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    • 专利摘要:
    The invention relates to a process for producing tetrafluoropropene, comprising, alternately: at least one step of reacting a chlorinated compound with hydrofluoric acid in the gaseous phase, in the presence of a fluorination catalyst, the proportion any oxygen present being less than 0.05 mol% relative to the chlorinated compound; a step of regenerating the fluorination catalyst by contacting the fluorination catalyst with a regeneration flow comprising an oxidizing agent. The invention also relates to an installation adapted to the implementation of this method.
    公开号:FR3059999A1
    申请号:FR1761894
    申请日:2017-12-11
    公开日:2018-06-15
    发明作者:Dominique Deur-Bert；Anne Pigamo；Laurent Wendlinger
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    Holder (s): ARKEMA FRANCE Public limited company.
    Agent (s): ARKEMA FRANCE Public limited company.
    PROCESS FOR THE MANUFACTURE OF TETRAFLUOROPROPENE.
    FR 3,059,999 - A1 (5y) The invention relates to a process for the manufacture of tetrafluoropropene, comprising, alternately:
    at least one step of reacting a chlorinated compound with hydrofluoric acid in the gas phase, in the presence of a fluorination catalyst, the proportion of oxygen possibly present being less than 0.05 mol.% relative to the chlorine compound;
    a step of regenerating the fluorination catalyst by bringing the fluorination catalyst into contact with a regeneration flow comprising an oxidizing agent.
    The invention also relates to an installation suitable for implementing this method.
    PROCESS FOR THE MANUFACTURE OF TETRAFLUOROPROPENE
    FIELD OF THE INVENTION
    The present invention relates to a process for the manufacture of tetrafluoropropene (HFO-1234), and in particular to 2,3,3,3-tetrafluoropropene (HFO-1234yf), as well as to an installation suitable for the implementation of this process.
    TECHNICAL BACKGROUND
    Greenhouse gases are gaseous components that absorb infrared radiation emitted from the earth's surface, thereby contributing to the greenhouse effect. One of the factors driving global warming is the increase in their concentration in the atmosphere.
    The production of chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) used in refrigeration and air conditioning systems was thus successively regulated by the Montreal and then Kyoto protocols. There is a need to develop new molecules which are just as effective and which in particular have the lowest possible global warming potential. This is the case of hydrofluoroolefins, and in particular HFO-1234yf, which is a particularly useful compound.
    It is known to produce hydrofluoroolefins or hydrofluorocarbons by fluorination of hydrochloroolefins or hydrochlorocarbons in particular. This fluorination is generally a catalytic fluorination using hydrofluoric acid as a fluorinating agent.
    The fluorination reaction must generally be carried out at an elevated temperature (over 300 ° C), in the gas phase, in the presence of a solid supported or bulk catalyst.
    It is known to provide a co-supply with an oxidizing agent, in particular air, or possibly chlorine, to preserve the lifetime of the catalyst and limit the deposition of coke on its surface during the reaction step.
    Document US 8,614,361 describes a process for manufacturing HFO-1234yf by reacting HCFO-1233xf with HF in the presence of a high oxygen content.
    Document US Pat. No. 8,618,338 describes a process for the manufacture of fluoroolefin in two stages, in particular a first stage of reaction in the liquid phase from 1,1,2,3-tetrachloropropene (HCO-1230xa) for obtaining the intermediate HCFO-1233xf and a second gas phase reaction step from HCFO-1233xf to obtain HFO-1234yf.
    The document WO 2013/088195 teaches a process for manufacturing HFO-1234yf in two stages, a first stage of fluorination in the gas phase of 1,1,1,2,3-pentachloropropane (HCC-240db) and / or 1, 1,2,2,3pentachloropropane (HCC-240aa) to obtain the intermediate HCFO-1233xf, then a second gas phase reaction step from HCFO-1233xf to obtain HFO-1234yf.
    WO 2012/098421 and WO 2012/098422 teach the activation and regeneration of fluorination catalysts.
    The document WO 2013/182816 describes a chemical reaction process for the alternating implementation of a catalytic reaction phase and a catalyst regeneration phase in a reactor.
    There is still a need to improve the manufacturing processes for HFO-1234 such as HFO-1234yf, and in particular to produce these compounds with a high yield and in a high degree of purity.
    SUMMARY OF THE INVENTION
    The invention relates first of all to a process for manufacturing tetrafluoropropene, comprising, alternately:
    at least one step of reacting a chlorinated compound with hydrofluoric acid in the gas phase, in the presence of a fluorination catalyst, the proportion of oxygen possibly present being less than 0.05 mol.% relative to the chlorine compound;
    a step of regenerating the fluorination catalyst by bringing the fluorination catalyst into contact with a regeneration flow comprising an oxidizing agent.
    According to one embodiment, the reaction step of the chlorinated compound with hydrofluoric acid is carried out essentially in the absence of oxygen, and preferably essentially in the absence of any oxidizing agent.
    According to one embodiment, the regeneration flow contains at least 1 mol.% Of oxygen relative to the total regeneration flow.
    According to one embodiment, the step of reacting the chlorinated compound with hydrofluoric acid is carried out in a single reactor, separated in time with respect to the step of regenerating the fluorination catalyst.
    According to one embodiment, the step of reacting the chlorinated compound with hydrofluoric acid is carried out in at least one first reactor, simultaneously with the implementation of the step of regenerating the fluorination catalyst in at least one second reactor.
    According to one embodiment, the tetrafluoropropene is 2,3,3,3tetrafluoropropene.
    According to one embodiment, the tetrafluoropropene is 1,3,3,3tetrafluoropropene.
    According to one embodiment, the chlorinated compound is chosen from tetrachloropropenes, chlorotrifluoropropenes, pentachloropropanes and mixtures of these.
    According to one embodiment, the chlorinated compound is 2-chloro-3,3,3trifluoropropene, and the tetrafluoropropene is 2,3,3,3-tetrafluoropropene.
    According to one embodiment, the chlorinated compound is 1,1,1,2,3pentachloropropane and / or 1,1,2,2,3-pentachloropropane, and the tetrafluoropropene is 2,3,3,3-tetrafluoropropene .
    According to one embodiment, the chlorinated compound is 1-chloro-3,3,3trifluoropropene, and the tetrafluoropropene is 1,3,3,3-tetrafluoropropene.
    According to one embodiment, the method comprises:
    a preliminary step of manufacturing the chlorinated compound, which is preferably a preliminary step of reacting a preliminary compound with hydrofluoric acid in the gas phase, in the presence of a preliminary fluorination catalyst, the proportion of oxygen optionally present being less than 0.05 mol.% relative to the preliminary compound.
