• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    abstract “process for the manufacture of hydrofluorolefins” is a process for the synthesis of hydrochlorofluorolefins (hcfo) and / or hydrofluorolefins (hfo). the process is based on the fluorination steps of hydrochloropropenes or hydrochloropropanes to form hydrochlorofluoropropenes and / or hydrofluoropropenes, followed by the catalytic gas-phase fluorination of hydrochlorofluoropropenes to form hydrofluoropropenes. the process produces 1,1,1,2-tetrafluoropropene (hfo-1234yf) from “raw material”, such as tetrachloropropenes, 1,1,2,3 tetrachloropropene (hco-1230xa) and / or 1,1,1 , 2 tetrachloropropene (hco-1230xf) or pentachloropropanes, hcc-240db, hcc-240aa and / or hcc-240ab that are precursors to tetrachloropropenes. the process of the present invention comprises the steps of: a) fluorination in liquid or gas phase of tetrachloropropene (which can be formed by fluorination in gas phase of pentachloropropane), in the presence or absence of a homogeneous or heterogeneous catalyst; to form the intermediate product hcfo-1233xf and, subsequently, b) gas phase catalytic fluorination of the intermediate hcfo-1233xf to form the hydrofluoropropene 1,1,1,2-tetrafluoropropene product (hfo-1234yf).
    公开号:BR112014011907B1
    申请号:R112014011907
    申请日:2012-11-06
    公开日:2020-01-28
    发明作者:Bin Chen Benjamin；Y Elsheikh Maher；Bonnet Philippe
    申请人:Arkema Inc；
    IPC主号:
    专利说明:

    "PROCESS FOR THE MANUFACTURE OF HYDROFLUOROLEFINS FIELD OF THE INVENTION [001] The present invention relates to a process for the manufacture of a hydrofluoropropene. More particularly, the present invention relates to a process for making the hydrofluoropropene 1,1,1,2-
    tetrafluoropropene (HFO-1234yf) The from 1,1,2,3- tetrachloropropene (HCC-1230x) and / or your isomer 1,1,1,2- tetrachloropropene (HCC-1230xf). The materials of match
    for the process may be tetrachloropropene (s) or its precursor materials, such as 1,1,1,2,3-pentachloropropane (HCC-240db), 1,1,2,2,3-pentachloropropane (HCC-240aa) and / or 1,1,1,2,2-pentachloropropane (HCC-240ab). The process comprises two stages, in which the first stage is a fluorination in liquid or gaseous phase in the presence or absence of a homogeneous or heterogeneous catalyst in order to form the intermediate product of hydrochlorofluoropropene 1,1,1-trifluoro-2-chloropropene (HCFO -1233xf), followed by a second step comprising a 1,1,1-trifluoro-2-chloropropene catalyzed gas fluorination (HCFO1233xf) in order to form the desired 1,1,1,2tetrafluoropropene (HFO- 1234yf) and the co-products, firstly, 1,1,1,2,2-pentafluoropropane (HFC-245cb). Co-products can be recycled back to the second gas phase reaction. Preferably, the catalyst of the second stage is a chromium-based catalyst, such as CrOmFn, with 1.5 <m <3 and 0 <n <3, supported or unsupported.
    BACKGROUND OF THE INVENTION [002] The Montreal Protocol for the protection of the ozone layer, signed in October 1987, requires the
    Petition 870190095777, of 25/09/2019, p. 9/27
    2/14 gradual suppression of the use of chlorofluorocarbons (CFCs). The most ozone-friendly materials, such as hydrofluorocarbons (HFCs), for example, chlorofluorocarbons replaced by HFC-134a. These compounds proved to be greenhouse gases, which cause global warming and were regulated by the Kyoto Protocol on Climate Change. Emerging replacement materials, hydrofluoropropenes, have been shown to be environmentally acceptable, that is, they have zero ozone depletion potential (ODP) and an acceptable low GWP. The present invention is directed to a process for manufacturing hydrofluorolefins, such as hydrofluoropropenes and / or hydrochlorofluorolefins. The process of the present invention is based on a two-step reaction process that includes fluorination in gas or liquid phase, followed by fluorination in catalytic gas phase in order to produce the desirable fluorolefins.
