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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: i) supplying a current A comprising at least one starting compound selected from the group consisting of 2-chloro-3 , 3,3-trifluoropropene and 2,3-dichloro -1,1,1-trifluoropropane; and ii) in an adiabatic reactor comprising a fixed bed composed of an inlet and an outlet, bringing said stream A into contact with HF in the presence or not of a catalyst to produce a stream B comprising 2,3,3, 3-tetrafluoropropene, characterized in that the temperature at the inlet of the fixed bed of said adiabatic reactor is between 300 ° C and 400 ° C and the longitudinal temperature difference between the inlet of the fixed bed and the outlet of the fixed bed of said reactor is below 20 ° C.
    公开号:FR3082203A1
    申请号:FR1855107
    申请日:2018-06-12
    公开日:2019-12-13
    发明作者:Bertrand Collier；Dominique Deur-Bert；Anne Pigamo；Audrey Riehl；Laurent Wendlinger
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    Process for the production of 2,3,3,3-tetrafluoropropene and installation for the implementation thereof
    Technical field of the invention
    The present invention relates to the production of hydrofluoroolefins, in particular 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. For example, US 2009/0240090 discloses 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 2013/088195 is a process for the preparation of 2,3,3,3tetrafluoropropene from 1,1,1,2,3-pentachloropropane and / or 1,1,2,2,3pentachloropropane, comprising stages: (a) catalytic reaction of 1,1,1,2,3pentachloropropane and / or 1,1,2,2,3-pentachloropropane with HF to a reaction mixture comprising HCl, 2-chloro-3,3,3- trifluoropropene, 2,3,3,3-tetrafluoropropene, unreacted HF and optionally 1,1,1,2,2-pentafluoropropane; (b) separation of the reaction mixture into a first stream comprising HCl and 2,3,3,3-tetrafluoropropene and a second stream comprising HF, 2-chloro-3,3,3-trifluoropropene and optionally 1,1,1,2 , 2pentafluoropropane; (c) catalytic reaction of said second stream into a reaction mixture comprising 2,3,3,3-tetrafluoropropene, HCl, 2-chloro-3,3,3-trifluoropropene, unreacted HF and optionally 1,1,1, 2,2-pentafluoropropane and (d) feeding the reaction mixture obtained in step c) directly to step a) without separation.
    In the processes for producing 2,3,3,3-tetrafluoropropene, the control and control of the reaction temperature is an important parameter which makes it possible to achieve the reaction kinetics, the conversions and the selectivities. This is also particularly recommended to avoid thermal decompositions of thermally sensitive compounds which can impact the activity of the catalyst by the formation of coke and thus considerably reduce the lifetime of the catalyst.
    It is known from WO2008 / 054781 that a temperature (300-350 ° C) promotes the formation of 1234yf, 245cb, 1233xf, while a higher temperature (350-450 ° C) promotes the formation of the 1234ze, 245fa, 1233zd isomers.
    It is therefore important to control and control the temperature of the gases entering the reactors but also to control and control at any point of the catalytic mass, if there is one.
    A multitubular reactor is by definition the ideal isothermal reactor to be able to control the reaction temperature and obtain a reaction temperature as homogeneous as possible since the catalyst is distributed in tubes and a fluid can circulate in the shell around the tubes to either remove reaction heat in the event of an exothermic reaction, or provide heat in the event of an endothermic reaction. On the other hand, when large quantities of catalysts have to be used, the production of a multitubular reactor may prove impossible since it would require too many tubes and a homogeneous distribution of the gases in each of the tubes is therefore very difficult. to achieve. In addition, the maintenance of large multitubular reactors is much more delicate and expensive; in particular, the catalyst change operations require a long immobilization of the reactor both to drain the used catalyst and to fill each tube extremely homogeneously with new catalyst. This negative aspect will be reinforced when the lifetime of the catalyst is short.
    Therefore, the use of an adiabatic fixed bed reactor is preferred. However, this type of reactor does not exhibit heat exchange with an external environment by definition. Indeed, the adiabatic reactor is characterized by an inhomogeneous temperature at any point of the fixed bed and thus, by a temperature gradient both radial and longitudinal, due to the reaction heats and heat losses at the external walls of the reactor.
    Document US 2016/0347692 describes the implementation of a radical production process in homogeneous gas phase of chlorinated or fluorinated propene in an adiabatic flow reactor controlling the turbulence of the flows entering the reactor.
    There is nevertheless a need to improve the processes for producing 2,3,3,3tetrafluoropropene in adiabatic reactors.
    Summary of the invention
    According to a first aspect, the present invention relates to a method for producing
    2,3,3,3-tetrafluoropropene comprising the steps:
    i) supply of a stream A comprising at least one starting compound selected from the group consisting of 2-chloro-3,3,3-trifluoropropene and 2,3-dichloro-1,1,1 trifluoropropane; and it) in an adiabatic reactor comprising a fixed bed composed of an inlet and an outlet, bringing said stream A into contact with HF in the presence or not of a catalyst to produce a stream B comprising 2,3,3, 3-tetrafluoropropene, characterized in that the temperature at the inlet of the fixed bed of said adiabatic reactor is between 300 ° C and 400 ° C and the longitudinal temperature difference between the inlet of the fixed bed and the outlet of the fixed bed of said reactor is below 20 ° C.
    The value of the longitudinal temperature difference is considered in absolute value.
    According to a preferred embodiment, the temperature at the inlet of the fixed bed of said reactor is between 330 ° C and 360 ° C and the longitudinal temperature difference between the inlet of the fixed bed of said reactor and the outlet of the fixed bed of said reactor is below 20 ° C.