    According to one embodiment, the preliminary reaction step is carried out alternately with:
    a step of regenerating the preliminary fluorination catalyst by bringing the preliminary fluorination catalyst into contact with a regeneration flow comprising an oxidizing agent.
    According to one embodiment, the preliminary compound is 1,1,1,2,3pentachloropropane and / or 1,1,2,2,3-pentachloropropane, the chlorinated compound is 1-chloro-3,3,3 -trifluoropropene and the tetrafluoropropene is 2,3,3,3tetrafluoropropene.
    According to one embodiment, the method comprises:
    - the collection of a product flow at the end of the preliminary reaction stage;
    - Separating the product stream into a first stream comprising hydrochloric acid and tetrafluoropropene and a second stream comprising hydrofluoric acid and the chlorinated compound;
    the use of said second stream to carry out the reaction step of the chlorinated compound with hydrofluoric acid; and
    - optionally, the collection of a product stream at the end of the reaction step of the chlorinated compound with hydrofluoric acid, and the recycling of the latter in the preliminary reaction step.
    The invention also relates to an installation for manufacturing tetrafluoropropene, comprising at least one gas phase fluorination reactor comprising a bed of fluorination catalyst, said gas phase fluorination reactor being configured to be supplied alternately by:
    - a reaction flow supply system comprising a chlorinated compound and hydrofluoric acid, the proportion of oxygen possibly present in this reaction flow being less than 0.05 mol.% relative to the chlorinated compound; and
    - a regeneration flow supply system comprising an oxidizing agent.
    According to one embodiment, the reaction flow is essentially devoid of oxygen, and preferably of any oxidizing agent.
    According to one embodiment, the regeneration flow contains at least 1 mol.% Of oxygen relative to the total regeneration flow.
    According to one embodiment, the installation comprises a single reactor configured to be supplied alternately by the reaction flow supply system and the regeneration flow supply system.
    According to one embodiment, the installation comprises a plurality of reactors, each configured to be supplied alternately by a reaction flow supply system and a regeneration flow supply system.
    According to one embodiment, the installation is configured such that when one reactor is supplied by the reaction flow supply system, another reactor is supplied by the regeneration flow supply system.
    According to one embodiment, the installation is configured so that:
    - the reaction flow supply system supplies the bottom reactor and the regeneration flow supply system supplies the bottom reactor; or
    - the reaction flow supply system supplies the bottom reactor and the regeneration flow supply system supplies the reactor at the head; or
    - the reaction flow supply system supplies the reactor at the head and the regeneration flow supply system supplies the reactor at the bottom; or
    - the reaction flow supply system supplies the reactor at the head and the regeneration flow supply system supplies the reactor at the head.
    According to one embodiment:
    - the tetrafluoropropene is 2,3,3,3-tetrafluoropropene; or
    - The tetrafluoropropene is 1,3,3,3-tetrafluoropropene.
    According to one embodiment, the chlorinated compound is chosen from tetrachloropropenes, chlorotrifluoropropenes, pentachloropropanes and mixtures of these; and preferably:
    the chlorinated compound is 2-chloro-3,3,3-trifluoropropene and the tetrafluoropropene is 2,3,3,3-tetrafluoropropene; or
    - The chlorinated compound is 1,1,1,2,3-pentachloropropane and / or
    1,1,2,2,3-pentachloropropane, and the tetrafluoropropene is 2,3,3,3tetrafluoropropene; or
    - The chlorinated compound is 1-chloro-3,3,3-trifluoropropene, and the tetrafluoropropene is 1,3,3,3-tetrafluoropropene.
    According to one embodiment, the installation includes:
    - at least one unit for the production of chlorinated compounds, which preferably is at least one preliminary fluorination reactor; configured to be powered by:
    - a reaction system supply system comprising a preliminary compound and hydrofluoric acid, the proportion of oxygen possibly present in this reaction flow being less than 0.05 mol.% relative to the preliminary compound.
    According to one embodiment, the preliminary fluorination reactor is also configured to be supplied by a regeneration flow supply system comprising an oxidizing agent.
    According to one embodiment, the preliminary compound is 1,1,1,2,3pentachloropropane and / or 1,1,2,2,3-pentachloropropane, the chlorinated compound is 1-chloro-3,3,3 -trifluoropropene and tetrafluoropropene is 2,3,3,3tetrafluoropropene.
    According to one embodiment, the installation includes:
    - at least a first catalytic fluorination reactor;
    - at least one second catalytic fluorination reactor;
    - a product flow collection system connected at the outlet of the first catalytic fluorination reactor;
    - a separation unit supplied by the product flow collection system;
    - a first collection line and a second collection line connected at the outlet of the separation unit, the first collection line being configured to transport a stream comprising hydrochloric acid and tetrafluoropropene and the second collection line being configured to transport a stream comprising hydrofluoric acid and chlorine compound;
    - an intermediate collection system connected at the outlet of the second reactor;
    - a first reaction system supply system configured to supply the first reactor, the latter itself being supplied by the intermediate collection system;
    - a second reaction system supply system configured to supply the second reactor, the latter itself being supplied by the second collection line;
    - a regeneration flow supply system configured to supply the first reactor and / or the second reactor; and
    - a system for collecting gas flows from regeneration.
    According to one embodiment, the installation comprises at least two second reactors configured so that when one of these reactors is supplied by the second reaction flow supply system, the other reactor is supplied by the d 'regeneration flow supply.
    According to one embodiment, the installation comprises at least two first reactors and two second reactors configured so that when one of the first reactors and one of the second reactors are respectively supplied by the first flow supply system reaction system and the second reaction flow supply system, the other first reactor and the other second reactor are supplied by the regeneration flow supply system; and which, preferably, is configured so that the same regeneration flow coming from the regeneration flow supply system passes successively through the first reactor then the second reactor, or passes successively through the second reactor then the first reactor .
    According to one embodiment, the installation comprises a single second reactor, configured to be supplied sequentially either by the second reaction flow supply system, or by the regeneration flow supply system.
    According to one embodiment, the installation comprises a single first reactor and a single second reactor, configured to be supplied sequentially either by the second reaction flow supply system, or by the regeneration flow supply system. ; and which, preferably, is configured so that the same regeneration flow coming from the regeneration flow supply system passes successively through the first reactor then the second reactor, or passes successively through the second reactor then the first reactor .
