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    • 专利摘要:
    The present invention relates to a process for producing 2,3,3,3-tetrafluoropropene comprising the steps of: i) in a first reactor, contacting a stream A comprising 2-chloro-3,3,3-trifluoropropene with hydrofluoric acid in the gas phase in the presence of a catalyst to produce a stream B comprising unreacted 2,3,3,3-tetrafluoropropene, HF and 2-chloro-3,3,3-trifluoropropene; and ii) in a second reactor, contacted in the gas phase in the presence or absence of a hydrofluoric acid catalyst with a stream comprising at least one chlorinated compound selected from the group consisting of 1,1,1,2,3 -pentachloropropane, 2,3-dichloro-1,1,1-trifluoropropane, 2,3,3,3-tetrachloropropene and 1,1,2,3-tetrachloropropene to produce a stream C comprising 2-chloro-3,3, 3-trifluoropropene, characterized in that the stream B obtained in step i) feeds said second reactor used for step ii); and in that the electrical conductivity of said stream A supplied in step i) is less than 15 mS / cm.
    公开号:FR3078700A1
    申请号:FR1851954
    申请日:2018-03-07
    公开日:2019-09-13
    发明作者:Laurent Wendlinger；Dominique Deur-Bert；Anne Pigamo
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    Technical field of the invention
    The present invention relates to the production of hydrofluoroolefins. More particularly, the present invention relates to the production of 2,3,3,3-tetrafluoropropene.
    Technological background of the invention
    Halogenated hydrocarbons, in particular fluorinated hydrocarbons such as hydrofluoroolefins, are compounds which have a useful structure as functional materials, solvents, refrigerants, blowing agents and monomers for functional polymers or starting materials for such monomers. Hydrofluoroolefins such as 2,3,3,3-tetrafluoropropene (HFO-1234yf) attract attention because they offer promising behavior as refrigerants with low global warming potential.
    The processes for producing fluoroolefins are usually carried out in the presence of a starting material such as an alkane containing chlorine or an alkene containing chlorine, and in the presence of a fluorinating agent such as hydrogen fluoride. These processes can be carried out in the gas phase or in the liquid phase, with or without the catalyst.
    We know for example from US 2009/0240090, a gas phase process for the preparation of 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) from 1,1,1,2,3pentachloropropane (HCC-240db ). The HCFO-1233xf thus produced is converted into 2-chloro-
    1.1.1.2- tetrafluoropropane (HCFC-244bb) in the liquid phase then the latter is converted into
    2.3.3.3- tetrafluoropropene.
    Also known from WO 2011/077192, a process for preparing 2,3,3,3tetrafluoropropene comprising in particular a step of bringing 2-chloro-3,3,3trifluoropropene into contact with HF in the gas phase in the presence of a catalyst of fluoridation.
    There is always a need for more efficient processes for producing 2,3,3,3-tetrafluoropropene.
    Summary of the invention
    The present invention relates to a process for the production of 2,3,3,3tetrafluoropropene comprising the steps:
    i) in a first reactor, bringing a stream A comprising 2-chloro-3,3,3trifluoropropene into contact with hydrofluoric acid in the gas phase in the presence of a catalyst to produce a stream B comprising 2.3, 3,3-tetrafluoropropene, HCl, HF and 2-chloro-3,3,3trifluoropropene unreacted; and ii) in a second reactor, brought into contact in the gas phase in the presence or absence of a hydrofluoric acid catalyst with a stream comprising at least one chlorinated compound selected from the group consisting of 1,1,1,2,3 -pentachloropropane, 2,3-dichloro-l, l, ltrifluoropropane, 2,3,3,3-tetrachloropropene and 1,1,2,3-tetrachloropropene to produce a stream C comprising 2-chloro-3,3,3- trifluoropropene, characterized in that the stream B obtained in step i) feeds said second reactor used for step ii); and in that the electrical conductivity of said current A supplied in step i) is less than 15 mS / cm.
    The present process makes it possible to optimize and improve the production of 2,3,3,3tetrafluoropropene. An electrical conductivity value of less than 15 mS / cm of current A before the implementation of the fluorination or dehydrohalogenation step makes it possible to guarantee optimum efficiency of the reaction in terms of conversion and selectivity. If a catalyst is present, such a value also ensures optimum efficiency of the catalyst.
