process for preparing the compound of formula (I):
• the present invention makes it possible to meet the need expressed above. It provides more particularly processes for the preparation of 1-chloro
• HCFO-1233zd refers to 1-chloro
• HCFO-1233zd therefore covers HCFO-1233zdZ, HCFO-1233zdE, and all mixtures of the two isomeric forms in all proportions.
• the invention relates to a process for the preparation of 1-chloro-3,3,3-trifluoropropene comprising:
• the provision of the compound of formula (I) can be carried out by any means known to those skilled in the art.
• the compound of formula (I) used in the process according to the invention may be a commercial product available directly in this form.
• the provision of the compound of formula (I) therefore consists in providing the compound of formula (I) for the latter to be subjected to dehydrobromination.
• the provision of the compound of formula (I) can also comprise or consist in the synthesis of the compound of formula (I) from reagents.
• the dehydrobromination can be carried out in situ or ex situ with respect to the synthesis of the compound of formula (I). The synthesis can be performed extemporaneously with respect to dehydrobromination or at an earlier period.
• Dehydrobromination can be carried out by any means known to those skilled in the art for selectively removing the bromine atom.
• the chlorine atom is also a leaving group but bromine is a better leaving group. It is thus possible to adapt the operating conditions of dehydrobromination to selectively remove bromine.
• Dehydrobromination can be carried out in the liquid phase. Alternatively, it can be performed in the gas phase. It can be catalyzed or carried out in the absence of catalyst.
• the dehydrobromination can be carried out in the presence of a catalyst or in the absence of catalyst.
• a catalyst is preferably selected from tetraalkylammonium halides, especially tetrabutylammonium bromide, solid metal-supported catalysts, and a combination thereof. The list is not exhaustive.
• Dehydrobromination in the liquid phase can be carried out in the presence of a base or in the absence of a base. When a base is present, its strength is adapted to favor dehydrobromination with respect to dehydrochlorination.
• bases which can be used for the dehydrobromination of the compound of formula (I) are the hydroxides or carbonates of alkali and alkaline earth metals, in particular potassium hydroxide, tertiary amines and secondary amines, in particular triethylamine. The list is not exhaustive.
• liquid phase dehydrobromation may be thermal, i.e., heat induced.
• the liquid phase dehydrobromination is carried out at a temperature of 50 ° C to 200 ° C, preferably 70 ° C to 160 ° C.
• the reaction is preferably carried out at a temperature of 20 ° C. to 90 ° C. ° C, even more preferably from 30 ° C to 80 ° C.
• liquid phase dehydrobromation is performed at a temperature of 20 ° C to 30 ° C, or 30 ° C to 40 ° C, or 40 ° C to 50 ° C, or 50 ° C to 60 ° C, or 60 ° C to 70 ° C , or from 70 ° C to 80 ° C, or from 80 ° C to 90 ° C.
• the dehydrobromation in the liquid phase takes place under a pressure of 1 bar at 30 bar, preferably from 1 bar to 10 bar.
• the dehydrobromation in the liquid phase is carried out for a period of 6 hours to 48 hours, preferably 12 hours to 36 hours. In other embodiments, the dehydrobromation in the liquid phase is carried out for a period of 6h to 12h, or 12h to 18h, or 18h to 24h, or 24h to 30h, or 30h to 36h, or 36h at 42h, or from 42h to 48h.
• the dehydrobromination When the dehydrobromination is carried out in the gas phase, it can be carried out in the presence of a catalyst or in the absence of catalyst. Preferably, it is carried out in the presence of a catalyst, the catalyst being preferentially chosen from active activated carbons or not, the alkaline or alkaline-earth salts impregnated on an inorganic support such as alumina, magnesium oxide, and a combination thereof.
• a catalyst being preferentially chosen from active activated carbons or not, the alkaline or alkaline-earth salts impregnated on an inorganic support such as alumina, magnesium oxide, and a combination thereof.
• the dehydrobromination in the gas phase may be thermal.
• the gas phase dehydrobromination is carried out at a temperature of 100 ° C to 500 ° C, preferably 150 ° C to 350 ° C.
