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Definitions

• the invention relates to a process for purifying 2,3,3,3-tetrafluoro-1-propene.
• the invention also relates to a process for producing and purifying 2,3,3,3-tetrafluoro-1-propene.
• Hydrofluorocarbons such as 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf)
• HFOs hydrofluoroolefins
• HFO-1234yf 2,3,3,3-tetrafluoro-1-propene
• hydrofluoroolefin manufacturing processes involve a fluorination and / or dehydrohalogenation reaction. These reactions are carried out in the gas phase and generate impurities which must therefore be eliminated to obtain the desired compound in a degree of purity sufficient for the intended applications.
• impurities are isomers of the main compounds intended to be obtained by the process for the production of 2,3,3,3-tetrafluoro-1-propene in addition to the latter, ie 2-chloro-3,3,3-trifluoro-1- propene (1233xf) and 1,1,1,2,2-pentafluoropropane (245cb).
• 2-chloro-3,3,3-trifluoro-1-propene (1233zd) 1,3,3,3-tetrafluoro-1-propene (1234ze) and 1,1, 1,3,3-pentafluoropropane (245fa)
• these can accumulate in the reactor and thus prevent the formation of the products of interest.
• EP 0 864 554 discloses a process for purifying a mixture comprising 1,1,1,3,3-pentafluoropropane (245fa) and 1-chloro-3,3,3-trifluoro-trans-1-propene (1233zd ) by distillation in the presence of a solvent having a boiling point higher than that of 1-chloro-3,3,3-trifluoro-trans-1-propene.
• WO 03/068716 discloses a process for recovering pentafluoroethane from a mixture comprising pentafluoroethane and chloropentafluoroethane by distillation in the presence of hexafluoropropene.
• WO 98/19982 also discloses a process for purifying 1,1-difluoroethane by extractive distillation.
• the method comprises contacting an extractant with a mixture of 1,1-difluoroethane and vinyl chloride.
• the extraction agent is chosen from hydrocarbons, alcohols and chlorocarbons having a boiling point of between 10 ° C. and 120 ° C.
• US2015 / 291490 also discloses a process for separating 2,3,3,3-tetrafluoro-1-propene and chloromethane (40).
• the choice of particular operating conditions may favor the presence of certain impurities or isomers thereof.
• impurities such as 1,3,3,3-tetrafluoro-1-propene (1234ze) can be observed just like that of 1-chloro-3,3,3-trifluoro-1-propene (1233zd), and 1,1,1,3,3-pentafluoropropane (245fa).
• impurities may arise from secondary reactions induced by intermediately produced compounds during the production of 2,3,3,3-tetrafluoro-1-propene, and may have physical properties such that their removal may be complex.
• the present invention allows the production of 2,3,3,3-tetrafluoro-1-propene with improved purity.
• the stream comprising 2,3,3,3-tetrafluoro-1-propene formed in step b) is recovered.
• This stream may be optionally purified to achieve a degree of purity suitable for particular commercial specifications.
• said first composition, said second composition and said third composition also comprise trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E); step c) being the recovery and separation of said third composition, preferably by distillation, to form on the one hand a stream comprising said organic extraction agent and on the other hand a stream comprising chloromethane (40) and trans -1,3,3,3-tetrafluoro-1-propene (1234ze-E).
• said organic extraction agent is a solvent selected from the group consisting of hydrocarbons, hydrohalocarbon, alcohol, ketone, amine, ester, ether, aldehyde, nitrile, carbonate, thioalkyl, amide and heterocycle; or the organic extractant is difluorodiethylsilane or triethylfluorosilane; preferably from the group consisting of ketone, amine, ester, ether, alcohol, heterocycle and aldehyde.
• said organic extraction agent may have a boiling point of between 10 and 150 ° C.
• PI represents the saturated vapor pressure of 2,3,3,3-tetrafluoro-1-propene
• Y2 s represents the coefficient of activity of chloromethane (40) in said organic infinite dilution extractant
• P2 represents the saturating vapor pressure of chloromethane (40);
• the separation factor is greater than or equal to 1.2, preferably greater than or equal to 1.4, more preferably greater than or equal to 1.6, in particular greater than or equal to 1.8, more particularly greater than or equal to 2.0.
• said organic extraction agent may be chosen so as to also have a separation factor and a particular absorption capacity with respect to the trans-1,3,3,3-tetrafluoroethylene.
• 1-propene (1234ze-E) This may make it possible to favor the separation between 2,3,3,3-tetrafluoro-1-propene (1234yf) and trans-1,1,3,3-tetrafluoro-1-propene (1234ze-E) if the latter is present in said first composition to be purified.
• PI represents the saturated vapor pressure of 2,3,3,3-tetrafluoro-1-propene
• s represents the activity coefficient of trans-1, 3,3,3-tetrafluoro-1-propene (1234
• P2 represents the saturated vapor pressure of trans-1, 3,3,3-tetrafluoro-1-propene (1234ze-E); advantageously, the separation factor is greater than or equal to 1.2, preferably greater than or equal to 1.4, more preferably greater than or equal to 1.6, in particular greater than or equal to 1.8, more particularly greater than or equal to at 2.0;
• said first composition is an azeotropic or quasi-azeotropic composition comprising 2,3,3,3-tetrafluoro-1-propene, chloromethane (40) and trans-1,3,3,3-tetrafluoroethylene.
• said organic extraction agent is chosen from the group consisting of methylformate, -methoxy-1-propene, ethoxy-ethene, propanone, methylacetate, isobutanal, isopropylformate, ethylacetate, butanone, n-propylformate, 1, 2- dimethoxyethane, isopropylacetate, 1-methoxy-2-propanamine, 2-methoxyethanamine, 2-methylbutanal, tert-butylacetate, ethylpropionate, dioxane, 3-pentanone, 2-pentanone, 2-methoxy-1propanamine, trimethoxymethane, 1,3- dioxane, 3,3-dimethyl-2-butanone, 2-ethoxyethanamine, sec-butylacetate, n-methyl-1,2-ethanediamine, 4-methyl-2-pentanone, 1,2-diaminoethane, butyronitrile
• the stream comprising 2,3,3,3-tetrafluoro-1-propene formed in step b) is recovered and is free of chloromethane (40).