    [003] Methods for preparing hydrofluoroalkenes are known. For example, WO2007 / 079431 discloses processes for the production of fluorinated olefins, including hydrofluoropropenes. Processes that are widely described as a single reaction or two or more reactions involve fluorination of compounds of the formula C (X) mCCl (Y) nC (X) m to at least one compound of the formula CF3CF = CHZ, where each X, Y and Z is independently H, F, Cl, I or Br and each m is independently 1, 2 or 3 and n is 0 or 1. Examples and preferred modalities reveal multi-step processes, such as the reaction sequence, in which a 1,1,2,3-tetrachloropropene raw material (1230x) is fluorinated in a catalyzed gas phase reaction
    Petition 870190095777, of 25/09/2019, p. 10/27
    3/14 to form a compound such as 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf). The 2-chloro-3,3,3-trifluoropropene is then converted to 2-chloro-2,3,3,3tetrafluoropropane (HCFC-244bb) through a catalyzed liquid phase reaction. Followed by dehydrochlorination of 2chloro-2,3,3,3-tetrafluoropropane (HCFC-244bb) to 2,3,3,3tetrafluoropropene (HFO-1234yf) through a catalyzed gas phase reaction.
    SUMMARY OF THE INVENTION [004] The present invention provides a process for producing the hydrofluoropropene 1,1,1,2-tetrafluoropropene (HFO-1234yf) from raw material, such as tetrachloropropenes, 1,1,2,3 tetrachloropropene (HCO -1230x) and / or 1,1,1,2 tetrachloropropene (HCO-1230xf) or pentachloropropanes, HCC-240db, HCC-240aa and / or HCC-240ab, which are precursors of tetrachloropropenes. The process of the present invention comprises the steps of:
    a) fluorination in liquid or gaseous phase of tetrachloropropene (which can be formed by fluorination in gas phase of pentachloropropane), in the presence or absence of a homogeneous or heterogeneous catalyst; in order to form the intermediate product of HCFO-1233xf and subsequently
    b) fluorination in catalytic gas phase of the intermediate HCFO1233xf in order to form the hydrofluoropropene 1,1,1,2-tetrafluoroprepene product (HFO-1234yf). The reaction sequence can be summarized as:
    Petition 870190095777, of 25/09/2019, p. 11/27
    4/14
    Fluorination of GP or LIQ
    1230xa, 1230xf, 240db, 240aa, 240ab + HF —► 1233 xf
    GP CAT
    1233xf + HF
    1234yf + 245cb recycling
    DETAILED DESCRIPTION OF THE INVENTION
    The first stage of the present invention concerns the fluorination in liquid or gaseous phase of a hydrochloropropene, such as HCO-1230xa or HCO-1230xf, in the absence or presence of a catalyst selected from homogeneous or heterogeneous catalysts in order to form the hydrochlorofluoropropene
    2-chloro-3,3,3-trifluoropropene (HCFO-1233xf). The hydrochloropropene can be formed by gas-fluorination of a hydrochloropropane, such as HCC-240db, HCC-240aa or HCC-240ab. Hydrochloropropane fluorination can be a separate step or it can occur on site with hydrochloropropene gas fluorination.
    [006] HCO-1230xf can be isomerized in the presence of acid catalyst in order to produce HCO-1230xa, as shown in Scheme 1
    CCl 2 _ Cl * CCI 2 - CIH, ccl 2 allylic reorganization P H ; · CH 2 CI *
    HC1 --►
    Cl
    Scheme 1. Isomerization from 1230xf to 1230x [007]
    HCO-1230xa or its HCO-1230xf isomer can be obtained by thermal dehydrochlorination of hydrocarbons, such as HCC-240db, HCC-240aa and / or HCC-240ab, as shown in Scheme 2.
