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    • 专利摘要:
    The invention relates to a composition comprising at least 99% by weight of 1,1,1,2,3-pentachloropropane, and comprising at least one compound selected from a list of additional compounds consisting of trichloropropanes, tetrachloropropanes, various pentachloropropanes. 1,1,1,2,3-pentachloropropane, hexachloropropanes, heptachloropropanes, dichloropropenes, trichloropropenes, tetrachloropropenes, pentachloropropenes and hexachloropropene, said compound being present in the composition in a weight content of less than or equal to 500 ppm. The invention also relates to the use of this composition for the manufacture of 2,3,3,3-tetrafluoropropene.
    公开号:FR3027303A1
    申请号:FR1459926
    申请日:2014-10-16
    公开日:2016-04-22
    发明作者:Bertrand Collier；Dominique Deur-Bert；Laurent Wendlinger
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The present invention relates to compositions based on F-240db (1,1,1,2,3-pentachloropropane) and their use in particular. for the production of F-1234yf (2,3,3,3-tetrafluoropropene). TECHNICAL BACKGROUND The F-1234yf is a compound of major interest for refrigeration and air conditioning systems, given the new environmental regulations. It is known to produce hydrofluoroolefins such as F-1234yf by fluorination of hydrochloro-olefins or hydrochlorocarbons in particular. This fluorination is generally a catalytic fluorination using hydrofluoric acid as fluorinating agent. Among the routes for obtaining F-1234yf, it is in particular known to use F-240db (1,1,1,2,3-pentachloropropane) as the starting compound. For example, reference is made to WO 2013/088195 in this regard.
    [0002] It is desirable to produce F-1234yf having a low content of impurities. In particular, the formation of certain toxic and / or flammable impurities and / or which are difficult to separate from F-1234yf must be minimized. There is therefore a need to provide means for obtaining F-1234yf compositions of satisfactory purity. SUMMARY OF THE INVENTION The invention firstly relates to a composition comprising at least 99% by weight of 1,1,1,2,3-pentachloropropane, and comprising at least one compound selected from a list of additional compounds consisting of trichloropropanes, tetrachloropropanes, pentachloropropanes other than 1,1,1,2,3-pentachloropropane, hexachloropropanes, heptachloropropanes, dichloropropenes, trichloropropenes, tetrachloropropenes, pentachloropropenes and hexachloropropene, said compound being present in the composition in a weight content of less than or equal to 500 ppm.
    [0003] According to one embodiment, said compound is present in the composition in a weight content of less than or equal to 250 ppm; preferably less than or equal to 150 ppm; more particularly less than or equal to 100 ppm; more particularly less than or equal to 50 ppm; and ideally less than or equal to 10 ppm.
    [0004] According to one embodiment, the composition comprises a plurality of compounds selected from said list of additional compounds, each of said compounds of said plurality of compounds being present in the composition in a weight content of less than or equal to 500 ppm; preferably less than or equal to 250 ppm; preferably less than or equal to 150 ppm; more particularly less than or equal to 100 ppm; more particularly less than or equal to 50 ppm; and ideally less than or equal to 10 ppm. According to one embodiment, the composition comprises a plurality of compounds selected from said list of additional compounds, the total weight content of all the compounds of said list being less than or equal to 1000 ppm; preferably less than or equal to 500 ppm; preferably less than or equal to 250 ppm; preferably less than or equal to 150 ppm; more particularly less than or equal to 100 ppm; more particularly less than or equal to 50 ppm; and ideally less than or equal to 10 ppm.
    [0005] According to one embodiment, the composition comprises at least 99.5% by weight, and preferably at least 99.8% by weight, and more preferably at least 99.9% by weight, of 1.1, 1,2,3-pentachloropropane. According to one embodiment, the composition comprises at least one compound selected from the group consisting of 1,1,1,3-tetrachloropropane, 3,3,3-trichloropropene and 1,1,3-trichloropropene; and the weight content of each of these compounds in the composition is less than or equal to 100 ppm, preferably less than or equal to 50 ppm; and, optionally, the total weight content of the compounds of this group in the composition is less than or equal to 100 ppm, preferably less than or equal to 50 ppm. According to one embodiment, the composition comprises at least one compound chosen from trichloropropenes and tetrachloropropanes, the weight content of each of these compounds in the composition being less than or equal to 250 ppm, preferably less than or equal to 150 ppm; and, optionally, the total weight content of trichloropropenes and tetrachloropropanes in the composition is less than or equal to 250 ppm, preferably less than or equal to 150 ppm. According to one embodiment, the composition comprises at least one compound chosen from pentachloropropenes and hexachloropropanes, the weight content of each of these compounds in the composition being less than or equal to 50 ppm, preferably less than or equal to 10 ppm; and, optionally, the total weight content of the pentachloropropenes and hexachloropropanes in the composition is less than or equal to 50 ppm, preferably less than or equal to 10 ppm. According to one embodiment, the composition comprises at least one compound chosen from hexachloropropene and heptachloropropanes, the weight content of each of these compounds in the composition being less than or equal to 50 ppm, preferably less than or equal to 10 ppm; and, optionally, the total weight content of hexachloropropene and heptachloropropanes in the composition is less than or equal to 50 ppm, preferably less than or equal to 10 ppm.
    [0006] According to one embodiment, the composition comprises at least one compound chosen from dichloropropenes and trichloropropanes, the weight content of each of these compounds in the composition being less than or equal to 50 ppm, preferably less than or equal to 10 ppm; and, optionally, the total weight content of the dichloropropenes and trichloropropanes in the composition is less than or equal to 50 ppm, preferably less than or equal to 10 ppm. According to one embodiment, the composition comprises at least one compound selected from the group consisting of 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene, 1,1,1,3,3 pentachloropropane and 1,1,2,3,3-pentachloropropane, and the weight content of each of these compounds in the composition is less than or equal to 500 ppm, preferably less than or equal to 300 ppm; and, optionally, the total weight content of the compounds of this group in the composition is less than or equal to 500 ppm, preferably less than or equal to 300 ppm.
    [0007] The invention also relates to a process for producing 2,3,3,3-tetrafluoropropene, comprising: - providing a composition as described above; the reaction of this composition with hydrofluoric acid in the gas phase. According to one embodiment, the method comprises a single catalytic fluorination step.
    [0008] According to one embodiment, the process comprises two successive stages of catalytic fluorination, namely: the reaction of the composition with hydrofluoric acid in the gaseous phase, to produce an intermediate product; optionally, a purification of the intermediate product; then - reacting the intermediate product with hydrofluoric acid in the gas phase, to produce 2,3,3,3-tetrafluoropropene; the intermediate product is preferably 2-chloro-3,3,3-trifluoropropene. The present invention overcomes the disadvantages of the state of the art. It more particularly provides compositions based on F-240db whose impurity content makes it possible to minimize the presence of harmful impurities in the F-1234yf manufactured therefrom. Indeed, the impurities present in the F-1234yf depend in part on the impurities initially present in the F-240db which is used to manufacture it. During the fluorination reaction (s), some of the F-240db impurities can be converted to different impurities in F-1234yf. The control of the impurities present in the F-240db thus indirectly makes it possible to control the impurities present in the F-1234yf. Such indirect control may be advantageous in that the impurities of F-1234yf may be more difficult to separate from F-1234yf than the impurities of F-240db over F-240db. This is particularly the case when the impurities of F-1234yf have a very close boiling point or form an azeotrope or azeotrope with it.