    The invention also relates to a composition comprising tetrafluoropropene and containing, in molar proportions:
    - less than 100 ppm of chloromethane; and or
    - less than 100 ppm of 1,1-difluoroethane; and or
    - less than 100 ppm of fluoromethane; and or
    - less than 100 ppm of difluoromethane.
    According to one embodiment, the tetrafluoropropene is 2,3,3,3tetrafluoropropene.
    According to one embodiment, the composition contains, in molar proportions:
    - less than 50 ppm of chloromethane; and or
    - less than 50 ppm of 1,1-difluoroethane; and or
    - less than 50 ppm of fluoromethane; and or
    - less than 50 ppm of difluoromethane.
    The present invention overcomes the drawbacks of the state of the art. It more particularly provides a process for manufacturing HFO-1234 (and in particular HFO-1234yf) having a high yield and supplying the desired product in a high degree of purity.
    This is accomplished thanks to the discovery by the present inventors that certain reaction stages of fluorination can be carried out essentially in the absence of an oxidizing agent such as oxygen, without the lifetime of the fluorination catalyst being visibly affected on a determined period, provided that there are intermediate stages of regeneration.
    As an advantage, this results in obtaining a gas flow of HFO-1234 of higher purity since it is obtained essentially in the absence of oxygen during the reaction. The content of carbon oxides as well as of compounds containing one or two carbons is significantly reduced compared to the state of the art. The downstream treatment and the final purification of the desired product are thus simplified, guaranteeing the obtaining of the final product preferably with a purity greater than or equal to 98%, advantageously greater than or equal to 99%, and very advantageously greater than or equal to 99, 8% by weight. The hydrochloric acid co-produced is also more easily recoverable.
    BRIEF DESCRIPTION OF THE FIGURES
    Figures 1a and 1b schematically show an embodiment of an installation according to the invention with a single catalytic fluorination reactor, in two different operating configurations.
    Figures 2a and 2b schematically represent an embodiment of an installation according to the invention with two catalytic fluorination reactors, in two different operating configurations.
    FIG. 3 schematically represents an embodiment of an installation according to the invention with three catalytic fluorination reactors, in a particular operating configuration.
    Figures 4a and 4b schematically represent an embodiment of an installation according to the invention with a single catalytic fluorination reactor, in two different operating configurations.
    FIGS. 5a and 5b schematically represent an embodiment of an installation according to the invention with two catalytic fluorination reactors, in two different operating configurations.
    FIG. 6 schematically represents an embodiment of an installation according to the invention with three catalytic fluorination reactors, in a particular operating configuration.
    Figures 7 to 11 schematically represent embodiments of installations according to the invention for the production of HFO-1234yf in two stages.
    DESCRIPTION OF EMBODIMENTS OF THE INVENTION
    The invention is now described in more detail and without limitation in the description which follows.
    Unless otherwise stated, the percentages and proportions indicated are by mass values.
    The invention provides for producing HFO-1234 by catalytic fluorination in the gas phase; according to the invention, this catalytic fluorination is alternated with the regeneration of the fluorination catalyst. In certain embodiments, the invention provides for the production of HFO-1234 in several fluorination stages.
    Fluorination reaction for obtaining HFO-1234
    The invention provides at least one fluorination step, making it possible to produce HFO-1234 from a chlorinated compound.
    HFO-1234 can in particular be HFO-1234yf or else HFO1234ze (1,3,3,3-tetrafluoropropene), and this in cis or trans form or in the form of a mixture of cis and trans forms.
    By “chlorinated compound” is meant an organic compound comprising one or more chlorine atoms. This compound preferably contains 3 carbon atoms.
    This chlorinated compound is preferably a propane or a propene having substituents chosen from F, Cl, I and Br (preferably from F and Cl), and comprising at least one substituent Cl.
    It is understood that by “chlorinated compound” is also meant mixtures of compounds.
    Preferably, the chlorinated compound is a tetrachloropropene, a chlorotrifluoropropene, a pentachloropropane or a mixture of these.
    In one embodiment, the chlorinated compound is 2-chloro-3,3,3trifluoropropene (HCFO-1233xf), to produce HFO-1234yf.
    In another embodiment, the chlorine compound is 1-chloro-3,3,3trifluoropropene (HCFO-1233zd), to produce HFO-1234ze.
    In another embodiment, the chlorinated compound is 1,1,1,2,3pentachloropropane (HCC-240db), or 1,1,2,2,3-pentachloropropane (HCC240aa), or a mixture of the two , to produce HFO-1234yf.
    According to yet another embodiment, the chlorinated compound is
    2.3- dichloro-1,1,1-trifluoropropane (HCFC-243db), to produce
    HFO-1234yf.
    According to yet another embodiment, the chlorinated compound is
    1.1.2.3- tetrachloropropene (HCO-1230xa), or 2,3,3,3-tetrachloropropene (HCO-1230xf), or a mixture of these two compounds, to produce HFO1234yf.
    The conversion of the chlorinated compound to HFO-1234 can be a direct conversion or an indirect conversion (that is to say involving an intermediate product).
    The fluorination of the chlorinated compound to HFO-1234 is implemented in one or more fluorination reactors in the gas phase comprising a bed of fluorination catalyst.
    The catalyst used can 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 FeCb, chromium oxyfluoride, chromium oxides (possibly subjected to fluorination treatments), chromium fluorides and their mixtures. Other possible catalysts are supported catalysts on carbon, antimony-based catalysts, aluminum-based catalysts (e.g. AIF3 and AI2O3, alumina oxyfluoride and alumina fluoride).
    It is generally possible to use a chromium oxyfluoride, a fluoride or an aluminum oxyfluoride, or a supported or unsupported catalyst containing a metal such as Cr, Ni, Fe, Zn, Ti, V, Zr, Mo, Ge, Sn, Pb, Mg, Sb.
    Reference may be made in this regard to document WO 2007/079431 (on p.7, 1.1-5 and 28-32), in document EP 939071 (paragraph [0022]), in document WO 2008/054781 (in p.9 l.22-p.1O I.34), and to document WO 2008/040969 (claim 1), to which express reference is made.
    The catalyst is more particularly 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 Cr / Ni molar ratio (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 with aluminum, for example alumina, activated alumina or aluminum derivatives, such as aluminum halides and aluminum oxyhalides, for example described in the document US 4,902,838, or obtained by the activation process described above.
    The catalyst may comprise chromium and nickel in an activated or inactive form, on a support which has been subjected to activation or not.