    Petition 870190095777, of 25/09/2019, p. 12/27
    5/14
    240db CC1 3 CHC1 CH 2 C1 -► 1230x CC1 2 = C (C1) CH 2 C1 + HC1
    240aa CH 2 C1 CC1 2 CHC1 2 -► 1230x CC1 2 = C (C1) CH 2 C1 + HC1
    240ab CC1 3 CC1 2 CH 3 - * 1230xf CH 2 = C (C1) CC1 3 -► 1230x CC1 2 = C (C1) CH 2 C1 + HC1
    Scheme 2. Dehydrochlorination of HCC-240db, HCC-240aa and / or HCC-240ab for HCO-1230xa.
    [008] In one embodiment, the first stage of the process of the present invention comprises the fluorination in liquid phase of tetrachloropropene with HF, preferably without using the catalyst. The HF for
    reason molar in tetrachloropropene is, preferably, in fence from 3 to 1 about 500 to 1 , more preferably, in fence of 10 The 1 to about 200 The 1. Temperatures in reaction can vary from about 20 ° C at about 400 ° C,
    preferably, from about 100 ° C to about 350 ° C. Operating pressures can range from about 0.07 to about 6.20 MPa (about 10 to about 900 psia), preferably from about atmospheric pressure to about 4.83 MPa (700 psia). Generally, the residence time is about ¼ to 24 hours, preferably about ½ hour to about 2 hours. Any non-reactive raw material can be easily separated from the desired product due to the large difference in its boiling points. Preferably, the reaction vessel is constructed from HF resistant material, such as 316L stainless steel, INCONEL ® or HASTELLOY ® . The reaction can be carried out by a continuous process or by batch.
    [009] The main by-product of this reaction is hydrogen chloride (HCl), which can be removed by conventional means, known in the art as absorption or distillation. After removing the HCl, the product flow
    Petition 870190095777, of 25/09/2019, p. 13/27
    6/14 contains the desired hydrochlorofluoropropene product, HCFC1233xf, and may include non-reactive by-products and starting materials, which include, but are not limited to: HF, pentafluoropropanes, such as 245cb, and chlorotetrafluoropropanes, such as 244bb. This flow with or without separation of the co-products provides the feed flow for the second reaction step.
    [0010] Optionally, the first liquid phase fluorination step can be performed in the presence of a catalyst. The catalyst can be a homogeneous fluorination catalyst selected from catalysts such as SbCl5, TiCl4 and SnCl4. The level of the homogeneous fluorination catalyst used can vary between 0.1 and 10 mol% of the organic present. The homogeneous fluorination catalyst is activated first with HF, in which the HCl by-product is expelled. The activation process can be carried out at a temperature ranging between room temperature and 200 ° C, preferably between room temperature and 100 ° C. Fluorination in liquid phase can be performed continuously or in batch conditions. When the antimony catalyst is used, a low level of chlorine gas ranging from about 1 to 10 mol% can be provided in order to extend the life of the catalyst.
    [0011] In an alternative modality, the first step is performed in the gas phase and a heterogeneous catalyst is used. This catalyst can be selected from a supported or unsupported chromium based catalyst. A cocatalyst selected from the group nickel, zinc, cobalt or magnesium can be used. The level of cocatalyst can vary between 1 and 50% by weight of the
    Petition 870190095777, of 25/09/2019, p. 14/27
    7/14 catalyst, preferably between 5 and 10% by weight. The incorporation of the cocatalyst can occur through processes known in the art, such as adsorption from aqueous or non-aqueous solution, intimate physical mixing of the cocatalyst and catalyst or co-precipitation of aqueous or non-aqueous solutions. When a supported catalyst is used, the support can be selected from the group activated carbon, graphite, fluorinated graphite, alumina, fluorinated alumina, chromium oxide, fluorinated chromium oxide, magnesium and fluorinated magnesium. The preparation of the supported catalyst can take place through processes known in the art such as adsorption of aqueous or non-aqueous solutions, coprecipation of aqueous or non-aqueous solution or by mixing the support and mixing the catalyst / cocatalyst.
