Process for the recovery and separation of unsaturated fluorinated hydrocarbons

Description

Technical field of the invention

[0001] The present invention relates to a process for recovering and separating unsaturated fluorinated hydrocarbons. In particular, the present invention relates to a process for recovering and separating unsaturated fluorinated hydrocarbons contained in insulating foams. Technological background of the invention

[0002] The disposal or recycling of refrigerators involves the removal of bulky waste and its delivery to specific reprocessing plants. The scrapping of this type of device is known in particular from DE2850130. This involves in particular crushing the different elements, their separation and then recycling the different materials if possible. Foam recycling processes with recovery of blowing agents are described in documents EP 0 392 760 A2, WO 93 / 22077 A1, US 2006 / 200964 A1, EP 0 514 106 A2, WO 02 / 02209 A2, EP 0 636 429 A2 and CN 106 807 723 A.

[0003] Refrigerators contain insulating foams, generally made from a polyurethane-based polymer. These foams also contain blowing agents. The blowing agent compositions used include hydrohalocarbons. As legislation surrounding hydrohalocarbon derivatives has evolved over time, devices containing insulating foams may contain CFCs (chlorofluorocarbons), HFCs (hydrofluorocarbons), or HFOs (hydrofluoroolefins). Indeed, hydrofluoroolefins are attracting attention because they offer promising behavior with low global warming potential. There is therefore a need to treat and recycle devices containing insulating foams containing new generations of blowing agents, but also a need to treat and recycle devices containing insulating foams regardless of the generation of blowing agents used. Summary of the invention

[0004] The present invention relates to a process for recovering and upgrading unsaturated fluorinated hydrocarbons comprising the steps of: (a) the supply of a foam M1 consisting of pores containing a composition C1 comprising at least one unsaturated fluorinated hydrocarbon; b1) optionally the grinding or compression of said foam M1 provided in step a) to form a crushed foam or a compressed foam; b2) optionally recovering at least part of said composition C1 comprising at least one unsaturated fluorinated hydrocarbon released during step b1); c) depolymerization or dissolution of said foam M1 provided in step a) or said crushed or compressed foam obtained in step b1); d) recovering at least part of said composition C1comprising at least one unsaturated fluorinated hydrocarbon released in gaseous form during step c) and optionally mixing the latter with said at least part of the composition recovered in step b2) to form a stream A comprising at least one unsaturated fluorinated hydrocarbon; e) recovering and separating said stream A formed in step d) into a plurality of streams, at least one of which B1 comprises said at least one unsaturated fluorinated hydrocarbon.

[0005] According to a preferred embodiment, the unsaturated fluorinated hydrocarbon comprises three or four carbon atoms.

[0006] According to a preferred embodiment, said unsaturated fluorinated hydrocarbon contains a single carbon-carbon double bond.

[0007] According to a preferred embodiment, said foam M1consists of polyurethane, polyolefin, poly-(methyl methacrylate), polyhydroxyalkanoate, polylactic acid, polyimide, poly(vinyl chloride), poly(ethylene / vinyl acetate), poly(ether-imide), poly(methacrylimide), polycarbonate or polystyrene or a mixture thereof, preferably the foam consists of polyurethane, polyolefin, poly-(methyl methacrylate) or polystyrene.

[0008] According to another preferred embodiment, said foam M1 provided in step a) is made of polystyrene; and step c) is carried out in the presence of an organic solvent capable of dissolving the polystyrene or step c) is carried out by depolymerization of the polystyrene thermally.

[0009] According to a preferred embodiment, said foam M1provided in step a) is made of polyurethane and step c) is carried out by an alcoholysis or hydrolysis or ammonolysis or aminolysis reaction.

[0010] In the context of the present invention, the ammonolysis reaction refers to the reaction of polyurethane with NH 3 . The aminolysis reaction refers to the reaction of polyurethane or a primary amine or a secondary amine.

[0011] According to a preferred embodiment, step c) results in the formation of polyol compounds, the latter being recovered, purified and recycled in a polyurethane production process.

[0012] According to a preferred embodiment, step e) of separating said stream is carried out by distillation, azeotropic distillation, distillation under pressure, extractive distillation, cold separation, absorption in a solvent or a combination thereof.

[0013] According to a preferred embodiment, said flowA is subjected to an adsorption step before step e) or said stream B1 is subjected to an adsorption step after step e).

[0014] According to a preferred embodiment, said at least one unsaturated fluorinated hydrocarbon included in said composition C1 is selected from the group consisting of 3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene, (E / Z)-1,3,3,3-tetrafluoropropene, (E / Z)-1,2,3,3,3-pentafluoropropene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene and 1,2-dichloro-3,3,3-trifluoropropene, (E / Z)-1,1,1,4,4,4-hexafluorobut-2-ene, 2,4,4,4-tetrafluorobut-1-ene and mixtures thereof.

[0015] According to a preferred embodiment, said composition C1also comprises a hydrofluorocarbon other than said at least one unsaturated fluorinated hydrocarbon, an alkane, methyl formate, an inert gas, an alcohol, an ether, a fluorinated ether, an unsaturated fluorinated ether, a ketone, a fluoroketone, a chlorofluorocarbon or water; or a mixture thereof. According to a preferred embodiment, said hydrofluorocarbon different from said at least one unsaturated fluorinated hydrocarbon is selected from the group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea).

[0016] According to a preferred embodiment, said chlorofluorocarbon is selected from the group consisting of trichlorofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, dichlorotetrafluoroethane, chloropentafluoroethane.

[0017] According to a preferred embodiment, said flow A comprises a content of said at least one fluorinated hydrocarbon of between 50 and 99% by volume based on the total volume of said stream A. According to another preferred embodiment, step a) also comprises: the supply of a foam M2 consisting of pores containing a composition C2comprising a hydrofluorocarbon selected from the group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), or the provision of a foam M3 consisting of pores containing a composition C3 comprising a chlorofluorocarbon selected from the group consisting of trichlorofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, dichlorotetrafluoroethane, chloropentafluoroethane, or providing a mixture of said foams M2 And M3.

[0018] According to a preferred embodiment, the foam M 2 and the foam M3 are made of a polymer identical to that of said foam M1.

[0019] According to a preferred embodiment, the composition C2 and the composition C3 are free of unsaturated fluorinated hydrocarbons.

[0020] According to this other preferred embodiment, said method comprises the steps: b1) optionally the crushing or compression of said foam M1, of said foam M2 and / or said foam M3 provided in step a) to form a crushed foam or a compressed foam; b2) optionally recovering at least part of said composition C1 and at least part of said composition C2 and / or at least a part of said composition C3, released during step b1); c) the depolymerization or dissolution of said foam M1and said foam M2 and / or said foam M3 provided in step a) or said crushed or compressed foam obtained in step b1); d) recovering at least part of said composition C1 and at least part of said composition C2 and / or at least part of said composition C3 , released during step c) and optionally their mixture with those recovered in step b2) to form a flow A ; e) the recovery and separation of said flow A in a plurality of streams including at least one stream B1 comprises said at least one unsaturated fluorinated hydrocarbon.

[0021] According to this other preferred embodiment, said flow A comprises a content of said at least one fluorinated hydrocarbon of between 0.1 and 50% by volume based on the total volume of said flow A. Detailed description of the invention

[0022] The present invention relates to a process for recovering and upgrading fluorinated hydrocarbons. The term "unsaturated fluorinated hydrocarbon" refers to a hydrocarbon compound comprising at least one fluorine atom on its carbon chain and at least one carbon-carbon double bond. The unsaturated fluorinated hydrocarbon may contain two, three or four carbon atoms. Preferably, the unsaturated fluorinated hydrocarbon comprises three or four carbon atoms and one carbon-carbon double bond.

[0023] Preferably, the present method comprises in particular the step of: (a) the supply of a foam M1 consisting of pores containing a composition C1comprising at least one unsaturated fluorinated hydrocarbon. Said foam is for example derived from devices such as refrigerators, freezers, cold storage devices, LNG carriers (transport of liquefied gas). As described in the prior art, the devices containing the foam are recycled via a first step of dismantling said devices to sort the different constituents. For example, in refrigerating devices, the refrigerant composition contained in the cooling circuit is sucked up to be recycled in parallel. The different components, such as the motor, the refrigeration unit, the switches, the ferrous or non-ferrous heavy metals, the aluminum are dismantled and directed or transported to specific sorting channels. Once the different elements have been sorted, the foam is recovered and treated according to the steps described in the present method. Said foam is a porous material.The said pores contained in the foam contain a composition. C1 comprising at least one unsaturated fluorinated hydrocarbon. However, over time, the composition containing at least one unsaturated fluorinated hydrocarbon remains absorbed by the foam as such. The present invention makes it possible to maximize the recovery of said composition containing at least one unsaturated fluorinated hydrocarbon.

[0024] According to a preferred embodiment, said at least one unsaturated fluorinated hydrocarbon included in said composition C1is selected from the group consisting of 3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene, (E / Z)-1,3,3,3-tetrafluoropropene, (E / Z)-1,2,3,3,3-pentafluoropropene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene and 1,2-dichloro-3,3,3-trifluoropropene, (E / Z)-1,1,1,4,4,4-hexafluorobut-2-ene, 2,4,4,4-tetrafluorobut-1-ene and mixtures thereof. In particular, said unsaturated fluorinated hydrocarbon is 1-chloro-3,3,3-trifluoropropene.