    According to a preferred embodiment, step i) is carried out in the presence of a catalyst, preferably a chromium-based catalyst, in particular said catalyst comprises a chromium oxyfluoride or a chromium oxide or a fluoride. chromium or a mixture thereof; and step ii) is carried out in the presence or absence of a catalyst, advantageously step ii) is carried out in the presence of a catalyst, preferably a chromium-based catalyst, in particular said catalyst comprises a chromium oxyfluoride or a chromium oxide or a chromium fluoride or a mixture of these.
    According to a preferred embodiment, the catalyst is based on chromium and also comprises a cocatalyst selected from the group consisting of Ni, Zn, Co, Mn or Mg, preferably the cocatalyst content is between 0, 01% and 10% based on the total weight of the catalyst.
    According to a preferred embodiment, stream C also comprises 2,3,3,3tetrafluoropropene, HF, HCl and 1,1,1,2,2-pentafluoropropane.
    According to a preferred embodiment, stream C is purified, preferably by distillation, to form a stream Cl comprising 2,3,3,3-tetrafluoropropene, HCl and 1,1,1,2,2pentafluoropropane, and a stream C2 comprising HF and 2-chloro-3,3,3-trifluoropropene.
    According to a preferred embodiment, said stream C2 is recycled in step i).
    According to a preferred embodiment, said current C2 recycled in step i) has an electrical conductivity of less than 15 mS / cm.
    According to a preferred embodiment, said stream B and said at least one chlorinated compound are brought into contact prior to the entry thereof into said second reactor.
    According to a preferred embodiment, the pressure at the inlet of said first reactor in step i) is greater than the pressure at the inlet of said second reactor in step ii), preferably the pressure difference between the pressure at the inlet of said first reactor and the pressure at the inlet of said second reactor is from 100 mbar to 3.5 bar, advantageously from 150 mbar to 3.0 bar, preferably from 300 mbar to 2.5 bar, more preferably from 400 mbar to 2.0 bar, in particular from 750 mbar to 1.75 bar, more particularly from 1 to 1.5 bar.
    According to a preferred embodiment, the temperature at which step i) is implemented is different from that at which step ii) is implemented; and the difference between the temperature at which step i) is carried out and the temperature at which step ii) is carried out is greater than 0.2 ° C., advantageously greater than 0.5 ° C., preferably greater than 1 ° C, more preferably greater than 5 ° C, in particular greater than 10 ° C; and less than 60 ° C, advantageously less than 55 ° C, preferably less than 50 ° C, more preferably less than 45 ° C, in particular less than 40 ° C, more particularly less than 35 ° C, preferably less at 30 ° C, preferably less than 25 ° C, particularly preferably less than 20 ° C.
    According to a preferred embodiment, step i) is carried out at a temperature below the temperature at which step ii) is carried out; and the difference between the temperature at which step i) is carried out and the temperature at which step ii) is carried out is greater than 0.2 ° C., advantageously greater than 0.5 ° C., preferably greater than 1 ° C, more preferably greater than 5 ° C, in particular greater than 10 ° C; and less than 60 ° C, advantageously less than 55 ° C, preferably less than 50 ° C, more preferably less than 45 ° C, in particular less than 40 ° C, more particularly less than 35 ° C, preferably less at 30 ° C, preferably less than 25 ° C, particularly preferably less than 20 ° C.
    According to a preferred embodiment, stream C is cooled to a temperature below 100 ° C., then distilled to form a stream Cl comprising 2,3,3,3tetrafluoropropene, HCl and 1,1,1,2,2-pentafluoropropane , and a stream C2 comprising HF and 2-chloro-3,3,3-trifluoropropene; the temperature at the top of the distillation column is from -35 ° C to 10 ° C and the distillation is carried out at a pressure is from 2 to 6 bara; said second stream obtained at the bottom of the distillation column is recycled in step i).
    According to a preferred embodiment, step i) and / or step ii) are carried out in the presence of hydrofluoric acid having an electrical conductivity of less than 10 mS / cm.