    [0009] DESCRIPTION OF EMBODIMENTS OF THE INVENTION The invention is now described in more detail and in a nonlimiting manner in the description which follows. All contents are by weight unless otherwise stated. Nomenclature The following table provides the nomenclature of a number of compounds which are involved in the invention. Formula Notation Full name CF3-CH3 F-143a 1,1,1-trifluoroethane CC13-CHCI-CCI3 F-220da 1,1,1,2,3,3,3-heptachloropropane CHC12-CC12-CCI3 F-220aa 1, 1,1,2,2,3,3-heptachloropropane CF3-CHCI-CF3 F-226da 2-chloro-1,1,1,3,3,3-hexafluoropropane CF3-CHF-CCIF2 F-226ea 1-chloro 1,1,2,3,3,3-hexafluoropropane CF3-CFC1-CHF2 F-226ba 2-chloro-1,1,2,3,3,3-hexafluoropropane CF3-CF2-CHFC1 F-226ca 3-chloro 1,1,1,2,2,3-hexafluoropropane CCIF2-CF2-CHF2 F-226cb 1-chloro-1,1,2,2,3,3-hexafluoropropane CC13-CH2-CCI3 F-230fa 1,1, 1,3,3,3-hexachloropropane CHCl2-CHCl3-CCl3 F-230da 1,1,1,2,3,3-hexachloropropane CHCl2-CCl2-CHCl2 F-230aa 1,1,2,2,3,3- hexachloropropane CH2CI-CC12-CCI3 F-230ab 1,1,1,2,2,3-hexachloropropane CF3-CH2-CF3C1 F-235fa 3-chloro-1,1,1,3,3-pentafluoropropane CF3-CHF-CHFCl F-235ea 1-chloro-1,2,3,3,3-pentafluoropropane CHF2-CHF-CCIF2 F-235eb 1-chloro-1,1,2,3,3-pentafluoropropane CHCIF-CF2-CHF2 F-235ca 3 -chloro-1,1,2,2,3-pentafluoropropane CH2CI-CF2-CF3 F-235cb 3-chloro-1,1,1,2,2-pentafluoropropan e CH2F-CF2-CC1F2 F-235cc 1-chloro-1,1,2,2,3-pentafluoropropane CHF2-CHC1-CF3 F-235da 2-chloro-1,1,1,3,3-pentafluoropropane CHF2-CC1F -CHF2 F-235ba 2-chloro-1,1,2,3,3-pentafluoropropane CH2F-CCIF-CF3 F-235bb 2-chloro-1,1,1,2,3-pentafluoropropane CF3-C-CF3 236fa 1,1,1,3,3,3-hexafluoropropane CHF2-CF2-CHF2 F-236ca 1,1,2,2,3,3-hexafluoropropane CH2F-CF2-CF3 F-236cb 1,1,1,2 , 2,3-hexafluoropropane CHF2-CHF-CF3 F-236ea 1,1,1,2,3,3-hexafluoropropane CHC12-CH2-CCI3 F-240fa 1,1,1,3,3-pentachloropropane CHCl2-CHCl3 CHCl2 F-240da 1,1,2,3,3-pentachloropropane CH2Cl-CHCl3-CCl3 F-240db 1,1,1,2,3-pentachloropropane CF12Cl-CCl2-CHCl2 F-240aa 1,1,2,2, 3-pentachloropropane CH3-CC12-CCI3 F-240ab 1,1,1,2,2-pentachloropropane CH2F-CF2-CHF2 F-245ca 1,1,2,2,3-pentafluoropropane Formula Rating Full Name CF3-CF2-CH3 F-245cb 1,1,1,2,2-pentafluoropropane CHF2-CHF-CHF2 F-245ea 1,1,2,3,3-pentafluoropropane CH2F-CHF-CF3 F-245eb 1,1,1,2,3 -pentafluoropropane CHF2-CH2-CF3 F-245fa 1,1,1,3,3-pentafluoropropane CHC12-CF1 2-CHCl2 F-250fa 1,1,3,3-tetrachloropropane CH2Cl-CH2-CCI3 F-250fb 1,1,1,3-tetrachloropropane CH2Cl-CHCl3-CHCl2 F-250da 1,1,2,3-tetrachloropropane CH3 -CHCI-CCI3 F-250db 1,1,1,2-tetrachloropropane CF12CI-CC12-CF12C1 F-250aa 1,2,2,3-tetrachloropropane CH3-CC12-CHCl2 F-250ab 1,1,2,2-tetrachloropropane CF2CI-CH2-CH2F F-253fa 1-chloro-1,1,3-trifluoropropane CH2CI-CH2-CF3 F-253fb 1-chloro-3,3,3-trifluoropropane CF2CI-CH2-CH2F F-253fc 1-chloro 1,1,3-trifluoropropane CH2F-CCIF-CH2F F-253ba 2-chloro-1,2,3-trifluoropropane CHF2-CCIF-CH3 F-253bb 2-chloro-1,1,2-trifluoropropane CH2Cl-CF2-CH2F F-253ca 1-chloro-2,2,3-trifluoropropane CHFCI-CF2-CH3 F-253cb 1-chloro-1,2,2-trifluoropropane CHF2-CHF-CH2CI F-253ea 3-chloro-1,1,2 trifluoropropane-trifluoropropane trifluoropropane CCF2-CHF-CH3 F-253ec-1-chloro-1,1,2-trifluoropropane CF12CI-CF12-CF1C12 F-260fa 1-trifluoropropane CHCIF-CHF-CH2F F-253eb 1-chloro-1,2,3-trifluoropropane 1,3-trichloropropane CH3-CH2-CCI3 F-260fb 1,1,1-trichloropropane CH2Cl-CHCl2-CH2ClF-260da 1,2,3-trichloropropane CH3-CHCl3 -CHCl2 F-260db 1,1,2-trichloropropane CH3-CCI2-CH2Cl-F-260aa 1,2,2-trichloropropane CCl3-CCI = CCl2 F-1210xa hexachloropropene CF3-CCl = CCl2 F-1213xa 1,1,2- trichloro-3,3,3-trifluoropropene CF2Cl-CCl = CFCI F-1213xb 1,2,3-trichloro-1,3,3-trifluoropropene CFCI2-CCI = CF2 F-1213xc 2,3,3-trichloro-1, 1,3-trifluoropropene CCI3-CF = CF2 F-1213yc 3,3,3-trichloro-1,1,2-trifluoropropene CFC12-CF = CFCI F-1213yb 1,3,3-trichloro-1,2,3- trifluoropropene CF2CI-CF = CCl2 F-1213a1,1,3-trichloro-2,3,3-trifluoropropene CCI2F-CF = CF2 F-1214yc 3,3-dichloro-1,1,2,3-tetrafluoropropene CCIF2-CCI = CF2 F-1214xc 2,3-dichloro-1,1,3,3-tetrafluoropropene CCIF2-CF = CFCI F-1214yb 1,3-Dichloro-1,2,3,3-tetrafluoropropene Formula Rating Full Name CF3-CCI = CFCI F-1214xb 1,2-dichloro-1,3,3,3-tetrafluoropropene CF3-CF = CCl2 F-1214α 1,2-dichloro-2,3,3,3-tetrafluoropropene CF3-CF = CF2 F- 1216yc hexafluoropropene CHC12-CCI = CCl2 F-1220xa 1,1,2,3,3-pentachloropropene CC13-CCI = CHCl3 F-1220xd 1,2,3,3,3-pentachloropropene CC 13-CH = CCI2 F-1220za 1,1,3,3,3-pentachloropropene CF3-CCI = CHCI F-1223xd 1,2-dichloro-3,3,3-trifluoropropene CF2CI-CCI = CHF F-1223xe2, 3-dichloro-1,3,3-trifluoropropene CHFCI-CCl = CF2 F-1223xc 2,3-dichloro-1,1,3-trifluoropropene CFCI2-CH = CF2 F-1223zc 3,3-dichloro-1,1, 3-trifluoropropene CF2Cl-CH = CFCl4 F-1223zb 1,3-dichloro-1,3,3-trifluoropropene CF3-CH = CCl2 F-1223za 1,1-dichloro-3,3,3-trifluoropropene CHF2-CF = CCl2 F-1223α 1,1-dichloro-2,3,3-trifluoropropene CF₂Cl-CF = CHClI-1223yd 1,3-dichloro-2,3,3-trifluoropropene CFCl₂-CF = CHF F-1223ye 3,3-dichloro 1,2,3-trifluoropropene CHCl2-CF = CF2 F-1223yc 3,3-dichloro-1,1,2-trifluoropropene CHFCI-CF = CF2 F-1224yc 3-chloro-1,1,2,3-tetrafluoropropene CHF2-CCI = CF2 F-1224xc 2-chloro-1,1,3,3-tetrafluoropropene CF2CI-CH = CF2 F-1224zc 3-chloro-1,1,3,3-tetrafluoropropene CHF2-CF = CFCI F-1224yb 1-chloro-1,2,3,3-tetrafluoropropene CF3-CH = CFCI F-1224zb 1-chloro-1,3,3,3-tetrafluoropropene CCIF2-CF = CHF F-1224ye 3-chloro-1,2, 3,3-tétrafluoropropèn e CF3-CCI = CHF F-1224xe 2-chloro-1,3,3,3-tetrafluoropropene CF3-CF = CHCI F-1224yd 1-chloro-2,3,3,3-tetrafluoropropene CF3-CH = CF2 F- 1225zc 1,1,3,3,3-pentafluoropropene CHF2-CF = CF2 F-1225yc 1,1,2,3,3-pentafluoropropene CF3-CF = CHF F-1225ye 1,2,3,3,3-pentafluoropropene CH2Cl-CCl = CCl2 F-1230xa 1,1,2,3-tetrachloropropene CHCl2-CCI = CHCl3 F-1230xd 1,2,3,3-tetrachloropropene CCI3-CCI = CH2 F-1230xf 2,3,3,3- tetrachloropropene CHC12-CH = CCl2 F-1230za 1,1,3,3-tetrachloropropene CCl3-CH = CHCl3-1230zd 1,3,3,3-tetrachloropropene CF3-CCI = CH2 F-1233xf 2-chloro-3,3 , 3-trifluoropropene CCIF2-CF = CH2 F-1233yf 3-chloro-2,3,3-trifluoropropene CHF2-CF = CHCI F-1233yd 1-chloro-2,3,3-trifluoropropene Formula Rating Full name CF3-CH = CHCI F-1233zd 1-chloro-3,3,3-trifluoropropene CHF2-CCI = CHF F-1233xe 2-chloro-1,3,3-trifluoropropene CHCIF-CF = CHF F-1233ye 3-chloro-1,2, 3-trifluoropropene CCIF2-CH = CHF F-1233ze 3-chloro-1,3,3-trifluoropropene CH2Cl-CF = CF2 F-1233yc 3-chloro-1,1,2-trifluoropropene CF H2-CCI = CF2 F-1233xc 2-chloro-1,1,3-trifluoropropene CFCIH-CH = CF2 F-1233zc 3-chloro-1,1,3-trifluoropropene CFH2-CF = CFCI F-1233yb 1-chloro 1,2,3-trifluoropropene CF2H-CH = CFCI F-1233zb 1-chloro-1,3,3-trifluoropropene CF3-CF = CH2 F-1234yf 2,3,3,3-tetrafluoropropene CF3-CH = CHF F- 1234ze 1,3,3,3-tetrafluoropropene CH2F-CF = CF2 F-1234yc 