• the reaction is preferably carried out at a temperature of 50 ° C. to 400 ° C., still more preferably 80 ° C to 250 ° C.
• the dehydrobromination in the gaseous phase takes place at a pressure of 1 bar at 100 bar, preferably at 5 bar at 30 bar.
• the dehydrobromation in the gas phase is carried out for a period of 1 second to 5 hours, preferably 3 seconds to 1 hour.
• the invention relates to a process for preparing the compound of formula (I):
• bromotrifluoromethane comprising the addition reaction of bromotrifluoromethane to vinyl chloride.
• bromotrifluoromethane is meant the compound of formula
• the compound of formula (I) is also called "1,1,1-trifluoro-3-chloro-3-bromopropane" in the present description.
• the addition reaction can take place in the liquid phase or in the gas phase. Whether the addition reaction is carried out in the liquid phase or in the gas phase, it can be catalyzed or carried out in the absence of catalyst.
• the catalyst is a copper catalyst, a palladium catalyst, an iron catalyst, or a combination thereof.
• copper catalyst is meant a catalyst comprising at least one copper chemical element, regardless of its form (atom or ion).
• the catalyst comprises a metal, preferably selected from copper, palladium or iron, and at least one ligand.
• the ligand is an amine or an acetylacetone.
• the catalyst is Pd [P (C6H5) 3] 4.
• Suitable solvents are alkyl halides and aromatic alkanes, halogenated or not. The list is not exhaustive.
• the addition reaction in liquid phase can be carried out in the absence of solvent, preferably under pressure of an inert gas so as to keep the reagents in liquid form.
• the addition reaction in the liquid phase is carried out at a temperature of 0 ° C. to 300 ° C., preferably between 20 ° C. and 250 ° C., more preferably between 150 ° C. and 250 ° C. C.
• the liquid phase addition reaction is carried out at from 0 ° C to 20 ° C, or from 20 ° C to 40 ° C, or from 40 ° C to 60 ° C, or from 60 ° C to 60 ° C.
• the addition reaction in the liquid phase is carried out for a period of from 1 h to 72 h, preferably from 2 h to 50 h.
• the addition reaction is carried out in the gas phase, it can be carried out in the presence of a catalyst.
• the catalyst is chosen from solid catalysts of metal salt type impregnated on an inorganic support such as alumina, and magnesium oxide.
• the addition reaction in the gaseous phase is carried out at a temperature of between 50 ° C. and 300 ° C., preferably between 100 ° C. and 200 ° C.
• the gas phase addition reaction is carried out at 50 ° C to 70 ° C, or at 70 ° C to 90 ° C, or at 90 ° C to 110 ° C, or 110 ° C to 130 ° C, or 130 ° C to 150 ° C, or 150 ° C to 170 ° C, or 170 ° C to 190 ° C, or 190 ° C to 210 ° C, or from 210 ° C to 230 ° C, or from 230 ° C to 250 ° C, or from 250 ° C to 270 ° C, or from 270 ° C to 290 ° C, or from 290 ° C to 300 ° C.
• the gas phase addition reaction is carried out for a period of 5 seconds to 1 hour, preferably 10 seconds to 30 minutes.
• the addition reaction whether carried out in the liquid phase or in the gas phase, takes place in an autoclave.
• the pressure at which the addition reaction is carried out is at least the autogenous pressure of the mixture of reagents and products in the autoclave at the reaction temperature.
• the process for preparing the compound of formula (I) according to the second aspect of the invention is particularly advantageous for carrying out the step of providing a compound of formula (I) of the process according to the first aspect of the invention. .
• the compound of formula (I) is advantageously synthesized by an addition reaction, and particularly preferably, the compound of Formula (I) is formed by the addition reaction of bromotrifluoromethane to vinyl chloride.
• the process for preparing 1-chloro-3,3,3-trifluoropropene according to the invention comprises:
• the compound of formula (I) obtained by the addition reaction is isolated from the reaction mixture.
• the compound of formula (I) is isolated by distillation.
• the compound of formula (I) isolated is then subjected to dehydrobromination according to the method of the invention.
