(19)
(11)EP 2 766 329 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
13.01.2021 Bulletin 2021/02

(21)Application number: 12840080.1

(22)Date of filing:  10.10.2012
(51)International Patent Classification (IPC): 
C07C 17/20(2006.01)
C07C 21/18(2006.01)
C07C 17/25(2006.01)
B01J 19/02(2006.01)
(86)International application number:
PCT/US2012/059441
(87)International publication number:
WO 2013/055726 (18.04.2013 Gazette  2013/16)

(54)

PROCESS FOR PRODUCING 2,3,3,3-TETRAFLUOROPROPENE

VERFAHREN ZUR HERSTELLUNG VON 2,3,3,3-TETRAFLUORPROPEN

PROCÉDÉ DE PRODUCTION DE 2, 3, 3, 3 TÉTRAFLUOROPROPÈNE


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 14.10.2011 US 201161547330 P

(43)Date of publication of application:
20.08.2014 Bulletin 2014/34

(73)Proprietor: Honeywell International Inc.
Morris Plains, NJ 07950 (US)

(72)Inventors:
  • WANG, Haiyou
    Amherst, NY 14228 (US)
  • TUNG, Hsueh Sung
    Getzville, NY 14068 (US)

(74)Representative: Stepney, Gregory John 
Withers & Rogers LLP 4 More London Riverside
London SE1 2AU
London SE1 2AU (GB)


(56)References cited: : 
WO-A1-2010/059493
WO-A2-2010/123154
US-A1- 2006 106 263
US-A1- 2010 048 961
US-A1- 2011 105 807
WO-A1-2011/010024
US-A- 5 607 572
US-A1- 2009 240 090
US-A1- 2010 331 583
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    FIELD OF INVENTION



    [0001] This invention relates to a process for preparing fluorinated organic compounds, more particularly to a process for preparing fluorinated olefins, and even more particularly to a process for producing 2,3,3,3-tetrafluoropropene (HFO-1234yf).

    BACKGROUND OF THE INVENTION



    [0002] Hydrofluoroolefins (FIFOs), such as tetrafluoropropenes (including 2,3,3,3-tetrafluoropropene (HFO-1234yf)), are now known to be effective refrigerants, fire extinguishants, heat transfer media, propellants, foaming agents, blowing agents, gaseous dielectrics, sterilant carriers, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, displacement drying agents and power cycle working fluids. Unlike chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), both of which potentially damage the Earth's ozone layer, HFOs do not contain chlorine and, thus, pose no threat to the ozone layer. HFO-1234yf has also been shown to be a low global warming compound with low toxicity and, hence, can meet increasingly stringent requirements for refrigerants in mobile air conditioning. Accordingly, compositions containing HFO-1234yf are among the materials being developed for use in many of the aforementioned applications.

    [0003] Several methods of preparing HFOs are known. For example, U.S. Patent No. 4,900,874 (Ihara et al.) describes a method of making fluorine containing olefins by contacting hydrogen gas with fluorinated alcohols. Although this appears to be a relatively high-yield process, commercial scale handling of hydrogen gas at high temperature is hazardous. Also, the cost of commercially producing hydrogen gas, such as building an on-site hydrogen plant, is economically costly.

    [0004] U.S. Patent No. 2,931,840 (Marquis) describes a method of making fluorine containing olefins by pyrolysis of methyl chloride and tetrafluoroethylene or chlorodifluoromethane. This process is a relatively low yield process and a very large percentage of the organic starting material is converted to unwanted and/or unimportant byproducts, including a sizeable amount of carbon black which tends to deactivate the catalyst used in the process.

    [0005] The preparation of HFO-1234yf from trifluoroacetylacetone and sulfur tetrafluoride has been described (See Banks, et al., Journal of Fluorine Chemistry, Vol. 82, Iss. 2, p. 171-174 (1997)). Also, U.S. Patent No. 5,162,594 (Krespan) discloses a process wherein tetrafluoroethylene is reacted with another fluorinated ethylene in the liquid phase to produce a polyfluoroolefin product.

    [0006] US5607572A relates to a method and apparatus for removing oxygen from an oxygen containing inert gas such as nitrogen, argon and the like and to particular apparatus useful in said removal at a point-of-use site.

    [0007] US2006/106263A1 relates to the production and purification of hydrofluoroolefin compounds, and further relates to processes utilizing azeotrope compositions for separation of hydrofluoroolefins from hydrofluorocarbons and hydrogen fluoride.

    [0008] However, there remains a need for an economic means of producing hydrofluoroolefins, such as HFO-1234yf. The present invention satisfies this need among others.