1,1,2,3-tetrafluoropropene CHF2-CH = CF2 F-1234zc 1,1,3,3-tetrafluoropropene CHF2-CF = CHF F -1234ye 1,2,3,3-tetrafluoropropene CH3-CCI = CCl2 F-1240xa 1,1,2-trichloropropene CH2Cl-CCl = CHCl2 F-1240xd 1,2,3-trichloropropene CHCl2-CCI = CH2 F-1240xf 2 , 3,3-trichloropropene CH2Cl-CH = CCl2 F-1240za 1,1,3-trichloropropene CHCl2-CH = CHCl2 F-1240zd 1,3,3-trichloropropene CCI3-CH = CH2 F-1240zf 3,3,3-trichloropropene trichloropropene CCIF2-CH = CH2 F-1242zf 3-chloro-3,3-difluoropropene CHCIF-CF = CH2 F-1242yf 3-chloro-2,3-difluoropropene CHF2-CCI = CH2 F-1242xf 2-chloro-3.3 -difluoropropene CH3-CCI = CF2 F-1242xc 2-chloro-1,1-difluoropropene CH2Cl-CH = CF2 F-1242zc 3-chloro-1,1-difluoroprop ee CH2CI-CF = CHF F-1242ye 3-chloro-1,2-difluoropropene CH2F-CCI = CHF F-1242xe 2-chloro-1,3-difluoropropene CHFCI-CH = CHF F-1242ze 3-chloro-1,3 -difluoropropene CH2F-CF = CHCI F-1242yd 1-chloro-2,3-difluoropropene CHF2-CH = CHCI F-1242zd 1-Chloro-3,3-difluoropropene CH2F-CH = CF2 F-1243zc 1,1,3- trifluoropropene CH3-CF = CF2 F-1243yc 1,1,2-trifluoropropene CF3-CH = CH2 F-1243zf 3,3,3-trifluoropropene CH2F-CF = CHF F-1243ye 1,2,3-trifluoropropene CHF2-CF = CH2 F-1243yf 2,3,3-trifluoropropene Formula Notation Full name CHF2-CH = CHF F-1243ze 1,3,3-trifluoropropene CH3-CH = CCl2 F-1250za 1,1-dichloropropene CH3-CCI = CHCl3 1250xd 1,2-dichloropropene CH2Cl-CCl = CH2 F-1250xf 2,3-dichloropropene CH2Cl-CH = CHCl2 F-1250zd 1,3-dichloropropene CHCl2-CH = CH2 F-1250zf 3,3-dichloropropene CH3-CH = CF2 F-1252zc 1,1-difluoropropene CH3-CF = CHF F-1252ye 1,2-difluoropropene CH2F-CF = CH2 F-1252yf 2,3-difluoropropene CHF2-CH = CH2 F-1252zf 3,3-difluoropropene When the compounds above exist in the form of e two cis and trans isomers, the name of the compound (for example F-1234ze) indifferently designates one or the other form or a mixture of the two forms. The maximum levels indicated are then total contents vis-à-vis the two possible forms. On the other hand, F-220 is generally used to denote all the heptachloropropane compounds, F-230 the hexachloropropane compounds and so on, using the notation in Table 1 above without the two letters. finals. Compositions According to the Invention The invention proposes compositions based on F-240db. The content of F-240db is greater than or equal to 99%. According to some embodiments, it is greater than or equal to 99.1%, or 99.2%, or 99.3%, or 99.4%, or 99.5%, or 99, 6%, or 99.7%, or 99.8%, or 99.9%. The compositions according to the invention also comprise at least one compound selected from a list of additional compounds which is constituted by the series F-220, F-230, F-240 (with the exception of F-240db), F- 250, F-260 as well as the F-1210, F-1220, F-1230, F-1240 and F-1250 series, said compound being present in the composition in a content of less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm.
    [0010] Said at least one compound may be present at a content of greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm. For example, said at least one compound may be present in a content of 1 to 5 ppm; or at a content of 5 to 10 ppm; or in a content of 10 to 25 ppm; or at a content of 25 to 50 ppm; or at a level of 50 to 75 ppm; or at a level of 75 to 100 ppm; or at a level of 100 to 150 ppm; or in a content of 150 to 200 ppm; or in a content of 200 to 250 ppm; or in a content of 250 to 300 ppm; or at a level of 300 to 350 ppm; or at a level of 350 to 400 ppm; or at a level of 400 to 450 ppm; or at a level of 450 to 500 ppm. One embodiment relates to such compositions which comprise a plurality (two, three, four or more than four) compounds selected from the list of additional compounds above, the content of each of said compounds being less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm. Each compound of this plurality can then be present in a content greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm. For example, each compound of this plurality may be present in a content of 1 to 5 ppm; or at a content of 5 to 10 ppm; or in a content of 10 to 25 ppm; or at a content of 25 to 50 ppm; or at a level of 50 to 75 ppm; or at a level of 75 to 100 ppm; or at a level of 100 to 150 ppm; or in a content of 150 to 200 ppm; or in a content of 200 to 250 ppm; or in a content of 250 to 300 ppm; or at a level of 300 to 350 ppm; or at a level of 350 to 400 ppm; or at a level of 400 to 450 ppm; or at a level of 450 to 500 ppm.
    [0011] One embodiment relates to such compositions in which the content of each of the compounds of the above list of additional compounds optionally present in the composition (with the exception of F-240aa, F-1230xf and F-1230xa, which may possibly be present in higher amounts) is less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm. Each compound of the list of additional compounds can then be present in a content greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 PPm. For example, each compound in the list of additional compounds (with the exception of F-240aa, F-1230xf and F-1230xa, which may optionally be present in higher amounts) may be present in a range of from 1 to 5 ppm; or at a content of 5 to 10 ppm; or in a content of 10 to 25 ppm; or at a content of 25 to 50 ppm; or at a level of 50 to 75 ppm; or at a level of 75 to 100 ppm; or at a level of 100 to 150 ppm; or in a content of 150 to 200 ppm; or in a content of 200 to 250 ppm; or in a content of 250 to 300 ppm; or at a level of 300 to 350 ppm; or at a level of 350 to 400 ppm; or at a level of 400 to 450 ppm; or at a level of 450 to 500 ppm. The compositions according to the invention may in particular comprise one or more compounds of the F-220 series, each being present in the composition in a content of less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm; and the total content of F-220 series compounds in the composition, preferably, less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm. It should be noted that the compound (s) of the F-220 series may then be present in a content greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm. Similarly, the total content of compounds of the F-220 series in the composition may be greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm. For example, the compound (s) of the F-220 series may be present in a content of 1 to 5 ppm; or at a content of 5 to 10 ppm; or in a content of 10 to 25 ppm; or at a content of 25 to 50 ppm; or at a level of 50 to 75 ppm; or at a level of 75 to 100 ppm; or at a level of 100 to 150 ppm; or in a content of 150 to 200 ppm; or in a content of 200 to 250 ppm; or in a content of 250 to 300 ppm; or at a level of 300 to 350 ppm; or at a level of 350 to 400 ppm; or at a level of 400 to 450 ppm; or at a level of 450 to 500 ppm.