[0025] According to a preferred embodiment, said composition C1 may also comprise a hydrofluorocarbon other than said at least one fluorinated hydrocarbon, an alkane, carbon dioxide, methyl formate, an inert gas, an alcohol, an ether, a fluorinated ether, an unsaturated fluorinated ether, a ketone, a fluoroketone, a chlorofluorocarbon or water; or a mixture thereof.

[0026] Said hydrofluorocarbon different from said at least one fluorinated hydrocarbon may be selected from the group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea).

[0027] Preferably, said chlorofluorocarbon is selected from the group consisting of trichlorofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, dichlorotetrafluoroethane and chloropentafluoroethane.

[0028] According to a particular embodiment, the present method may comprise the steps of: b1) optionally the crushing or compression of said foam M1 provided in step a) to form a crushed or compressed foam; b2) optionally recovering at least part of said composition C1 comprising at least one unsaturated fluorinated hydrocarbon released during step b1).

[0029] Said step b1) can be implemented using suitable grinders or compressors known to those skilled in the art. Said grinding is carried out so as to obtain a ground foam. Said compression is carried out so as to obtain a compressed and densified foam. The grinding or compression of the foam results in the release of at least a portion of said composition comprising at least one fluorinated hydrocarbon. The ground foam can be of variable shape and dimensions. According to a preferred embodiment, the ground foam has a dimension of between 0.05 cm and 15 cm. Said dimension expressed here is the largest dimension of said ground foam. Below 0.05 cm, said foam can degrade and possibly soften or melt. Beyond 15 cm, the release of said composition is not optimal.Preferably, the crushed foam has a dimension of between 0.1 cm and 14 cm, advantageously the crushed foam has a dimension of between 0.1 cm and 13 cm, preferably the crushed foam has a dimension of between 0.5 cm and 12 cm, more preferably the crushed foam has a dimension of between 1 cm and 11 cm, in particular the crushed foam has a dimension of between 1 and 5 cm.

[0030] As mentioned above, during this step b1) of grinding or compression, said composition C1 comprising at least one unsaturated fluorinated hydrocarbon contained in said foam M1 will be at least partly released. Thus, during step b2), at least part of said composition C1 comprising at least one unsaturated fluorinated hydrocarbon released during step b1) is recovered. Said at least part of said composition C1can be recovered by a suction device. Preferably, said steps b1) and b2) are carried out in a hermetically sealed treatment chamber comprising said suction device. The latter comprises at least one or more suction nozzles capable of recovering at least part of said composition C1 comprising at least one unsaturated fluorinated hydrocarbon released during the grinding or compression step b1).

[0031] According to a particular embodiment, prior to the implementation of step b1) said foam M1 is placed under partial vacuum. This allows the air surrounding it to be evacuated. Preferably, said foam is placed under a pressure of less than 0.9 bar relative and greater than 0.1 bar relative, preferably under a pressure of less than 0.8 bar relative and greater than 0.2 bar relative. Said at least part of said composition C1comprising at least one unsaturated fluorinated hydrocarbon recovered in step b2) can be purified. Said purification can be carried out by passing said at least one part of said composition C1 comprising at least one unsaturated fluorinated hydrocarbon in dust filters. Said dust filters may have pores whose size varies between 0.5 µm and 10 µm. This purification step makes it possible to optionally eliminate particles which have been sucked up at the same time as said at least one part of said composition C1 comprising at least one unsaturated fluorinated hydrocarbon. Subsequent to this purification step, said at least one part of said composition C1 comprising at least one unsaturated fluorinated hydrocarbon may be stored before being further processed as will be described in the present application in steps d) and e).

[0032] The foam provided in step a) and the crushed or compressed foam in step b1) if steps b1) and b2) have been carried out can be combined to be treated according to step c) of the present method.

[0033] Said method thus comprises a step c) of: c) depolymerization or dissolution of the foam M1 provided in step a) and / or said crushed or compressed foam obtained in step b1).

[0034] The choice between depolymerization or dissolution depends on the type of foam to be treated. A person skilled in the art, with their general knowledge, will be able to recognize the most suitable technique. For example, when a polyurethane foam is treated in step c), depolymerization will be preferred. Conversely, when a polystyrene foam is treated in step c), dissolution and depolymerization are possible.

[0035] According to a preferred embodiment, said foam M1consists of polyurethane, polyolefin, poly-(methyl methacrylate), polyhydroxyalkanoate, polylactic acid, polyimide, poly(vinyl chloride), poly(ethylene / vinyl acetate), poly(ether-imide), poly(methacrylimide), polycarbonate or polystyrene or a mixture thereof, preferably the foam consists of polyurethane, polyolefin, poly-(methyl methacrylate) or polystyrene.

[0036] Preferably, said foam is comprised of polyurethane. Polyurethane foam as described herein encompasses polymers comprising only polyurethane units and also copolymers comprising polyurethane units. Preferably, said polyurethane foam comprises at least 20% by weight of polyurethane units based on the total weight of said foam.According to a preferred embodiment, said polyurethane foam comprises at least 30% by weight of polyurethane units based on the total weight of said foam, advantageously at least 40% by weight of polyurethane units based on the total weight of said foam, preferably at least 50% by weight of polyurethane units based on the total weight of said foam, more preferably at least 60% by weight of polyurethane units based on the total weight of said foam, in particular at least 70% by weight of polyurethane units based on the total weight of said foam, more particularly at least 80% by weight of polyurethane units based on the total weight of said foam.

[0037] According to the present invention, the term "polyurethane units" refers to a compound comprising the unit -[R 1< -NH-CO-OR 2< ]n- wherein the substituents R 1< and R 2< may be selected from the group consisting of C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 6 -C 30 aryl; and n is greater than 3, preferably greater than 10, in particular greater than 50. The term "alkyl" means a linear or branched alkyl group containing at least 1, and at most 30 carbon atoms. The alkyl group may be substituted by an unsubstituted aryl group, OH, C 1 -C 10 alkoxy, a carbonyl or carboxyl group. The term "alkenyl" means a linear or branched alkenyl group containing at least 2, and at most 30 carbon atoms. The alkenyl group comprises at least one carbon-carbon double bond. The alkenyl group may comprise two or three carbon-carbon double bonds.The alkenyl group may be substituted by unsubstituted aryl, OH, C 1 -C 10 alkoxy, carbonyl or carboxyl. The term "aryl" refers to an aromatic hydrocarbon ring containing the specified number of carbon atoms substituted or unsubstituted by unsubstituted C 1 -C 10 alkyl, carbonyl, carboxyl, OH, C 1 -C 10 alkoxy.

[0038] When the foam used in the process is a polyurethane foam, step c) preferably implements a depolymerization step. Said depolymerization can be carried out by alcoholysis, hydrolysis, ammonolysis or aminolysis reactions.

[0039] The alcoholysis reaction comprises bringing the polyurethane foam, whether crushed or compressed or not, preferably crushed or compressed, into contact with an alcohol. Preferably, the alcohol has a boiling point of between 30°C and 350°C, advantageously between 50°C and 325°C, preferably between 60°C and 300°C. Preferably, the alcohol is selected from glycerol, methanol or a glycol compound. Preferably, said glycol compound has a molecular weight of less than 1000 g / mol, in particular less than 500 g / mol. According to a preferred embodiment, the glycol compound is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, di-, tri-, tetra-1,2-propylene glycol, butane diol and hexane diol.The molar ratio between the alcohol and the unit -[R 1< -NH-CO-OR 2< ]- is between 1 / 1 and 5 / 1, advantageously between 1 / 1 and 4 / 1, preferably between 1 / 1 and 3 / 1, in particular between 1 / 1 and 2 / 1. Said alcoholysis reaction can be carried out in the presence of an amine of formula R 3< n NH 3-n in which R 3< is an alkyl radical comprising from 1 to 10 carbon atoms, optionally substituted by one or more OH groups or one or more NH2 groups; and n is 1 or 2. If the amine comprises several R 3< groups as defined above, these can be identical or different or linked together to form a heterocycle. Preferably, said amine is of formula R 3< n NH 3-n in which R 3< is an alkyl radical comprising from 1 to 4 carbon atoms substituted by one or more OH groups or one or more NH 2 groups; n being as defined above.In particular, said amine may be a compound whose molecular weight is less than 200 g / mol, preferably less than 150 g / mol. More particularly, said amine may be chosen from methanol amine, ethanol amine, diethanol amine, dipropanol amine and triethanol amine and combinations thereof. Alternatively, said amine may be HMTA (i.e. hexamethylenetetramine). The alcoholysis reaction may also be carried out in the presence of a catalyst. Said catalyst may be an acetate of an alkali metal such as lithium acetate, sodium acetate or potassium acetate. The amount of catalyst may be between 0.01% and 5% relative to the weight of polyurethane foam, advantageously between 0.1% and 5% by weight, preferably between 0.5% and 5% by weight and more preferably between 1% and 5% by weight. The implementation of depolymerization by alcoholysis results in the formation of polyol compounds and possibly urethane compounds.