    Reference may be made to document WO 2009/118628 (in particular on p.4, l.30-p.7 1.16), to which express reference is made here.
    Another preferred embodiment is based on a mixed catalyst containing chromium and at least one element chosen from Mg and Zn. The atomic ratio of Mg or Zn / Cr is preferably from 0.01 to 5.
    Before its use, the catalyst is preferably subjected to activation 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 from 250 to 500 ° C and more particularly from 300 to 400 ° C. The activation time is preferably from 1 to 200 h and more particularly from 1 to 50 h.
    This activation can be followed by a final fluorination activation step in the presence of an oxidizing agent, HF and organic compounds.
    The molar ratio HF / organic compounds is preferably from 2 to 40 and the molar ratio oxidizing agent / organic compounds is preferably from 0.04 to 25. The temperature of the final activation is preferably from 300 to 400 ° C and its duration preferably from 6 to 100 h.
    The gas phase fluorination reaction can be carried out:
    - With a HF / chlorine compound molar ratio of 1: 1 to 150: 1, preferably from 3: 1 to 100: 1 and more particularly preferably from 5: 1 to 50: 1;
    - with a contact time of 1 to 100 s, preferably 1 to 50 s and more particularly 2 to 40 s (volume of catalyst divided by the total incoming flow, adjusted to the operating temperature and 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) from 100 to 500 ° C, preferably from 200 to 450 ° C, and more particularly from 250 to 400 ° C.
    The flux composing the reaction medium can comprise, in addition to HF and the chlorinated compound, additional compounds, in particular other halohydrocarbons or halohydroolefins.
    The duration of the reaction step is typically from 10 to 2000 hours, preferably from 50 to 500 hours and more particularly from 70 to 300 hours.
    According to the invention, the proportion of oxygen optionally present in the reaction medium is less than 0.05 mol.% Relative to the chlorinated compound, more preferably still less than 0.02 mol.% Or less than 0.01 mol. %. Traces of oxygen may possibly be present, but preferably the fluorination step is carried out essentially in the absence of oxygen, or in the total absence of oxygen.
    Preferably, the proportion of any oxidizing agent (such as oxygen and chlorine) possibly present in the reaction medium is less than 0.05 mol.% Relative to the chlorinated compound, more preferably still less than 0.02 mol. % or less than 0.01 mol.%. Traces of oxidizing agent may possibly be present, but preferably the step is carried out essentially in the absence of oxidizing agent, or in the total absence of oxidizing agent.
    The product flow from the fluorination step of the chlorinated compound into HFO-1234 can undergo appropriate treatments (distillation, washing, etc.) in order to recover the HFO-1234 in purified form and separate it from the other compounds present (HCl , Unreacted HF, unreacted chlorine compound, other organic). One or more flows can be recycled.
    The HCl in particular can be subjected to a purification according to the process described in application No. FR 13/61736, to which reference is expressly made.
    Catalyst regeneration
    In each reactor used for the fluorination of the chlorinated compound to HFO-1234, said fluorination can be alternated with phases of regeneration of the catalyst, in the presence of oxygen.
    One can for example pass from the reaction phase to the regeneration phase when the conversion of the chlorinated compound drops below a predetermined threshold, for example of 50%.
    If necessary, beforehand, a transition period consisting in decompressing the reaction gas phase is ensured. It can be followed by a sweeping phase using an inert gas or by a vacuum in order to completely eliminate the reagents present.
    The regeneration stream preferably contains at least 1 mol.% Oxygen in total. It can be pure air but the flow can also contain an inert gas useful for ensuring a certain dilution, for example nitrogen, argon, helium or else hydrofluoric acid in proportions varying from 0 to 95%, preferably from 5 to 85%, and more particularly preferably from 10 to 80%. The flow rate of the regeneration flow is preferably kept high enough to avoid external diffusion regimes.
    The temperature in the regeneration stage is for example from 100 to 500 ° C, preferably from 200 to 450 ° C and more particularly from 250 to 400 ° C. It may be practical to perform the regeneration at the same temperature as the reaction.
    The pressure in the regeneration stage is for example atmospheric pressure at 15 bar absolute. It is preferably approximately equal to atmospheric pressure.
    The duration of the regeneration step is typically from 10 to 2000 hours, preferably from 50 to 500 hours and more particularly from 70 to 300 hours.
    The regeneration can be carried out in co-current or counter-current flow with respect to the direction of the flow used during the reaction period.
    This regeneration step makes it possible to recover the initial activity of the catalyst. Several cycles can thus be linked without significantly altering the activity of the catalyst, which makes it possible to increase its service life.
    At the end of the regeneration step, the reactor can be placed under vacuum so as to eliminate the inert gases and the oxygen introduced, prior to the reintroduction of the organics.
    Installations according to the invention for the implementation of the fluorination step described above
    The fluorination step described above can be carried out with a single reactor. In this case, it is operated alternately in reaction and in regeneration. Production is then discontinued.
    Otherwise, the fluorination step described above can be carried out with a plurality of reactors, for example two, three or more than three reactors. In this case, it is possible to operate at least one reactor in reaction while at least one other is operating in regeneration, and thus possibly to ensure continuous production.
    Referring to Figures 1a and 1b, an embodiment with a single reactor is described.
    The installation then includes a reactor 10, capable of being supplied either by a reaction flow supply system 2a, or by a regeneration flow supply system 2b.
    At the outlet of the reactor 10 are connected both a product flow collection system 3a and a gas flow collection system from the regeneration 3b.
    "Supply system" and "collection system" means a single pipe or a set of several pipes.
    A system of inlet valves 20 and a system of outlet valves 30 are provided to allow switching between the respective supply and collection systems.
    During the reaction step (FIG. 1a), the inlet valve system 20 is positioned so that the reactor 10 is supplied by the reaction flow supply system 2a; and the outlet valve system 30 is positioned so that the reactor 10 feeds the product flow collection system 3a, which directs the product flow to downstream processing units for production gases.
    During the regeneration step (FIG. 1b), the inlet valve system 20 is positioned so that the reactor 10 is supplied by the regeneration flow supply system 2b; and the outlet valve system 30 is positioned so that the reactor 10 supplies the system for collecting the flow of gas from the regeneration 3b, which directs the flow of gas from the regeneration to downstream processing units for these gases.
    The reactor 10 alternately connects production and regeneration periods sequentially. Production is discontinued.
    Referring to Figures 2a and 2b, an embodiment with two reactors is now described.