    [0012] For example, the total content of F-220 series compounds in the composition may be from 1 to 5 ppm; or from 5 to 10 ppm; or from 10 to 25 ppm; or from 25 to 50 ppm; or from 50 to 75 ppm; or 75 to 100 ppm; or from 100 to 150 ppm; or from 150 to 200 ppm; or from 200 to 250 ppm; or 250 to 300 ppm; or from 300 to 350 ppm; or from 350 to 400 ppm; or from 400 to 450 ppm; or from 450 to 500 ppm. The compositions according to the invention may especially comprise one or more compounds of the F-230 series, each being present in the composition in a content of less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm; and the total content of F-230 series compounds in the composition, preferably, less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm. It should be noted that the compound (s) of the F-230 series may then be present in a content greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm. Similarly, the total content of F-230 series compounds in the composition may be greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm. For example, the compound (s) of the F-230 series may be present in a content of 1 to 5 ppm; or at a content of 5 to 10 ppm; or in a content of 10 to 25 ppm; or at a content of 25 to 50 ppm; or at a level of 50 to 75 ppm; or at a level of 75 to 100 ppm; or at a level of 100 to 150 ppm; or in a content of 150 to 200 ppm; or in a content of 200 to 250 ppm; or in a content of 250 to 300 ppm; or at a level of 300 to 350 ppm; or at a level of 350 to 400 ppm; or at a level of 400 to 450 ppm; or at a level of 450 to 500 ppm.
    [0013] For example, the total content of F-230 series compounds in the composition may be from 1 to 5 ppm; or from 5 to 10 ppm; or from 10 to 25 ppm; or from 25 to 50 ppm; or from 50 to 75 ppm; or 75 to 100 ppm; or from 100 to 150 ppm; or from 150 to 200 ppm; or from 200 to 250 ppm; or 250 to 300 ppm; or from 300 to 350 ppm; or from 350 to 400 ppm; or from 400 to 450 ppm; or from 450 to 500 ppm. The compositions according to the invention may in particular comprise one or more compounds of the F-240 series, each (except F-240db and except F-240aa, which may also lead to F-1234yf) being present in the composition in one form. content less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm; and the total content of F-240 series compounds (except F-240db and F-240aa) in the composition, preferably, less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm. It should be noted that the compound (s) of the F-240 series (except F-240db and F-240aa) may then be present in a content greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater or equal to 3 ppm, or greater than or equal to 5 ppm. Similarly, the total content of F-240 series compounds (except F-240db and F-240aa) in the composition may be greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm. For example, the compound (s) of the F-240 series (except F-240db and F-240aa) may be present in a content of 1 to 5 ppm; or at a content of 5 to 10 ppm; or in a content of 10 to 25 ppm; or at a content of 25 to 50 ppm; or at a level of 50 to 75 ppm; or at a level of 75 to 100 ppm; or at a level of 100 to 150 ppm; or in a content of 150 to 200 ppm; or in a content of 200 to 250 ppm; or in a content of 250 to 300 ppm; or at a level of 300 to 350 ppm; or at a level of 350 to 400 ppm; or at a level of 400 to 450 ppm; or at a level of 450 to 500 ppm. For example, the total content of F-240 series compounds (except F-240db and F-240aa) in the composition may be from 1 to 5 ppm; or from 5 to 10 ppm; or from 10 to 25 ppm; or from 25 to 50 ppm; or from 50 to 75 ppm; or 75 to 100 ppm; or from 100 to 150 ppm; or from 150 to 200 ppm; or from 200 to 250 ppm; or 250 to 300 ppm; or from 300 to 350 ppm; or from 350 to 400 ppm; or from 400 to 450 ppm; or from 450 to 500 ppm. F-240db and F-240aa may be present in significantly greater amounts than those listed above.
    [0014] The compositions according to the invention may especially comprise one or more compounds of the F-250 series, each being present in the composition in a content of less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm; and the total content of F-250 series compounds in the composition, preferably, less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm.
    [0015] It should be noted that the compound (s) of the F-250 series may then be present in a content greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm. Similarly, the total content of F-250 series compounds in the composition may be greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm. For example, the compound (s) of the F-250 series may be present in a content of 1 to 5 ppm; or at a content of 5 to 10 ppm; or in a content of 10 to 25 ppm; or at a content of 25 to 50 ppm; or at a level of 50 to 75 ppm; or at a level of 75 to 100 ppm; or at a level of 100 to 150 ppm; or in a content of 150 to 200 ppm; or in a content of 200 to 250 ppm; or in a content of 250 to 300 ppm; or at a level of 300 to 350 ppm; or at a level of 350 to 400 ppm; or at a level of 400 to 450 ppm; or at a level of 450 to 500 ppm. For example, the total content of F-250 series compounds in the composition may be from 1 to 5 ppm; or from 5 to 10 ppm; or from 10 to 25 ppm; or from 25 to 50 ppm; or from 50 to 75 ppm; or 75 to 100 ppm; or from 100 to 150 ppm; or from 150 to 200 ppm; or from 200 to 250 ppm; or 250 to 300 ppm; or from 300 to 350 ppm; or from 350 to 400 ppm; or from 400 to 450 ppm; or from 450 to 500 ppm.
    [0016] The compositions according to the invention may in particular comprise one or more compounds of the F-260 series, each being present in the composition in a content of less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm; and the total content of F-260 series compounds in the composition, preferably, less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm.
    [0017] It should be noted that the compound (s) of the F-260 series may then be present in a content greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm. Similarly, the total content of the F-260 series compounds in the composition may be greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm. For example, the compound (s) of the F-260 series may be present in a content of 1 to 5 ppm; or at a content of 5 to 10 ppm; or in a content of 10 to 25 ppm; or at a content of 25 to 50 ppm; or at a level of 50 to 75 ppm; or at a level of 75 to 100 ppm; or at a level of 100 to 150 ppm; or in a content of 150 to 200 ppm; or in a content of 200 to 250 ppm; or in a content of 250 to 300 ppm; or at a level of 300 to 350 ppm; or at a level of 350 to 400 ppm; or at a level of 400 to 450 ppm; or at a level of 450 to 500 ppm. For example, the total content of F-260 series compounds in the composition may be from 1 to 5 ppm; or from 5 to 10 ppm; or from 10 to 25 ppm; or from 25 to 50 ppm; or from 50 to 75 ppm; or 75 to 100 ppm; or from 100 to 150 ppm; or from 150 to 200 ppm; or from 200 to 250 ppm; or 250 to 300 ppm; or from 300 to 350 ppm; or from 350 to 400 ppm; or from 400 to 450 ppm; or from 450 to 500 ppm.
    [0018] The compositions according to the invention may in particular comprise F-1210xa, in a content of less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm.
    [0019] It should be noted that the F-1210xa can then be present in a content greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm. For example, F-1210xa may be present at a level of 1 to 5 ppm; or at a content of 5 to 10 ppm; or in a content of 10 to 25 ppm; or at a content of 25 to 50 ppm; or at a level of 50 to 75 ppm; or at a level of 75 to 100 ppm; or at a level of 100 to 150 ppm; or in a content of 150 to 200 ppm; or in a content of 200 to 250 ppm; or in a content of 250 to 300 ppm; or at a level of 300 to 350 ppm; or at a level of 350 to 400 ppm; or at a level of 400 to 450 ppm; or at a level of 450 to 500 ppm. The compositions according to the invention may especially comprise one or more compounds of the F-1220 series, each being present in the composition in a content of less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm; and the total content of compounds of the F-1220 series in the composition, preferably being less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm. It should be noted that the compound (s) of the F-1220 series may then be present in a content greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm. Likewise, the total content of compounds of the F-1220 series in the composition may be greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm.