• the term "Lacking" means that the stream comprising 2,3,3,3-tetrafluoro-1-propene comprises less than 50 ppm, advantageously less than 20 ppm, preferably less than 10 ppm of the compound in question on the basis of the total weight of the current .
• the method may also comprise, prior to step a), the steps:
• step ii distilling said composition of step i) to remove at the top of the column impurities having a boiling point below the boiling point of 2,3,3,3-tetrafluoro-1-propene and forming a first stream comprising 2,3,3,3-tetrafluoro-1-propene, chloromethane (40), and optionally or not heavy and / or trans-1,3,3,3-tetrafluoro-1-propene impurities (1234 E) recovered at the bottom of the distillation column; preferably distilling said composition of step i) to remove at the top of the column impurities having a boiling point below the boiling point of 2,3,3,3-tetrafluoro-1-propene and forming a first stream comprising 2,3,3,3-tetrafluoro-1-propene, chloromethane (40), trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E) and optionally or not heavy impurities, recovered bottom of distillation column;
• A) fluorination in the presence of a catalyst of a compound of formula CX (Y) 2-CX (Y) m -CH m XY (I) in which X and Y independently represent H, F, or Cl and m 0 or 1; and / or fluorination in the presence of a catalyst of a compound of formula (CX n Y 3-n) p CH Xi- X2 pCH m m (II) wherein X is independently of each other Cl, F, I or Br ; Y is independently of each other H, Cl, F, I or Br; n is 1, 2 or 3; and m is 0, 1 or 2; and p is 0 or 1;
• the organic extractant is selected from the group consisting of methylformate, ethoxy-ethene, propanone, methylacetate, isobutanal, isopropylformate, ethylacetate, butanone, isopropylacetate, 2-methoxyethanamine, tert -butylacetate, dioxane, 3-pentanone, 2-pentanone, 1,3-dioxane, 3,3-dimethyl-2-butanone, sec-butylacetate, 4-methyl-2-pentanone, 1,2-diaminoethane, 1-methoxy2 propanol, 1,2-propanediamine, diethylcarbonate, n-butylacetate, 2-methoxyl-propanol, 1-ethoxy-2-propanol, hexanal; preferably methylformate, propanone, butanone, isopropylacetate, 2-methoxyethanamine,
• said composition comprises between 75 and 99.99% by weight of 2,3,3,3-tetrafluoro-1-propene, between 0.01 and 25% by weight of trans-1,3, 3,3-tetrafluoro-1-propene (1234ze-E), and less than 1% by weight of chloromethane (40) based on the total weight of the composition.
• FIGS. 1a-c schematically represent a device implementing a process for purifying 2,3,3,3-tetrafluoro-1-propene according to a particular embodiment of the present invention.
• FIG. 2 diagrammatically represents a device implementing a process for producing 2,3,3,3-tetrafluoro-1-propene according to a particular embodiment of the present invention. Detailed description of the invention
• hydrocarbon refers to linear or branched compounds of C1-C20 alkane, C3-C20 cycloalkane, C2-C20 alkene, C3-C20 cycloalkene, C6-C18 arene.
• alkane refers to compounds of formula C n H2n + 2 in which n is from 1 to 20.
• C1-C20 alkane includes, for example, pentane, hexane, heptane, octane, nonane, decane or isomers thereof.
• C2-C20 alkene refers to hydrocarbon compounds comprising one or more carbon-carbon double bonds and comprising from 2 to 20 carbon atoms.
• C3-C20 cycloalkane refers to a saturated hydrocarbon ring having 3 to 20 carbon atoms.
• C 6 -C 18 aryl refers to cyclic and aromatic hydrocarbon compounds having from 6 to 18 carbon atoms.
• C3-C20 cycloalkene refers to cyclic hydrocarbon compounds comprising from 3 to 20 carbon atoms and comprising one or more carbon-carbon double bonds.
• alkyl denotes a monovalent radical derived from a linear or branched alkane comprising from 1 to 20 carbon atoms.
• cycloalkyl refers to a monovalent radical derived from a cycloalkane comprising from 3 to 20 carbon atoms.
• aryl denotes a monovalent radical derived from an arene comprising from 6 to 18 carbon atoms.
• alkenyl refers to a monovalent radical of 2 to 20 carbon atoms and at least one carbon-carbon double bond.
• alkynyl refers to a monovalent radical of 2 to 20 carbon atoms and at least one carbon-carbon triple bond.
• halogen refers to a group -F, -Cl, -Br or -I.
• cycloalkenyl refers to a monovalent radical derived from a cycloalkene having 3 to 20 carbon atoms.
• C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 cycloalkenyl, C6-C18 aryl substituents may or may not be substituted by one or more -OH substituents, halogen, -N a C (O) b , -C (O) NR a R b , -CN, -NO 2 , -NR a R b , -OR a , -SR a , -COR 2 R a , -OC (0) OR a , -OC (O) R a , -C (O) H, -C (O) R a in which R a and R b are independently of each other hydrogen, C 1 -C 6 alkyl, Unsubstituted C20, unsubstituted C 2 -C 20 alkenyl, unsubstituted
• hydrohalocarbons refers to compounds of the formula R a X wherein R a is selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-cycloalkenyl.
• R a is selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-cycloalkenyl.
• C20, C6-C18 aryl and X represents a chlorine, fluorine, bromine or iodine atom.
• the substituents C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 3 -C 20 cycloalkenyl and C 6 -C 18 aryl may or may not be substituted by one or more -OH substituents, halogen, -NR a C (O) R b , -C (O) NR a R b -CN, -N0 2 , -NR a R b , -OR a , - SR a, -C0 2 R a, -OC (0) OR a, -OC (0) R a, -C (0) H, -C (0) R a wherein R a and R b are as defined above.
• alcohol refers to hydrocarbons or hydrohalocarbons as defined above in which at least one hydrogen atom is replaced by a hydroxyl group -OH.
• ketone refers to hydrocarbons comprising at least one or more carbonyl functional groups R c -C (O) -R d in which R c and R d are independently of one another a C 1 -C 4 alkyl.