    According to a preferred embodiment, in step ii), the HF / starting compound molar ratio is adjusted so as to keep the longitudinal temperature difference between the inlet of the fixed bed and the outlet of the fixed bed of the reactor less than 20 ° C.
    According to a preferred embodiment, in step ii), the HF / starting compound molar ratio is greater than or equal to 5, advantageously greater than or equal to 10, preferably greater than or equal to 12.
    According to a preferred embodiment, said reactor comprises side walls comprising an interior layer, an intermediate layer disposed on said interior layer and an insulating layer disposed on said intermediate layer; and the difference in radial temperature between a point located in the center of the fixed bed of said reactor and a point located in the radial plane at the level of the inner layer of the side wall of said reactor is less than 10 ° C. Said inner layer is that in contact with the reagents. The value of the radial temperature difference is considered as an absolute value.
    According to a preferred embodiment, said reactor comprises side walls comprising an interior layer, an intermediate layer disposed on said interior layer and an insulating layer disposed on said intermediate layer; said insulating layer being made of an M2 heat-insulating material whose thickness varies between 1 mm and 500 mm.
    According to a preferred embodiment, the M2 heat-insulating material is selected from the group consisting of rock wool, glass wool, silicate fibers, calcium magnesium silicates, calcium silicates, microporous insulators, cellular glass , expanded perlite, exfoliated vermiculite.
    According to a preferred embodiment, the pressure at the inlet of said reactor is between 3 and 15 bara.
    According to a preferred embodiment, stream B comprises, in addition to 2,3,3,3tetrafluoropropene, HF, HCl, 2-chloro-3,3,3-trifluoropropene or 2,3-dichloro-l, l, ltrifluoropropane n ' unreacted and 1,1,1,2,2-pentafluoropropane; and has an electrical conductivity less than 15 mS / cm.
    According to a second aspect, the present invention relates to an installation for manufacturing 2,3,3,3-tetrafluoropropene, comprising:
    - an adiabatic reactor comprising a bottom, a cover and side walls joining between the bottom and the cover, at least one fixed bed and at least one rod supporting one or more temperature sensor (s); said bottom, said cover and said side walls each comprise at least one inner layer, an intermediate layer disposed on said inner layer and an insulating layer disposed around said intermediate layer; said inner layer being made of an Ml material comprising a mass content of nickel of at least 30%; said intermediate layer being made of a material ΜΓ comprising at least 70% by weight of iron; said insulating layer being made of an M2 heat-insulating material selected from the group consisting of rock wool, glass wool, silicate fibers, calcium magnesium silicates, calcium silicates, microporous insulators, cellular glass, expanded perlite, exfoliated vermiculite; the length of said at least one rod supporting one or more temperature sensor (s) being at least equal to the height of said fixed bed; and said at least one rod comprising at least one temperature sensor disposed in said fixed bed.
    a reaction flow supply system for said reactor comprising a supply line for hydrofluoric acid and at least one supply line for a stream A comprising 2-chloro-3,3,3-trifluoropropene or 2, 3-dichloro-1,1,1-trifluoropropane;
    - a system for collecting and purifying the outlet flow from said reactor;
    - At least one conductivity meter capable of measuring the electrical conductivity of the reaction flow entering said reactor.
    Brief description of the figures
    FIG. 1 schematically represents a reactor according to a particular embodiment of the present invention.
    FIG. 2 schematically represents a view in longitudinal section of a reactor according to a particular embodiment of the present invention.
    FIG. 3 schematically represents a cross-sectional view of a reactor according to a particular embodiment of the present invention.
    Figure 4 schematically shows a sectional view of the side walls of a reactor according to a particular embodiment of the present invention.
    FIG. 5 schematically represents an installation for manufacturing 2,3,3,3tetrafluoropropene according to a particular embodiment of the present invention.
    Detailed description of the invention
    The present invention relates to a process for producing 2,3,3,3tetrafluoropropene. Preferably, said process for producing 2,3,3,3-tetrafluoropropene comprises the steps:
    i) supply of a stream A comprising at least one starting compound selected from the group consisting of 2-chloro-3,3,3-trifluoropropene and 2,3-dichloro-1,1,1 trifluoropropane; and ii) in an adiabatic reactor comprising a fixed bed composed of an inlet and an outlet, bringing said stream A into contact with HF in the presence or not of a catalyst to produce a stream B comprising 2,3,3, 3-tetrafluoropropene.
    Preferably, the temperature at the inlet of the fixed bed of said reactor is between 300 ° C and 400 ° C and the longitudinal temperature difference between the inlet of the fixed bed and the outlet of the fixed bed of the reactor is less than 20 ° vs.
    Preferably, the temperature at the inlet of the fixed bed of said reactor is between 320 ° C and 400 ° C, preferably between 320 ° C and 375 ° C, more preferably between 320 ° C and 360 ° C, in particular between 330 ° C and 360 ° C. In this step i), a temperature above 400 ° C can make the catalyst irreversibly inactive while a temperature below 300 ° C prevents the fluorination reaction from being carried out.
    As mentioned above, in an adiabatic reactor, the temperature within the reactor, and in particular within the fixed bed, varies longitudinally, i.e. the temperature varies between the inlet of the reactor and the outlet of the reactor, in particular between the inlet of the fixed bed and the outlet of the fixed bed. FIG. 2 represents a schematic view in longitudinal section of a reactor 1 according to a particular embodiment of the present invention and comprising a fixed bed 5. The longitudinal temperature difference ATa is defined by the temperature difference between the inlet of the fixed bed 9 and the exit from the fixed bed 10.