    [0012] When a chromium based catalyst such as
    Cr2O3, is used in the first stage, it is subjected to an activation of HF in the presence or absence of a charger, such as nitrogen or air. In a typical activation process, in a first step, the catalyst is dried at a temperature between 100 ° and 200 ° C, in the presence of a carrier gas such as nitrogen. After drying, the catalyst is activated with HF in the presence of carrier gas, such as nitrogen or air. Typically, the HF activation step can be started at about 100 ° C, with the use of a diluted mixture of HF in nitrogen or in an air mixture, which is gradually increased in such a way as to maintain the temperature of the catalyst well below 400 ° C. Then, the air or nitrogen thinner is gradually decreased. Then, the reactor pressure is
    Petition 870190095777, of 25/09/2019, p. 15/27
    8/14 increased to approximately the desired reaction pressure, for example, 0.07 to 6.20 MPa (10 to 900 psia), and the pure HF is gradually added over another 18 hours. The HF activation step is followed by a second air activation step, in which the catalyst is heated to approximately 300 to 400 ° C, preferably between 330 to 360 ° C for approximately 24 hours in a dry air flow. Preferably, the resulting HF and activated air catalyst have a composition close to CrOmFn, with 1.5 <m <3 and 0 <n <3. Preferably, the activated catalyst has a fluorine content of about 35 to 40% by weight, a surface area is between 10 and 100 m 2 / g, pore volume is between 0.1 and 1 m 3 / g,% friction is preferably between about 1 and 5% and the compression force is approximately 0.14 to 0.69 MPa (20 to 100 psi).
    [0013] In an alternative embodiment, the first stage of the process may comprise the gas phase fluorination of tetrachloropropene with HF, preferably without the use of a catalyst. The processing conditions for catalyzed and non-catalyzed gas fluorination are similar to the liquid phase step described above, for example; the operating temperature can vary between 100 and 500 ° C, preferably between 200 and 450 ° C. It is an advantage to use a contact time between 1 and 100 seconds, preferably between 5 and 20 seconds. Due to the fact that HCl is generated as a co-product in the process, it is preferable to operate the process under pressure, between 0.07 and 6.89 MPa (10 and 1,000 psi) and, more preferably, between atmospheric pressure and 2.76 MPa (400 psi). It is better than a coalimentation of an oxygen containing gas, as
    Petition 870190095777, of 25/09/2019, p. 16/27
    9/14 air, extend the life of the catalyst by minimizing the need to end the process to remove carbon deposits. The molar ratio of HF to organic can vary between 1/1 to 100/1 with the molar ratio of HF / organic preferably between 5/1 to 40/1.
    [0014] The tetrachloropropene starting material of the present invention, HCO-1230xa or HCO-1230xf, can be prepared by dehydrochlorination in the gas phase of pentachloropropanes, such as HCC-240db, HCC-240aa and / or HCC2240ab in the gas phase in the presence of a catalyst. Preferably, the catalyst is a supported or unsupported Cr 3 based catalyst. Preferably, the catalyst is activated, as described above. A cocatalyst selected from the group nickel, zinc and magnesium can be used. The operating temperature can vary between 200 and 500 ° C and is preferably between 200 and 400 ° C. The operating pressure can vary within the range of 0.69 and 6.89 MPa (100 to 1,000 psi), and is preferably between 1.38 and 2.76 MPa (200 and 400 psi). The molar ratio of HF to organic food is preferably between 5/1 to 40/1, and the contact time is between 10 and 100 seconds. To perform the process for an extended period of time without catalyst deactivation, it is advantageous to use a molar ratio of oxygen to organic food between 1 and 10% by volume. Oxygen can be fed, like pure oxygen or oxygen containing gas, like air or a mixture of oxygen and nitrogen.