    Detailed description of the present invention
    The present invention relates to a process for the production of 2,3,3,3tetrafluoropropene comprising the steps:
    i) in a first reactor, bringing a stream A comprising 2-chloro-3,3,3trifluoropropene into contact with hydrofluoric acid in the gas phase in the presence of a catalyst to produce a stream B comprising 2.3, 3,3-tetrafluoropropene, HCl, HF and 2-chloro-3,3,3trifluoropropene unreacted; and ii) in a second reactor, brought into contact in the gas phase in the presence or absence of a hydrofluoric acid catalyst with a stream comprising at least one chlorinated compound selected from the group consisting of 1,1,1,2,3 -pentachloropropane, 2,3-dichloro-l, l, ltrifluoropropane, 2,3,3,3-tetrachloropropene and 1,1,2,3-tetrachloropropene to produce a stream C comprising 2-chloro-3,3,3- trifluoropropene.
    Preferably, the stream B obtained in step i) feeds said second reactor used for step ii).
    According to a preferred embodiment, the electrical conductivity of said current A supplied in step i) is less than 15 mS / cm. Advantageously, the electrical conductivity of said current A supplied in step i) is less than 14 mS / cm, preferably less than 13 mS / cm, more preferably less than 12 mS / cm, in particular less than 11 mS / cm, more particularly less than 10 mS / cm, preferably less than 9 mS / cm, advantageously less than 8 mS / cm, preferably less than 7 mS / cm, more preferably less than 6 mS / cm, particularly preferably less than 5 mS / cm. The electrical conductivity is measured using an inductive conductivity measuring cell and according to the practice known to those skilled in the art. Preferably, the measuring cell is coated with a material resistant to a corrosive medium, in particular resistant to hydrofluoric acid.
    The electrical conductivity of said current A is measured prior to step i). Preferably, the electrical conductivity of said current A is measured when the latter is in liquid form. Said method according to the present invention can therefore comprise a step of heating and vaporizing said stream A prior to the implementation of step i) to supply said stream A in gaseous form. Preferably, said current A implemented in step i) is in gaseous form when it is brought into contact with HF.
    Preferably, step i) is carried out in the presence of a catalyst. Preferably, step ii) is carried out in the presence or absence of a catalyst, in particular step ii) is carried out in the presence of a catalyst. Preferably, the catalyst is based on chromium. Preferably, the chromium-based catalyst can be a chromium oxide (for example CrCh, CrO 3 or C ^ Ch), a chromium oxyfluoride or a chromium fluoride (for example OF3) or a mixture of these. The chromium oxyfluoride may contain a fluorine content of between 1 and 60% by weight based on the total weight of the chromium oxyfluoride, advantageously between 5 and 55% by weight, preferably between 10 and 52% by weight, more preferably between 15 and 52% by weight, in particular between 20 and 50% by weight, more particularly between 25 and 45% by weight, preferably between 30 and 45% by weight, more preferably between 35 and 45% by weight of fluorine based on the total weight of chromium oxyfluoride. The catalyst can also comprise a co-catalyst chosen from the group consisting of Ni, Co, Zn, Mg, Mn, Fe, Zn, Ti, V, Zr, Mo, Ge, Sn, Pb, Sb; preferably Ni, Co, Zn, Mg, Mn; in particular Ni, Co, Zn. The content by weight of the cocatalyst is between 1 and 10% by weight based on the total weight of the catalyst. The catalyst can be supported or not. A support such as alumina, activated alumina, aluminum halides (AIF3 for example), aluminum oxyhalides, activated carbon, magnesium fluoride or graphite can be used.
    Preferably, the catalyst can have a specific surface between 1 and 100 m 2 / g, preferably between 5 and 80 m 2 / g, more preferably between 5 and 70 m 2 / g, ideally between 5 and 50 m 2 / g , in particular between 10 and 50 m 2 / g, more particularly between 15 and 45 m 2 / g.
    According to a preferred embodiment, the electrical conductivity of said current comprising at least one chlorine compound selected from the group consisting of 1,1,1,2,3pentachloropropane, 2,3-dichloro-l, l, l-trifluoropropane, 2, 3,3,3-tetrachloropropene and
    1,1,2,3-tetrachloropropene is less than 15 mS / cm. Advantageously, the electrical conductivity of said current comprising at least one chlorine compound selected from the group consisting of 1,1,1,2,3-pentachloropropane, 2,3-dichloro-l, l, l-trifluoropropane, 2,3,3 , 3tetrachloropropene and 1,1,2,3-tetrachloropropene is less than 14 mS / cm, preferably less than 13 mS / cm, more preferably less than 12 mS / cm, in particular less than 11 mS / cm, more particularly less than 10 mS / cm, preferably less than 9 mS / cm, advantageously less than 8 mS / cm, preferably less than 7 mS / cm, more preferably less than 6 mS / cm, particularly preferred way less than 5 mS / cm.