    Preferably, the longitudinal temperature difference between the inlet of the fixed bed of said reactor and the outlet of the fixed bed of said reactor is less than 20 ° C, advantageously less than 19 ° C, preferably less than 18 ° C, more preferably less at 17 ° C, in particular less than 16 ° C, more particularly less than 15 ° C, preferably less than 14 ° C, advantageously less than 13 ° C, preferably less than 12 ° C, more preferably less than 11 ° C, more preferably less than 10 ° C.
    According to a preferred embodiment, step ii) is carried out in the presence of a catalyst, preferably a chromium-based catalyst. Preferably, the chromium-based catalyst can be a chromium oxide (for example CrCh, Crûs or CrjOa), a chromium oxyfluoride or a chromium fluoride (for example CrFa) 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 may or may not be supported. A support such as alumina, for example in its alpha form, 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 another preferred embodiment, step ii) is carried out in the absence of catalyst. In this case, said fixed bed contains an inert solid. The inert solid can be corundum, silicon carbide, quartz balls or rings, a metal lining with a metal M1 as defined in the present application or nickel balls. According to a preferred embodiment, step ii) is carried out at atmospheric pressure or at a pressure greater than this, advantageously at a pressure greater than 1.5 bara, preferably at a pressure greater than 2, 0 bara, in particular at a pressure greater than 2.5 bara, more particularly at a pressure greater than 3.0 bara. Preferably, step ii) is carried out at a pressure between atmospheric pressure and 20 bara, preferably between 2 and 18 bara, more preferably between 3 and 15 bara. 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. 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.
    Preferably, in step ii), the HF / said starting compound molar ratio is greater than or equal to 5, advantageously greater than or equal to 10, preferably greater than or equal to 12. Advantageously, the HF molar ratio / said compound starting range is between 12: 1 and 150: 1, preferably between 12: 1 and 125: 1, more preferably between 12: 1 and 100: 1.
    As mentioned above, in an adiabatic reactor, the temperature within the reactor, and in particular within the fixed bed, varies radially, i.e. the temperature varies between the center of the reactor and the side walls of the reactor located in the same plane, in particular between the center of the fixed bed and the side wall of the reactor located in the same plane.
    The control of the radial temperature in the fixed bed can be carried out by insulating the side walls of said reactor with an insulating material of a defined thickness. Thus, said side walls each comprise at least one inner layer and an insulating layer disposed around said inner layer. Preferably, an intermediate layer is disposed between said inner layer and said insulating layer.
    FIG. 3 represents a transverse view along the section plane (a, a ') of a reactor 1 according to an embodiment of the present invention and comprising a fixed bed 5. The side walls 3 of said reactor comprise an inner layer 21 , an intermediate layer 22 disposed on said inner layer 21 and an insulating layer 23 disposed on said intermediate layer 22 (Figure 4). The difference in radial temperature ATb is defined by the difference between a point located in the center of the fixed bed 5 of the reactor and a point 12 located in the radial plane at the level of the inner layer 21 of the side wall 3 of said reactor (Figure 3) .
    Thus, the difference in radial temperature between a point located in the center of the fixed bed of the reactor and a point situated in the radial plane at the level of the inner layer of the side wall of said reactor is less than 10 ° C, advantageously less than 9 ° C, preferably less than 8 ° C, more preferably less than 7 ° C, in particular less than 6 ° C, more particularly less than 5 ° C.
    According to a preferred embodiment, said inner layer has a thickness of between 0.01 and 20 mm. Preferably, said inner layer may have a thickness of between 0.05 and 15 mm, preferably between 0.1 and 10 mm, more preferably between 0.1 and 5 mm.
    Said inner layer can be made of an Ml material comprising a mass content of nickel of at least 30%. Advantageously, the material M1 comprises at least 40% by weight of nickel based on the total weight of the material Ml. Preferably, the material M1 comprises at least 45% by weight of nickel, more preferably at least 50% by weight of nickel, in particular at least 55% by weight of nickel, more particularly at least 60% by weight of nickel, preferably at least 65% by weight of nickel, more preferably at least 70% by weight of nickel based on the total weight of the material Ml. The material M1 can also comprise chromium in a content of less than 35% by weight based on the total weight of the material Ml, advantageously less than 30% by weight, preferably less than 20% by weight, more preferably less than 15% by weight. weight, in particular less than 10% by weight, more particularly less than 5% by weight based on the total weight of the material Ml. The material M1 can also comprise molybdenum in a content of less than 35% by weight based on the total weight of the material Ml, advantageously less than 30% by weight, preferably less than 20% by weight, more preferably less than
    15% by weight, in particular less than 10% by weight, more particularly less than 5% by weight based on the total weight of the material Ml. Preferably, the material M1 comprises at least 40% by weight of nickel based on the total weight of the material Ml, preferably at least 45% by weight of nickel, more preferably at least 50% by weight of nickel, in particular at least 55% by weight of nickel, more particularly at least 60% by weight of nickel, preferably at least 65% by weight of nickel, more preferably at least 70% by weight of nickel based on the total weight of the material Ml ; and less than 35% by weight of chromium, advantageously less than 30% by weight, preferably less than 20% by weight, more preferably less than 15% by weight, in particular less than 10% by weight, more particularly less than 5 % by weight of chromium based on the total weight of the material Ml; and less than 35% by weight of molybdenum, advantageously less than 30% by weight, preferably less than 20% by weight, more preferably less than 15% by weight, in particular less than 10% by weight, more particularly less than 5 % by weight of molybdenum, based on the total weight of the material Ml. The material M1 can also comprise cobalt in a content of less than 10% by weight based on the total weight of the material Ml, advantageously less than 8% by weight, preferably less than 6% by weight, more preferably less than 4% by weight. weight, in particular less than 3% by weight, more particularly less than 2% by weight based on the total weight of the material Ml. The material Ml can also comprise tungsten in a content of less than 10% by weight based on the total weight of the material Ml, advantageously less than 9% by weight, preferably less than 8% by weight, more preferably less than 7% by weight. weight, in particular less than 6% by weight, more particularly less than 5% by weight based on the total weight of the material Ml. The material M1 can also comprise iron in a content of less than 25% by weight based on the total weight of the material Ml, advantageously less than 20% by weight, preferably less than 15% by weight, more preferably less than 10% by weight. weight, in particular less than 7% by weight, more particularly less than 5% by weight based on the total weight of the material Ml. The material M1 can also comprise manganese in a content of less than 5% by weight based on the total weight of the alloy, advantageously less than 4% by weight, preferably less than 3% by weight, more preferably less than 2% by weight, in particular less than 1% by weight, more particularly less than 0.5% by weight based on the total weight of the material Ml. The material M1 can also comprise copper in a content of less than 50% by weight, advantageously less than 45% by weight, preferably less than 40% by weight, more preferably less than 35% by weight, in particular less than 30%. by weight, more particularly less than 25% by weight of copper based on the total weight of the material Ml.