    [0020] For example, the compound (s) of the F-1220 series may be present in a content of 1 to 5 ppm; or at a content of 5 to 10 ppm; or in a content of 10 to 25 ppm; or at a content of 25 to 50 ppm; or at a level of 50 to 75 ppm; or at a level of 75 to 100 ppm; or at a level of 100 to 150 ppm; or in a content of 150 to 200 ppm; or in a content of 200 to 250 ppm; or in a content of 250 to 300 ppm; or at a level of 300 to 350 ppm; or at a level of 350 to 400 ppm; or at a level of 400 to 450 ppm; or at a level of 450 to 500 ppm. For example, the total content of F-1220 series compounds in the composition may be from 1 to 5 ppm; or from 5 to 10 ppm; or from 10 to 25 ppm; or from 25 to 50 ppm; or from 50 to 75 ppm; or 75 to 100 ppm; or from 100 to 150 ppm; or from 150 to 200 ppm; or from 200 to 250 ppm; or 250 to 300 ppm; or from 300 to 350 ppm; or from 350 to 400 ppm; or from 400 to 450 ppm; or from 450 to 500 ppm. The compositions according to the invention may in particular comprise one or more compounds of the F-1230 series, each (except F-1230xf and F-1230xa, precursors of F-1234yf) being present in the composition in a content of less than or equal to at 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm; and the total content of F-1230 series compounds (except F-1230xf and F-1230xa) in the composition, preferably being less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm.
    [0021] It should be noted that the F-1230 series compound (s) (except F-1230xa and F-1230xf) may be present at a level greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater or greater. equal to 3 ppm, or greater than or equal to 5 ppm. Similarly, the total content of F-1230 series compounds (except F-1230xa and F-1230xf) in the composition may be greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm.
    [0022] For example, the compound (s) of the F-1230 series (except F-1230xa and F1230xf) may be present in a content of 1 to 5 ppm; or at a content of 5 to 10 ppm; or in a content of 10 to 25 ppm; or at a content of 25 to 50 ppm; or at a level of 50 to 75 ppm; or at a level of 75 to 100 ppm; or at a level of 100 to 150 ppm; or in a content of 150 to 200 ppm; or in a content of 200 to 250 ppm; or in a content of 250 to 300 ppm; or at a level of 300 to 350 ppm; or at a level of 350 to 400 ppm; or at a level of 400 to 450 ppm; or at a level of 450 to 500 ppm. For example, the total content of F-1230 series compounds (except F-1230xa and F-1230xf) in the composition can be from 1 to 5 ppm; or from 5 to 10 ppm; or from 10 to 25 ppm; or from 25 to 50 ppm; or from 50 to 75 ppm; or 75 to 100 ppm; or from 100 to 150 ppm; or from 150 to 200 ppm; or from 200 to 250 ppm; or 250 to 300 ppm; or from 300 to 350 ppm; or from 350 to 400 ppm; or from 400 to 450 ppm; or from 450 to 500 ppm.
    [0023] F-1230xf and F-1230xa may be present in significantly greater amounts than those listed above. The compositions according to the invention may especially comprise one or more compounds of the F-1240 series, each being present in the composition in a content of less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm; and the total content of F-1240 series compounds in the composition, preferably, less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm. It should be noted that the compound (s) of the F-1240 series can then be present in a content greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm. Similarly, the total content of F-1240 series compounds in the composition may be greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm. For example, the compound (s) of the F-1240 series may be present in a content of 1 to 5 ppm; or at a content of 5 to 10 ppm; or in a content of 10 to 25 ppm; or at a content of 25 to 50 ppm; or at a level of 50 to 75 ppm; or at a level of 75 to 100 ppm; or at a level of 100 to 150 ppm; or in a content of 150 to 200 ppm; or in a content of 200 to 250 ppm; or in a content of 250 to 300 ppm; or at a level of 300 to 350 ppm; or at a level of 350 to 400 ppm; or at a level of 400 to 450 ppm; or at a level of 450 to 500 ppm. For example, the total content of F-1240 series compounds in the composition may be from 1 to 5 ppm; or from 5 to 10 ppm; or from 10 to 25 ppm; or from 25 to 50 ppm; or from 50 to 75 ppm; or 75 to 100 ppm; or from 100 to 150 ppm; or from 150 to 200 ppm; or from 200 to 250 ppm; or 250 to 300 ppm; or from 300 to 350 ppm; or from 350 to 400 ppm; or from 400 to 450 ppm; or from 450 to 500 ppm. The compositions according to the invention may especially comprise one or more compounds of the F-1250 series, each being present in the composition in a content of less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm; and the total content of F-1250 series compounds in the composition, preferably, less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm. It should be noted that the compound (s) of the F-1250 series may then be present in a content greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm. Similarly, the total content of F-1250 series compounds in the composition may be greater than or equal to 1 ppm, or greater than or equal to 2 ppm, or greater than or equal to 3 ppm, or greater than or equal to 5 ppm. For example, the compound (s) of the F-1250 series may be present in a content of 1 to 5 ppm; or at a content of 5 to 10 ppm; or in a content of 10 to 25 ppm; or at a content of 25 to 50 ppm; or at a level of 50 to 75 ppm; or at a level of 75 to 100 ppm; or at a level of 100 to 150 ppm; or in a content of 150 to 200 ppm; or in a content of 200 to 250 ppm; or in a content of 250 to 300 ppm; or at a level of 300 to 350 ppm; or at a level of 350 to 400 ppm; or at a level of 400 to 450 ppm; or at a level of 450 to 500 ppm. For example, the total content of F-1250 series compounds in the composition may be from 1 to 5 ppm; or from 5 to 10 ppm; or from 10 to 25 ppm; or from 25 to 50 ppm; or from 50 to 75 ppm; or 75 to 100 ppm; or from 100 to 150 ppm; or from 150 to 200 ppm; or from 200 to 250 ppm; or 250 to 300 ppm; or from 300 to 350 ppm; or from 350 to 400 ppm; or from 400 to 450 ppm; or from 450 to 500 ppm. F-1243zf which induced cardiac toxicity in the sub-chronically exposed rat is a particularly undesirable impurity. Although the mechanism of action of this effect and its relevance to humans is not yet established, the maximum level allowed in F-1243zf in F-1234yf could be very low. Now the F-1243zf forms a quasi-azeotrope with F-1234yf. These two compounds are therefore inseparable by conventional distillation. Therefore, it is desirable to adjust the compositions according to the invention so as to limit the presence of F-1243zf precursors therein. Possible precursors of F-1243zf (by fluorination reaction) are F-1240za, F-1240zf, F-250fb (via one of the two previous ones), F-250da (via F-1240za) and the F-250db (via the F-1240zf). Thus, advantageous compositions according to the invention: comprise at least one compound from those of series F-1240 and F-250, in a content: less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; or comprise one or more of the F-1240 and F-250 series, the total content of all these compounds being less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; or else - comprise at least one of F-1240za, F-1240zf, F-250fb, F-250da and F-250db, in a content: less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; or comprise one or more of F-1240za, F-1240zf, F-250fb, F-250da and F-250db, the total content of all these compounds being less than or equal to 250ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm. F-1225ye also showed some degree of toxicity in the sub-chronically exposed rat. Moreover, it is a flammable substance. It is therefore desirable to limit its presence in admixture with F-1234yf (for example at a content of less than or equal to 5 ppm), and for this it is desirable to limit the presence of its precursors mixed with F-240db. Possible precursors of F-1225ye (by fluorination reaction) are F-1220xd, F-230da (via F-1220xd) and F-230ab (via F-1220xd). Thus, advantageous compositions according to the invention: comprise at least one compound from those of series F-1220 and F-230, in a content: less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; or comprise one or more of F-1220 and F-230, the total content of all these compounds being: 250 ppm or less; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; or else - comprise at least one of F-1220xd, F-230da and F-230ab, in a content: less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; or else - comprise one or more of F-1220xd, F-230da and F-230ab, the total content of all these compounds being: less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm.
    [0024] F-1225zc is another compound with different potential toxicological effects. It is therefore desirable to limit its presence in F-1234yf. But its boiling point is close to that of F-1234yf, which makes its separation by conventional distillation difficult. Therefore, it is desirable to adjust the compositions according to the invention so as to limit the presence of F-1225zc precursors therein. Possible precursors of F-1225zc (by fluorination reaction) are F-1220za, F-230fa (via F-1220za) and F-230da (via F-1220za). Thus, advantageous compositions according to the invention: comprise at least one compound among F-1220za, F-230fa and F-230da, in a content: less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; or comprise one or more of F-1220za, F-230fa and F-230da, the total content of all these compounds being less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm. More generally, it is thought that, because of their reactivity, the molecules which have a group = CF2 also have risks of toxicological effects. This concerns, in addition to the F-1225zc, the F-1234yc, the F-1234zc, the F -1225yc, F-1243zc, F-1243yc, F-1252zc and F-1216yc. Among these compounds, the most troublesome are F-1216yc, F-1243yc and F-1252zc, because of the difficulties in separating these compounds from F-1234yf because of their boiling point close to that of F-1234yf .