    [0015] The second reaction step of the present invention relates to a gas-phase catalytic fluorination of the hydrochlorofluoropropene HCFO-1233xf from the first
    Petition 870190095777, of 25/09/2019, p. 17/27
    10/14 reaction step to form the hydrofluoropropene 1,1,1,2tetrafluoropropene (HFO-1234yf) and the co-products, mainly HCC-245cb. The reaction sequence of the second step can be summarized as:
    GPCAT
    1233xf CH 2 = C (C1) CF 3 + HF —► 1234yf CH 2 = C (F) CF 3 + 245cb
    4____________________________________________________________I recycling [0016] The second step involves putting the hydrochlorofluoropropene HFO-1233xf in contact with HF under conditions sufficient to produce the hydrofluorolefin 1,1,1,2-tetrafluoropropene (HFO-1234yf). The HF: hydrochlorofluoropropene molar ratio is typically about 0.5: 1 to 40: 1, and is preferably about at least 1: 1 to improve conversion and, preferably, no more than about 10: 1 , to produce low levels of excess HF, which are recovered downstream. Typically, temperatures from about 250 ° C to about 600 ° C are used, preferably from about 300 ° C to about 500 ° C. Typically, pressures range from about atmospheric pressure to about 2.76 MPa (400 psi), preferably about 0.34 to 1.38 MPa (50 to 200 psi). Preferably, the process is carried out in a contact time between 1 and 100 seconds in the presence of oxygen or oxygen containing gas, such as air, with the use of 1 to 200% by volume of oxygen based on the 1233xf feed. The formed by-products, such as 245cb and / or 244bb, can be recycled.
    [0017] Various fluorination catalysts can be used, as a chromium-based catalyst, which is both unsupported and supported. When supported, support
    Petition 870190095777, of 25/09/2019, p. 18/27
    11/14 is selected from fluorinated alumina, activated carbon and the like. The chromium catalyst is used alone or in the presence of a cocatalyst, such as zinc, magnesium, cobalt or nickel. Three preferred chromium catalysts are: pure chromium oxide, chromium / zinc with zinc catalyst, as a cocatalyst, chromium / nickel cocatalyst with nickel and chromium / nickel supported on fluorinated alumina. The preparation of that last catalyst is disclosed, for example, in US Patent No. 5,731,481. Preferably, the chromium-based catalysts are activated before use, in a two-step procedure, as described above.
    [0018] The reaction product of the second fluorination step will include, in addition to the desired hydrofluoropropene, non-reactive hydrochlorofluoropropene (HCFC-1233xf), pentafluoropropane (HFC-245cb) and monochlorotetrafluoropropane (HCFC-244bb). These by-products can be separated from the desired hydrofluoropropene in a series of two or more separation columns with the largest HFC245cb by-product which is recycled for the second gas-phase fluorination reaction or catalytically dehydrochlorinated to 1234yf in a separate gas-phase reactor, using the same catalyst formulation used in the second stage.
    [0019] The tetrachloropropene raw material of the present invention can be formed in several ways, as will be understood by a person skilled in the art.
    EXAMPLES
    Examples 1
    Petition 870190095777, of 25/09/2019, p. 19/27
    12/14 [0020] 1,1,2,3 tetrachloropropene (HCO-1230xa) non-catalyzed fluorination in liquid phase for 2-chloro-
    3,3,3-trifluoropropene (HCFO-1233xf).
    [0021] 0.28 mol of HCO-1230xa can be loaded in a 300 ml Hastelloy C autoclave, equipped with a gas inlet valve, a mechanical stirrer and an outlet cooling tower. 3.5 moles of HF gas can be condensed in the autoclave. The reaction mixture would be gradually heated to 120 ° C, with continuous stirring for approximately ½ hour. The excess gas pressure resulting from the formation of HCl could be expelled through a 2.76 MPa (400 psi) pressure relief valve in the cooling tower. The material with the highest boiling point would be retained at room temperature. Volatile organic products could be dried over anhydrous calcium sulfate and collected in a cryogenic trap. Almost 0.28 mol of the product 2-chloro-3,3,3-trifluoropropene would be found in the cryogenic trap. Examples 1, 2 and 3, summarized in Table 1, were calculated based on reactions comparable with closely related materials.