    According to a preferred embodiment, said intermediate layer has a thickness of between 0.1 and 50 mm. Preferably, said intermediate layer may have a thickness of between 0.5 and 40 mm, preferably between 1 and 30 mm, more preferably between 1 and 25 mm. According to a preferred embodiment, said intermediate layer 22 is disposed between said inner layer 21, in contact with the reagents, and said insulating layer 23 (Figure 4). Said intermediate layer 22 can be made of a material ΜΓ. According to a preferred embodiment, the material ΜΓ comprises at least 70% by weight of iron, advantageously at least 75% by weight, preferably at least 80% by weight, more preferably at least 85% by weight, in particular at least 90% by weight, more particularly at least 95% by weight of iron based on the total weight of the material ΜΓ. The material ΜΓ can also comprise less than 2% by weight of carbon, advantageously less than 1.5% by weight, preferably less than 1% by weight, more preferably less than 0.75% by weight, in particular less than 0 , 5% by weight, more particularly less than 0.2% by weight, preferably less than 0.1% by weight based on the total weight of the material ΜΓ. More particularly, the material ΜΓ can comprise between 0.01 and 0.2% by weight of carbon based on the total weight of the material ΜΓ. The material ΜΓ can also comprise less than 2% by weight of molybdenum, advantageously less than 1.5% by weight, preferably less than 1.25% by weight, more preferably less than 1% by weight of molybdenum based on the weight total material ΜΓ. More particularly, the material ΜΓ can comprise between 0.1 and 1% by weight of molybdenum based on the total weight of the material ΜΓ. The material ΜΓ can also comprise less than 5% by weight of chromium, advantageously less than 4% by weight, preferably less than 3% by weight, more preferably less than 2% by weight, in particular less than 1% by weight of chromium based on the total weight of the material ΜΓ. More particularly, the material ΜΓ can comprise between 0.5 and 2% by weight of chromium based on the total weight of the material ΜΓ. The material ΜΓ can also comprise less than 2% by weight of silicon, advantageously less than 1.5% by weight, preferably less than 1.25% by weight, more preferably less than 1% by weight of silicon based on the weight total material ΜΓ. More particularly, the material ΜΓ can comprise between 0.1 and 1.5% by weight of silicon based on the total weight of the material ΜΓ. The material ΜΓ can also comprise less than 2% by weight of manganese, advantageously less than 1.5% by weight, preferably less than 1.25% by weight, more preferably less than 1% by weight of manganese based on the weight total material ΜΓ. More particularly, the material ΜΓ can comprise between 0.1 and 1% by weight of manganese based on the total weight of the material M1 '.
    Preferably, said insulating layer is made of an M2 heat-insulating material. Said M2 heat-insulating material is selected from the group consisting of rock wool, glass wool, silicate fibers, calcium-magnesium silicates, calcium silicates, microporous insulators, cellular glass, expanded perlite, vermiculite exfoliated. Silicate fibers include, for example, aluminosilicate fibers. In particular, the side walls of said reactor comprise an insulating layer made of an M2 heat-insulating material whose thickness varies between 1 mm and 500 mm, preferably between 5 mm and 400 mm.
    According to a preferred embodiment, the pressure at the inlet of said reactor is atmospheric pressure or a pressure greater than this, advantageously the pressure at the inlet of said reactor is greater than 1.5 bara, preferably greater than 2 , 0 bara, in particular greater than 2.5 bara, more particularly greater than 3.0 bara. Preferably, step ii) is carried out at a pressure at the inlet of said reactor between atmospheric pressure and 20 bara, preferably between 2 and 18 bara, more preferably between 3 and 15 bara.
    According to a preferred embodiment, stream A comprises 2-chloro-3,3,3trifluoropropene or 2,3-dichloro-1,1,1,-trifluoropropane, HF and optionally 1,1,1,2,2pentafluoropropane.
    According to a preferred embodiment, stream B comprises, in addition to 2,3,3,3tetrafluoropropene, HF, HCl, 2-chloro-3,3,3-trifluoropropene or 2,3-dichloro-l, l, ltrifluoropropane n ' unreacted and optionally 1,1,1,2,2-pentafluoropropane.
    According to a preferred embodiment, stream B is purified, preferably by distillation, to form a first stream comprising 2,3,3,3-tetrafluoropropene, HCl and optionally 1,1,1,2,2-pentafluoropropane, and a second stream comprising HF and 2-chloro-3,3,3-trifluoropropene or 2,3-dichloro-1,1,1-trifluoropropane.