    [0025] Therefore, it is desirable to adjust the compositions according to the invention so as to limit the presence of precursors of F-1216yc therein. Possible precursors of F-1216yc (by fluorination reaction) are F-1210xa, F-220da (via F-1210xa) and F-220aa (via F-1210xa). Thus, advantageous compositions according to the invention: comprise at least one compound from those of series F-1210 and F-220, in a content: less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; or comprise one or more of the F-1210 and F-220 series, the total content of all these compounds being: 250 ppm or less; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; or else - comprise at least one of F-1210xa, F-220da and F-220aa, in a content: less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or at 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; or comprise one or more of F-1210xa, F-220da and F-220aa, the total content of all of these compounds being: 250 ppm or less; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm. It is also desirable to adjust the compositions according to the invention so as to limit the presence of precursors of F-1243yc therein. Possible precursors of F-1243yc (by fluorination reaction) are F-1240xa and F-250ab (via F-1240xa). Thus, advantageous compositions according to the invention: comprise at least one compound from F-1240xa and F-250ab, in a content: less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; or else - comprise one or more of F-1240xa and F-250ab, the total content of all these compounds being: less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm. It is also desirable to adjust the compositions according to the invention so as to limit the presence of precursors of F-1252zc therein. Possible precursors of F-1252zc (by fluorination reaction) are F-1250za, F-260fb (via F-1250za) and F-260db (via F-1250za). Thus, advantageous compositions according to the invention: comprise at least one compound from those of series F-1250 and F-260, in a content: less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; or comprise one or more of the F-1250 and F-260 series, the total content of all these compounds being: 250 ppm or less; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; or else - comprise at least one of F-1250za, F-260fb and F-260db, in a content: less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; or comprise one or more of F-1250za, F-260fb and F-260db, the total content of all these compounds being: 250 ppm or less; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm. In addition, F-1234ze is a substance that must not be present in too high a quantity mixed with F-1234yf. For example, the content of F-1234ze in F-1234yf should be less than or equal to 500 ppm. However, the boiling point of F-1234ze is close to that of F-1234yf, which makes conventional distillation separation difficult. For this reason, it is desirable to limit the presence of F-1234ze precursors in admixture with F-240db. Possible precursors of F-1234ze (by fluorination reaction) are F-1230za, F-1230zd, F-240fa and F-240da. Thus, advantageous compositions according to the invention: comprise at least one of F-1230za, F-1230zd, F-240fa and F-240da, in a content: less than or equal to 500 ppm; or from 400 to 500 ppm; or from 300 to 400 ppm; or from 200 to 300 ppm; or from 100 to 200 ppm; or less than or equal to 100 ppm, and for example from 1 to 100 ppm; or comprise one or more of F-1230za, F-1230zd, F-240fa and F-240da, the total content of all these compounds being: less than or equal to 500 ppm; or from 400 to 500 ppm; or from 300 to 400 ppm; or from 200 to 300 ppm; or from 100 to 200 ppm; or less than or equal to 100 ppm, and for example from 1 to 100 ppm.
    [0026] In view of the foregoing, advantageous compositions according to the invention include one or more of F-1240za, F-1240zf, F-250fb, F-250da and F-250db, the total content. all of these compounds being: less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; and furthermore - comprise one or more of F-1220za, F-230fa and F-230da, the total content of all such compounds being: 250 ppm or less; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; and furthermore - include one or more of F-1210xa, F-220da and F-220aa, the total content of all such compounds being: less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; and furthermore - comprise one or more of F-1240xa and F-250ab, the total content of all these compounds being: less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; and furthermore - include one or more of F-1250za, F-260fb and F-260db, the total content of all such compounds being: 250 ppm or less; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; and furthermore - comprise one or more of F-1220xd, F-230da and F-230ab, the total content of all these compounds being: less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; and furthermore - comprise one or more of F-1230za, F-1230zd, F-240fa and F-240da, the total content of all these compounds being: less than or equal to 500 ppm; or from 400 to 500 ppm; or from 300 to 400 ppm; or from 200 to 300 ppm; or from 100 to 200 ppm; or less than or equal to 100 ppm, and for example from 1 to 100 ppm. In addition, F-250fb, F-1240za and F-1240zf may be intermediate compounds in the production of F-240db, as set forth below. They are also precursors of F-1243zf and F-1243yc. Therefore, advantageous compositions according to the invention: comprise at least one of F-250fb, F-1240za and F-1240zf, in a content: less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; or comprise one or more of F-250fb, F-1240za and F-1240zf, the total content of all these compounds being less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm.
    [0027] Preparation of the Compositions According to the Invention The manufacture of F-240db is known, for example, from US Pat. No. 8,304,589, to which reference is expressly made herein. The document proposes a process in three steps: reaction of carbon tetrachloride with ethylene to produce F-250fb; thermal dehydrochlorination of F-250fb to obtain F-1240za or F-1240zf; and adding chlorine to F-1240za or F-1240zf to obtain F-240db.
    [0028] Certain variants of this process are also described in the documents US 4,650,914, US 2009/0216055, US 2014/0206911 and US 2013/0165705, to which reference is expressly made herein. A two-step process may also be contemplated, as described in US 3,446,859, to which reference is made herein specifically: reaction of methyl chloride with tetrachlorethylene to produce F-1230xa; hydrochlorination of F-1230xa to obtain F-240db. A one-step process can also be envisaged by reacting dichloromethane with trichlorethylene.
    [0029] The compositions according to the invention can then be obtained by carrying out one or more separation steps of F-240db with respect to the other compounds mentioned above. These separation steps can preferably be carried out by absorption / washing and distillation. Alternatively to the conventional distillation or in combination with it, it is also possible to provide separation by extractive distillation, physicochemical separations molecular sieve, alumina or activated carbon or a membrane separation. A first separation is generally carried out using a distillation (packed column, packed column) at atmospheric pressure or under reduced pressure. The pressure chosen is less than 760 mmHg, preferably less than 450 mmHg and more preferably less than 200 mmHg. Inherently, the pressure of the column determines the temperature conditions for a selected degree of separation. F-240db can be recovered by operating the distillation at a temperature below 180 ° C, preferably below 160 ° C and more preferably below 130 ° C. A single column or a distillation train can be used. Under selected conditions, the purity of the F-240db after distillation reaches at least 99.8%. A second separation can be carried out using an adsorption on zeolite or activated carbon. The active zeolites or carbons that can be used in the F-240db purification process advantageously have an average pore size of 3.4 to 11 A, preferably 3.4 to 10 A. If the zeolite or activated carbon has a size of with an average pore greater than 11 A, the amount of adsorbed F-240db increases, whereas if the average pore size is less than 3.4 A, the adsorption capacity of the zeolite or activated carbon is reduced.
    [0030] The zeolite preferably has an Si / Al ratio of 2 or less. If the Si / Al ratio of the zeolite is greater than two, some impurities are likely not to be selectively adsorbed. The zeolite is preferably at least one member selected from the group consisting of 4A molecular sieves, 5A molecular sieve, 10X molecular sieve and 13X molecular sieves.
    [0031] By using these zeolites, the water content in F-240db can also be reduced at the same time. The zeolite and the activated carbon are preferably used individually for the regeneration of the adsorbent, but these can also be used as a mixture. The proportions of zeolite and activated carbon in the mixture are not particularly important, however, it is preferable to use a higher amount of zeolite, which reduces the water content in the F-240db. To treat F-240db with zeolite and / or activated carbon in the liquid phase, a batch process or a continuous process may be used. Industrially, a method of continuously passing the F-240db on a fixed bed is preferable. Liquid hourly space velocity (LHSV) may be appropriately selected depending on the content of impurities to be removed and the amount of F-240db to be treated. In general, the space velocity is preferably from 1 to 50 hr-1. Industrially the purification process can alternatively use two adsorption towers. The treatment temperature of F-240db is 0 ° C to 120 ° C, preferably 20 ° C to 80 ° C. If the process temperature is above 120 ° C, the equipment cost may increase due to heating of the apparatus, whereas if the process temperature is below 0 ° C cooling equipment may be required. The pressure is 0 to 3 MPa, preferably 0 to 1 MPa. If the pressure is higher than 3 MPa, profitability may decrease due to the pressure requirements of the device. A membrane separation technique can also be used in addition to an adsorption on activated carbon or on zeolite, or alternatively to these techniques. Membrane separation can be carried out in the gas phase according to a continuous process operated at low pressure or at reduced pressure. The pressure chosen is less than 5 bar, preferably less than 2 bar and more preferably less than atmospheric pressure. The choice of the membrane depends on the properties of the impurities to be separated from the F-240db (difference in solubility, diffusivity and permeability).