• amine refers to hydrocarbons comprising at least one or more amine -NR C R C functional groups in which R c and R d are as defined above, R c and R d being able to be linked together for form with the nitrogen atom to which they are attached an aromatic or non-aromatic heterocycle comprising from 4 to 10 members.
• esters refers to compounds of formula R c -C (O) -O-R d in which R c and R d are as defined above, R c and R d being able to be linked to each other for form with the ester group a ring comprising from 4 to 20 carbon atoms.
• ether refers to compounds of the formula R c -O-R d wherein R c and R d are as defined above, where R c and R d may be linked together to form with the atom oxygen to which they are attached a heterocycle comprising from 4 to 20 carbon atoms.
• nitrile refers to compounds comprising at least one or more functional groups -CN.
• carbonate refers to compounds of the formula R c -O-C (O) -O-R d wherein R c and R d are as defined above.
• thioalkyl relates to compounds of formula c S d wherein R c and R d are as defined above.
• amide relates to compounds of formula R c C (O) NR e R d wherein R c and R d are as defined above, R e being defined as R c ; R c and R d being bonded together to form with the amide group -C (O) N- to which they are attached a cyclic amide comprising from 4 to 10 members, preferably from 4 to 7 members.
• the cyclic amide may also include one or more carbon-carbon double bonds.
• the cyclic amide may also be substituted or unsubstituted by one or more substituents as defined above.
• heterocycle refers to a carbon ring comprising from 4 to 10 members, at least one of which is a heteroatom selected from the group consisting of O, S, P and N.
• the heterocycle may comprise one or more carbon-carbon double bonds. carbon or one or more carbon-heteroatom double bonds or one or more heteroatom-heteroatom double bonds.
• the heterocycle may comprise 1, 2, 3, 4 or 5 heteroatoms as defined above.
• the heterocycle may comprise 1, 2 or 3 heteroatoms selected from oxygen, nitrogen or sulfur.
• the heterocycle may be a 4- to 6-membered carbon ring of which 1, 2 or 3 members are heteroatoms selected from O or N.
• the heterocycle may or may not be substituted by one or more substituents selected from -OH , halogen, -NR a C (O) R b , -C (O) NR a R b -CN, -NO 2 , -NR a R b , -OR a , -SR a , -CO 2 R a , - OC (O) OR a , -OC (O) R a , -C (O) H, -C (O) R a in which R a and R b are as defined above.
• azeotropic composition denotes a liquid mixture of two or more compounds that behaves as a single substance, and boils at a fixed temperature, keeping a liquid phase composition identical to that of the gas phase.
• azeotropic composition refers to a liquid mixture of two or more compounds having a constant boiling point or which tends not to split when boiled or evap- orated.
• organic extractant refers to a compound having at least one carbon atom.
• the invention relates to a process for purifying 2,3,3,3-tetrafluoro-1-propene (1234yf).
• the purification process is carried out from a first composition comprising 2,3,3,3-tetrafluoro-1-propene and chloromethane (40).
• said method comprises the steps of:
• the stream comprising said organic extraction agent is recycled in step a) of the present process.
• said first composition may comprise trans-1,1,3,3-tetrafluoro-1-propene (1234ze-E).
• said second composition may comprise trans-1,1,3,3-tetrafluoro-1-propene (1234ze-E).
• Said third composition may thus comprise trans-1,1,3,3-tetrafluoro-1-propene (1234ze-E).
• step c) of the present process may consist in the recovery and separation of said third composition, preferably by distillation, to form on the one hand a stream comprising said organic extraction agent and on the other hand a current including chloromethane (40) and trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E).
• the present process may be a process for purifying 2,3,3,3-tetrafluoro-1-propene (1234yf) from a first composition comprising 2,3,3,3-tetrafluoro-1-propene, chloromethane (40) and trans-1,33,3-tetrafluoro-1-propene (1234ze-E), said process comprising the steps of:
• Said first composition may comprise between 75 and 99.99% by weight of 2,3,3,3-tetrafluoro-1-propene on the basis of the total weight of the first composition, advantageously between 80 and 99.9% by weight, of preferably between 85 and 99.8% and in particular between 90 and 99.5% by weight of 2,3,3,3-tetrafluoro-1-propene on the basis of the total weight of the first composition.
• said first composition may comprise less than 1% by weight of chloromethane (40) based on the total weight of the first composition, preferably between 1 and 5000 ppm by weight, preferably between 1 and 2000 ppm and in particular between 10 and 1500 ppm by weight of chloromethane (40) based on the total weight of the first composition.
• said first composition may comprise between 0.01 and 25% by weight of trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E) based on the total weight of the first composition preferably between 0.1 and 20% by weight, preferably between 0.2 and 15% by weight, in particular between 0.5 and 10% by weight, more particularly between 3 and 10% by weight of trans-1, 3,3,3- tetrafluoro-1-propene (1234ze-E) based on the total weight of the first composition.
• said organic extraction agent may be a solvent selected from the group consisting of hydrocarbons, hydrohalocarbon, alcohol, ketone, amine, ester, ether, aldehyde, nitrile, carbonate, thioalkyl, amide and heterocycle.
• the organic extractant may be difluorodiethylsilane or triethylfluorosilane.
• said organic extractant may be selected from the group consisting of ketone, amine, ester, ether, alcohol, heterocycle and aldehyde.
• the heterocycle may be a 4- to 6-membered carbon ring of which 1, 2 or 3 members are heteroatoms selected from O or N, preferably O.
• the hydrocarbons are selected from the group consisting of 2,2-dimethylbutane, 3-methylpentane, 2,4-dimethylpentane, cyclohexane, cyclohexene, methylcyclohexane, 2,4,4-trimethyl-1-pentene, 2,2, 4-trimethyl-2-pentene, 1- methylcyclohexene, toluene, 2,3-dimethylhexane, ethylcyclohexane, ethylbenzene, 1,4-dimethylbenzene, 1,3-dimethylbenzene, 1,2,3-trimethylcyclohexane, 1,2-dimethylbenzene, styrene.