    Preferably, said stream B is distilled under conditions sufficient to form said first stream comprising 2,3,3,3-tetrafluoropropene, HCl and optionally 1,1,1,2,2-pentafluoropropane, and said second stream comprising HF and 2-chloro-3,3,3trifluoropropene. 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.
    According to a preferred embodiment, said stream B obtained in step b) is cooled before the purification mentioned above. In particular, said stream B obtained in step b) is cooled to a temperature below 100 ° C., then distilled to form said first stream comprising 2,3,3,3-tetrafluoropropene, HCl and optionally 1,1,1 , 2,2pentafluoropropane, and said second stream comprising HF and 2-chloro-3,3,3-trifluoropropene or 2,3-dichloro-l, l, l-trifluoropropane; 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 stream B 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. Cooling the product stream obtained to such temperatures can facilitate subsequent distillation.
    The cooling of said stream B can be carried out by means of one or a plurality of heat exchangers. The cooling of said stream B 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.
    Said second stream comprising HF and 2-chloro-3,3,3-trifluoropropene or 2,3-dichloro1,1,1-trifluoropropane can be recycled in step ii).
    The first stream comprising 2,3,3,3-tetrafluoropropene, HCl and optionally 1,1,1,2,2-pentafluoropropane can be purified, preferably by distillation, to form a third stream, preferably at the top of the column. distillation, comprising HCl and a fourth stream comprising 2,3,3,3-tetrafluoropropene and optionally 1,1,1,2,2pentafluoropropane.
    Preferably, the method according to the present invention is carried out continuously.
    Preferably, the process is carried out continuously and in the gas phase.
    Preferably, said current A has an electrical conductivity of less than 15 mS / cm. Advantageously, the electrical conductivity of said current A 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 at 5 mS / cm. Preferably, step ii) is carried out in the presence of hydrofluoric acid having an electrical conductivity of less than 10 mS / cm, preferably less than 5 mS / cm. Preferably, said second current which can be recycled in step ii) has an electrical conductivity of less than 15 mS / cm, advantageously less than 10 mS / cm, preferably less than 5 mS / cm.
    The electrical conductivity of said current A or of HF or of said second current is measured prior to step i) or ii). Preferably, the electrical conductivity of the current under consideration or of the HF is measured when the latter is in liquid form. Said method according to the present invention can therefore comprise a step of heating the current under consideration or of HF prior to the implementation of step i) or ii) to supply said current A and HF in gaseous form. Preferably, said current A implemented in step i) is in gaseous form when it is brought into contact with HF.
    According to a second aspect of the present invention, an adiabatic reactor 1 is provided. Preferably, said reactor 1 comprises a bottom 4, a cover 2 and side walls 3 connecting between the bottom 4 and the cover 2, at least one fixed bed 5 and at least one rod 6 supporting one or more temperature sensors 7a , 7b (Figure 1).
    Preferably, said bottom 4, said cover 2 and said side walls 3 each comprise at least one interior layer 21, an intermediate layer 22 disposed on said interior layer and an insulating layer 23 disposed around said intermediate layer 22. Said interior layers 21 , intermediate 22 and insulating 23 are made respectively of a material Ml, ΜΓ and M2 as described above.
    According to a preferred embodiment, said insulating layer 23 can be covered by a base layer 24. Thus, said insulating layer 23 is disposed between said intermediate layer 22 and said base layer 24 (Figure 4). Said base layer 24 can be made of an M3 material. Said M3 material can be a metallic coating made with sheets of aluminum, stainless steel or galvanized steel. Preferably, said base layer has a thickness of between 0.2 mm and 2 mm.
    Said inner layer 21, said intermediate layer 22, said insulating layer 23 and said base layer 22 can be placed one on the other according to techniques well known to those skilled in the art.
    Preferably, the length of said at least one rod 6 is at least equal to the height of said fixed bed 5. In particular, said at least one rod 6 comprises at least one sensor, or at least two sensors or at least 3 sensors of temperature, advantageously at least 5 temperature sensors, preferably at least 7 temperature sensors, in particular at least 10 temperature sensors, preferably at least 12 temperature sensors, preferably at least 15 temperature sensors.
    Preferably, at least one of said one or more temperature sensors, supported by said at least one rod, is arranged in said fixed bed 5. In particular, at least two or three or four or five or six or seven temperature sensors, supported by said at least one rod, are arranged in said fixed bed 5
    Preferably, each rod 6 can comprise either an identical number or a different number of temperature sensors. In particular, each rod can include a temperature sensor in the sky and / or in the bottom of the reactor (Figure 1, Reference 7b and 7b '). Likewise, the temperature sensors 7a, 7b can be distributed equidistantly or in a more targeted manner according to the needs for controlling the temperature profile in the fixed bed.
    Preferably, said reactor can comprise at least two canes 6, more preferably at least three canes 6, in particular at least four canes 6. In particular, said reactor can comprise between 1 and 20 canes 6, advantageously between 2 and 15 canes 6 , preferably between 3 and 10 rods 6.
    Preferably, the reactor 1 is supplied with hydrocarbon compound 14 by supply lines 13. The reactor also comprises effluent or outlet lines 15 making it possible to evacuate the reaction mixture 16 from the reactor (Figure 1).
    Preferably, the reactor supply or output lines are made of material capable of also resisting corrosion, for example made of Ml material covered with a layer of M2 material and with a base layer made of a material M3. The supply lines can be tubular in shape. Alternatively, the supply or output lines may comprise an inner layer, preferably made of a material M1 as described above, an insulating layer, preferably made of a material M2 as described above, and a base layer, preferably made of an M3 material as described above. The reactor also includes one or more dephlegmator (s), one or more dip tube (s), one or more raw material introduction device (s), one or more support and retaining grid (s) of the catalyst. Said one or more dephlegmator (s) and / or said one or more dip tube (s) and / or said one or more device (s) for introducing the raw materials and / or said one or more grid (s) ) supporting and retaining the catalyst may comprise an inner layer, preferably made of a material M1 as described above.