    [0032] The membrane separation is carried out at a temperature dependent on the chosen pressure, less than 250 ° C, preferably less than 230 ° C and more preferably less than 180 ° C. When F-240db containing impurities is brought into contact with zeolite and / or activated carbon in the liquid phase and / or is purified on gas phase membrane under the conditions described above, F-240db can be obtained with purity greater than 99.9%. Manufacture of F-1234yf The compositions according to the invention can be used for the manufacture of F-1234yf having desired specifications, by one or more fluorination steps. The fluorination is preferably a catalytic gas phase fluorination with HF. The catalyst used 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. Mention may be made, for example, of FeCl 3, chromium oxyfluoride, chromium oxides (optionally subjected to fluorination treatments), chromium fluorides and mixtures thereof. Other possible catalysts are carbon supported catalysts, antimony catalysts, aluminum catalysts (eg AlF3 and Al2O3, alumina oxyfluoride and alumina fluoride).
    [0033] It is generally possible to use a chromium oxyfluoride, a fluoride or an aluminum oxyfluoride, or a supported or non-supported catalyst containing a metal such as Cr, Ni, Fe, Zn, Ti, V, Zr, Mo, Ge or Sn. Pb, Mg, Sb. Reference can be made in this regard to document WO 2007/079431 (at p.7, 1.1-5 and 28-32), EP 939071 (paragraph [0022]), WO 2008/054781 (at p.9). I.22-p.10 1.34), and WO 2008/040969 (claim 1), to which reference is expressly made. The catalyst is more preferably based on chromium and it is more particularly a mixed catalyst comprising chromium. According to one embodiment, 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 chromium, and from 0.5 to 20% by weight of nickel, preferably from 2 to 10% of each. 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 Pat. 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. Reference can be made to WO 2009/118628 (in particular in p.4, I.30-p.71.16), to which reference is expressly made herein. 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. Prior to use, the catalyst is preferably activated with air, oxygen or chlorine and / or with HF. For example, 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.
    [0034] 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 gas phase fluorination reaction can be carried out: with an HF / chlorine compound molar ratio of from 1: 1 to 150: 1, preferably from 3: 1 to 100: 1 and more preferably from 5: 1 to 50: 1; with a contact time of 1 to 100 seconds, preferably 1 to 50 seconds and more particularly 2 to 40 seconds (volume of catalyst divided by the total incoming flow, adjusted to the temperature and to the operating pressure); at an absolute pressure ranging from 0.1 to 50 bar, preferably from 0.3 to 15 bar; at a temperature (temperature of the catalyst bed) of 100 to 500 ° C, preferably of 200 to 450 ° C, and more particularly of 250 to 400 ° C.
    [0035] The duration of the reaction step is typically from 10 to 2000 hours, preferably from 50 to 500 hours and more preferably from 70 to 300 hours. An oxidizing agent, preferably 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. The fluorination product stream may undergo appropriate treatments (distillation, washing, etc.) to recover purified F-1234yf and separate it from other compounds present (HCI, unreacted HF, unreacted F-240db). other organic compounds). One or more streams can be recycled. It is also possible to provide catalyst regeneration steps, as described, for example, in documents WO 2012/098421 and WO 2012/098422 to which reference is expressly made. F-1234yf production can also be provided in two steps: first, fluorinating the F-240db composition to produce F-1233xf, and then fluorinating F-1233xf to produce F-1234yf. The same reactor or successive reactors can be used to carry out these steps. This type of process is described in particular in document WO 2013/088195 to which reference is expressly made.
    [0036] The flux of F-1234yf obtained preferably contains: - less than 500 ppm, or 250 ppm, or 200 ppm, or 150 ppm, or 100 ppm, or 50 ppm, or 25 ppm, or 10 ppm, or 5 ppm F-1243zf; and / or - less than 500 ppm, or 250 ppm, or 200 ppm, or 150 ppm, or 100 ppm, or 50 ppm, or 25 ppm, or 10 ppm, or 5 ppm, of F-1225zc; and / or - less than 500 ppm, or 250 ppm, or 200 ppm, or 150 ppm, or 100 ppm, or 50 ppm, or 25 ppm, or 10 ppm, or 5 ppm, of F-1216yc; and / or - less than 500 ppm, or 250 ppm, or 200 ppm, or 150 ppm, or 100 ppm, or 50 ppm, or 25 ppm, or 10 ppm, or 5 ppm, of F-1243yc; and / or - less than 500 ppm, or 250 ppm, or 200 ppm, or 150 ppm, or 100 ppm, or 50 ppm, or 25 ppm, or 10 ppm, or 5 ppm, of F-1252zc; and / or - less than 500 ppm, or 250 ppm, or 200 ppm, or 150 ppm, or 100 ppm, or 50 ppm, or 25 ppm, or 10 ppm, or 5 ppm, of F-1225ye; and / or - less than 500 ppm, or 250 ppm, or 200 ppm, or 150 ppm, or 100 ppm, or 50 ppm, or 25 ppm, or 10 ppm, or 5 ppm, of F-1234ze. Preferably, these contents are obtained at the end of the fluorination, without (or before any) purification step of the product stream. EXAMPLES The examples below illustrate in a comparative manner the fluorination reaction of F-240db compositions to obtain F-1234yf. The catalyst used (50 mL) is a mass catalyst based on chromium oxide. The activation comprises the following steps: - A drying step at atmospheric pressure under a stream of nitrogen at a temperature of about 275 ° C for 120 hours. - A first activation step at a temperature of about 275 ° C under a nitrogen and hydrofluoric acid mixture gradually reducing the nitrogen for 41 hours. A plateau under pure HF is then observed for 41 hours, increasing the temperature to 350 ° C. A second activation step with air for 101 hours at 350 ° C. before carrying out the fluorination reaction. Example 1 In this example, a fluorination reaction is carried out from a composition containing F-240db at a high purity (content F-240db greater than 99.95%). The reaction conditions are as follows: HF / F-240db molar ratio: 20; oxygen / F-240db molar ratio: 0.2; - contact time: 10 s; - pressure: atmospheric pressure; temperature: 350 ° C. After 125 hours under these conditions, the gas flow leaving the reactor is analyzed, after washing, by gas chromatography. The conversion of F-240db is 100%. The flow analysis is shown in the table below (values in mol%): Product detected CO concentration 0.91 CO2 1.50 F-143a 0.23 F-1234yf 8.31 F-245cb 1.84 F -1233xf 85.98 F-1223xd 1.23 Other traces At the end of this preliminary reaction stage, the products are separated by distillation on a Sulzer-type packed column. The F1234yf obtained is very pure (purity greater than 99.95%).
    [0037] Example 2 In this example, a fluorination reaction is carried out from a composition containing 99.43% F-240db and 0.57% F-250fb. The conditions of the reaction are as follows: HF / chlorinated organic mole ratio: 20; - Oxygen / organic chlorine mole ratio: 0.2; - contact time: 10 s; - pressure: atmospheric pressure; temperature: 350 ° C.
    [0038] After 51 hours under these conditions, the gas stream leaving the reactor is analyzed, after washing, by gas chromatography. The conversion of F-240db and F-250fb is 100%. The flow analysis is shown in the table below (values in mol%): Product detected CO concentration 1.63 CO2 0.82 F-143a 0.22 F-1243zf 0.54 F-1234yf 12.67 F -245cb 3.02 F-1242zf traces F-1233xf 80.49 F-253fb traces F-1223xd 0.61 Other traces After this preliminary reaction stage, the products are separated by distillation on a packed column. Sulzer type. The results obtained show that F-1243zf and F-1234yf do not separate by distillation.
    [0039] Industrially, the use of such a raw material would lead to obtaining a flow of F-1234yf containing more than 500 ppm F-1243zf.
    [0040] Example 3 In this example, a fluorination reaction of a composition containing 99.62% F-240db and 0.38% F-230fa is carried out. The conditions of the reaction are the same as in Example 2.