• the hydrohalocarbons are selected from the group consisting of chloroethane, bromofluoromethane, 1-bromo-1,2-difluoroethylene, trichlorofluoromethane, 1-chloro-1,1-difluoropropane, 1,1,1-trifluoro-2-bromoethane, 1,1-Dichloro-2,2,2-trifluoroethane, 1,2-dichloro-1,1,2-trifluoroethane, 1,1-dichloroethylene, 2-chloro-2-fluoropropane, 1-chloro-2,2- difluoroethane, 2-chloropropane, bromoethane, 2-chloro-1,1,1,3,3-pentafluoropropane, 1-chloro-1,2,2-trifluoropropane, iodomethane, 3-chloropropene, 3-chloro-1, 1, 1-Trifluoropropane, 1,1,1-t
• (dimethylamino) ethanol 3-hexanol, 2-hexanol, 2-ethoxy-1-propanol, 3,3,4,4,5,5,6,6-octafluoro-1-pentanol, 2,3-dimethylbutanol, 2-ethyl-1-butanol, 2-methyl-1-pentanol, 2-propoxyethanol, 1-propoxy-2-propanol, 2-aminophenol.
• the ketones are selected from the group consisting of propanone, butanone, 3-pentanone, 2-pentanone, 3,3-dimethyl-2-butanone, 4-methyl-2-pentanone, 2-hexanone, 5-hexenone and the like. 2-one, 4-methyl-2-hexanone.
• the amines are selected from the group consisting of ethylamine, isopropylamine, ethylmethylamine, 2-amino-2-methylpropane, n-propylamine, isopropylmethylamine, diethylamine, 2-butanamine, n-methylpropylamine, 1-butylamine, diisopropylamine, 3- methyl-2-butanamine, 3-pentylamine, n-methylbutylamine, 1-methoxy-2-propanamine, 2-methoxyethanamine, 2-methoxy-1propanamine, n-pentylamine, n-methylhydroxylamine, dipropylamine, 2-ethoxyethanamine, n-methyl- 1,2-ethanediamine, pyridine, 1,2-diaminoethane, 1,2-propanediamine, 2-ethylbutylamine, n-ethylethylenediamine, 1,1-diethoxy-n, n-dimethylmethan
• the esters are selected from the group consisting of methylformate, methylacetate, isopropylformate, ethylacetate, n-propylformate, isopropylacetate, tert-butylacetate, ethylpropionate, sec-butylacetate, diethylcarbonate, n-butylacetate, bromoaceticacidmethylester, methylhexanoate.
• the ethers are selected from the group consisting of 2,2,2-trifluoroethylmethylether, 1,1,2,2-tetrafluoroethylmethylether, 2-methoxy-1-propene, diethylether, ethoxyethene, dimethoxymethane, methylcyclopropylether, 2- ethoxy-propane, methyl-t-butylether, ethyll, 1,2,2-tetrafluoroethylether, chloromethoxymethane, diisopropylether, 2-ethoxy-2-methylpropane, 2-ethoxy-butane, 1-methoxy-2-methylbutane,
• the aldehydes are selected from the group consisting of acetaldehyde, ethanedial, isobutanal, methylglyoxal, 2-methylbutanal, 2,6-dimethyl-5-heptenal, hexanal.
• the carbonate is diethylcarbonate.
• the amide is ethanethioamide.
• the thioalkyls are selected from the group consisting of ethanethiol, dimethylsulfide, 2-propanetiol, 4-methoxy-2-methyl-2-butanethiol, tert-butylthiol, 1-propanethiol, thiophene, 2-butanethiol, 2-methyl- 1-propanethiol, diethylsulfide, butanethiol, 3, mercapto-1,2-propanediol, tetrahydrothiophene, 1-pentanethiol.
• the heterocycles are selected from the group consisting of furan, 1,2-epoxypropane, dioxane, 1,3-dioxane, piperidine, 1,3,5-trioxane, n-methylmorpholine, 2-methylpyrazine, 1-methylpiperazine, n-ethyl-morpholine, 2,6-dimethylmorpholine, 3-furfural.
• Said organic extraction agent may be chloroethane, ethylamine, bromofluoromethane, 1-bromo-1,2-difluoroethylene, acetaldehyde, trichlorofluoromethane, 1-chloro-1,1-difluoropropane, 1,1,1-trifluoro-2-bromoethane, 1,1-Dichloro-2,2,2-trifluoroethane, 1,2-dichloro-1,1,2-trifluoroethane, 2,2,2-trifluoroethylmethylether, 1,1-dichloroethylene, furan, methylformate, isopropylamine, 1, 1,2,2-tetrafluoroethylmethylether, 2-methoxy-1-propene, diethylether, 1,2-epoxypropane, ethanethiol, 2-chloro-2-fluoropropane, ethoxyethene, 1-chloro-2,2-difluor
• said organic extraction agent may be chloroethane, ethylamine, bromofluoromethane, 1-bromo-1,2-difluoroethylene, acetaldehyde, 1-chloro-1,1-difluoropropane, 1,1,1-trifluoro-2-bromoethane, 1,1-Dichloro-2,2,2-trifluoroethane, 1,2-dichloro-1,1,2-trifluoroethane, furan, methylformate, isopropylamine, 2-methoxy-1-propene, diethyl ether, 1,2-epoxypropane, andhanethiol, 2-chloro-2-fluoropropane, ethoxy-ethene, 1-chloro-2,2-difluoroethane, dimethylsulfide, 2-chloropropane, bromoethane, dimethoxymethane, 1-chloro-1,2,2-trifluoropropan
• said organic extraction agent can be acetaldehyde, methylformate, 2-methoxy-1-propene, 1,2-epoxypropane, ethoxy-ethene, dimethoxymethane, 1-chloro-1,2,2-trifluoropropane, 3-chloro 1,1,1-Trifluoropropane, ethanedial, 1-chloro-1,2,2,3-tetrafluoropropane, 3-chloro-1,1,1,3-tetrafluoropropane, 2-chloro-1,1,1,3 tetrafluoropropane, propanone, methylacetate, 4-methoxy-2-methyl-2-butanethiol, difluorodiethylsilane, isobutanal, isopropylformate, methylglyoxal, 2,3-dichloro-1,1,1-trifluoropropane, ethylacetate, butanone, n-propylformat
• said organic extraction agent may be methylformate, methoxy-1-propene, ethoxy-ethene, propanone, methylacetate, isobutanal, isopropylformate, ethylacetate, butanone, n-propylformate, 1,2-dimethoxyethane, isopropylacetate, methoxy-2-propanamine, 2-methoxyethanamine, 2-methylbutanal, tert-butylacetate, ethylpropionate, dioxane, 3-pentanone, 2-pentanone, 2-methoxy-1propanamine, trimethoxymethane, 1,3-dioxane, 3,3-dimethyl- 2-butanone, 2-ethoxyethanamine, sec-butylacetate, n-methyl-1,2-ethanediamine, 4-methyl-2-pentanone, 1,2-diaminoethane, butyronitrile, 1-methoxy-2-propanol,
• the organic extractant can be methylformate, ethoxy-ethene, propanone, methylacetate, isobutanal, isopropylformate, ethylacetate, butanone, isopropylacetate, 2-methoxyethanamine , tert-butylacetate, dioxane, 3-pentanone, 2-pentanone, 1,3-dioxane, 3,3-dimethyl-2-butanone, sec-butylacetate, 4-methyl-2-pentanone, 1,2-diaminoethane, 1 - methoxy-2-propanol, 1,2-propanediamine, diethylcarbonate, n-but
• chloromethane and trans-1,3,3,3-tetrafluoro-1-propene can be separated from 2,3,3,3-tetrafluoro-1-propene.