[0040] The hydrolysis reaction comprises bringing the polyurethane foam, whether crushed or compressed or not, preferably crushed or compressed, into contact with water. The step of depolymerizing the polyurethane foam by hydrolysis is preferably carried out at high pressure, advantageously at a pressure greater than 2 bar absolute, preferably greater than 5 bar absolute, in particular greater than 10 bar absolute. The step of depolymerizing the polyurethane foam by hydrolysis is preferably carried out at a temperature of 100°C to 300°C, preferably 150°C to 300°C. Thus, the water is at least partly in the form of water vapor. The reaction time for this hydrolysis step is from 1 minute to 5 hours, preferably from 5 minutes to 2 hours, in particular from 10 minutes to 1 hour. The implementation of depolymerization by hydrolysis results in the formation of polyol compounds, amine compounds and CO2.

[0041] The step of depolymerizing polyurethane foams can be carried out by decomposition in the presence of NH 3 (ammonolysis reaction), a primary amine or a secondary amine (aminolysis reaction). The primary or secondary amine is preferably of formula R 4 < R 5 < R 6 < N in which R 4 < , R 5 < and R 6 < are independently of each other selected from H, C 1 -C 10 alkyl substituted or not by an NH 2 group and C 1 -C 10 alkenyl substituted or not by an NH 2 group, preferably H, C 1 -C 5 alkyl substituted or not by an NH 2 group and C 1 -C 5 alkenyl substituted or not by an NH 2 group; provided that at least one of the groups R 4< , R 5< or R 6< represents a hydrogen and that R 4< , R 5< and R 6< are not simultaneously a hydrogen. In particular, the amine may be diethylenetriamine, triethylenetetramine. This step may be carried out at a temperature between 50°C and 300°C, preferably between 100°C and 250°C.The depolymerization step by reaction with an amine results in the formation of polyol and amine compounds.

[0042] Regardless of the method used for the polyurethane foam depolymerization step, the present process may comprise a step of recovering and purifying the polyol compounds formed during step c). The purification of the polyol compounds may be carried out by distillation, centrifugation or by extraction in the presence of a solvent. After purification, preferably, the purified polyol compounds are used in a polyurethane production process.

[0043] According to another preferred embodiment, said foam is made of polystyrene. In this case, step c) is carried out by bringing said polystyrene foam into contact with an organic solvent capable of solubilizing said foam. In the present invention, the term "polystyrene" refers to a polymer or copolymer comprising at least one unit of formula -[CH 2 CH(C 6 R 7< 5 )] n -in which C 6 R 7< 5 represents an aromatic carbon ring in which R 7< is independently H or a C1-C5 alkyl; and in which n is greater than 3, preferably greater than 10, in particular greater than 50. Preferably, this dissolution step can be carried out at a temperature ranging from 10°C to 150°C, preferably from 20°C to 100°C. According to a preferred embodiment, said organic solvent is selected from the group consisting of n-octane, n-dodecane, cyclohexane, methylcyclohexane, benzene, toluene, naphthalene, styrene, o-xylene, ethylbenzene,p-diethylbenzene, p-cymene, chloromethane, 1,1-dichloroethylene, ethylene dichloride, chloroform, 1,1-dichloroethane, trichloroethylene, carbon tetrachloride, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, 1,4-dioxane, dibenzyl ether, acetone, methyl ethyl ketone, cyclohexanone, diethyl ketone, acetophenone, methyl isobutyl ketone, methyl isoamyl ketone, isophorone, di-(isobutyl) ketone, methyl acetate, ethyl formate, propylene-1,2-carbonate, ethyl acetate, diethyl carbonate, n-butyl acetate, 2-ethoxyethyl acetate, isoamyl acetate, 2-nitropropane, nitrobenzene, ethylenediamine, pyridine, morpholine, analine, N-methyl-2-pyrrolidone, cyclohexylamine, quinoline, N,N-dimethylformamide, carbon disulfide, dimethyl sulfoxide, ethanediol, ethanol, allyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, benzyl alcohol, cyclohexanol, diacetone alcohol, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, 1-decanol, benzoic acid, stearic acid, phenol, resorcinol, m-cresol, methyl salicylate, ethylene glycol, glycerol and propylene glycol or a mixture thereof.,

[0044] Contact between the organic solvent and the polystyrene foam results in the formation of a liquid phase L containing said organic solvent and dissolved polystyrene. A mixture of two or more organic solvents as mentioned above may be considered as said liquid phase L evolves over time due to the dissolution of polystyrene in it; i.e. the liquid phase Lwill become concentrated in polystyrene. Thus, a solvent may be able to dissolve polystyrene when the liquid phase is low in polystyrene concentration but no longer be able to dissolve polystyrene when the liquid phase becomes more concentrated in polystyrene. It may therefore be useful to use a mixture of solvents in which one of the solvents dissolves polystyrene in a low concentration liquid phase and the other solvent dissolves polystyrene in a more concentrated liquid phase. Thus, the organic solvent mixture can be selected so as to allow dissolution of polystyrene regardless of the polystyrene concentration in the liquid phase L. This liquid phase L can be purified further. The purification of this liquid phase Lincludes for example a distillation step, filtration and / or precipitation by contact with a non-solvent. Distillation can be used when a mixture of organic solvents is used, in particular when the organic solvents form an azeotropic mixture. The latter can be recovered and recycled to be brought back into contact with polystyrene. Filtration makes it possible to eliminate residues insoluble in said organic solvent. The purification can also include a subsequent precipitation and washing step. Thus, the liquid phase L is preferably brought into contact with a non-solvent capable of precipitating the polystyrene contained in the liquid phase L.The organic solvent(s) and the non-solvent are recovered, separated and recycled. Preferably, the organic solvent(s) and the non-solvent are identical and are capable of dissolving or precipitating the polystyrene depending on the pressure and temperature conditions. It will thus be sufficient to vary the pressure and temperature conditions to precipitate the polystyrene and recover the organic solvent(s). The polystyrene thus precipitated is then subjected to one or more washing steps with said non-solvent. The volume ratio between the non-solvent and the liquid phase L is 2:1 to 4:1. Said non-solvent is preferably a linear or branched C 6 -C 10 alkane, in particular a linear or branched C 6 -C 8 alkane. The washing step(s) are generally followed by a step of drying said precipitated polystyrene at a temperature between 100°C and 130°C, preferably between 115°C to 125°C.

[0045] According to another embodiment, said foam made of polystyrene can be depolymerized in step c). The depolymerization of the polystyrene is preferably carried out thermally. Thus, said foam made of polystyrene is preferably heated to a temperature of between 200°C and 500°C. At such a temperature, the polystyrene is in the molten state and then depolymerizes. According to a particular embodiment, the depolymerization can be carried out in the presence of a radical initiator, advantageously a radical initiator of peroxide type. Preferably, the radical initiator is selected from the group consisting of an organic peroxide, an inorganic peroxide or superoxide such as Barium peroxide (BaO 2 ), Potassium superoxide (KO 2 ), Cesium superoxide (CsO 2 ), a percarbonate, a peroxyhydrate compound, their salts and their mixture.Examples of catalysts for initiating depolymerization include hydrogen peroxide (H 2 O 2 ), azobisisobutyronitrile (AIBN), sodium carbonate peroxyhydrate (2Na 2 CO 3 .3H 2 O 2 ), potassium carbonate peroxyhydrate (2Na 2 CO 3 .3H 2 O 2 ), magnesium carbonate peroxyhydrate (2Na 2 CO 3 .3H 2 O 2 ), ammonium carbonate peroxyhydrate ((NH 4 ) 2 CO 3 .H 2 O 2 ), urea peroxide (CO(NH 2 ) 2 .H 2 O 2 ), sodium sulfate peroxyhydrate (2Na 2 SO 4 .H 2 O 2 .2H 2 O), complexes of H 2 O 2 and inorganic salts, poly(vinyl pyrrolidone) polymer peroxyhydrate (PVP.H 2 O 2 ), persulfates, permanganates, perborates, peroxyhydrates of salts of phosphates.

[0046] According to another embodiment, said foam is made of poly-(methyl methacrylate). The term "poly-(methyl methacrylate)" refers to a polymer comprising units of formula -[CH 2 -CH(CH 3 )(C(O)-O-CH 3 )]n with n greater than 3, preferably greater than 10, in particular greater than 50. Step c) can be carried out by thermal depolymerization, preferably at a temperature of 200°C to 500°C. At such a temperature, the poly-(methyl methacrylate) is in the solid or molten state. According to a particular embodiment, the depolymerization can be carried out in the presence of a radical initiator, advantageously a radical initiator of peroxide type.Preferably, the radical initiator is selected from the group consisting of an organic peroxide, an inorganic peroxide or superoxide such as Barium peroxide (BaO 2 ), Potassium superoxide (KO 2 ), Cesium superoxide (CsO 2 ), a percarbonate, a peroxyhydrate compound, their salts as well as their mixture. Examples of catalysts for initiating depolymerization include hydrogen peroxide (H 2 O 2 ), azobisisobutyronitrile (AIBN), sodium carbonate peroxyhydrate (2Na 2 CO 3 .3H 2 O 2 ), potassium carbonate peroxyhydrate (2Na 2 CO 3 .3H 2 O 2 ), magnesium carbonate peroxyhydrate (2Na 2 CO 3 .3H 2 O 2 ), ammonium carbonate peroxyhydrate ((NH 4 ) 2 CO 3 .H 2 O 2 ), urea peroxide (CO(NH 2 ) 2 .H 2 O 2 ), sodium sulfate peroxyhydrate (2Na 2 SO 4 .H 2 O 2 .2H 2 O), complexes of H 2 O 2 and inorganic salts, poly(vinyl pyrrolidone) polymer peroxyhydrate (PVP.H 2 O 2 ), persulfates, permanganates, perborates, peroxyhydrates of salts of phosphates.