• the 1-chloro-3,3,3-trifluoropropene formed by the dehydrobromination of the compound of formula (I) may be trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zdE), cis-1- chloro-3,3,3-trifluoropropene (HCFO-1233zdZ) or a mixture thereof.
• the process according to the invention further comprises a step of purifying 1-chloro-3,3,3-trifluoropropene.
• This step can be implemented by any method known to those skilled in the art.
• the process according to the invention further comprises a step of isolating trans-1-chloro-3,3,3-trifluoropropene.
• This step makes it possible in particular to separate the trans-isomer of 1-chloro-3,3,3-trifluoropropene from the cis isomer.
• the isolation of the trans isomer can for example be carried out by distillation.
• the process according to the invention further comprises a step of isomerization of cis-1-chloro-3,3,3-trifluoropropene in trans-1-chloro-3,3,3-trifluoropropene
• the step may for example be carried out in a gaseous phase, preferably in the presence of a catalyst, for example fluorinated chromium oxide, preferably at a temperature of 50 ° C to 350 ° C.
• the invention relates to a composition comprising 1-chloro-3,3,3-trifluoropropene and the compound of formula (I):
• the compound of formula (I) is present in the composition in a molar proportion of less than 5% (i.e. in a molar proportion of from 0% to 5% inclusive). In other embodiments, the compound of formula (I) is present in the composition in a molar proportion of less than 4%, or less than 3%, or less than 2%, or less than 1%, or less than 0.5%, or less than 0.3%, or less than 0.1%, or less than 0.05%, or less than 0.01%.
• the compound of formula (I) is present in the composition in a molar proportion of 0% excluded to 0.01% inclusive, or 0.01% inclusive to 0.05% inclusive, or 0% , 05% included at 0.08% inclusive, or 0.08% inclusive at 0.1% inclusive, or 0.1% inclusive at 0.5% inclusive, or 0.5% at 0.8 % included, or from 0.8% included to 1, 0% included, or from 1, 0% included to 1, 5% included, or from 1, 5% included to 2.0% inclusive, or from 2.0 % included at 2.5% inclusive, or 2.5% included at 3.0% inclusive, or 3.0% inclusive at 3.5% inclusive, or 3.5% inclusive at 4.0% inclusive , or 4.0% inclusive to 4.5% inclusive, or 4.5% to 5.0% inclusive.
• composition according to the invention is obtained by a process as described above.
• composition according to the invention is obtained by a process as described above and then by purification of the product stream, in particular 1-chloro-3,3,3-trifluoropropene, more particularly the trans-1-chloro-3,3,3-trifluoropropene, for example by distillation.
• the molar proportion of trans-1-chloro-3,3,3-trifluoropropene relative to the total 1-chloro-3,3,3-trifluoropropene is greater than or equal to 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 91%, or 92%, or 93%, or 94%, or 95%, or 96%, or 97%, or 98%, or 99%, or 99.5%, or 99.6%, or 99.7%, or 99.8% %, or 99.9%, or 99.95%, or 99.99%.
• the volatile HCFO-1233zd formed is assayed by gas chromatography.
• the reaction mixture comprises 75 mol% of HCFO-1233zd.
• the mixture obtained contains 72 g of bromotrifluoromethane (ie 89% of the introduced bromotrifluoromethane), 0.625 g of vinyl chloride (ie 17% of the vinyl chloride introduced), 6.8 g of 1,1,1-trifluoro-3-chloro. 3-bromopropane, and a liquid residue containing a little 1,1,1-trifluoro-3-chloro-3-bromopropane and corresponding telomers.
• 1,1,1-Trifluoro-3-chloro-3-bromopropane (whose boiling point is 91-92 ° C) is then purified by distillation.
• the recovered product is mixed with 1 mmol of tetrabutylammonium bromide and 25 cm 3 of a 20% aqueous solution of potassium hydroxide. The mixture is heated at 50 ° C for 24 hours.

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• 2017
  • 2017-11-23 FR FR1761090A patent/FR3073842B1/fr not_active Expired - Fee Related
• 2018
  • 2018-11-08 WO PCT/FR2018/052772 patent/WO2019102093A2/fr not_active Ceased
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