• the organic extraction agent to be used may be selected depending on the compounds present in said first composition.
• the organic extractant can be selected depending on the separation factor and the absorption capacity established for a particular composition.
• the choice of the organic extraction agent may optionally be based on other commercial or environmental criteria, such as, for example, the cost of the organic extraction agent, its availability on the market, its toxic or flammable properties.
• the boiling point of the organic extractant may be from 10 ° C to 200 ° C, preferably from 10 ° C to 190 ° C, preferably from 10 ° C to 180 ° C, in particular 10 ° C C at 170 ° C, more preferably from 10 ° C to 160 ° C, and preferably from 10 ° C to 150 ° C.
• PI represents the saturated vapor pressure of 2,3,3,3-tetrafluoro-1-propene
• Y2 the activity coefficient of chloromethane (40)
• P2 represents the saturating vapor pressure of chloromethane (40).
• Said separation factor calculated for a 2,3,3,3-tetrafluoro-1-propene / chloromethane pair as detailed above, may be greater than or equal to 1.2, advantageously greater than or equal to 1.4, more preferably greater than or equal to 1.6, preferably greater than or equal to 1.8, more preferably greater than or equal to 2.0.
• the absorption capacity C2, s calculated for a 2,3,3,3-tetrafluoro-1-propene / chloromethane pair as detailed above, is greater than or equal to 0.40, preferably greater than or equal to 0.40. equal to 0.60, more preferably greater than or equal to 0.60, in particular greater than or equal to 1.0, more particularly greater than or equal to 1.1, more preferably greater than or equal to 1.2.
• said organic extraction agent may have a separation factor Si, 2 greater than 1.1, advantageously greater than or equal to 1.2 , preferably greater than or equal to 1.4, more preferably greater than or equal to 1.6, in particular greater than or equal to 1.8 and more particularly greater than or equal to 2.0; and an absorption capacity C2, s greater than or equal to 0.20, advantageously greater than or equal to 0.40, preferably greater than or equal to 0.60, more preferably greater than or equal to 0.80, in particular greater than or equal to 0.80, equal to 1.0, more preferably greater than or equal to 1.1, preferably greater than or equal to 1.2.
• said organic extraction agent when the composition contains trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E), said organic extraction agent can be selected so as to also have a factor of particular separation from trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E).
• PI represents the saturated vapor pressure of 2,3,3,3-tetrafluoro-1-propene
• s represents the activity coefficient of trans-1, 3,3,3-tetrafluoro-1-propene (1234
• P2 represents the saturated vapor pressure of trans-1, 3,3,3-tetrafluoro-1-propene
• the separation factor Si, 2 may be greater than or equal to 1.1, advantageously greater than or equal to 1.2, preferably greater than or equal to 1.4, more preferably greater than or equal to 1.6, in particular greater than or equal to 1.8, more particularly greater than or equal to 2.0.
• the absorption capacity C2, s is greater than or equal to 0.40, preferably greater than or equal to 0.60, more preferably greater than or equal to 0.60, in particular greater than or equal to 0.80, plus particularly greater than or equal to 0.9, preferably greater than or equal to 1.0.
• Said first composition may be an azeotropic or quasi-azeotropic composition comprising 2,3,3,3-tetrafluoro-1-propene, chloromethane (40) and optionally non-trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E).
• said first composition is an azeotropic or quasi-azeotropic composition comprising 2,3,3,3-tetrafluoro-1-propene, chloromethane (40) and trans-1,3,3,3-tetrafluoro-1-propene ( 1234ze-E).
• the content of each of the compounds in this particular composition is as expressed above with reference to the individual contents of each of the compounds.
• the second composition may comprise 2,3,3,3-tetrafluoro-1-propene, chloromethane (40), said organic extraction agent, and optionally or non-trans-1,3,3,3-tetrafluoro-1 -propene (1234ze-E).
• the second composition may comprise 2,3,3,3-tetrafluoro-1-propene, chloromethane (40), said organic extractant, and trans-1,1,3,3-tetrafluoro-1-propene (1234ze-E).
• said organic extraction agent can have:
• said organic extractant may have a separation factor greater than or equal to 1.2, preferably greater than or equal to 1.4, more preferably greater than or equal to 1.6, in particular greater than or equal to 1.8, more particularly greater than or equal to 2.0 ;
• said organic extraction agent may be selected so as to have a separation factor greater than or equal to 1.2 and so as to have an absorption capacity greater than or equal to 0.4 for the two binary pairs 2 , 3,3,3-tetrafluoro-1-propene / trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E) and 2,3,3,3-tetrafluoro-1-propene / chloromethane ( 40).