    According to a particular embodiment, the hydrofluoric acid used in step ii) comes from stream B of step i). Hydrofluoric acid can also be added to stream B before, or simultaneously with, bringing it into contact with said stream comprising at least one chlorinated compound as defined in the present invention.
    According to a preferred embodiment, said stream B, to which hydrofluoric acid is optionally added, and said at least one chlorinated compound are brought into contact prior to the entry of these into said second reactor. Preferably, said at least one chlorinated compound is in the liquid state. This is vaporized by mixing with said stream B, to which hydrofluoric acid is optionally added. The resulting mixture is then in gaseous form. In particular, the mixing between said stream B, to which hydrofluoric acid is optionally added, and said at least one chlorinated compound is carried out in a static mixer. Preferably, said at least one chlorinated compound is introduced into the static mixer via one or more spray nozzles. Said at least one chlorinated compound is thus sprayed in the form of droplets before being vaporized by mixing with said stream B, to which hydrofluoric acid is optionally added; thus forming a mixture in gaseous form. Spraying said at least one chlorinated compound in the form of fine droplets makes it possible to ensure a more efficient vaporization of the latter. For example, the average diameter of the droplets thus produced can be less than 500 μm.
    According to a preferred embodiment, the pressure at the inlet of said first reactor is atmospheric pressure or a pressure greater than this, advantageously the pressure at the inlet of said first reactor is greater than 1.5 bara, preferably greater at 2.0 bara, in particular greater than 2.5 bara, more particularly greater than 3.0 bara. Preferably, step i) is carried out at a pressure at the inlet of said first reactor of between atmospheric pressure and 20 bara, preferably between 2 and 18 bara, more preferably between 3 and 15 bara.
    Preferably, step i) of the present method is implemented with a contact time between 1 and 100 s, preferably between 2 and 75 s, in particular between 3 and 50 s. Preferably, the HF / 1233xf molar ratio can vary between 1: 1 and 150: 1, preferably between 2: 1 and 125: 1, more preferably between 3: 1 and 100: 1. An oxidant, such as oxygen or chlorine, can be added during step i). The molar ratio of the oxidant to the hydrocarbon compound can be between 0.005 and 2, preferably between 0.01 and 1.5. The oxidant can be pure oxygen, air or a mixture of oxygen and nitrogen.
    According to a preferred embodiment, the pressure at the inlet of said first reactor in step i) is greater than the pressure at the inlet of said second reactor in step ii), preferably the pressure difference between the pressure at the inlet of said first reactor and the pressure at the inlet of said second reactor is from 100 mbar to 3.5 bar, advantageously from 150 mbar to 3.0 bar, preferably from 300 mbar to 2.5 bar, more preferably from 400 mbar to 2.0 bar, in particular from 750 mbar to 1.75 bar, more particularly from 1 to 1.5 bar.
    As mentioned above, the pressure at the inlet of said second reactor is lower than that at the inlet of said first reactor. Thus, the pressure at the inlet of said second reactor can be lower than atmospheric pressure. The pressure at the inlet of said second reactor can be greater than 1.5 bara while being lower than that at the inlet of said first reactor, preferably greater than 2.0 bara while being lower than that at the inlet of said first first reactor, in particular greater than 2.5 bara while being less than that at the inlet of said first reactor, more particularly greater than 3.0 bara while being less than that at the inlet of said first reactor. Preferably, step ii) is carried out at a pressure between atmospheric pressure and 20 bara while being lower than that at the inlet of said first reactor, preferably between 2 and 18 bara while being lower than that at the inlet of said first reactor, more preferably between 3 and 15 bara while being less than that at the inlet of said first reactor.
    Preferably, step ii) of the present method is implemented with a contact time between 1 and 100 s, preferably between 2 and 75 s, in particular between 3 and 50 s. Preferably, the HF / chlorine compound molar ratio can vary between 1: 1 and 150: 1, preferably between 2: 1 and 125: 1, more preferably between 3: 1 and 100: 1. An oxidant, such as oxygen or chlorine, can be added during step ii). The molar ratio of the oxidant to the hydrocarbon compound can be between 0.005 and 2, preferably between 0.01 and 1.5. The oxidant can be pure oxygen, air or a mixture of oxygen and nitrogen.