    Preferably, the fixed bed 5 comprises a catalyst or an inert solid or both. The inert solid can be corundum, silicon carbide, quartz balls or rings, a metal lining with a metal M1 as defined in the present application or nickel balls. Preferably, when the fixed bed 5 comprises a catalyst, the inert solid is placed on the upper part 17 and the lower part 18 of the fixed bed 5, said catalyst 19c being located between the layers of the inert solid 19a and 19b, in the part central 20 of the fixed bed 5. In an alternative embodiment, when the fixed bed 5 comprises a catalyst, the inert solid is placed in the upper part 17 or in the lower part 18 of the fixed bed 5. In an alternative embodiment , when the fixed bed 5 comprises a catalyst, no layer of inert solid is placed in the fixed bed. In an alternative embodiment, in which the reactor does not contain catalyst, the lower part 18, the central part 20 and the upper part 17 of the fixed bed 5 can contain only inert solid. This alternative embodiment can be implemented when, for example, step ii) of the process according to the present invention is carried out in the absence of catalyst. In this case, the inert solid makes it possible to improve the distribution of the gases inside the reactor. Preferably, the inert solid is corundum or nickel beads.
    Preferably, the fixed bed 5 contains a layer of catalyst 19c in its central part 20. In a preferred embodiment, the catalyst is distributed homogeneously in the fixed bed. The homogeneous distribution of the catalyst in the fixed bed makes it possible to minimize disturbances in the flow of gases and to avoid hot spots within the catalyst layer. The presence of hot spots can lead to irreversible crystallization of the catalyst resulting in deactivation of the latter. The fixed bed is loaded using the specific method of dense catalyst loading. This method is known to those skilled in the art. It makes it possible to obtain an optimal distribution of the catalyst inside the reactor while avoiding fading (channeling) during the reaction and the attrition of the catalyst. In general, the apparent mass density of the catalyst in the fixed bed is greater than the theoretical mass density of the latter. The apparent mass density is determined according to standard ASTM D1895.
    Preferably, said reactor is a gas phase fluorination reactor.
    The present invention makes it possible to implement a process for producing 2,3,3,3tetrafluoropropene with a greater quantity of catalyst, if this is carried out in the presence of catalyst. In addition, controlling and controlling the temperature radially and longitudinally makes it possible to maintain a conversion and a selectivity of the reactions.
    According to a third aspect of the invention, a plant for manufacturing 2,3,3,3tetrafluoropropene is provided. Preferably, the installation comprises an adiabatic reactor according to the present invention, a reaction flow supply system for said reactor, a system for collecting and purifying the output flow from said reactor. Preferably, said installation also comprises at least one conductivity meter capable of measuring the electrical conductivity of the reaction flow entering said reactor.
    Preferably, said installation also comprises a heat exchanger supplied by the outlet stream and connected to a first distillation column. Preferably, said installation also comprises a compressor supplied with the current coming from said first distillation column. Preferably, said installation comprises a second distillation column supplied with a current from the compressor. Said second distillation column aims to eliminate all or part of the HCl present in the stream conveyed to it. Said installation can also include a plurality of other distillation columns for purifying 2,3,3,3-tetrafluoropropene.
    An installation according to a particular embodiment of the present invention is illustrated in FIG. 5. Preferably, the reaction flow supply system of the reactor 101 comprises a line for hydrofluoric acid 102 and a line for 2-chloro-3,3,3-trifluoropropene 105 is brought in. 2-chloro-3,3,3-trifluoropropene and HF can be mixed before contacting with the catalyst in reactor 101. Preferably, the outlet flow 107 includes unreacted 2-chloro-3,3,3-trifluoropropene, HF, HCl, 2,3,3,3tetrafluoropropene and optionally 1,1,1,2,2-pentafluoropropane. The installation includes a heat exchanger 108 capable of cooling the outlet flow 107 from said reactor 101 to form a cooled current. The outlet stream 107 is routed to a cooling device 108. The outlet stream 107 is thus cooled to a temperature from 0 ° C to 70 ° C before being introduced into a distillation column 109 via a pipe 110. L 'installation can therefore include a first distillation column 109 supplied by said cooled stream. The distillation column 109 is configured so as to allow separation between on the one hand hydrochloric acid and 2,3,3,3-tetrafluoropropene and optionally 1,1,1,2,2pentafluoropropane and on the other hand hydrofluoric acid and 2-chloro-3,3,3-trifluoropropene.