• said organic extractant can be selected from the group consisting of chloroethane, ethylamine, bromofluoromethane, 1-bromo-1,2-difluoroethylene, acetaldehyde, 1-chloro-1,1-difluoropropane, 1,1,1-trifluoro -2-bromoethane, 1,1-dichloro-2,2,2-trifluoroethane, 1,2-dichloro-1,1,2-trifluoroethane, furan, methylformate, isopropylamine, 2-methoxy-1-propene, diethyl ether, 1 , 2-epoxypropane, ethanethiol, 2-chloro-2-fluoropropane, ethoxy-ethene, 1-chloro-2,2-difluoroethane, dimethylsulfide, 2-chloropropane, bromoethane, dimethoxymethane, 1-chloro-1
• said organic extraction agent may be selected so as to have a separation factor greater than or equal to 1.4 and so as to have an absorption capacity greater than or equal to 0.6 for the two binary pairs 2 , 3,3,3-tetrafluoro-1-propene / trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E) and 2,3,3,3-tetrafluoro-1-propene / chloromethane ( 40).
• said organic extraction agent may be selected so as to have a separation factor greater than or equal to 1.6 and so as to have an absorption capacity greater than or equal to 0.8 for the two binary pairs 2 , 3,3,3-tetrafluoro-1-propene / trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E) and 2,3,3,3-tetrafluoro-1-propene / chloromethane ( 40).
• said organic extraction agent may be selected from the group consisting of methylformate, methoxy-1-propene, ethoxy-ethene, propanone, methylacetate, isobutanal, isopropylformate, ethylacetate, butanone, n-propylformate, 1,2-dimethoxyethane, isopropylacetate 1-methoxy-2-propanamine, 2-methoxyethanamine, 2-methylbutanal, tert-butylacetate, ethylpropionate, dioxane, 3-pentanone, 2-pentanone, 2-methoxy-1propanamine, trimethoxymethane, 1,3-dioxane, 3,3 -dimethyl-2-butanone, 2-ethoxyethanamine, sec-butylacetate, n-methyl-1,2-ethanediamine, 4-methyl-2-pentanone, 1,2-diaminoethane, butyronitrile, 1-methoxy-2
• said organic extractant may be methylformate, ethoxyethene, propanone, methylacetate, isobutanal, isopropylformate, ethylacetate, butanone, isopropylacetate, 2-methoxyethanamine, tert-butylacetate, dioxane, 3-pentanone, 2-pentanone, , 3-dioxane, 3,3-dimethyl-2-butanone, sec-butylacetate, 4-methyl-2-pentanone, 1,2-diaminoethane, 1-methoxy-2-propanol, 1,2-propanediamine, diethylcarbonate, n butylacetate, 2-methoxyl-propanol, 1-ethoxy-2-propanol, hexanal.
• said organic extraction agent may be methylformate, propanone, butanone, isopropylacetate, 2-methoxyethanamine, tert-butylacetate, dioxane, 1,3-dioxane, sec-butylacetate, 1,2-diaminoethane, 1-methoxy-2-propanol 1,2-propanediamine, n-butylacetate, 2-methoxyl-propanol, 1-ethoxy-2-propanol, hexanal.
• the stream comprising 2,3,3,3-tetrafluoropropene separated in step b) of the present process is subsequently purified or liquefied and stored.
• traces of organic extractant may be present in the stream comprising 2,3,3,3-tetrafluoropropene.
• the traces of organic extraction agent in said stream are less than 10 ppm, preferably less than 1 ppm, in particular less than 500 ppb, more particularly less than 100 ppb.
• the present process thus makes it possible to purify 2,3,3,3-tetrafluoro-1-propene.
• the content of chloromethane (40) and / or trans-1, 3,3,3-tetrafluoro-1-propene (1234ze-E) in the stream comprising 2,3,3,3-tetrafluoro-1-propene , obtained in step b) of the present purification process is less than the content thereof or thereof in said first composition.
• the content of chloromethane (40) and trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E) in the stream comprising 2,3,3,3-tetrafluoro-1-propene, obtained in step b) of the present purification process is less than their respective content in said first composition.
• the content of chloromethane (40) and / or trans-1,,3,3-tetrafluoro-1-propene (1234ze-E) can be reduced by 50%, advantageously by 75%, preferably by 90% in particular 95%, more particularly 98%.
• the stream comprising 2,3,3,3-tetrafluoro-1-propene obtained in step b) of the present purification process may be free of chloromethane (40) and / or trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E) when this or these are present in said first composition.
• the stream comprising 2,3,3,3-tetrafluoro-1-propene obtained in stage b) of the present purification process may be free of chloromethane (40) and the content of trans-1,3 3,3-tetrafluoro-1-propene (1234ze-E) can be reduced by 50%, advantageously by 75%, preferably 90%, in particular by 95%, more particularly by 98%.
• the contents are expressed in percentage by weight.
• said first composition implemented in step a) of the present process can be previously purified before being used. Indeed, if said first composition comprises impurities having a boiling point below the boiling point of 2,3,3,3-tetrafluoro-1-propene and optionally heavy impurities, the present process may comprise prior to step a) the steps:
• composition comprising 2,3,3,3-tetrafluoro-1-propene, impurities having a boiling point below the boiling point of 2,3,3,3- tetrafluoro-1-propene, and chloromethane (40) and optionally or non-trans-1,,3,3-tetrafluoro-1-propene (1234ze-E), and optionally or not heavy impurities;
• step ii distilling said composition of step i) to remove at the top of the column impurities having a boiling point below the boiling point of 2,3,3,3-tetrafluoro-1-propene and forming a first stream comprising 2,3,3,3-tetrafluoro-1-propene, chloromethane (40) and optionally or non-trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E), and optionally or not heavy impurities recovered at the bottom of the distillation column;
• the present method may comprise, before step a) the steps:
• composition comprising 2,3,3,3-tetrafluoro-1-propene, impurities having a boiling point below the boiling point of 2,3,3,3- tetrafluoro-1-propene, and chloromethane (40) and trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E), and optionally or not heavy impurities;
• step ii distilling said composition of step i) to remove at the top of the column impurities having a boiling point below the boiling point of 2,3,3,3-tetrafluoro-1-propene and forming a first stream comprising 2,3,3,3-tetrafluoro-1-propene, chloromethane (40) and trans-1,,3,3,3-tetrafluoro-1-propene (1234ze-E), and optionally or not heavy impurities recovered at the bottom of the distillation column;
• said first stream recovered in step ii ') or said second stream recovered in step iii') corresponds to said first composition implemented in step a).