    According to a preferred embodiment, step i) is carried out at a temperature between 310 ° C and 420 ° C, advantageously between 310 ° C and 400 ° C, preferably between 310 ° C and 375 ° C, more preferably between 310 ° C and 360 ° C, in particular between 330 ° C and 360 ° C.
    According to a preferred embodiment, step ii) is carried out at a temperature between 320 ° C and 440 ° C, advantageously between 320 ° C and 420 ° C, preferably between 330 ° C and 400 ° C, more preferably between 330 ° C and 390 ° C, in particular between 340 ° C and 380 ° C.
    Step i) can be carried out at a temperature different or equal to that of step ii). When stage i) is carried out at a temperature different from that of stage ii), stage i) can be carried out at a temperature lower than that of stage ii) or at a higher temperature to that of step ii).
    According to a preferred embodiment, the difference between the temperature at which step i) is carried out and the temperature at which step ii) is carried out is greater than 0.2 ° C., advantageously greater than 0.5 ° C, preferably greater than 1 ° C, more preferably greater than 5 ° C, in particular greater than 10 ° C; and less than 60 ° C, advantageously less than 55 ° C, preferably less than 50 ° C, more preferably less than 45 ° C, in particular less than 40 ° C, more particularly less than 35 ° C, preferably less at 30 ° C, preferably less than 25 ° C, particularly preferably less than 20 ° C.
    Preferably, step i) is carried out at a temperature below the temperature at which step ii) is carried out; and the difference between the temperature at which step i) is carried out and the temperature at which step ii) is carried out is greater than 0.2 ° C., advantageously greater than 0.5 ° C., preferably greater than 1 ° C, more preferably greater than 5 ° C, in particular greater than 10 ° C.
    Preferably, step i) is carried out at a temperature below the temperature at which step ii) is carried out; and the difference between the temperature at which step i) is carried out and the temperature at which step ii) is carried out is greater than 0.2 ° C., advantageously greater than 0.5 ° C., preferably greater than 1 ° C, more preferably greater than 5 ° C, in particular greater than 10 ° C, and less than 60 ° C, advantageously less than 55 ° C, preferably less than 50 ° C, more preferably less than 45 ° C, in particular less than 40 ° C, more particularly less than 35 ° C, preferably less than 30 ° C, preferably less than 25 ° C, particularly less than 20 ° C.
    Alternatively, step i) is implemented at a temperature higher than the temperature at which step ii) is implemented; and the difference between the temperature at which step i) is carried out and the temperature at which step ii) is carried out is greater than 0.2 ° C., advantageously greater than 0.5 ° C., preferably greater than 1 ° C, more preferably greater than 5 ° C, in particular greater than 10 ° C.
    Preferably, step i) is carried out at a temperature higher than the temperature at which step ii) is carried out; and the difference between the temperature at which step i) is carried out and the temperature at which step ii) is carried out is greater than 0.2 ° C., advantageously greater than 0.5 ° C., preferably greater than 1 ° C, more preferably greater than 5 ° C, in particular greater than 10 ° C, and less than 60 ° C, advantageously less than 55 ° C, preferably less than 50 ° C, more preferably less than 45 ° C, in particular less than 40 ° C, more particularly less than 35 ° C, preferably less than 30 ° C, preferably less than 25 ° C, particularly less than 20 ° C.
    Preferably, in addition to 2-chloro-3,3,3-trifluoropropene, stream C also comprises 2,3,3,3-tetrafluoropropene, HF, HCl and 1,1,1,2,2-pentafluoropropane. This can be purified, preferably by distillation, to form a stream C1 comprising 2,3,3,3tetrafluoropropene, HCl and 1,1,1,2,2-pentafluoropropane, and a stream C2 comprising HF and 2chloro-3 , 3,3-trifluoropropene.
    Preferably, said stream C is distilled under conditions sufficient to form said stream Cl comprising 2,3,3,3-tetrafluoropropene, HCl and 1,1,1,2,2-pentafluoropropane, and said stream C2 comprising HF and 2 chloro-3,3,3-trifluoropropene. In particular, the distillation can be carried out at a pressure of 2 to 6 bara, more particularly at a pressure of 3 to 5 bara. In particular, the temperature at the top of the distillation column is from -35 ° C to 10 ° C, preferably from -20 ° C to 0 ° C.