[0047] Alternatively, when said foam is made of poly-(methyl methacrylate), step c) can be carried out by dissolving it in an organic solvent, capable of dissolving the poly-(methyl methacrylate). Preferably, said organic solvent is methyl methacrylate. The use of methyl methacrylate to dissolve the poly-(methyl methacrylate) is interesting because the liquid phase thus formed can be used, after a possible filtration step, in a process for producing poly-(methyl methacrylate). Alternatively, said organic solvent can be selected from the group consisting of toluene, acetone, butanone, cyclohexanone, nitroethane, chloroform, dichloromethane, benzene, chlorobenzene, xylene, methoxybenzene, diethylphthalate, methoxypropyl acetate, ethyl acetate, ethyl lactate, formic acid.

[0048] Preferably, the dissolution of the poly-(methyl methacrylate) foam is carried out at a temperature of 20°C to 200°C, preferably 25°C to 100°C, preferably 30 to 80°C. The dissolution can be carried out under pressure.

[0049] According to another embodiment, said foam consists of polyhydroxyalkanoate (i.e. PHA), preferably polypropiolactone or poly-3-hydroxypropionate. In this case, step c) is carried out by depolymerization. Preferably, the depolymerization is carried out by hydrolysis or thermally. The thermal depolymerization is carried out at a temperature above 100°C, advantageously above 150°C, preferably above 200°C; and below 400°C, preferably below 300°C. Preferably, the thermal depolymerization is carried out in the presence of an inert gas, such as nitrogen, CO 2 or argon. Preferably, the thermal depolymerization is carried out at a pressure below 1 bar absolute. Alternatively, the thermal depolymerization may be carried out under partial vacuum.Preferably, the thermal depolymerization is carried out in the presence of a depolymerization catalyst. Preferably, said depolymerization catalyst is selected from the group consisting of acid catalysts, such as mixed oxides, zeolites, aluminas, titanium or zirconium oxides doped with one or more of the elements P, S, W, B, Nb, Ta.

[0050] Alternatively, step c) may be carried out by hydrolysis. In this case, step c) is carried out at a temperature of 20°C to 100°C in the presence of water.

[0051] The implementation of step c) with polypropiolactone type foams allows the formation of 3-hydroxypropionic acid which can be subsequently recovered as acrylic acid in a specific process.

[0052] According to another embodiment, said foam consists of polylactic acid, that is to say that it contains units of formula -[CH(CH 3 )-C(O)O-]n with n greater than 3, preferably greater than 10, in particular greater than 50. Step c) can be carried out by dissolution or depolymerization. The dissolution of the polylactic acid can be carried out in the presence of an organic solvent selected from tetrahydrofuran, dioxane, dioxolane, m-cresol, pyridine, N-methylpyrrolidone, butyrolactone, ethylacetate, propylene carbonate, acetone, acetonitrile, nitrobenzene, dimethylacetamide dichloromethane, chloroform. Alternatively, the dissolution of the polylactic acid can be carried out in the presence of an organic solvent such as a lactic acid ester. Lactic acid ester can be methyl lactate, ethyl lactate, isopropyl lactate, butyl lactate, hexyl lactate.The dissolution step can be followed by a filtration step to remove any particles that are not soluble in the organic solvent.

[0053] The depolymerization of polylactic acid may be carried out by hydrolysis at a temperature of 80°C to 180°C, preferably 100°C to 150°C, in particular 120°C to 140°C. The depolymerization by hydrolysis may be carried out at a pressure of less than 1 bara or at a pressure of 1 bara to 10 bara. The depolymerization by hydrolysis may be carried out in the presence of water or an alkaline solution of NaOH or KOH. The depolymerization by hydrolysis may optionally be carried out in the presence of a catalyst such as a Lewis acid selected from tin octoate, tin lactate, antimony octoate, zinc octoate, APTS or triazabicyclodecene. Depolymerization by hydrolysis can optionally be carried out in the presence of a catalyst such as a Bronsted acid.

[0054] Depolymerization by hydrolysis of polylactic acid results in the formation of lactic acid which can be recovered through further use in polylactic acid production processes or by dehydration to acrylic acid, or conversion to esters.

[0055] According to another embodiment, said foam may be a polyolefin. Preferably, the polyolefin is polyethylene or polypropylene. In this case, step c) is carried out by dissolving in an organic solvent. Step c) may be carried out at a temperature of 100°C to 300°C. Said organic solvent may be dimethylformamide, dimethyl sulfoxide, xylenes, tetralin, decalin or 1,2,4-trichlorobenzene. After dissolution, the liquid phase formed by the polyolefin dissolved in the organic solvent may be filtered to optionally remove insoluble particles. After filtration, the polyolefin dissolved in the liquid phase may be precipitated according to techniques known to those skilled in the art. According to another embodiment, said foam may be polyimide, polycarbonate or poly(ether imide). In this case, the foam is treated by depolymerization as described above for polyurethane.

[0056] According to another embodiment, said foam may be poly(methacryl imide). In this case, the foam is treated as described above for poly(methyl methacrylate). The depolymerization of poly(methacryl imide) makes it possible to generate methacrylonitrile which can be recovered in a manner equivalent to that of methyl methacrylate.

[0057] According to another embodiment, said foam may be poly(vinyl chloride) or poly(ethylene / vinyl acetate). In this case, the foam is treated as described above for a polyolefin. In the case of poly(vinyl chloride), the latter may be recovered by precipitation by injection of steam which causes the evaporation of the solvent.

[0058] According to an alternative embodiment, when said foam is made of polyolefin, polystyrene or poly(vinyl chloride) or poly(ethylene / vinyl acetate), step c) can be carried out by devolatilization. Said foam is heated to a temperature such that said foam is in the molten state. Said composition C1 contained in the pores of said foam is thus released in the gaseous state and recovered for use in step d) of the present process.

[0059] During step c), the depolymerization or dissolution of the foam will lead to the release of said composition C1 comprising at least one unsaturated fluorinated hydrocarbon. Thus, the present process comprises the step of: d) recovering at least a portion of said composition C1comprising at least one unsaturated fluorinated hydrocarbon released during step c) and optionally mixing it with said at least part of the composition recovered in step b2) to form a stream A comprising at least one unsaturated fluorinated hydrocarbon.

[0060] Said at least part of said composition C1 can be recovered by a suction device. Preferably, said steps c) and d) are carried out in a hermetically sealed treatment chamber comprising said suction device in order to limit the contamination of the gases of the composition by air gases. The latter comprises at least one or more suction nozzles capable of recovering at least a portion of said composition comprising at least one fluorinated hydrocarbon released during step c). Said at least a portion of said composition C1comprising at least one fluorinated hydrocarbon recovered in step d) can be mixed with said at least one part of the composition C1 recovered in step b2) to form a stream A comprising at least one fluorinated hydrocarbon. Said stream A can be purified by passing through one or more dust filters. Said dust filters may have pores whose size varies between 0.5 µm and 10 µm. This purification step makes it possible to possibly eliminate particles that have been sucked up at the same time as said flow A.

[0061] The said flow A formed in step d) is recovered and purified in order to separate the constituents included therein.

[0062] Thus, the present method comprises a step of: e) recovery and separation of said flow A formed in step d) into a plurality of streams, at least one of which B1 comprises said at least one unsaturated fluorinated hydrocarbon.

[0063] Thus, the said flow A comprises said at least one unsaturated fluorinated hydrocarbon selected from the group consisting of 3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene, (E / Z)-1,3,3,3-tetrafluoropropene, (E / Z)-1,2,3,3,3-pentafluoropropene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene and 1,2-dichloro-3,3,3-trifluoropropene, (E / Z)-1,1,1,4,4,4-hexafluorobut-2-ene, 2,4,4,4-tetrafluorobut-1-ene, and mixtures thereof.

[0064] Depending on the constituents of said composition C1, said flow Amay also comprise a hydrofluorocarbon other than said at least one unsaturated fluorinated hydrocarbon, an alkane, methyl formate, an inert gas, an alcohol, an ether, a fluorinated ether, an unsaturated fluorinated ether, a ketone, a fluoroketone, a chlorofluorocarbon or water; or a mixture thereof. Preferably, said hydrofluorocarbon other than said at least one unsaturated fluorinated hydrocarbon is selected from the group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea).

[0065] Preferably, the inert gas is nitrogen, argon or CO2 or a mixture thereof.

[0066] Preferably, the chlorofluorocarbon is selected from the group consisting of trichlorofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, dichlorotetrafluoroethane and chloropentafluoroethane.