• Said impurities having a boiling point below the boiling point of 2,3,3,3-tetrafluoro-1-propene may be trifluoromethane (F23), monofluoromethane (F41), difluoromethane (F32), pentafluoroethane (F125), 1,1,1-trifluoroethane (F143a), trifluoropropyne or 1-chloro-pentafluoroethane (F115).
• Heavy impurities may contain, for example, 1,1,1,3,3,3-hexafluoropropane (236fa), 1,1,1,2,3,3-hexafluoropropane (236ea), 1,1,1,2,3 , 3,3-heptafluoropropane (227ca), cis-1,3,3,3-tetrafluoro-1-propene (1234ze-Z), dimers or trimers derived from any of the compounds present in the composition or the current Considered, for example, C4 or C5 hydrocarbons such as hexafluorobutene (1336), heptafluorobutene (1327), octafluorobutane (338), nonafluoropentene (1429), heptafluoropentene (1447).
• C4 or C5 hydrocarbons such as hexafluorobutene (1336), heptafluorobutene (1327), octafluorobutane
• the present invention provides a process for producing 2,3,3,3-tetrafluoro-1-propene.
• this process may include its purification. So, the The present invention provides a process for producing 2,3,3,3-tetrafluoro-1-propene comprising the steps of:
• A) fluorination in the presence of a catalyst of a compound of the formula CX (Y) 2-CX (Y) m -CHmXY (I) wherein X and Y are independently H, F, or Cl and m 0 or 1 ; and / or fluorination in the presence of a catalyst of a compound of formula (CX n Y 3-n) p CH Xi- X2 pCH m m (II) wherein X is independently of each other Cl, F, I or Br ; Y is independently of each other H, Cl, F, I or Br; n is 1, 2 or 3; and m is 0, 1 or 2; and p is 0 or 1;
• the process for producing 2,3,3,3-tetrafluoro-1-propene comprising the steps of:
• a third composition comprising said organic extraction agent and chloromethane (40) and optionally or non-trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E); and
• A) fluorination in the presence of a catalyst of a compound of the formula CX (Y) 2-CX (Y) m -CHmXY (I) wherein X and Y are independently H, F, or Cl and m 0 or 1 ; and / or fluorination in the presence of a catalyst of a compound of formula (CX n Y 3-n) p CH Xi- X2 pCH m m (II) wherein X is independently of each other Cl, F, I or Br ; Y is independently of each other H, Cl, F, I or Br; n is 1, 2 or 3; and m is 0, 1 or 2; and p is 0 or 1;
• the stream recovered in stage B) of the process for producing 2,3,3,3-tetrafluoro-1-propene may comprise hydrofluoric acid.
• the stream recovered in step B) prior to step C), can be pre-distilled () to remove HF at the bottom of the distillation column.
• a stream comprising 2,3,3,3-tetrafluoro-1-propene, chloromethane (40) and optionally non-trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E) is recovered at the top.
• distillation column preferably a stream comprising 2,3,3,3-tetrafluoro-1-propene, chloromethane (40) and trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E).
• This latter stream recovered at the top of the distillation column is then subjected to stage C) of the process for producing 2,3,3,3-tetrafluoro-1-propene.
• the stream recovered in stage B) from the process for producing 2,3,3,3-tetrafluoro-1-propene may comprise impurities having a boiling point below the boiling point 2,3,3,3-tetrafluoro-1-propene.
• the stream recovered in stage B) prior to step C), can be subjected to preliminary distillation B2 '), which may or may not be subsequent to stage ⁇ ), in order to eliminate the said impurities at the top of the distillation column.
• the first stream comprises 2,3,3,3-tetrafluoro-1-propene, chloromethane (40) and trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E).
• This latter stream recovered at the top of the distillation column is then subjected to stage C) of the process for producing 2,3,3,3-tetrafluoro-1-propene.
• the stream recovered in stage B) of the process for producing 2,3,3,3-tetrafluoro-1-propene may also comprise HCl.
• Hydrochloric acid can be recovered by distillation before or after step ⁇ independently of the other steps of the process.
• Step A) is carried out from 1,1,2,3-tetrachloropropene, 2,3,3,3-tetrachloropropene, 1,1,3,3-tetrachloropropene, 1,3 , 3,3-tetrachloropropene, 1,1,1,2,3-pentachloropropane, 1,1,1,3,3-pentachloropropane, 1,1,2,2,3-pentachloropropane, 1,2 -dichloro-3,3,3-trifluoropropane, 2-chloro-2,3,3,3-tetrafluoropropane, 1,1,1,2,2-pentafluoropropane, 1-chloro-1,3,3, 3-tetrafluoropropane and 1,1,1,3,3-pentafluoropropane, preferably from 1,1,1,2,3-pentachloropropane, 1,1,2,3,3-tetrachloropropene, of 1,1,1 2,2-pentafluoropropane
• the mixture comprises, in this particular embodiment, 2,3,3,3-tetrafluoro-1-propene, chloromethane and trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E), impurities having a boiling point below the boiling point of 2,3,3,3-tetrafluoro-1-propene and heavy impurities.
• the mixture is transferred to a distillation column 2 via line 3.
• the impurities having a boiling point below the boiling point of 2,3,3,3-tetrafluoro-1-propene are recovered at the top of the column. 2 and conveyed via line 5 to an incinerator or a purification device 15.
• distillation carried out in 6 aims to separate heavy impurities of the other constituents of the mixture.
• the distillation operating conditions are therefore suitable for this purpose.
• the heavy impurities are recovered at the bottom of the distillation column 8 and the other constituents are recovered at the top of the distillation column and conveyed to the extractive distillation column 9 via the line 7.
• the extractive distillation carried out at 9 is intended to separate the 2, 3,3,3-tetrafluoro-1-propene of the other components of the mixture mentioned above.
• the extractive distillation device 9 is fed with the organic extraction agent 17 selected according to the method described in the present application.
• the 2,3,3,3-tetrafluoro-1-propene is recovered at the top of the extractive distillation device 9 to be stored or purified via line 11.