    In a first configuration (FIG. 2a), the reaction step is carried out in a first reactor 10 and the regeneration step is carried out in a second reactor 11. In a second configuration (FIG. 2b), the reaction step is carried out in the second reactor 11 and the regeneration step is carried out in the first reactor 10. In this way, the production is continuous.
    Each reactor 10, 11 is provided with a respective inlet valve system 20, 21 as well as a respective outlet valve system 30, 31 in order to allow the passage from one configuration to the other. It can be provided that the reaction flow supply system 2a, the regeneration flow supply system 2b, the product flow collection system 3a and the gas flow collection system from regeneration 3b are common. for the two reactors 10, 11, as illustrated, or else provide separate systems dedicated to each reactor 10, 11.
    Referring to Figure 3, an embodiment with three reactors is now described.
    In the illustrated configuration, the reaction step is carried out in a first reactor 10, a second reactor 11 is on standby, and the regeneration step is carried out in a third reactor 12. The standby step is a state in which the reactor has been regenerated and is ready to start again in reaction. In other configurations not illustrated, the states of the reactors 10, 11, 12 are switched. In this way, continuous production can be ensured.
    Each reactor 10, 11, 12 is provided with a respective inlet valve system 20, 21, 22 as well as a respective outlet valve system 30, 31, 32 in order to allow the passage from a configuration to the 'other. It can be provided that the reaction flow supply system 2a, the regeneration flow supply system 2b, the product flow collection system 3a and the gas flow collection system from regeneration 3b are common. for the three reactors 10, 11, 12 as illustrated, or else provide separate systems dedicated to each reactor 10, 11, 12.
    In the embodiments of FIGS. 1a, 1b, 2a, 2b and 3, the flows in the reactors are oriented in the same direction for the fluorination and for the regeneration.
    According to variants, the flows in the reactors can be oriented in the opposite direction between the fluorination and the regeneration.
    Thus, in Figures 4a and 4b is shown an embodiment with a single reactor 10, which is similar to the embodiment of Figures 1a and 1b, with the difference that the flows are reversed between fluorination and regeneration. For example, if the reaction flow supply system 2a feeds the reactor 10 at the bottom, then the regeneration flow supply system 2b feeds the reactor 10 at the head (or vice versa). Similarly, if the product flow collection system 3a is connected at the head of the reactor 10, then the gas flow collection system from the regeneration 3b is connected at the bottom of the reactor 10 (or vice versa).
    Similarly, in Figures 5a and 5b is shown an embodiment with two reactors 10, 11, which is similar to the embodiment of Figures 2a and 2b, with the difference that the flows are reversed between fluorination and regeneration. For example, if the reaction flow supply system 2a supplies the reactors 10, 11 at the bottom, then the regeneration flow supply system 2b supplies the reactors 10, 11 at the head (or vice versa). Similarly, if the product flow collection system 3a is connected at the top of the reactors 10, 11, then the gas flow collection system from the regeneration 3b is connected at the bottom of the reactors 10,11 (or vice versa ).
    Similarly, in Figure 6 is shown an embodiment with three reactors 10, 11, 12, which is similar to the embodiment of Figure 3, with the difference that the flows are reversed between fluorination and regeneration. For example, if the reaction flow supply system 2a supplies the reactors 10, 11, 12 at the bottom, then the regeneration flow supply system 2b supplies the reactors 10, 11, 12 at the head (or vice versa) . Similarly, if the product flow collection system 3a is connected at the top of the reactors 10, 11, 12 then the gas flow collection system from the regeneration 3b is connected at the bottom of the reactors 10, 11, 12 ( or vice versa).
    Processes according to the invention in several stages
    In certain embodiments, the invention provides for several successive reaction steps, and preferably: first a preliminary step for manufacturing the chlorinated compound mentioned above; then the fluorination step of the chlorinated compound to HFO-1234.
    Preferably, the preliminary step is itself a fluorination step.
    In this case, this step converts a preliminary compound to the chlorinated compound mentioned above. In such a case, it should be noted that the chlorinated compound contains at least one fluorine atom (since it comes from a fluorination step) as well as at least one chlorine atom (since it is then subjected to the fluorination step described above to provide HFO-1234).
    The "preliminary compound" is advantageously an organic compound (preferably with 3 carbon atoms) which comprises at least two chlorine atoms (and which comprises more chlorine atoms than the "chlorinated compound").
    The preliminary compound may preferably be a propane or a propene having substituents chosen from F, Cl, I and Br (preferably from F and Cl), and comprising at least two C1 substituents. Propane is more particularly preferred.
    It is understood that by "preliminary compound" is also meant mixtures of compounds.
    According to a preferred embodiment, the preliminary compound is HCC-240db or HCC-240aa, or a mixture of the two, and the chlorinated compound is HCFO-1233xf, to produce HFO-1234yf.
    According to yet another embodiment, the preliminary compound is HCFC-243db, and the chlorine compound is HCFO-1233xf, to produce HFO-1234yf.
    According to yet another embodiment, the preliminary compound is HCO-1230xa or HCO-1230xf or a mixture of these two compounds, and the chlorinated compound is HCFO-1233xf, to produce HFO-1234yf.
    The conversion of the preliminary compound into the chlorinated compound can be a direct conversion or an indirect conversion (that is to say involving an intermediate product).
    It is possible to carry out the fluorination of the preliminary compound into the chlorinated compound in the liquid phase. However, it is preferably a fluorination in the gas phase, in the presence of a fluorination catalyst. It can be implemented in one or more fluorination reactors in series or in parallel.
    The fluorination catalyst can be of the same type as described above for the fluorination of the chlorinated compound to HFO-1234. The above description regarding activation of the catalyst also applies.
    The fluorination reaction in the gas phase of the preliminary compound into the chlorinated compound can in particular be carried out:
    - with an HF / organic molar ratio of 3: 1 to 100: 1, preferably from 5: 1 to 50: 1 (the term “organic” designates all of the compounds of the reaction medium containing one or more carbon atoms) ;
    - at an absolute pressure ranging from 0.1 to 50 bar, preferably from 0.3 to 15 bar;
    - with a contact time of 1 to 100 s, preferably from 1 to 50 s and more particularly 2 to 40 s (volume of catalyst divided by the total incoming flow, adjusted to the operating temperature and pressure);
    - At a temperature (temperature of the catalyst bed) from 100 to 500 ° C, preferably from 200 to 450 ° C, and more particularly from 250 to 400 ° C.