[0067] According to a preferred embodiment, said flow Acomprises 1-chloro-3,3,3-trifluoropropene and a hydrofluorocarbon other than said at least one unsaturated fluorinated hydrocarbon selected from the group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea). Alternatively, said stream A comprises 1-chloro-3,3,3-trifluoropropene and an inert gas as described above

[0068] Alternatively, the content of said at least one unsaturated fluorinated hydrocarbon in said stream Ais between 50% and 99% by volume based on the total volume of said flow A. The content of said at least one unsaturated fluorinated hydrocarbon in said stream A may be between 51% and 99% vol., between 52% and 99% vol., between 53% and 99% vol., between 54% and 99% vol., between 55% and 99% vol., between 56% and 99% vol., between 57% and 99% vol., between 58% and 99% vol., between 59% and 99% vol., between 60% and 99% vol., between 61% and 99% vol., between 62% and 99% vol., between 63% and 99% vol., between 64% and 99% vol., between 65% and 99% vol., between 66% and 99% vol., between 67% and 99% vol., between 68% and 99% by vol., between 69% and 99% by vol., between 70% and 99% by vol., between 71% and 99% by vol., between 72% and 99% by vol., between 73% and 99% by vol., between 74% and 99% by vol., or between 75% and 99% by vol. The content of said at least one unsaturated fluorinated hydrocarbon in said stream Amay also be between 75% and 98% by vol., between 75% and 97% by vol., between 75% and 96% by vol., between 75% and 95% by vol., between 75% and 94% by vol., between 75% and 93% by vol., between 75% and 92% by vol., between 75% and 91% by vol., or between 75% and 90% by vol. based on the total volume of said stream A. The said flow A with the above-mentioned contents can be obtained when the process is carried out from foams M1 whose pores contain the said composition C1 .

[0069] As mentioned in the present application, the present method also makes it possible to treat and recycle foams containing previous generations of blowing agents and this simultaneously with the treatment of the foams. M1 comprising new generation blowing agents. Thus, in the present process, step a) may also comprise: the supply of a foam M2consisting of pores containing a composition C2 comprising a hydrofluorocarbon selected from the group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), or the provision of a foam M3 consisting of pores containing a composition C3 comprising a chlorofluorocarbon selected from the group consisting of trichlorofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, dichlorotetrafluoroethane, chloropentafluoroethane, or providing a mixture of said foamsM2 And M3.

[0070] When step a) provides foams M2 and / or M3 in addition to the foam M1, the foam M2 and the foam M3 are made of a polymer identical to that of said foam M1. Thus, the implementation of step c) is carried out in the same way in the presence of foams M2 and / or M3 only for the foam M1.

[0071] Preferably, mosses M2 And M3 contain older generation blowing agents. Thus, the composition C2 and the composition C3 are free of unsaturated fluorinated hydrocarbon as defined in the present application (representing the new generation of blowing agents). Preferably, the composition C2 and the composition C3are free of unsaturated fluorinated hydrocarbon comprising a carbon-carbon double bond; in particular, the composition C2 and the composition C3 are free of unsaturated fluorinated hydrocarbons comprising three or four carbon atoms and a carbon-carbon double bond. More particularly, the composition C2 and the composition C3 are free of unsaturated fluorinated hydrocarbon selected from the group consisting of 3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene, (E / Z)-1,3,3,3-tetrafluoropropene, (E / Z)-1,2,3,3,3-pentafluoropropene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene and 1,2-dichloro-3,3,3-trifluoropropene, (E / Z)-1,1,1,4,4,4-hexafluorobut-2-ene, 2,4,4,4-tetrafluorobut-1-ene and mixtures thereof. Preferably, the composition C2 and the composition C3 are devoid of 1-chloro-3,3,3-trifluoropropene.

[0072] When foams M2 and / or M3 were provided in step a), the method comprises the following steps b) to e): b1) optionally the crushing or compression of said foam M1, of said foam M2 and / or said foam M3 provided in step a) to form a crushed foam or a compressed foam; b2) optionally recovering at least part of said composition C1 and at least part of said composition C2 and / or at least part of said composition C3, released during step b1); c) depolymerization or dissolution of said foam M1 and said foam M2 and / or said foam M3 provided in step a) or said crushed or compressed foam obtained in step b1); d) recovering at least part of said composition C1 and at least part of said composition C2and / or at least part of said composition C3, released during step c) and optionally their mixture with those recovered in step b2) to form a flow A ; e) the recovery and separation of said flow A in a plurality of streams including at least one stream B1 comprises said at least one unsaturated fluorinated hydrocarbon.

[0073] Thus, according to a particular embodiment, the present method comprises the steps: (a) the supply of a foam M1 consisting of pores containing a composition C1 comprising at least one unsaturated fluorinated hydrocarbon; and providing a foam M2 consisting of pores containing a composition C2comprising a hydrofluorocarbon selected from the group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), or the provision of a foam M3 consisting of pores containing a composition C3 comprising a chlorofluorocarbon selected from the group consisting of trichlorofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, dichlorotetrafluoroethane, chloropentafluoroethane, or providing a mixture of said foams M2 And M3; b1) optionally the crushing or compression of said foam M1 , of said foam M2 and / or said foam M3 provided in step a) to form a crushed foam or a compressed foam; b2) optionally recovering at least part of said composition C1 and at least part of said composition C2 and / or at least part of said composition C3, released during step b1); c) depolymerization or dissolution of said foam M1 and said foam M2 and / or said foam M3 provided in step a) or said crushed or compressed foam obtained in step b1); d) recovering at least part of said composition C1 and at least part of said composition C2 and / or at least part of said composition C3,released during step c) and optionally their mixture with those recovered in step b2) to form a flow A ; e) the recovery and separation of said flow A in a plurality of streams including at least one stream B1 comprises said at least one unsaturated fluorinated hydrocarbon.

[0074] In this embodiment, preferably, said flow A comprises a content of said at least one fluorinated hydrocarbon of between 0.1 and 50% by volume based on the total volume of said stream A. In particular, the content of said at least one unsaturated fluorinated hydrocarbon in said stream A is between 0.1 and 50% by volume based on the total volume of said flow A. The content of said at least one unsaturated fluorinated hydrocarbon in said stream Amay be between 0.5% and 50% by vol., between 1% and 50% by vol., between 2% and 50% by vol., between 3% and 50% by vol., between 4% and 50% by vol., between 5% and 50% by vol., between 6% and 50% by vol., between 7% and 50% by vol., between 8% and 50% by vol., between 9% and 50% by vol., between 10% and 50% by vol., between 11% and 50% by vol., between 12% and 50% by vol., between 13% and 50% by vol., between 14% and 50% by vol., between 15% and 50% by vol., between 16% and 50% by vol., between 17% and 50% by vol. vol., between 18% and 50% by vol., between 19% and 50% by vol., between 20% and 50% by vol., between 21% and 50% by vol., between 22% and 50% by vol., between 23% and 50% by vol., between 24% and 50% by vol., or between 25% and 50% by vol. The content of said at least one unsaturated fluorinated hydrocarbon in said stream Amay also be between 0.1% and 49% by vol., between 0.1% and 48% by vol., between 0.1% and 47% by vol., between 0.1% and 46% by vol., between 0.1% and 45% by vol., between 0.1% and 44% by vol., between 0.1% and 43% by vol., between 0.1% and 42% by vol., between 0.1% and 41% by vol., between 0.1% and 40% by vol., between 0.1% and 39% by vol., between 0.1% and 38% by vol., between 0.1% and 37% by vol., between 0.1% and 36% by vol., between 0.1% and 35% by vol., between 0.1% and 34% by vol., between 0.1% and 33% by vol., between 0.1% and 32% by vol., between 0.1% and 31% by vol., between 0.1% and 30% by vol., between 0.1% and 29% by vol., between 0.1% and 28% by vol., between 0.1% and 27% by vol., between 0.1% and 26% by vol., between 0.1% and 25% by vol., between 0.1% and 24% by vol., between 0.1% and 23% by vol., between 0.1% and 22% by vol., between 0.1% and 21% by vol., or between 0.1% and 20% by vol. based on the total volume of said stream A. The said flow Awith the contents mentioned above can be obtained when the process is carried out from a mixture of foams, a part of the foams containing compounds other than said unsaturated fluorinated hydrocarbon, for example said hydrofluorocarbon different from said at least one unsaturated fluorinated hydrocarbon as defined in the present invention or a chlorofluorocarbon.

[0075] The said flow A is preferably separated by distillation, azeotropic distillation, pressure distillation, extractive distillation, cold separation, absorption in a solvent or a combination thereof. The separation of said stream A by any of the above techniques results in the formation of a plurality of streams B including at least one flow B1 comprises said unsaturated fluorinated hydrocarbon, preferably comprising 1-chloro-3,3,3-trifluoropropene (i.e. HCFO-1233zd).

[0076] In this stream B1,the molar content of said at least one unsaturated fluorinated hydrocarbon, preferably HCFO-1233zd, is greater than the molar content of said at least one unsaturated fluorinated hydrocarbon, preferably HCFO-1233zd, in said stream A. The temperature and pressure conditions applied for these distillations are such that the molar content of at least one said unsaturated fluorinated hydrocarbon, preferably HCFO-1233zd, in said stream B1 is greater than 80%, advantageously greater than 85%, preferably greater than 90%, in particular greater than 95%.