• the mixture recovered at the bottom of the extractive distillation device 9 comprises in particular the organic extraction agent 17, chloromethane (40) and trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E).
• the mixture recovered at the bottom of the extractive distillation device 9 is conveyed via line 12 to a distillation device 13 intended to separate the organic extraction agent from the other compounds present.
• the organic extraction agent is recovered at the bottom of distillation device 13 and recycled via line 16 to the extractive distillation device 9.
• the compounds recovered at the top of distillation device 13 are conveyed via line 14 to line 5 to be cremated or purified in 15.
• Fig. 2 schematically illustrates a device implementing a process for producing 2,3,3,3-tetrafluoropropene according to a particular embodiment of the present invention.
• the hydrofluoric acid 21 is brought into contact with 1,1,1,2,3-pentachloropropane (240db) 22 in a reactor 23.
• the mixture obtained in particular comprising 2,3,3,3-tetrafluoro-1-propene , chloromethane (40) and trans-1, 3,3,3-tetrafluoro-1-propene (1234ze-E), is recovered at the reactor outlet and sent to a distillation column 25 via line 24.
• the mixture can also be include HCl, HF and heavy or lower boiling impurities than 2,3,3,3-tetrafluoro-1-propene.
• the stream obtained at the bottom of the distillation column comprising HF and optionally heavy impurities is conveyed to the purification device 27 via the conduit 26 to purify HF which will be recycled optionally to 23.
• the other constituents of the mixture are conveyed via the conduit 28 to a Purification device 29 for purifying 2,3,3,3-tetrafluoro-1-propene.
• the purification device 29 may be any of the devices illustrated in FIGS. la-lb.
• the catalyst used in the present process for producing 2,3,3,3-tetrafluoropropene may for example be based on a metal comprising a transition metal oxide or a derivative or a halide or an oxyhalide of such a metal.
• a metal comprising a transition metal oxide or a derivative or a halide or an oxyhalide of such a metal.
• FeCU chromium oxyfluoride
• chromium oxides possibly subjected to fluorination treatments
• chromium fluorides and mixtures thereof may be mentioned.
• Other possible catalysts are carbon-supported catalysts, antimony catalysts, aluminum catalysts (eg AlF 3 and Al 2 O 3, alumina oxyfluoride and alumina fluoride).
• the catalyst is more preferably based on chromium and it is more particularly a mixed catalyst comprising chromium.
• a mixed catalyst comprising chromium and nickel is used.
• the molar ratio Cr / Ni (based on the metal element) is generally 0.5 to 5, for example 0.7 to 2, for example about 1.
• the catalyst may contain from 0.5 to 20% by weight of nickel.
• the metal may be present in metallic form or in the form of a derivative, for example an oxide, halide or oxyhalide. These derivatives are preferably obtained by activation of the catalytic metal.
• the support is preferably made of aluminum, for example alumina, activated alumina or aluminum derivatives, such as aluminum halides and aluminum oxyhalides, for example described in US 4,902,838, or obtained by the activation method described above.
• the catalyst may comprise chromium and nickel in an activated or non-activated form, on a support which has been subjected to activation or not.
• Another preferred embodiment is based on a chromium-containing mixed catalyst and at least one element selected from Mg and Zn.
• the atomic ratio of Mg or Zn / Cr is preferably from 0.01 to 5.
• the catalyst Prior to use, the catalyst is preferably activated with air, oxygen or chlorine and / or with HF.
• the catalyst is preferably subjected to activation with air or oxygen and HF at a temperature of 100 to 500 ° C, preferably 250 to 500 ° C and more preferably 300 to 400 ° C. ° C.
• the activation time is preferably from 1 to 200 hours and more particularly from 1 to 50 hours.
• This activation may be followed by a final fluorination activation step in the presence of an oxidizing agent, HF and organic compounds.
• the molar ratio of HF / organic compounds is preferably from 2 to 40 and the molar ratio of oxidation agent / organic compounds is preferably from 0.04 to 25.
• the temperature of the final activation is preferably from 300 to 400 ° C. C and its duration preferably from 6 to 100 h.
• the fluorination reaction in the gas phase can be carried out:
• contact time 3 to 100 seconds, preferably 4 to 75 seconds and more particularly 5 to 50 seconds (volume of catalyst divided by the total incoming flow, adjusted to the temperature and to the operating pressure);
• the duration of the reaction step is typically from 10 to 8000 hours, preferably from 50 to 5000 hours and more preferably from 70 to 1000 hours.
• An oxidizing agent preferably oxygen
• oxygen may optionally be added during the fluorination reaction.
• the oxygen / organic compounds molar ratio may be from 0.005 to 2, preferably from 0.01 to 1.5.
• the oxygen can be introduced pure or in the form of air or oxygen / nitrogen mixture. Oxygen can also be replaced by chlorine.
• yi s represents the activity coefficient of the first compound 1 in the organic extraction agent considered at infinite dilution
• PI represents the saturated vapor pressure of the first compound
• s represents the coefficient of activity of the second compound 2 of the binary pair in the organic extraction agent considered at infinite dilution
• P2 represents the saturating vapor pressure of the second compound.
• An absorption capacity is also calculated for each of the solvents studied and for a binary pair (1,2) considered.
• the binary pair 2,3,3,3-tetrafluoro-1-propene / chloromethane (40) and the binary pair 2,3,3,3- tetrafluoro-1-propene / trans-1,3,3,3- tetrafluoro-1-propene (1234ze-E) are considered to select the organic extraction agent.
• the solvents listed in Table 1 below were tested for the extractive distillation of a mixture comprising 2,3,3,3-tetrafluoro-1-propene, chloromethane (40) and trans-1,33,3-tetrafluoro-1-propene (1234ze-E).
• Extractive distillations carried out with the organic extraction agents listed in Table 1 above resulted in the separation between on the one hand 2,3,3,3-tetrafluoro-1-propene and on the other hand the chloromethane (40), trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E) and the organic extractant.
• the chloromethane (40) and trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E) remains in solution in the organic extraction agent. The latter was recovered by distillation and thus separated from chloromethane (40) and trans-1,3,3,3-tetrafluoro-1-propene (1234ze-E).

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• 2015
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