    The flow composing the reaction medium may comprise, in addition to the HF and the preliminary compound, additional compounds, in particular other halohydrocarbons or halohydroolefins. The stream may for example already include a fraction of HFO-1234.
    According to a preferred embodiment, there is not or essentially no oxygen (and possibly, there is not or essentially no other oxidizing agent) in the reaction medium.
    Thus, the presence of oxygen or an oxidizing agent is also avoided in the subsequent fluorination step, without having to carry out an intermediate separation of a flow of oxygen or oxidizing agent.
    The duration of the reaction step from the preliminary compound to the chlorinated compound is typically from 10 to 2000 hours, preferably from 50 to 500 hours and more particularly from 70 to 300 hours.
    At the end of this reaction step, a product flow is collected which comprises in particular chlorinated compound, unreacted preliminary compound, HF, HCl, possibly HFO-1234, and optionally secondary products such as in particular 1 , 1,1,2,2-pentafluoropropane (HFC-245cb).
    This product flow can then directly feed the fluorination step of the chlorinated compound into HFO-1234yf, described above.
    Alternatively, this product stream can be separated, for example by distillation, to provide for example a first stream comprising HCl and optionally HFO-1234, and a second stream comprising HF and chlorinated compound. The distillation can for example be carried out at a temperature of -90 to 150 ° C, preferably of -85 to 100 ° C and at a pressure of 0.1 to 50 bar abs and preferably from 0.3 to 5 bar abs .
    The first stream can be directed to an acid production unit to produce HCl and HFO-1234. HFO-1234 and the intermediate products can be recovered by known means such as extraction, washing, decanting and preferably distillation means.
    It should be noted that, according to the invention, at least one of the two fluorination stages described above is alternated with a stage of regeneration of the reactor (s) with a flow of oxidizing agent, as described above in connection with the fluorination of the chlorinated compound to HFO-1234. The above description therefore applies by analogy (including that relating to the various possible installations illustrated in Figures 1a to 6):
    - either to regeneration alternated with the fluorination of the preliminary compound into a chlorinated compound;
    - Either alternating regeneration with the fluorination of the chlorinated compound in HFO-1234;
    - Either at the alternating regeneration with the fluorination of the preliminary compound into the chlorinated compound and at the alternating regeneration with the fluorination of the chlorinated compound into the HFO-1234.
    Depending on the reaction conditions and the nature of the catalyst, the tendency of the catalyst to deactivate may be different, hence these various possible cases.
    Two-step HFO-1234yf manufacturing process
    Now, various embodiments are described in relation to the manufacture of HFO-1234yf in two stages from HCC-240db (it being understood that one can also use instead of HCC-240aa or a mixture of the two): a first stage of conversion of HCC-240db into HCFO1233xf, then a second stage of conversion of HCFO-1233xf into HFO1234yf, implemented in successive reactors.
    Referring to FIG. 7, according to one embodiment, an installation according to the invention can thus comprise a first fluorination reactor 40 for the implementation of the stage of preparation of HCFO-1233xf. It is understood that it is also possible to use instead a plurality of reactors, operating in series and / or in parallel.
    This first fluorination reactor 40 is supplied by a first supply system 39 in a reaction medium (comprising HF and HCC240db).
    At the outlet of the first fluorination reactor 40, there is a product flow collection system 41, which feeds a separation unit 42. This separation unit 42 can in particular be a distillation unit as described above.
    At the outlet of the separation unit 42, a first collection line 43 and a second collection line 44 are provided. The first collection line 43 is configured to transport a flow comprising in particular HCl and HFO-1234yf, and the second collection line 44 is configured to transport a flow comprising in particular HF and HCFO-1233xf.
    The first collection line 43 supplies additional processing units, not shown, which may in particular comprise an acid production unit, while the second collection line 44 provides recycling to at least one second gas phase fluorination reactor 48 which is used for the fluorination of HCFO-1233xf to HFO-1234yf. This second collection line 44 can therefore also be qualified as a recycling line. This second reactor 48 is supplied by a second supply system 46 in reaction medium, which itself is supplied by the second collection line 44 on the one hand and by an HF supply system 45 on the other hand.
    At the outlet of the second reactor 48 is connected an intermediate collection system 47. This in turn feeds the first feed system 39 in the reaction medium of the first reactor 40. A supply of HCC-240db is provided by a system of HCC-240db power supply 38.
    Preferably, in this installation and in all of the fluorination stages, the proportion of oxygen possibly present in the streams is less than 0.05 mol.% Relative to the majority organic compound, more preferably still less than 0.02 mol.% or less than 0.01 mol.%. Traces of oxygen may possibly be present, but preferably the whole process of fluorination of HCC-240db into HFO-1234yf is carried out essentially in the absence of oxygen, or in the total absence of oxygen.
    Preferably, the proportion of any oxidizing agent (such as oxygen and chlorine) possibly present in the reaction medium is less than
    0.05 mol.% Relative to the majority organic compound, more preferably less than 0.02 mol.% Or less than 0.01 mol.%. Traces of oxidizing agent can possibly be present, but preferably the whole process of fluorination of HCC-240db in HFO-1234yf is carried out essentially in the absence of oxidizing agent, or in the total absence of agent oxidant.
    In accordance with the invention, regeneration of the catalyst is planned, alternating with fluorination. This can relate to either the first reactor 40, or the second reactor 48, or the two reactors 40, 48. The regeneration is carried out as described above, by means of a flow of oxidizing agent. The means necessary for regeneration are not shown in Figure 7 but are similar to those described above.
    In FIG. 8 is illustrated a variant. This is identical to the embodiment of Figure 7 with the difference that it provides, instead of a single second reactor 48, two second reactors 48a, 48b. These are configured to operate alternately in fluorination mode and in regeneration mode, as described above in connection with FIGS. 2a and 2a.
    Thus, by controlling an inlet valve system 20, 21 and an outlet valve system 30, 31, it is ensured that:
    - In one phase, one of the second reactors 48a operates in fluorination mode, that is to say is supplied by the second supply system 46 in reaction medium and supplies the intermediate collection system 47; while the other of the second reactors 48b operates in regeneration mode, that is to say is supplied by a system for supplying the regeneration flow 49 and itself supplies a system for collecting the flow of gas from the regeneration 50 ;
    - In another phase, the configurations of the two reactors 48a, 48b are reversed.
    It should be noted that, in FIG. 8, a regeneration is shown taking place in the same direction as the fluorination. However, the flows can also be reversed, as described in connection with FIGS. 5a and 5b.