    Preferably, said stream C2 is recycled in step i). Said stream C2 can optionally be purified, in particular by distillation, before being recycled in step i). The purification of said second stream can possibly be implemented for impurities possibly present in it. Said current C2 recycled in step i) may have an electrical conductivity of less than 15 mS / cm.
    According to a preferred embodiment, said stream C obtained in step ii) is cooled before the purification mentioned above. In particular, said stream C obtained in step ii) is cooled to a temperature below 100 ° C., then distilled to form said first stream comprising 2,3,3,3-tetrafluoropropene, HCl and 1,1,1, 2,2-pentafluoropropane, and said second stream comprising HF and 2-chloro-3,3,3-trifluoropropene; the temperature at the top of the distillation column is from -35 ° C to 10 ° C and the distillation is carried out at a pressure of 2 to 6 bara; said second stream obtained at the bottom of the distillation column is recycled in step i).
    Said stream C can be cooled, before distillation, to a temperature below 95 ° C, advantageously below 90 ° C, preferably below 85 ° C, more preferably below 80 ° C, in particular below 70 ° C, more particularly less than 60 ° C, preferably less than 55 ° C, advantageously less than 50 ° C, preferably less than 40 ° C, more preferably less than 30 ° C, so particularly preferred less than 25 ° C, more particularly preferred less than 20 ° C. The cooling of the product stream obtained at such temperatures facilitates subsequent distillation.
    The cooling of said stream C can be carried out using one or a plurality of heat exchangers. The cooling of said stream C can be carried out by passing it through one, two, three, four, five, six, seven, eight, nine or ten heat exchangers, preferably the number of heat exchangers is between 2 and 8, in particular between 3 and 7.
    According to a preferred embodiment, step i) and step ii) are carried out in the presence of hydrofluoric acid having an electrical conductivity of less than 10 mS / cm, preferably less than 5 mS / cm. The electrical conductivity of hydrofluoric acid can be measured prior to its use in step i) and / or in step ii) of the present process. Preferably, the electrical conductivity of hydrofluoric acid is measured before step i) and / or step ii) and hydrofluoric acid is in liquid form during the measurement. The method can also include a step of heating and vaporizing hydrofluoric acid prior to the implementation of in step i) and / or in step ii) to provide hydrofluoric acid in gaseous form. Preferably, the hydrofluoric acid is in gaseous form when it is brought into contact with said stream A or with said at least one chlorinated compound.
    Preferably, the method according to the present invention is implemented continuously.
    Example
    The fluorination of HCFO-1233xf (2-chloro-3,3,3-trifluoropropene) into HFO-1234yf (2,3,3,3tetrafluoropropene) and optionally into HFC-245cb (1,1,1,2,2-pentafluoropropane ) is carried out in a first multitubular reactor. The product stream from this fluorination feeds a second reactor. Said second reactor is also supplied with a stream of hydrofluoric acid and 1,1,1,2,3-pentachloropropane (HCC-240db). The fluorination of HCC-240db into HCFO-1233xf (2-chloro-3,3,3-trifluoropropene) is carried out in the second multitubular reactor. A recycling loop, the flow of which is controlled, allows certain products to be brought back to the first reactor. The first and second reactors contain a mass catalyst based on chromium oxide. The catalyst is activated by a series of stages including drying, fluorination, treatment in air and fluorination with recycling. This treatment in several stages makes the catalytic solid active and selective. The flow leaving said second reactor is treated by distillation to form a stream comprising HFO-1234yf and HCl and optionally HFC-245cb and a stream comprising HF and HCFO-1233xf. This latter current comprising HF and HCFO-1233xf constitutes the current coming from the recycling loop (current C2).
    In the first reactor, the fluorination process is carried out according to the following operating conditions:
    An absolute pressure in the fluorination reactor of 6.1 bar absolute
    A molar ratio between the HF and the sum of the organics supplied by the recycling loop between 15 and 20 (i.e. the sum of the organics contained in the current from the recycling loop or current C2)
    Contact time between 18 and 20 seconds
    A constant temperature in the reactor of 330 ° C.
    In the second reactor, the fluorination process is carried out according to the following operating conditions:
    An absolute pressure in the fluorination reactor of 5.5 bar absolute
    A molar ratio between HF and the sum of the organics supplied by the recycling loop of between 12 and 15
    Contact time between 11 and 13 seconds
    A constant temperature in the reactor of 340 ° C.