    The stream of HF and of 2-chloro-3,3,3-trifluoropropene is recovered at the bottom of the distillation column 109 and recycled to the reactor 101 via line 112. The stream comprising 2,3,3,3- tetrafluoropropene and hydrochloric acid and optionally 1,1,1,2,2pentafluoropropane is recovered at the head of distillation column 109 to be conveyed by a line 111 to a compressor 113. According to a preferred embodiment, said installation comprises a compressor , preferably supplied by the stream from the head of said first distillation column 109. The compressor makes it possible to compress the stream comprising 2,3,3,3-tetrafluoropropene and hydrochloric acid at a pressure between 10 and 25 bara. The current thus compressed is conveyed via line 114 to a second distillation column 115. This is configured so as to separate on one side the 2,3,3,3-tetrafluoropropene and optionally 1,1,1,2 , 2-pentafluoropropane and the other hydrochloric acid. The hydrochloric acid is recovered and is at the head of the distillation column 115 to be conveyed to a purification device 118 via line 116. The purification device 118 for hydrochloric acid is a device known from the prior art, for example from WO 2015/079137. 2,3,3,3-tetrafluoropropene and optionally 1,1,1,2,2pentafluoropropane is recovered at the bottom of distillation column 115 to be conveyed by line 117 to a third distillation column 119. The distillation column 119 aims to separate the 2,3,3,3-tetrafluoropropene from the 1,1,1,2,2-pentafluoropropene possibly present in the outlet stream 107. The 2,3,3,3-tetrafluoropropene is recovered at the top of the column distillation to be conveyed to a purification device via line 121. The 1,1,1,2,2-pentafluoropropene recovered at the bottom of the distillation column is recycled to the reactor 101 via line 120. The purification device comprises in particular a device for removing HF 122 and one or more distillation columns capable of purifying the stream comprising 2,3,3,3-tetrafluoropropene from impurities which it could contain, such as, for example, 1.1, 1,2,2-pentafluoropropane and / or 1,3,3,3-tet rafluoropropène. The HF removal device 122 can remove the residual HF which can be recycled to the reactor 101 (not shown). The HF elimination device 122 may be able to allow the settling of HF or the absorption of HF. If the stream comprising 2,3,3,3-tetrafluoropropene contains impurities such as 1,3,3,3-tetrafluoropropene or 1,1,1,2,2-pentafluoropropane, this can be purified for example from next way. The stream comprising 2,3,3,3tetrafluoropropene is conveyed to a distillation column 124 by a line 123. The distillation column 124 is an extractive distillation column. An extractant 127 is added to the stream comprising 2,3,3,3-tetrafluoropene. The extractive distillation column 124 makes it possible to eliminate impurities possibly present in the stream comprising 2,3,3,3-tetrafluoropropene. These impurities may include 1,3,3,3tetrafluoropropene. A stream comprising 2,3,3,3-tetrafluoropene is recovered at the top of distillation column 124 and is conveyed by a line 128 to a distillation column 129. The distillation column 129 can make it possible to separate the 2,3, Residual 1,1,1,2,2-pentafluoropropane 3,3-tetrafluoropene. A stream 130 comprising 2,3,3,3-tetrafluoropene is recovered at the top of the distillation column. A stream 131 comprising the residual 1,1,1,2,2pentafluoropropane is recovered at the bottom of the distillation column; the latter can be recycled to the reactor 101. The stream 125 recovered at the bottom of the distillation column 124 comprises the organic extraction agent and 1,3,3,3-tetrafluoropropene. These are separated, for example by distillation, to form a stream 126 comprising 1,3,3,3tetrafluoropropene. The organic extraction agent is recycled in 127.
    As mentioned above, the stream from the bottom of the distillation column 119 and the stream from the bottom of the distillation column 109 are routed to the reactor 101 via lines 120 and 11 respectively. The two streams can be mixed before to be introduced into said reactor 101. In addition, before being introduced into said reactor 101, the electrical conductivity of the two streams or of the mixture thereof is measured by the conductimeter 132. The electrical conductivity of the HF and of the stream A can also be measured before their introduction into the reactor 101.
    权利要求:
    Claims (10)
    [1" id="c-fr-0001]
    claims
    1. Process for the production of 2,3,3,3-tetrafluoropropene comprising the steps:
    i) supply of a stream A comprising at least one starting compound selected from the group consisting of 2-chloro-3,3,3-trifluoropropene and 2,3-dichloro-1,1,1 trifluoropropane; and ii) in an adiabatic reactor comprising a fixed bed composed of an inlet and an outlet, bringing said stream A into contact with HF in the presence or not of a catalyst to produce a stream B comprising 2,3,3, 3-tetrafluoropropene, characterized in that the temperature at the inlet of the fixed bed of said adiabatic reactor is between 300 ° C and 400 ° C and the longitudinal temperature difference between the inlet of the fixed bed and the outlet of the fixed bed of said reactor is below 20 ° C.
    [2" id="c-fr-0002]
    2. Method according to claim 1 characterized in that the temperature at the inlet of the fixed bed of said reactor is between 330 ° C and 360 ° C and the longitudinal temperature difference between the inlet of the fixed bed of said reactor and the outlet of the fixed bed of said reactor is less than 20 ° C.
    [3" id="c-fr-0003]
    3. Method according to any one of the preceding claims, characterized in that, in step ii), the HF / starting compound molar ratio is adjusted so as to maintain the longitudinal temperature difference between the inlet of the fixed bed and the output of the fixed bed of the reactor below 20 ° C.
    [4" id="c-fr-0004]
    4. Method according to any one of the preceding claims, characterized in that, in step ii), the HF / starting compound molar ratio is greater than or equal to 5, advantageously greater than or equal to 10, preferably greater than or equal at 12.
    [5" id="c-fr-0005]
    5. Method according to any one of the preceding claims, characterized in that said reactor comprises side walls comprising an inner layer, an intermediate layer arranged on said inner layer and an insulating layer disposed on said intermediate layer; and the difference in radial temperature between a point located in the center of the fixed bed of said reactor and a point located in the radial plane at the level of the inner layer of the side wall of said reactor is less than 10 ° C.
    [6" id="c-fr-0006]
    6. Method according to any one of the preceding claims, characterized in that said reactor comprises side walls comprising an inner layer, an intermediate layer disposed on said inner layer and an insulating layer disposed on said intermediate layer; said insulating layer being made of an M2 heat-insulating material whose thickness varies between 1 mm and 500 mm.
    [7" id="c-fr-0007]
    7. Method according to the preceding claim characterized in that the heat-insulating material M2 is selected from the group consisting of rock wool, glass wool, silicate fibers, calcium-magnesium silicates, calcium silicates, microporous insulators , cellular glass, expanded perlite, exfoliated vermiculite.