[0077] The distillation separation step preferably comprises at least two distillation columns. The first distillation column makes it possible, for example, to remove a portion of the products having a boiling point lower than that of said at least one unsaturated fluorinated hydrocarbon, preferably lower than that of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd). The second distillation column makes it possible, for example, to remove a portion of the products having a boiling point higher than that of said at least one unsaturated fluorinated hydrocarbon, preferably higher than that of 1-chloro-3,3,3-trifluoropropene. Alternatively, the first distillation column makes it possible, for example, to remove a portion of the products having a boiling point higher than that of said at least one unsaturated fluorinated hydrocarbon, preferably higher than that of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd).The second distillation column makes it possible, for example, to eliminate a portion of the products having a boiling point lower than that of said at least one unsaturated fluorinated hydrocarbon, preferably lower than that of 1-chloro-3,3,3-trifluoropropene.

[0078] The said flow B1 is that obtained after said at least second distillation.

[0079] As indicated above, a plurality of streams are obtained in step e). In addition to the stream B1, a flow B2 comprising all or part of the composition C2 and / or C3 can also be obtained. The compounds contained in the composition C2 and / or C3 and retrieved from the stream B2can be recovered and used as an intermediate or precursor for the synthesis of pharmaceutical compounds, phytosanitary compounds, fluorinated polymers or for the manufacture of other fluorinated gases having applications in refrigeration, heat transfer fluids or blowing agents (for example, HFC-152a or HFC-143a can be used for the preparation of 1,1-difluoroethylene).

[0080] As mentioned above, extractive distillation can be used to separate the constituents present in said stream A. In this case, the said flow A is mixed with an organic extractant and the resulting mixture is distilled to form said stream B1 comprising said at least one fluorinated hydrocarbon.

[0081] Extractive distillation is particularly advantageous for separating said fluorinated hydrocarbon from said hydrofluorocarbon different from said at least one fluorinated hydrocarbon. Thus, said stream A comprising at least one fluorinated hydrocarbon and said hydrofluorocarbon different from said at least one fluorinated hydrocarbon is mixed with said organic extractant. The resulting mixture is distilled to form said stream B1 comprising said at least one fluorinated hydrocarbon and a flux B2 comprising said organic extractant and said hydrofluorocarbon other than said at least one fluorinated hydrocarbon.

[0082] Preferably, said organic extracting agent has a boiling point between 10°C and 200°C.

[0083] According to a preferred embodiment, said organic extractant has a separation factor S 1,2 greater than or equal to 1.1, said separation factor being calculated by the formula S 1,2 = (γ 1,S *P1) / (γ 2,S *P2) in which γ 1,S represents the activity coefficient of said at least one fluorinated hydrocarbon in said organic extractant at infinite dilution, P1 represents the saturated vapor pressure of said at least one fluorinated hydrocarbon, γ 2,S represents the activity coefficient of said hydrofluorocarbon different from said at least one fluorinated hydrocarbon and selected from the group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) in said organic extractant at infinite dilution,P2 represents the saturated vapor pressure of said hydrofluorocarbon other than said at least one fluorinated hydrocarbon and selected from the group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea); advantageously, the separation factor S 1,2 may be greater than or equal to 1.2, preferably greater than or equal to 1.4, more preferably greater than or equal to 1.5, in particular greater than or equal to 1.8, more particularly greater than or equal to 1.9.

[0084] According to a preferred embodiment, said organic extractant has a separation factor S 1,2 greater than or equal to 1.1, said separation factor being calculated by the formula S 1,2 = (γ 1,S *P1) / (γ 2,S *P2) in which γ 1,S represents the activity coefficient of one of the fluorinated hydrocarbons selected from the group consisting of 3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene, (E / Z)-1,3,3,3-tetrafluoropropene, (E / Z)-1,2,3,3,3-pentafluoropropene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene and 1,2-dichloro-3,3,3-trifluoropropene, (E / Z)-1,1,1,4,4,4-hexafluorobut-2-ene, 2,4,4,4-tetrafluorobut-1-ene and in said organic extractant at infinite dilution, P1 represents the saturated vapor pressure of one of the fluorinated hydrocarbons selected from the group consisting of 3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene, (E / Z)-1,3,3,3-tetrafluoropropene, (E / Z)-1,2,3,3,3-pentafluoropropene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene and 1,2-dichloro-3,3,3-trifluoropropene, (E / Z)-1,1,1,4,4,4-hexafluorobut-2-ene, 2,4,4,4-tetrafluorobut-1-ene, γ 2,S represents the activity coefficient of said hydrofluorocarbon different from said at least one fluorinated hydrocarbon and selected from the group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) in said organic extractant at infinite dilution, P2 represents the saturated vapor pressure of said hydrofluorocarbon different from said at least one fluorinated hydrocarbon and selected from the group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea); advantageously, the separation factor S 1.2 may be greater than or equal to 1.2, preferably greater than or equal to 1.4, more preferably greater than or equal to 1.5, in particular greater than or equal to 1.8, more particularly greater than or equal to 1.9.

[0085] The same compound should be considered for both γ 1,S and P1 values. Thus, if the activity coefficient considered for γ 1,S is that of 3,3,3-trifluoropropene, P1 represents the saturation vapor pressure of 3,3,3-trifluoropropene. The same compound should be considered for both γ 2,S and P2 values. Thus, if γ 2,S represents the activity coefficient of difluoromethane, then P2 represents the saturation vapor pressure of difluoromethane.

[0086] According to a preferred embodiment, said organic extractant has a separation factor S 1,2 greater than or equal to 1.1, said separation factor being calculated by the formula S 1,2 = (γ 1,S *P1) / (γ 2,S *P2) in which γ 1,S represents the activity coefficient of 1-chloro-3,3,3-trifluoropropene in said organic extractant at infinite dilution, P1 represents the saturated vapor pressure of 1-chloro-3,3,3-trifluoropropene, γ 2,S represents the activity coefficient of said hydrofluorocarbon different from said at least one fluorinated hydrocarbon and selected from the group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) in said organic extractant at infinite dilution,P2 represents the saturated vapor pressure of said hydrofluorocarbon other than said at least one fluorinated hydrocarbon and selected from the group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea); advantageously, the separation factor S 1,2 may be greater than or equal to 1.2, preferably greater than or equal to 1.4, more preferably greater than or equal to 1.5, in particular greater than or equal to 1.8, more particularly greater than or equal to 1.9.

[0087] In the present application, the saturated vapor pressure is considered for a temperature of 25°C.

[0088] According to a preferred embodiment, said organic extractant has an absorption capacity C 2,S greater than or equal to 0.20, said absorption capacity being calculated by the formula C 2,S = 1 / (γ 2,S ) in which γ 2,S represents the activity coefficient of said hydrofluorocarbon different from said at least one fluorinated hydrocarbon and selected from the group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) in said organic extractant at infinite dilution;advantageously, the absorption capacity C 2,S is greater than or equal to 0.40, preferably greater than or equal to 0.60, more preferably greater than or equal to 0.80, in particular greater than or equal to 0.90, more particularly greater than or equal to 1.0, preferably greater than or equal to 1.05. According to a preferred embodiment, said organic extraction agent is a solvent selected from the group consisting of hydrocarbon, hydrohalocarbon, alcohol, ketone, amine, ester, ether, aldehyde, nitrile, carbonate, thioalkyl, amide, heterocycle. Advantageously, said organic extraction agent is a solvent selected from the group consisting of alcohol, ketone, amine, ester and heterocycle.;

[0089] In the context of extractive distillation, the term "hydrocarbon" as used herein refers to linear or branched compounds of C 1 -C 20 alkane, C 3 -C 20 cycloalkane, C 5 -C 20 alkene, C 5 -C 20 cycloalkene, C 6 -C 18 arene. For example, the term alkane refers to compounds of the formula C n H 2n+2 in which n is between 1 and 20. The term C 1 -C 20 alkane includes, for example, pentane, hexane, heptane, octane, nonane, decane or isomers thereof. The term C 5 -C 20 alkene refers to hydrocarbon compounds comprising one or more carbon-carbon double bonds and comprising from 5 to 20 carbon atoms. The term C3-C20 cycloalkane refers to a saturated hydrocarbon ring containing 3 to 20 carbon atoms. The term C6-C18 aryl refers to cyclic and aromatic hydrocarbon compounds containing 6 to 18 carbon atoms.The term C5-C20 cycloalkene refers to cyclic hydrocarbon compounds comprising 5 to 20 carbon atoms and comprising one or more carbon-carbon double bonds. The term "alkyl" designates a monovalent radical derived from a linear or branched alkane comprising 1 to 20 carbon atoms. The term "cycloalkyl" designates a monovalent radical derived from a cycloalkane comprising 3 to 20 carbon atoms. The term "aryl" designates a monovalent radical derived from an arene comprising 6 to 18 carbon atoms. The term "alkenyl" designates a monovalent radical of 2 to 20 carbon atoms and at least one carbon-carbon double bond. The term "alkynyl" designates a monovalent radical of 2 to 20 carbon atoms and at least one carbon-carbon triple bond. The term "halogen" refers to a -F, -Cl, -Br or -I group. The term "cycloalkenyl" refers to a monovalent radical derived from a cycloalkene comprising 3 to 20 carbon atoms.The 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, C 6 -C 18 aryl substituents may be substituted or not by one or more substituents -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< , wherein R a< and R b< are independently of each other hydrogen, C 1 -C 20 alkyl unsubstituted, unsubstituted C 2 -C 20 alkenyl, unsubstituted C 2 -C 20 alkynyl, unsubstituted C 3 -C 20 cycloalkyl, unsubstituted C 3 -C 20 cycloalkenyl, unsubstituted C 6 -C 18 aryl. In the substituents -NR a< R b< , R a< and R b< may form with the nitrogen atom to which they are attached a saturated or unsaturated, aromatic or unaromatic heterocycle comprising from 5 to 10 members.