    The process is carried out with a current of HCFO-1233xf having two different electrical conductivity values: 6 and 20 mS / cm. The run is stopped when the conversion to 2chloro-3,3,3-trifluoropropene is less than 50% in the first reactor. Table 1 below shows the values obtained. The electrical conductivity of the HCFO-1233xf current is measured using a cell sold by Endress + Hauser and referenced under the term InduMax P CLS 50 coated with a perfluoroalkoxy (PFA) type polymer coating resistant to a corrosive medium. containing HF.
    Table 1
    Example Electrical conductivity (mS / cm) Duration of the run to reach a conversion <50% (h) 1 (inv.) 6 410 2 (comp.) 20 150
    The results detailed in Table 1 demonstrate that a current comprising HCFO1233xf and having an electrical conductivity of less than 15 mS / cm makes it possible to maintain a sufficiently high conversion for a long period of time. In fact, a conversion greater than 50% can be maintained up to 400 h when the electrical conductivity is 6 mS / cm (Example 1). Conversely, the conversion to HCFO-1233xf drops sharply when the electrical conductivity is too high (Example 2).
    权利要求:
    Claims (13)
    [1" id="c-fr-0001]
    1. Process for the production of 2,3,3,3-tetrafluoropropene comprising the steps:
    i) in a first reactor, bringing a stream A comprising 2-chloro-3,3,3trifluoropropene into contact with hydrofluoric acid in the gas phase in the presence of a catalyst to produce a stream B comprising 2.3, 3,3-tetrafluoropropene, HCl, HF and 2-chloro-3,3,3trifluoropropene unreacted; and ii) in a second reactor, brought into contact in the gas phase in the presence or absence of a hydrofluoric acid catalyst with at least one chlorine compound selected from the group consisting of 1,1,1,2,3-pentachloropropane, 2,3-dichloro-l, l, l-trifluoropropane, 2,3,3,3tetrachloropropene and 1,1,2,3-tetrachloropropene to produce a stream C comprising 2-chloro-3,3,3-trifluoropropene, characterized in that the stream B obtained in step i) feeds said second reactor used for step ii); and in that the electrical conductivity of said current A supplied in step i) is less than 15 mS / cm.
    [2" id="c-fr-0002]
    2. Method according to claim 1 characterized in that step i) is carried out in the presence of a catalyst, preferably a chromium-based catalyst, in particular said catalyst comprises a chromium oxyfluoride or a chromium oxide or a chromium fluoride or a mixture thereof; and step ii) is carried out in the presence or absence of a catalyst, advantageously step ii) is carried out in the presence of a catalyst, preferably a chromium-based catalyst, in particular said catalyst comprises a chromium oxyfluoride or a chromium oxide or a chromium fluoride or a mixture of these.
    [3" id="c-fr-0003]
    3. Method according to the preceding claim characterized in that the catalyst is based on chromium and also comprises a cocatalyst selected from the group consisting of Ni, Zn, Co, Mn or Mg, preferably the cocatalyst content is between 0.01% and 10% based on the total weight of the catalyst.
    [4" id="c-fr-0004]
    4. Method according to any one of the preceding claims, characterized in that the stream C also comprises 2,3,3,3-tetrafluoropropene, HF, HCl and 1,1,1,2,2pentafluoropropane.
    [5" id="c-fr-0005]
    5. Method according to any one of the preceding claims, characterized in that the stream C is purified, preferably by distillation, to form a stream Cl comprising 2,3,3,3-tetrafluoropropene, HCl and 1,1,1, 2,2-pentafluoropropane, and a C2 stream comprising HF and 2-chloro-3,3,3-trifluoropropene.
    [6" id="c-fr-0006]
    6. Method according to any one of the preceding claims, characterized in that said stream C2 is recycled in step i).
    [7" id="c-fr-0007]
    7. Method according to the preceding claim characterized in that said current C2 recycled in step i) has an electrical conductivity less than 15 mS / cm.
    [8" id="c-fr-0008]
    8. Method according to any one of the preceding claims, characterized in that said stream B and said at least one chlorinated compound are brought into contact prior to the entry thereof into said second reactor.