    In FIG. 9 another variant is illustrated. This is identical to the embodiment of FIG. 8 with the difference that not only two second reactors 48a, 48b are provided, but also, instead of a single first reactor, two first reactors 40a, 40b. These are configured to operate alternately in fluorination mode and in regeneration mode, as described above in connection with FIGS. 2a and 2b.
    In a first phase, which is that illustrated in the figure, the second supply system 46 in the reaction medium supplies one of the two second reactors 48a. The intermediate collection system 47 is connected at the outlet of this second reactor 48a, which makes it possible to collect an intermediate product flow. This feeds the first feed system 39 in a reaction medium (also with the HCC-240db feed system 38), which itself feeds one of the first two reactors 40a.
    The product flow collection system 41 is connected at the outlet of this first reactor 40a.
    Preferably simultaneously, the regeneration flow supply system 49 feeds the other second reactor 48b. An intermediate gas flow collection system from regeneration 52 is connected at the outlet of this second reactor 48b and supplies the other first reactor 40b at the inlet. The intermediate gas flow collection system from regeneration 50 is connected at the outlet of this first reactor 40b
    Alternatively, an intermediate supply of additional regeneration flow can be provided between the two reactors 48b, 40b. Alternatively again, provision may be made for regeneration by independent flows of these two reactors 48b, 40b.
    Alternatively again, regeneration can be provided with flows in the opposite direction to those of fluorination, according to the principles of FIGS. 5a and 5b
    In a second phase, not shown, the fluorination and regeneration configurations are reversed between the reactors.
    The passage from one configuration to the other is ensured by means of a set of valves: in the example illustrated, it acts of inlet valves 20, 21 which are located upstream of the second reactors 48a, 48b, outlet valves which are located downstream of the first reactors 40a, 40b, and finally an HCC-240db valve 51 located at the level of the HCC240db supply system 38.
    In FIG. 10 another variant is illustrated. This is analogous to the embodiment of FIG. 7. In this variant, sequential regeneration with respect to fluorination (and not simultaneous) is provided, on only one of the two reactors, namely the second reactor 48.
    To this end, the regeneration flow supply system 49 is connected at the inlet of the second reactor 48 and the gas flow collection system resulting from the regeneration 50 at the outlet of the second reactor 48. A system of valves at the inlet 20 and a system of outlet valves 30 makes it possible to ensure the tilting of the second reactor 48 either in fluorination or in regeneration.
    It should be noted that the flows in fluorination and in regeneration can be in the same direction or in the opposite direction.
    It should also be noted that the same means can also be provided for regeneration at the level of the first reactor 40, either in addition to or as a replacement, means for regenerating the second reactor 48.
    In FIG. 11 another variant is illustrated. This is analogous to the embodiment of FIG. 7. In this variant, provision is made for sequential regeneration with respect to fluorination (and not simultaneous), on the two reactors at the same time, namely the first reactor 40 and the second reactor 48.
    To this end, the regeneration flow supply system 49 is connected at the inlet of the second reactor 48 and the gas flow collection system originating from the regeneration 50 at the outlet of the first reactor 40. A system of valves at the inlet 20 and a system of valves at outlet 30 makes it possible to ensure the tilting of the reactors 40, 48 either in fluorination or in regeneration.
    It should be noted that the flows in fluorination and in regeneration can be in the same direction or in the opposite direction.
    All that has been described here in connection with the preparation of HFO-1234yf in two stages can be read in a similar manner by replacing the HCC-240db by another preliminary starting compound (and by replacing the HCFO-1233xf by another compound. chlorine). Likewise, what has been described here can be applied analogously to the preparation of other HFO-1234s.
    Another possibility of implementing the invention consists in: on the one hand producing chlorinated compound from the preliminary compound (for example HCFO-1233xf from HCC-240db or the like); and on the other hand produce HFO-1234 from the chlorine compound (for example HFO-1234yf from HCFO-1233xf); and this independently and separately, for example by isolating, storing and / or transporting the chlorinated compound between the two stages; and practicing the alternating regeneration according to the invention on the first stage or the second stage or both, independently.
    Products obtained
    The consequence of the absence or almost absence of oxygen during the reaction phase is the reduction in the level of impurities linked to combustion or degradation reactions of the molecules. The impurities are carbon oxides or dioxides as well as molecules containing fewer carbon atoms than the starting chlorine product.
    Thus, the invention makes it possible to obtain a flow of HFO-1234 (and in particular of HFO-1234yf) containing less chloromethane (HCC-40) and 1.1 difluoroethane (HFC-152a) than in the prior art . These compounds form an azeotrope with HFO-1234yf, which makes them difficult to purify.
    The invention also makes it possible to obtain a flux of HFO-1234 (and in particular of HFO-1234yf) containing less fluoromethane (HFC-41) and difluoromethane (HFC-32) than in the prior art. However, it is known that these compounds are extremely flammable.
    The molar proportion of each of these compounds in the flow of HFO1234 is thus preferably less than 100 ppm, and more particularly less than 50 ppm.
    According to one embodiment, this stream contains HFO-1234 (preferably HFO-1234yf) as well as from 1 to 50 ppm of HCC-40, from 1 to 50 ppm of HFC-152a, from 1 to 50 ppm of HFC- 41 and from 1 to 50 ppm of HFC-32.
    According to one embodiment, this stream is essentially free, and preferably is free, of HCC-40.
    According to one embodiment, this stream is essentially free, and preferably is free, of HFC-152a.
    According to one embodiment, this flow is essentially free, and preferably is free, of HFC-41.
    According to one embodiment, this stream is essentially devoid, and preferably is devoid of HFC-32.
    According to one embodiment, this stream contains at least 98% of HFO-1234, preferably at least 99%, and in particular at least 99.5% or even at least 99.8% by weight.
    The flow of HFO-1234 considered is either the flow obtained at the outlet of the fluorination reactor of the chlorinated compound into HFO-1234 (flow taken from the product flow collection system 3a in the figures), or the flow obtained at the outlet of the separation unit (flow taken from the first collection pipe 43 in the figures), ie the flow obtained subsequently again after separation of the HFO-1234 and the hydrochloric acid.
    In addition, the absence or near absence of oxygen also makes it possible to obtain a flow of hydrochloric acid of higher purity allowing easier recovery. Thus, the flow of hydrochloric acid recovered after separation from HFO-1234 is preferably devoid (or essentially devoid of) trifluoroacetic acid, COF2 or COFCI.
    EXAMPLES
    The following examples illustrate the invention without limiting it.