[0090] The term "hydrohalocarbons" refers to compounds of formula R a< X wherein R a< is selected from 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, C 6 -C 18 aryl and X represents a chlorine, fluorine, bromine or iodine atom. The 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, C 6 -C 18 aryl substituents may be substituted or not by one or more substituents -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< , wherein R a< and R b< are as defined above.

[0091] The term "alcohol" refers to hydrocarbons or hydrohalocarbons as defined above in which at least one hydrogen atom is replaced by a hydroxyl group -OH.

[0092] The term "ketone" refers to hydrocarbons comprising at least one or more carbonyl functional groups RC< -C(O)-R d< in which R c< and R d< are independently of each other 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, C 6 -C 18 aryl may or may not be substituted by one or more substituents -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, R c< and R d< being able to be linked together to form with the carbonyl group to which they are attached a cyclic ketone comprising from 4 to 10 members, preferably from 4 to 7 members. The cyclic ketone may also comprise one or more carbon-carbon double bonds.The cyclic ketone may also be substituted or unsubstituted by one or more substituents as defined above.

[0093] The term "amine" refers to hydrocarbons comprising at least one or more amine functional groups -NR c< R d< in which R c< and R d< are as defined above, R c< and R d< being able to be linked together to form with the nitrogen atom to which they are attached an aromatic or non-aromatic heterocycle comprising from 4 to 10 links.

[0094] The term “esters” refers to compounds of formula R c< -C(O)-OR d< in which R c< and R d< are as defined above, R c< and R d< being able to be linked together to form with the ester group a cycle comprising from 4 to 20 carbon atoms.

[0095] The term "ether" refers to compounds of formula R c< -OR d< in which R c< and R d< are as defined above, R c< and R d< being able to be linked together to form with the oxygen atom to which they are attached a heterocycle comprising from 4 to 20 carbon atoms.

[0096] The term "aldehyde" refers to compounds comprising at least one or more -C(O)-H functional groups.

[0097] The term "nitrile" refers to compounds comprising at least one or more -CN functional groups.

[0098] The term "carbonate" refers to compounds of the formula R c< -OC(O)-OR d< in which R c< and R d< are as defined above.

[0099] The term "thioalkyl" relates to compounds of formula R c< SR d< in which R c< and R d< are as defined above.

[0100] The term "amide" relates to compounds of formula R c< C(O)NR e< R d< in which R c< and R d< are as defined above, R e< having the same definition as R c< , R c< and R d< being able to be linked 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 comprise one or more carbon-carbon double bonds. The cyclic amide may also be substituted or not by one or more substituents as defined above.

[0101] The term "heterocycle" means a carbon ring comprising from 4 to 10 members of which at least one of the members 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 or one or more carbon-heteroatom double bonds or one or more heteroatom-heteroatom double bonds. Preferably, the heterocycle may comprise 1, 2, 3, 4 or 5 heteroatoms as defined above. In particular, the heterocycle may comprise 1, 2 or 3 heteroatoms selected from oxygen, nitrogen or sulfur. Preferably, the heterocycle may be a carbon ring comprising from 4 to 6 members of which 1, 2 or 3 members are heteroatoms selected from O or N.The heterocycle may or may not be substituted with 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. Preferably, the hydrocarbons are selected from the group consisting of cyclohexene, 1,3,5-triethylbenzene, 2,4,4-trimethyl-1-pentene, 1-methylcyclohexene, 1,4-dimethylbenzene, styrene, 1,3,5-trimethylbenzene, 1,2,4,5-tetramethylbenzene, 1,3-diethenylbenzene.

[0102] De préférence, les hydrohalocarbures sont sélectionnés parmi le groupe consistant en lodomethane, bromoethane, chlorobromomethane, iodoethane, 2-bromopropane, dichlorobromomethane, 2-chloropropane, 2-iodopropane, bromotrichloromethane, trichloroacetaldehyde, 1,2-dibromopropane, 2-bromobutane, 1,2-dichloropropane, 1,1,2-trichloroethane, 1,2,3-trichloropropene, 1,2-dibromoethane, 1-bromopropane, 3-bromopropene, 1-bromo-2-chloroethane, 1,2-dichloroethane, 1-iodopropane, 2-bromopentane, 1-bromo-3-methylbutane, tribromomethane, 1-bromobutane, 1-chloro-3-bromopropane, 1-bromopentane, 1,3-dichloropropane, 1-bromo-3-fluoropropane, 1,2-dibromo-1-fluoroethane, 1-bromo-1,2-difluoroethylene, bromofluoromethane, 1,1,1-trifluoro-2-bromoethane, 1-chloro-3-fluoropropane, 1-chloro-4-fluorobutane, 2-bromo-2-methylpropane, 2-chloro-2-methylpropane, 2-bromo-2-methylbutane, 2,3-dichloro-2-methylbutane, 1-iodobutane, 1,1,2-trichloropropane, 1,3-dichlorobutane, 2,3-dichlorobutane, 1,2,2-trichloropropane,cis-1,3-dichloropropene, trans-1,3-dichloropropene, 1,3-dichloro-trans-2-butene, 1,2-dichloro-2-butene, 2-chloro-2-methylbutane.,

[0103] De préférence, les alcools sont sélectionnés parmi le groupe consistant en méthanol, éthanol, 2-propanol, 2,2-dimethyl-1-propanol, 2,2,2-trifluoroethanol, tert-butanol, 2,2,3,3-tetraflouro-1-propanol, 2-chloro-1-propanol, propanol, 2-allyloxyethanol, 2-butanol, 2-aminophenol, 2-methyl-2-butanol, 2-ethyl-1-butanol, isobutanol, 3-pentanol, 1-butanol, 1-methoxy2-propanol, 1-(dimethylamino)-2-propanol, 2-methyl-1-pentanol, 3-methyl-3-pentanol, 2-methoxy1-propanol, 1-ethoxy-2-propanol, 4-methyl-2-pentanol, 2-chloroethanol, 1,2-octanediol, 2-(dimethylamino)-ethanol, 3-hexanol, 2-hexanol, 2-ethoxy-1-propanol, 1-pentanol, 2-propoxyethanol, 1-propoxy-2-propanol, 2,2-difluoroethanol, 1,1,1-trifluoro-2-propanol, 4,4,4-trifluorobutanol, 3-fluoropropanol, 2,3-dimethylbutanol, 1-chloro-2-methyl-2-propanol.

[0104] Preferably, 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-hexen-2-one, 4-methyl-2-hexanone, 1,1,1-trifluoro-2-propanone.

[0105] De préférence, les amines sont sélectionnées parmi le groupe consistant en éthylamine, 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, 2-methylpyridine, 4-methyl-2-hexanamine, hexylamine, cyclohexylamine, n-ethyl-2-dimethylaminoethylamine, 1,3-propanediamine, 2-heptanamine, n,n-diethylethylenediamine, 2,6-dimethylpyridine, 4-methylpyridine, n,n'-diethyl-1,2-ethanediamine, dimethylethanolamine, 1,1-diethoxy-n,n-dimethylmethanamine.

[0106] Preferably, the esters are selected from the group consisting of methylacetate, ethylacetate, n-propylformate, isopropylacetate, tert-butylacetate, ethylpropionate, sec-butylacetate, diethylcarbonate, n-butylacetate, bromoaceticacidmethylester, methylformate, methylhexanoate, isopropylformate.

[0107] De préférence, les éthers sont sélectionnés parmi le groupe consistant en diethylether, 2-ethoxy-propane, methyl-t-butylether, 2,2-dimethoxypropane, 1-ethoxy-2-methylpropane, 1,2-dimethoxyethane, diethoxymethane, 1-ethoxybutane, 1-methoxy-pentane, 1,2-dimethoxypropane, 1,1-diethoxyethane, trimethoxymethane, 2-chloro-1,1-dimethoxyethane, 2,2-diethoxypropane, 1,1-diethoxypropane, 2-methoxyethanol, methoxycyclohexane, chloromethoxymethane, ethoxyethanol, di-n-butylether, diisopropylether, 1-ethoxy-hexane, 1,1,1-triethoxyethane, 1-methoxy-2-acetoxypropane, dimethoxymethane, ethoxy-ethene, di-n-propylether, 2-methoxy-1-propene, 2,2,2-trifluoroethylmethylether, methylcyclopropylether, 2-ethoxy-2-methyl-propane, 2-ethoxy-butane, sec-butyl-tert-butylether, isobutyl-tert-butylether, 1-methoxy-2-methyl-butane, isopropyl-isobutyl-ether.