    [0041] After 62 hours under these conditions, the gas flow leaving the reactor is analyzed, after washing, by gas chromatography. The conversion of F-240db and F-230fa is 100%. The flow analysis is shown in the table below (values in% molar): Product detected Concentration CO 2.03 CO2 1.32 F-143a 0.19 F-1225zc 0.02 F-1234yf 11.04 F -245cb 2.41 F-236fa 0.18 F-1224 0.04 F-1233xf 81.51 F-226da traces F-235fa 0.01 F-1214 traces F-1223xd 1.24 F-1213xa 0.01 Unknown traces At the end of this preliminary reaction stage, the products are separated by distillation on a Sulzer-type packed column. The results obtained show that F-1225zc and F-1234yf poorly separate by distillation.
    [0042] Industrially, the use of such a raw material would lead to obtaining a flow of F-1234yf containing more than 500 ppm F-1225zc.
    权利要求:
    Claims (14)
    [0001]
    REVENDICATIONS1. Composition comprising at least 99% by weight of 1,1,1,2,3-pentachloropropane, and comprising at least one compound selected from a list of additional compounds consisting of trichloropropanes, tetrachloropropanes, pentachloropropanes different from 1,1, 1,2,3-pentachloropropane, hexachloropropanes, heptachloropropanes, dichloropropenes, trichloropropenes, tetrachloropropenes, pentachloropropenes and hexachloropropene, said compound being present in the composition in a weight content of less than or equal to 500 ppm.
    [0002]
    2. Composition according to claim 1, wherein said compound is present in the composition in a weight content of less than or equal to 250 ppm; preferably less than or equal to 150 ppm; more particularly less than or equal to 100 ppm; more particularly less than or equal to 50 ppm; and ideally less than or equal to 10 ppm.
    [0003]
    A composition according to claim 1 or 2, comprising a plurality of compounds selected from said list of additional compounds, each of said plurality of compounds being present in the composition in a weight content of less than or equal to 500 ppm; preferably less than or equal to 250 ppm; preferably less than or equal to 150 ppm; more particularly less than or equal to 100 ppm; more particularly less than or equal to 50 ppm; and ideally less than or equal to 10 ppm.
    [0004]
    4. Composition according to one of claims 1 to 3, comprising a plurality of compounds selected from said list of additional compounds, the total weight content of all compounds of said list being less than or equal to 1000 ppm; preferably less than or equal to 500 ppm; preferably less than or equal to 250 ppm; preferably less than or equal to 150 ppm; more particularly less than or equal to 100 ppm; more particularly less than or equal to 50 ppm; and ideally less than or equal to 10 ppm.
    [0005]
    5. Composition according to one of claims 1 to 4, which comprises at least 99.5% by weight, and preferably at least 99.8% by weight, and more preferably at least 99.9% by weight. , 1,1,1,2,3-pentachloropropane.
    [0006]
    6. Composition according to one of claims 1 to 5, comprising at least one compound selected from the group consisting of 1,1,1,3-tetrachloropropane, 3,3,3-trichloropropene and 1,1,3,3-tetrachloropropane. trichloropropene, and wherein the weight content of each of these compounds in the composition is less than or equal to 100 ppm, preferably less than or equal to 50 ppm; and wherein, optionally, the total weight content of the compounds of this group in the composition is less than or equal to 100 ppm, preferably less than or equal to 50 ppm.
    [0007]
    7. Composition according to one of claims 1 to 6, comprising at least one compound selected from trichloropropenes and tetrachloropropanes, the weight content of each of these compounds in the composition being less than or equal to 250 ppm, preferably less than or equal to at 150 ppm; and wherein, optionally, the total weight content of trichloropropenes and tetrachloropropanes in the composition is less than or equal to 250 ppm, preferably less than or equal to 150 ppm.
    [0008]
    8. Composition according to one of claims 1 to 7, comprising at least one compound selected from pentachloropropènes and hexachloropropanes, the weight content of each of these compounds in the composition being less than or equal to 50 ppm, preferably less than or equal to at 10 ppm; and wherein, optionally, the total weight content of the pentachloropropenes and hexachloropropanes in the composition is less than or equal to 50 ppm, preferably less than or equal to 10 ppm.
    [0009]
    9. Composition according to one of claims 1 to 8, comprising at least one compound selected from hexachloropropene and heptachloropropanes, the weight content of each of these compounds in the composition being less than or equal to 50 ppm, preferably lower or equal to 10 ppm; and wherein, optionally, the total weight content of hexachloropropene and heptachloropropanes in the composition is less than or equal to 50 ppm, preferably less than or equal to 10 ppm.
    [0010]
    10. Composition according to one of claims 1 to 9, comprising at least one compound selected from dichloropropènes and trichloropropanes, the weight content of each of these compounds in the composition being less than or equal to 50 ppm, preferably less than or equal to at 10 ppm; and wherein, optionally, the total weight content of the dichloropropenes and trichloropropanes in the composition is less than or equal to 50 ppm, preferably less than or equal to 10 ppm.
    [0011]
    11. Composition according to one of claims 1 to 10, comprising at least one compound selected from the group consisting of 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene, 1,1,3,3-tetrachloropropene, 1,3,3-pentachloropropane and 1,1,2,3,3-pentachloropropane, and wherein the weight content of each of these compounds in the composition is less than or equal to 500 ppm, preferably less than or equal to 300 ppm; and wherein, optionally, the total weight content of the compounds of this group in the composition is less than or equal to 500 ppm, preferably less than or equal to 300 ppm.
    [0012]
    12. Process for the production of 2,3,3,3-tetrafluoropropene, comprising: - the provision of a composition according to one of claims 1 to 11, - the reaction of this composition with hydrofluoric acid in gaseous phase. .
    [0013]
    The process of claim 12 comprising a single catalytic fluorination step.
    [0014]
    14. The method of claim 12, comprising two successive stages of catalytic fluorination, namely: the reaction of the composition with hydrofluoric acid in gaseous phase, to produce an intermediate product; optionally, a purification of the intermediate product; then - reacting the intermediate product with hydrofluoric acid in the gas phase, to produce 2,3,3,3-tetrafluoropropene; the intermediate product is preferably 2-chloro-3,3,3-trifluoropropene.
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    同族专利:
    公开号 | 公开日
    CN107074697A|2017-08-18|
    US10207971B2|2019-02-19|
    WO2016059322A1|2016-04-21|
    US20170226035A1|2017-08-10|
    FR3027303B1|2016-10-07|
    JP2020203898A|2020-12-24|
    EP3207010A1|2017-08-23|
    JP6807837B2|2021-01-06|
    US20190127302A1|2019-05-02|
    MX2017004282A|2017-07-19|
    JP2017531014A|2017-10-19|
    US10494321B2|2019-12-03|
    EP3207010B1|2021-05-19|
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    法律状态:
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    2016-04-22| PLSC| Publication of the preliminary search report|Effective date: 20160422 |
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    2018-09-13| PLFP| Fee payment|Year of fee payment: 5 |
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    2020-09-14| PLFP| Fee payment|Year of fee payment: 7 |
    2021-09-13| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1459926A|FR3027303B1|2014-10-16|2014-10-16|COMPOSITIONS BASED ON 1,1,1,2,3-PENTACHLOROPROPANE|FR1459926A| FR3027303B1|2014-10-16|2014-10-16|COMPOSITIONS BASED ON 1,1,1,2,3-PENTACHLOROPROPANE|
    EP15798153.1A| EP3207010B1|2014-10-16|2015-10-07|Compositions comprising 1,1,1,2,3 pentachloropropane|
    US15/518,605| US10207971B2|2014-10-16|2015-10-07|Compositions comprising 1,1,1,2,3 pentachloropropane|
    CN201580056352.1A| CN107074697A|2014-10-16|2015-10-07|Include the composition of 1,1,1,2,3 pentachloropropanes|
    JP2017520391A| JP6807837B2|2014-10-16|2015-10-07|Composition based on 1,1,1,2,3-pentachloropropane|
    PCT/FR2015/052692| WO2016059322A1|2014-10-16|2015-10-07|Compositions comprising 1,1,1,2,3 pentachloropropane|
    MX2017004282A| MX2017004282A|2014-10-16|2015-10-07|Compositions comprising 1,1,1,2,3 pentachloropropane.|
    US16/225,172| US10494321B2|2014-10-16|2018-12-19|Compositions comprising 1,1,1,2,3 pentachloropropane|
    JP2020136609A| JP2020203898A|2014-10-16|2020-08-13|Compositions based on 1,1,1,2,3 pentachloropropane|
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