    Table 1. Summary of results, fluorination in non-catalyzed liquid phase from 1230x to 1233xf
    Example 1 Temperature ° C 100 Pressure MPa (psia) 2.07(300)
    Petition 870190095777, of 25/09/2019, p. 20/27
    13/14
    HF / 1230za molar ratio 166 Lenght of stay,hours 5 % Conversion 1230x 100 % 1234yf 0.25 % 245cb 0.16 % 1233xf 97.2 Other 2.39
    1234yf is CF3CF = CH2
    245cb is CF3CF2CH3
    1233xf is CF3CCl = CH2
    244bb is CF3CFCICH3
    Examples 2 to 4 [0022] Gas-phase fluorination of HCO-1233xf at high temperature.
    [0023] An activated catalyst, of 15cc, could be loaded in a vertical fixed bed reactor (Hastelloy C of 50.8 cm by 2.54 cm (20 inches by 1 inch)). The HF could be fed as a liquid and converted to a gas using a vaporizer. The HCO-1233xf could be fed to the fixed bed reactor using a syringe pump and heated to 365 ° C. The reaction could be carried out at a pressure between 0.29 and 1.12 MPa (42 and 162 psi). Table 2 summarizes the calculations of the expected results using a variety of HCO1233xf / HF molar ratios and contact times based on reactions comparable with closely related materials.
    Petition 870190095777, of 25/09/2019, p. 21/27
    14/14
    Table 2. Summary of fluorination from 1233xf to
    1234yf, using unsupported Cr2O3 catalyst.
    Example 2 3 4 Temp ° C 365 365 365 Pressure MPa (psia) 0.33(48.5) 0.33(48.5) 1.16(169) Molar ratio O2 / 1233xf 0.5 0.5 0.5 Molar ratio HF / 1233x 10, 6 21.1 21.1 Contact time sec 3, 9 4 14 % Conversion 54.8 64, 1 73, 6 % 1234yf 58.3 56, 4 40, 6 % 245cb 36, 6 36, 5 59, 4 % 2 4 4bb 5, 1 7, 1 0
    1234yf is CF-CF = CH245cb is CF3CF2CH3
    244bb is CF3CFClCH3 [0024] Although the present invention has been described in relation to particular embodiments thereof, it is evident that various other forms and modifications of this invention will be obvious to those skilled in the art. In general, the appended claims and this invention are to be interpreted as encompassing all those obvious forms and modifications that are within the true spirit and scope of the present invention.
    权利要求:
    Claims (22)
    [1]
    1. Process to produce 1,1,1,2tetrafluoropropene characterized by the fact that it comprises the steps of:
    a) fluorate tetrachloropropene to form 2-chloro-
    3,3,3-trifluoropropene and HCl and first co-products and, later,
    b) fluorine said 2-chloro-3,3,3-tri-fluoropropene, in a gas phase, in the presence of a catalyst selected from the group consisting of supported chromium catalyst, unsupported chromium catalyst and mixtures of the said chromium catalyst, optionally further comprising a cocatalyst selected from the group consisting of nickel, cobalt and magnesium, to form 1,1,1,2-tetrafluoropropene and second co-products.
    [2]
    2. Process according to claim 1, characterized by the fact that step a) of fluorinating a tetrachloropropene comprises placing the tetrachloropropene in contact with hydrogen fluoride in the gas or liquid phase.
    [3]
    3. Process according to claim 2, characterized by the fact that step a) is performed in the presence of a catalyst.
    [4]
    4. Process according to claim 3, characterized by the fact that said catalyst is selected from the group consisting of homogeneous fluorination catalyst and heterogeneous catalyst.
    [5]
    5. Process, according to claim 4, characterized by the fact that said catalyst of
    Petition 870190095777, of 25/09/2019, p. 23/27
    2/4 homogeneous fluorination is selected from the group consisting of SbCl5, TiCl4, SnCl4.