    [8" id="c-fr-0008]
    8. Method according to any one of the preceding claims, characterized in that the pressure at the inlet of said reactor is between 3 and 15 bara.
    [9" id="c-fr-0009]
    9. Method according to any one of the preceding claims, characterized in that the stream B comprises, in addition to 2,3,3,3-tetrafluoropropene, HF, HCl, 2-chloro-3,3,3-trifluoropropene or 2,3 -dichloro-1,1,1, unreacted trifluoropropane and 1,1,1,2,2-pentafluoropropane; and has an electrical conductivity less than 15 mS / cm.
    [10" id="c-fr-0010]
    10. Plant for the production of 2,3,3,3-tetrafluoropropene, comprising:
    - an adiabatic reactor (101) comprising a bottom (4), a cover (2) and side walls (3) joining between the bottom (4) and the cover (2), at least one fixed bed (5) and at least one rod (6) supporting one or more temperature sensor (s) (7a, 7b); said bottom (4), said cover (2) and said side walls (3) each comprise at least one inner layer (21), an intermediate layer (22) disposed on said inner layer (21) and an insulating layer (23) disposed around said intermediate layer (22); said inner layer (21) being made of an Ml material comprising a mass content of nickel of at least 30%; said intermediate layer (22) being made of a material ΜΓ comprising at least 70% by weight of iron; said insulating layer (23) being made of an M2 heat-insulating material selected from the group consisting of rock wool, glass wool, silicate fibers, calcium-magnesium silicates, calcium silicates, microporous insulators, cellular glass, expanded perlite, exfoliated vermiculite; the length of said at least one rod (6) supporting one or more temperature sensor (s) (7a, 7b) being at least equal to the height of said fixed bed (5); and said at least one rod (6) comprising at least one temperature sensor (7a) disposed in said fixed bed.
    - a reaction flow supply system for said reactor comprising a line
    5 for supplying hydrofluoric acid (102) and at least one supply line (105) for a stream A comprising 2-chloro-3,3,3-trifluoropropene or 2,3-dichloro-l, l , trifluoropropane;
    - a system for collecting and purifying the outlet flow (107) from said reactor (101);
    - at least one conductimeter (132) capable of measuring the electrical conductivity of the flux
    10 reaction entering said reactor.
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    同族专利:
    公开号 | 公开日
    CN112313196A|2021-02-02|
    EP3807237A1|2021-04-21|
    FR3082203B1|2020-08-14|
    US20210253500A1|2021-08-19|
    WO2019239039A1|2019-12-19|
    US11136282B2|2021-10-05|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2009015317A1|2007-07-25|2009-01-29|Honeywell International Inc.|Improved method for producing 2-chloro-3,3,3,-trifluoropropene |
    WO2011044522A2|2009-10-09|2011-04-14|Dow Global Technologies, Inc|Adiabatic plug flow reactors and processes incorporating the same|
    EP3020695A1|2013-07-12|2016-05-18|Daikin Industries, Ltd.|Method for producing 2,3,3,3-tetrafluoropropene|FR3098127A1|2020-07-03|2021-01-08|Arkema France|Process for the production of 2,3,3,3-tetrafluoropropene and reactor for the implementation thereof|
    FR3098216A1|2020-07-03|2021-01-08|Arkema France|Process for the production of 2,3,3,3-tetrafluoropropene and installation for its implementation|US8058486B2|2004-04-29|2011-11-15|Honeywell International Inc.|Integrated process to produce 2,3,3,3-tetrafluoropropene|
    US8398882B2|2006-10-31|2013-03-19|E I Du Pont De Nemours And Company|Processes for the production of fluoropropanes and halopropenes and azeotropic compositions of 2-chloro-3,3,3-trifluoro-1-propene with HF and of 1,1,1,2,2-pentafluoropropane with HF|
    PL2791093T3|2011-12-14|2018-01-31|Arkema France|Process for the preparation of 2, 3, 3, 3 tetrafluoropropene|
    FR3013606B1|2013-11-28|2015-11-13|Arkema France|PROCESS FOR PURIFYING HYDROCHLORIC ACID|
    法律状态:
    2019-05-10| PLFP| Fee payment|Year of fee payment: 2 |
    2019-12-13| PLSC| Search report ready|Effective date: 20191213 |
    2020-05-12| PLFP| Fee payment|Year of fee payment: 3 |
    2021-05-13| PLFP| Fee payment|Year of fee payment: 4 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1855107A|FR3082203B1|2018-06-12|2018-06-12|PROCESS FOR THE PRODUCTION OF 2,3,3,3-TETRAFLUOROPROPENE AND INSTALLATION FOR IMPLEMENTING THE SAME.|
    FR1855107|2018-06-12|FR1855107A| FR3082203B1|2018-06-12|2018-06-12|PROCESS FOR THE PRODUCTION OF 2,3,3,3-TETRAFLUOROPROPENE AND INSTALLATION FOR IMPLEMENTING THE SAME.|
    US16/973,462| US11136282B2|2018-06-12|2019-06-06|Method for producing 2,3,3,3-tetrafluoropropene and facility for implementing said method|
    EP19742080.5A| EP3807237A1|2018-06-12|2019-06-06|Method for producing 2,3,3,3-tetrafluoropropene and facility for implementing said method|
    PCT/FR2019/051355| WO2019239039A1|2018-06-12|2019-06-06|Method for producing 2,3,3,3-tetrafluoropropene and facility for implementing said method|
    CN201980039119.0A| CN112313196A|2018-06-12|2019-06-06|Process for producing 2,3,3, 3-tetrafluoropropene and apparatus for implementing said process|
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