[0108] Preferably, the aldehydes are selected from the group consisting of acetaldehyde, isobutanal, methylglyoxal, 2-methylbutanal, 2,6-dimethyl-5-heptenal, hexanal, ethanedial.

[0109] Preferably, the nitriles are selected from the group consisting of acetonitrile, propionitrile, butyronitrile, valeronitrile, (methyleneamino)acetonitrile.

[0110] Preferably, the carbonate is diethyl carbonate.

[0111] Preferably, the amides include ethanethioamide.

[0112] Preferably, the thioalkyls are selected from the group consisting of ethanethiol, dimethylsulfide, 2-propanethiol, tert-butylthiol, 3-mercapto-1,2-propanediol, 1-propanethiol, butanethiol, tetrahydrothiophene, 1-pentanethiol, diethylsulfide, 2-butanethiol, 2-methyl-1-propanethiol, 4-methoxy-2-methyl-2-butanethiol.

[0113] Preferably, the heterocycles are selected from the group consisting of n-ethyl-morpholine, 1-methylpiperazine, n-methylmorpholine, 2-methylpyrazine, tetrahydrofuran, 1,3,5-trioxane, dioxane, 1,3-dioxane, piperidine, 2,6-dimethylmorpholine. Dioxane refers to 1,4-dioxane. The present method may also comprise a step involving contacting said flow A or said flow B1with an adsorbent. Said adsorbent may be a zeolite or a molecular sieve having a pore opening with an average diameter of between 3 Angstroms and 11 Angstroms, advantageously between 4 Angstroms and 10 Angstroms, preferably between 5 Angstroms and 10 Angstroms. The adsorbent may also contain noble metals such as silver, platinum, palladium, ruthenium, rhodium; preferably silver. The adsorbent may also be a polymer and contain these metals, in particular silver. This step may therefore be carried out after step d) and before step e) or after step e). The adsorption step may, for example, make it possible to eliminate one or more of said hydrofluorocarbons or to eliminate water which may be present in small quantities.

[0114] According to another embodiment, step e) is implemented by cold separation. In this case, said flow Ais cooled to a temperature such that said at least one unsaturated fluorinated hydrocarbon is in liquid form and thus formed said stream B1 . Thus, the other constituents of the flow A having a boiling point lower than that of said at least one unsaturated fluorinated hydrocarbon are in gaseous form and are removed by degassing. This may be useful for removing gases such as oxygen, nitrogen or carbon dioxide possibly present in the stream A. The said flow B1 can then be reheated to a temperature such that said at least one unsaturated fluorinated hydrocarbon is in gaseous form while maintaining the other constituents possibly present in said flow B1 in liquid form. Said at least one unsaturated fluorinated hydrocarbon is thus recovered with a high degree of purity.

[0115] According to another embodiment, step e) can be implemented in a pressurized distillation device comprising at least one or more rotating packed bed(s). In this case, said flow A is compressed and optionally cooled to a temperature such that said at least one fluorinated hydrocarbon is in liquid form. Said flow A thus compressed and optionally cooled is distilled in a pressurized distillation device comprising one or more rotating packed bed(s) to form and recover a flow B1 as defined in the present application. The speed of said at least one rotating packed bed is preferably from 100 to 3000 rpm, advantageously from 200 to 2500 rpm, preferably from 500 to 2000 rpm. In this case, step e) is preferably carried out at a pressure of 2 to 200 bars absolute, preferably from 5 to 100 bars absolute.

Claims

1. Process for recovering and upgrading unsaturated fluorinated hydrocarbons, comprising the steps of: a) providing a foam M1 consisting of pores containing a composition C1 comprising at least one unsaturated fluorinated hydrocarbon; b1) optionally grinding or compressing said foam M1 provided in step a) to form a ground foam or a compressed foam; b2) optionally recovering at least a portion of said composition C1 comprising at least one unsaturated fluorinated hydrocarbon and released during step b1) ; c) depolymerizing or dissolving said foam M1 provided in step a) or said ground or compressed foam obtained in step b1) ; d) recovering at least a portion of said composition C1 comprising at least one unsaturated fluorinated hydrocarbon and released in gaseous form during step c) and optionally mixing the latter with said at least a portion of the composition recovered in step b2) to form a stream A comprising at least one unsaturated fluorinated hydrocarbon; e) recovering and separating said stream A formed in step d) into a plurality of streams of which at least one stream B1 comprises said at least one unsaturated fluorinated hydrocarbon.

2. Process according to Claim 1, characterized in that the unsaturated fluorinated hydrocarbon comprises three or four carbon atoms.

3. Process according to either one of the preceding claims, characterized in that said unsaturated fluorinated hydrocarbon contains a single carbon-carbon double bond.

4. Process according to any one of the preceding claims, characterized in that said foam M1 consists of a polymer selected from the group consisting of polyurethane, polyolefin, poly(methyl methacrylate), polyhydroxyalkanoate, polylactic acid, polyimide, poly(vinyl chloride), poly(ethylene / vinyl acetate), poly(etherimide), poly(methacrylimide), polycarbonate or polystyrene, or a mixture thereof, preferably said foam consists of polyurethane, polyolefin, poly(methyl methacrylate) or polystyrene.

5. Process according to any one of the preceding claims, characterized in that said foam M1 provided in step a) consists of polystyrene; and step c) is carried out in the presence of an organic solvent capable of dissolving the polystyrene or step c) is carried out by thermal depolymerization of the polystyrene.

6. Process according to either one of preceding Claims 1 and 2, characterized in that said foam M1 provided in step a) consists of polyurethane and step c) is carried out by an alcoholysis or hydrolysis or ammonolysis or aminolysis reaction.

7. Process according to the preceding claim, characterized in that step c) results in the formation of polyol compounds, the latter being recovered, purified and recycled into a process for the production of polyurethane.

8. Process according to any one of the preceding claims, characterized in that step e) of separating said stream is carried out by distillation, azeotropic distillation, pressurized distillation, extractive distillation, cold separation, absorption in a solvent, or a combination thereof.

9. Process according to any one of the preceding claims, characterized in that said stream A is subjected to a step of adsorption prior to step e) or said stream B1 is subjected to a step of adsorption after step e).

10. Process according to any one of the preceding claims, characterized in that said at least one unsaturated fluorinated hydrocarbon included in said composition C1 is selected from the group consisting of 3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene, (E / Z)-1,3,3,3-tetrafluoropropene, (E / Z)-1,2,3,3,3-pentafluoropropene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene and 1,2-dichloro-3,3,3-trifluoropropene, (E / Z)-1,1,1,4,4,4-hexafluorobut-2-ene, 2,4,4,4-tetrafluorobut-1-ene, and mixtures thereof.

11. Process according to the preceding claim, characterized in that said composition C1 also comprises a hydrofluorocarbon other than said at least one unsaturated fluorinated hydrocarbon, an alkane, methyl formate, an inert gas, an alcohol, an ether, a fluorinated ether, an unsaturated fluorinated ether, a ketone, a fluoroketone, a chlorofluorocarbon or water, or a mixture thereof.

12. Process according to the preceding claim, characterized in that said hydrofluorocarbon other than said at least one unsaturated fluorinated hydrocarbon is selected from the group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea).

13. Process according to Claim 11, characterized in that said chlorofluorocarbon is selected from the group consisting of trichlorofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, dichlorotetrafluoroethane and chloropentafluoroethane.

14. Process according to any one of preceding Claims 1 to 13, characterized in that said stream A comprises a content of said at least one fluorinated hydrocarbon of between 50% and 99% by volume, based on the total volume of said stream A.

15. Process according to any one of the preceding claims, characterized in that step a) also comprises: - providing a foam M2 consisting of pores containing a composition C2 comprising a hydrofluorocarbon selected from the group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), or - providing a foam M3 consisting of pores containing a composition C3 comprising a chlorofluorocarbon selected from the group consisting of trichlorofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, dichlorotetrafluoroethane, chloropentafluoroethane, or - providing a mixture of said foams M2 and M3.

16. Process according to the preceding claim, characterized in that the foam M2 and the foam M3 consist of a polymer identical to that of said foam M1.

17. Process according to either one of Claims 15 and 16, characterized in that the composition C2 and the composition C3 are devoid of unsaturated fluorinated hydrocarbon.

18. Process according to any one of Claims 15 to 17, characterized in that it comprises the steps of: b1) optionally grinding or compressing said foam M1, said foam M2 and / or said foam M3 provided in step a) to form a ground foam or a compressed foam; b2) optionally recovering at least a portion of said composition C1 and at least a portion of said composition C2 and / or at least a portion of said composition C3, released during step b1) ; c) depolymerizing or dissolving said foam M1 and said foam M2 and / or said foam M3 provided in step a) or said ground or compressed foam obtained in step b1) ; d) recovering at least a portion of said composition C1 and at least a portion of said composition C2 and / or at least a portion of said composition C3, released during step c), and optionally mixing them with those recovered in step b2) to form a stream A; e) recovering and separating said stream A into a plurality of streams of which at least one stream B1 comprises said at least one unsaturated fluorinated hydrocarbon.

19. Process according to the preceding claim, characterized in that said stream A comprises a content of said at least one fluorinated hydrocarbon of between 0.1% and 50% by volume, based on the total volume of said stream A.