    [6]
    6. Process according to claim 4, characterized by the fact that said heterogeneous catalyst is a supported or unsupported chromium catalyst that further comprises, optionally, a cocatalyst selected from the group consisting of nickel, zinc, cobalt and magnesium.
    [7]
    7. Process, according to claim 1, characterized by the fact that it also comprises the step of separating HCl from said 2-chloro-3,3,3-tri-fluoropropene and HCl and first co-products before fluorination of 2 -chlor-
    3,3,3-tri-fluoropropene.
    [8]
    8. Process according to claim 1, characterized by the fact that said first co-products comprise pentafluoropropane and chlorotetrafluoropropane.
    [9]
    Process according to claim 4, characterized in that said pentafluoropropane comprises 1,1,1,2,2-pentafluoropropane and said chlorotetrafluoropropane comprises 1,1,1,2-tetrafluoro-2 chloropropane.
    [10]
    10. Process according to claim 1, characterized by the fact that it further comprises the step of separating said second co-products from said 1,1,1,2tetrafluoropropane.
    [11]
    11. Process according to claim 10, characterized by the fact that it further comprises the step of recycling said second separate by-products to step b.
    Petition 870190095777, of 25/09/2019, p. 24/27
    3/4
    [12]
    12. Process according to claim 1, characterized by the fact that said second co-products comprise pentafluoropropane and chlorotetrafluoropropane.
    [13]
    13. Process, according to claim 12, characterized by the fact that said pentafluoropropane comprises 1,1,1,2,2-pentafluoropropane and said chlorotetrafluoropropane comprises 1,1,1,2-tetrafluoro-2chloropropane.
    [14]
    14. Process according to claim 2, characterized by the fact that the ratio of tetrachloropropene to hydrogen fluoride ranges from about 1 to 3 to about 1 to 500.
    [15]
    15. Process according to claim 1, characterized by the fact that the ratio of tetrachloropropene to hydrogen fluoride ranges from about 1 to 10 to about 1 to 200.
    [16]
    16. Process, according to claim 1, characterized by the fact that the fluorination step of 2-chloro-3,3,3-tri-fluoropropene in a gas phase, in the presence of a catalyst, comprises placing said 2-chloro-3 , 3,3-tri-fluoropropene in contact with hydrogen fluoride.
    [17]
    17. Process according to claim 1, characterized by the fact that said catalyst is activated before use.
    [18]
    18. Process, according to claim 17, characterized by the fact that said catalyst is activated at a temperature between 200 and 400 ° C in a two-step process that comprises, first, the contact with HF, in
    Petition 870190095777, of 25/09/2019, p. 25/27
    4/4 then, contact with air in order to produce the formula catalyst such as CrOmFn, with 1.5 <m <3 and 0 <n <3.
    [19]
    19. Process, according to claim 1, characterized by the fact that it also comprises the step of isomerizing 1,1,1,2-tetrachloropropene, in the presence of an acid catalyst, to produce 1,1,2,3 -tetrachloropropene.
    [20]
    20. Process, according to claim 1, characterized by the fact that said tetrachloropropene is prepared by gas fluorination of one or more pentachloropropanes.
    [21]
    21. Process according to claim 1, characterized by the fact that said tetrachloropropene fluorination step is performed in the liquid phase in the presence of a homogeneous catalyst.
    [22]
    22. Process according to claim 1, characterized by the fact that said fluorination step of said tetrachloropropene is carried out in the gas phase in the presence of a heterogeneous catalyst.
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    法律状态:
    2019-07-09| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2019-12-17| B09A| Decision: intention to grant|
    2020-01-28| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/11/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/297,557|US8563789B2|2007-06-27|2011-11-16|Process for the manufacture of hydrofluoroolefins|
    PCT/US2012/063649|WO2013074324A1|2011-11-16|2012-11-06|Process for the manufacture of hydrofluoroolefins|
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