    There is a gas phase fluorination reactor equipped with a supply of HF, a supply of fresh organic products, a supply available for the co-supply of another gaseous compound and a line d 'feed from the recycling of unconverted reagents.
    The output of the gas stream from this reactor is led to a cooled pipe with a double jacket which makes it possible to cool and partially condense the reaction products before their introduction into the distillation column. The partially condensed flow is thus brought to a 1.5 m high distillation column filled with a metal lining of the Sulzer type which facilitates exchanges between the rising gas flow and the falling liquid reflux. The distillation column is equipped with a boiler at the bottom of the column and a condensing system at the top. This separation unit makes it possible to separate a top stream consisting mainly of the desired product (HFO-1234yf) and the HCl by-product. More or less significant quantities of the HFC-245cb by-product are also present. The flow at the bottom of the column consists mainly of HF and unconverted reagent (HCFO-1233xf) as well as the by-product HFC-245cb resulting from the addition of HF to HFO-1234yf. This flow at the bottom of the column is then recycled to the gas phase reactor. Traces of impurities are present in each of the streams.
    180 mL of chromium-based mass catalyst are introduced into the inconel reactor. It is first subjected to a drying period under 50 L / h of nitrogen at atmospheric pressure at 275 ° C overnight. Then, while maintaining the nitrogen and still at 275 ° C., a flow of HF is gradually added until a flow rate of 1 mol / h is obtained. This treatment is maintained overnight. The nitrogen is then cut and the oven temperature increased to 350 ° C. The treatment under pure HF is thus also maintained overnight. Finally, a treatment under 5 L / h of air is applied for at least 24 h.
    Following the catalyst activation treatment, the reagents HCFO-1233xf and HF are introduced into the recycling loop so as to fill this part of the installation while maintaining a molar ratio between hydrofluoric acid and organic 25. Start-up is done by supplying the liquid contained in the recycling loop to the reactor in the gas phase (a preheater ensures the prior vaporization of the reactants). The system then gradually balances between the unconverted reagents which are recycled, the formed products which are discharged and collected outside the system and the fresh reagents which are continuously supplied so as to exactly compensate for the quantity of products discharged. The level of liquid in the distillation column thus remains constant.
    The catalyst conversion evolves over time and decreases gradually. When the conversion drops below 50%, an air regeneration treatment is applied to the catalyst. This treatment makes it possible to fully recover the initial activity of the catalyst.
    The conversion is calculated from the molar content of HCFO-1233xf measured at the inlet of the reactor (sum of the recycling streams and fresh organic) and the content of HCFO-1233xf measured at the outlet of the reactor.
    Example 1 - catalytic results in the presence of air
    A test is carried out under the following operating conditions: the catalyst is freshly regenerated, the molar ratio between HF and the organics and 25, the contact time in the gas phase is 15 seconds, the temperature is 350 ° C. and 10 mol.% of oxygen is added relative to the sum of the organic materials introduced. The conversion of HCFO-1233xf obtained over time is given in Table 1 below. During this test, the gas flow leaving the head of the distillation column is analyzed by gas phase chromatography. The analysis is shown in Table 2 below (value in% of GC area).
    Example 2 - catalytic results without air
    We use the embodiment of Example 1 but without adding additional oxygen in the gas phase. The results obtained for the conversion over time are given in Table 1 below.
    The analysis of the gas flow leaving the distillation column is reported in Table 2 below (value in% of GC area). Carbon oxides and impurities in C1 and C2 have decreased significantly. The purity of the sum of the desired product HFO-1234yf and the recyclable by-product HFC-245cb increases.
    Example 1 Example 2 Time (h) Conversion ofHCFO-1233xf (%) Time (h) Conversion ofHCFO-1233xf (%) 4 78.6 15 77.6 8 77.4 19 78.5 12 76.3 24 77.8 16 77.2 27 78.3 21 78.7 31 76.9 28 76.2 35 74.5 32 76.8 39 72.8 36 76.9 43 71.7 40 75.9 48 72.7 48 75.6 51 72.9 52 73.4 55 73.2 60 73.4 59 73.6 64 72.1 63 74.1 71 70.2 71 70.9 80 67.8 82 70.9 84 65.0 86 69.4
    Table 1
    Detected product Example 1 Example 2 CO 3.2 0.22 CO 2 1.39 0.04 F23 0.13 Nd F41 0.06 Nd F32 0.03 Nd F125 0.17 Nd Trifluoropropyne 0.08 0.02 F 143a 0.36 0.04 F1234yf + 245cb 93.19 98.03 F40 0.26 Nd F 152a 0.02 Nd F1234zeE 1.10 1.62 F1233xf 0.01 Nd
    Table 2
    Nd: not detected
    权利要求:
    Claims (3)
    [1" id="c-fr-0001]
    1. Composition comprising tetrafluoropropene and containing, in molar proportions:
    - less than 100 ppm of chloromethane; and
    - less than 100 ppm of 1,1-difluoroethane; and or
    - less than 100 ppm of fluoromethane; and or
    - less than 100 ppm of difluoromethane.
    [2" id="c-fr-0002]
    2. Composition according to claim 1, in which the tetrafluoropropene is 2,3,3,3-tetrafluoropropene.
    [3" id="c-fr-0003]
    3. Composition according to claim 1 or 2, containing, in molar proportions:
    - less than 50 ppm of chloromethane; and
    - less than 50 ppm of 1,1-difluoroethane; and or
    - less than 50 ppm of fluoromethane; and or
    - less than 50 ppm of difluoromethane.
    1/6
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    法律状态:
    2018-02-02| PLFP| Fee payment|Year of fee payment: 4 |
    2018-06-12| PLFP| Fee payment|Year of fee payment: 5 |
    2018-06-22| PLSC| Search report ready|Effective date: 20180622 |
    2019-06-19| PLFP| Fee payment|Year of fee payment: 6 |
    2020-06-12| PLFP| Fee payment|Year of fee payment: 7 |
    2021-06-11| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1456303|2014-07-02|
    FR1456303A|FR3023286B1|2014-07-02|2014-07-02|PROCESS FOR THE PRODUCTION OF TETRAFLUOROPROPENE|
    FR1761894A|FR3059999B1|2014-07-02|2017-12-11|PROCESS FOR THE MANUFACTURE OF TETRAFLUOROPROPENE.|FR1761894A| FR3059999B1|2014-07-02|2017-12-11|PROCESS FOR THE MANUFACTURE OF TETRAFLUOROPROPENE.|
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