    [9" id="c-fr-0009]
    9. Method according to any one of the preceding claims, characterized in that the pressure at the inlet of said first reactor of step i) is greater than the pressure at the inlet of said second reactor of step ii), of preferably the pressure difference between the pressure at the inlet of said first reactor and the pressure at the inlet of said second reactor is from 100 mbar to 3.5 bar, advantageously from 150 mbar to 3.0 bar, preferably from 300 mbar at 2.5 bar, more preferably from 400 mbar to 2.0 bar, in particular from 750 mbar to 1.75 bar, more particularly from 1 to 1.5 bar.
    [10" id="c-fr-0010]
    10. Method according to any one of the preceding claims, characterized in that the temperature at which step i) is implemented is different from that at which step ii) is implemented; and the difference between the temperature at which step i) is carried out and the temperature at which step ii) is carried out is greater than 0.2 ° C., advantageously greater than 0.5 ° C., preferably greater than 1 ° C, more preferably greater than 5 ° C, in particular greater than 10 ° C; and less than 60 ° C, advantageously less than 55 ° C, preferably less than 50 ° C, more preferably less than 45 ° C, in particular less than 40 ° C, more particularly less than 35 ° C, preferably less at 30 ° C, preferably less than 25 ° C, particularly preferably less than 20 ° C.
    [11" id="c-fr-0011]
    11. Method according to the preceding claim characterized in that step i) is implemented at a temperature below the temperature at which step ii) is implemented; and the difference between the temperature at which step i) is carried out and the temperature at which step ii) is carried out is greater than 0.2 ° C., advantageously greater than 0.5 ° C., preferably greater than 1 ° C, more preferably greater than 5 ° C, in particular greater than 10 ° C; and less than 60 ° C, advantageously less than 55 ° C, preferably less than 50 ° C, more preferably less than 45 ° C, in particular less than 40 ° C, more particularly less than 35 ° C, preferably less at 30 ° C, preferably less than 25 ° C, particularly preferably less than 20 ° C.
    [12" id="c-fr-0012]
    12. Method according to any one of the preceding claims, characterized in that the stream C is cooled to a temperature below 100 ° C, then distilled to form a stream Cl comprising 2,3,3,3-tetrafluoropropene, HCl and 1 , 1,1,2,2-pentafluoropropane, and a C2 stream comprising HF and 2-chloro-3,3,3-trifluoropropene; the temperature at the top of the distillation column is from -35 ° C to 10 ° C and the distillation is carried out at a pressure is from 2 to 6 bara; said second stream obtained at the bottom of the distillation column is recycled in step i).
    [13" id="c-fr-0013]
    13. Method according to any one of the preceding claims, characterized in that step i) and / or step ii) are carried out in the presence of hydrofluoric acid having an electrical conductivity of less than 10 mS / cm.
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    同族专利:
    公开号 | 公开日
    US11084768B2|2021-08-10|
    WO2019170991A1|2019-09-12|
    FR3078700B1|2020-07-10|
    US20210002188A1|2021-01-07|
    CN111770908A|2020-10-13|
    EP3762355A1|2021-01-13|
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    法律状态:
    2019-02-13| PLFP| Fee payment|Year of fee payment: 2 |
    2019-09-13| PLSC| Publication of the preliminary search report|Effective date: 20190913 |
    2020-02-14| PLFP| Fee payment|Year of fee payment: 3 |
    2021-02-10| PLFP| Fee payment|Year of fee payment: 4 |
    2022-02-09| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1851954A|FR3078700B1|2018-03-07|2018-03-07|PROCESS FOR PRODUCING 2,3,3,3-TETRAFLUOROPROPENE|
    FR1851954|2018-03-07|FR1851954A| FR3078700B1|2018-03-07|2018-03-07|PROCESS FOR PRODUCING 2,3,3,3-TETRAFLUOROPROPENE|
    PCT/FR2019/050479| WO2019170991A1|2018-03-07|2019-03-04|Process for the production of 2,3,3,3-tetrafluoropropene|
    EP19715971.8A| EP3762355A1|2018-03-07|2019-03-04|Process for the production of 2,3,3,3-tetrafluoropropene|
    US16/976,599| US11084768B2|2018-03-07|2019-03-04|Process for the production of 2,3,3,3-tetrafluoropropene|
    CN201980015511.1A| CN111770908A|2018-03-07|2019-03-04|Production process of 2,3,3, 3-tetrafluoropropene|
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