    SUMMARY OF THE INVENTION



    [0009] The present invention relates, in part, to the surprising discovery that, during the dehydrochlorination of 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) to HFO-1234yf in a reactor, impurities formed through halogenation of the materials of the reactor leads to selectivity changeover from HFO-1234yf to 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf). Accordingly, the present invention relates to methods of improving HFO-1234yf selectivity by reducing the presence of impurities in the reactor, particularly, though not exclusively, during reactor shut-down and/or maintenance, or as caused by air or moisture in the feed materials. To this end, the presence of impurities is reduced and selectivity of the reaction to HFO-1234yf improved.

    [0010] In one aspect, the present invention relates to a process for removing impurities according to claim 1. As used herein, the definition of "substantially free" means that the amount of impurities in the reactor is reduced so as to measurably improve selectivity of the conversion of HCFC-244bb to HFO-1234yf and/or decrease selectivity in the conversion of HCFC-244bb to HCFO-1233xf. The impurities include but are not limited to, metal halides, metal oxides, and/or carbonaceous materials. The metal halides can comprise, for example, halides of Ni, Cr, Fe, Mo, Nb, Cu, and Co.

    [0011] In certain embodiments, the inert gas introduced into the reactor in the purging step includes, for example, He, Ar, N2, and combinations of these. In certain embodiments, the reactor is purged with the inert gas at a temperature of from about 100°C to about 700°C, about 200°C to about 600°C, about 300°C to about 500°C, or about 400°C to about 500°C. In one embodiment, purging is performed under conditions of continuous flow of inert gas. In another embodiment, the reactor is pressurized with inert gas and then depressurized for a few times sufficient to accomplish purging. Combinations of these embodiments may also be implemented.

    [0012] In certain embodiments, the step of oxidizing impurities in the reactor includes introducing an oxidizing agent into the reactor under conditions effective to burn off the carbonaceous material in the reactor. Such oxidizing agents include, but are not limited to, H2O, CO2, O2, air, O3, Cl2, N2O, and combinations of these. In certain embodiments, the oxidation is carried out at a temperature of from about 100°C to about 700°, about 200°C to about 600°C, about 300°C to about 500°C, or about 400°C to about 500°C. In one embodiment, oxidizing occurs under conditions of continuous flow of oxidizing agent. In another embodiment, the oxidizing agent is diluted or provided in diluted form. Suitable diluents include inert gases such as N2, Ar, and He. In one practice of this embodiment, the oxidizing agent is oxygen and is diluted with nitrogen. The dilution can be as high as practically possible, for example, about 0.1% volume of oxidizing agent. In a preferred embodiment, the concentration of oxidizing agent after dilution ranges from about 0.5 to about 21 vol%, preferably from 1 to about 5 vol%, and more preferably from about 2 to about 3 vol%.

    [0013] In certain embodiments, the step of reducing impurities in the reactor includes introducing a reducing agent into the reactor under conditions effective to convert any metal halides or metal oxides into metallic metals. Such reducing agents may include, but are not limited to, H2, NH3, CO, and CrC12 hydrocarbons and combinations of these. In certain embodiments, the reducing agent is diluted or provided in diluted form. Suitable diluents include inert gases such as N2, Ar, and He. In one practice of this embodiment, the reducing agent is hydrogen and is diluted with nitrogen. The dilution can be as high as practically possible, for example, about 0.1% volume of reducing agent. In a preferred embodiment, the concentration of reducing agent after dilution ranges from about 0.5 to about 20 vol%, preferably from about 1 to about 5 vol%, and more preferably from about 2 to about 2.5 vol%. In certain embodiments, the reduction is carried out at a temperature of from about 100°C to about 700°, about 200°C to about 600°C, about 300°C to about 500°C, or about 400°C to about 500°C. In one embodiment, reducing occurs under conditions of continuous flow of reducing agent. In one embodiment, the reactor thus subjected to reducing can be afterward kept under positive pressure, or be sealed, with reducing agent and/or inert gas so as to be ready for future use.

    [0014] In one aspect, the present invention relates to a process for preparing 2,3,3,3-tetrafluoropropene according to claim 2.

    [0015] Additional embodiments and advantages to the present invention will be readily apparent to one of skill in the art, based on the disclosure provided herein.

    DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS



    [0016] According to one embodiment, the present invention relates to a process for removing impurities from a reactor previously exposed to the dehydrohalogenation conversion of HCFC-244bb to HFO-1234yf. The reactor preferably, though not exclusively, comprises an inner metal alloy surface that contains one or more impurities that reduce selectivity to HFO-1234yf. Using one or more of the methods provided herein, the impurities are substantially removed from the reactor, particularly, though not exclusively, during reactor shut-down or maintenance. When the reactor is used in the manufacturing process for making HFO-1234yf using a starting or intermediate material comprising HCFC-244bb, it is substantially free of impurities. Accordingly, the present invention provides methods of removing impurities from the reactor to improve the overall efficiency of the HFO-1234yf conversion process.

    [0017] In certain aspects, the preparation of HFO-1234yf generally includes at least three reaction steps, as follows:
    1. (i) (CX2=CCl-CH2X or CX3-CCl=CH2 or CX3-CHCl-CH2X) + HF → 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) + HCl in a vapor phase reactor charged with a solid catalyst;
    2. (ii) 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) + HF → 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) in a liquid phase reactor charged with a liquid hydrofluorination catalyst; and
    3. (iii) 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) → 2,3,3,3-tetrafluoropropene (HFO-1234yf) in a vapor phase reactor
    wherein X is independently selected from F, Cl, Br, and I, provided that at least one X is not fluorine.

    [0018] The starting material in the first reaction step is one or more chlorinated compounds according to Formulas I, II, and/or III:

            CX2=CCl-CH2X     (Formula I)

            CX3-CCl=CH2     (Formula (II)

            CX3-CHCl-CH2X     (Formula III)

    wherein X is independently selected from F, Cl, Br, and I, provided that at least one X is not fluorine. In certain embodiments, these compounds contain at least one chlorine, a majority of X is chlorine, or all X is chlorine.

    [0019] In the first step, the starting composition (which, in certain embodiments comprises 1,1,2,3-tetrachloropropene (HCO-1230xa), 2,3,3,3-tetrachloropropene (HCO-1230xf) and/or 1,1,1,2,3-pentachloropropane (HCC-240db)) reacts with anhydrous HF in a first vapor phase reactor (fluorination reactor) to produce a mixture of at least HCFO-1233xf (2-chloro-3,3,3-trifluoropropene) and HCl. The reaction can be carried out at a temperature of about 200-400°C and a pressure of about 0-1.38 MPa gauge (0-200 psig). The effluent stream exiting the vapor phase reactor may optionally comprise additional components, such as un-reacted HF, un-reacted starting composition, heavy intermediates, HFC-245cb, or the like.

    [0020] This reaction may be conducted in any reactor suitable for a vapor phase fluorination reaction. The reactor may be constructed from materials which are resistant to the corrosive effects of hydrogen fluoride and catalyst such as Hastalloy, Inconel, Monel. In case of a vapor phase process, the reactor is filled with a vapor phase fluorination catalyst. Any fluorination catalysts known in the art may be used in this process. Suitable catalysts include, but are not limited to chromium, aluminum, cobalt, manganese, nickel and iron oxides, hydroxides, halides, oxyhalides, inorganic salts thereof and their mixtures any of which may be optionally halogenated. Combinations of catalysts suitable for the present invention nonexclusively include Cr2O3, FeCl3/C, Cr2O3/Al2O3, Cr2O3/AlF3, Cr2O3/carbon, CoCl2/Cr2O3/Al2O3, NiCl2/Cr2O3/Al2O3, CoCl2/AlF3, NiCl2/AlF3 and mixtures thereof. Chromium oxide/aluminum oxide catalysts are described in U.S. Pat. No. 5,155,082. Chromium (III) oxides such as crystalline chromium oxide or amorphous chromium oxide are preferred with amorphous chromium oxide being most preferred. Chromium oxide (Cr2O3) is a commercially available material which may be purchased in a variety of particle sizes. Fluorination catalysts having a purity of at least 98% are preferred. The fluorination catalyst is present in an excess but in at least an amount sufficient to drive the reaction.

    [0021] This first step of the reaction is not necessarily limited to a vapor phase reaction and may also be performed using a liquid phase reaction or a combination of liquid and vapor phases, such as that disclosed in U.S. Published Patent Application No. 20070197842. It is also contemplated that the reaction can be carried out batch wise, continuous, or a combination of these. For embodiments in which the reaction comprises a liquid phase reaction, the reaction can be catalytic or non-catalytic. Lewis acid catalysts, such as metal-halide catalysts, including antimony halides, tin halides, thallium halides, iron halides, and combinations of two or more of these, may be employed. In certain embodiments, metal chlorides and metal fluorides are employed, including, but not limited to, SbCl5, SbCl3, SbF5, SnCl4, TiCl4, FeCl3 and combinations of two or more of these.

    [0022] In the second step of the process for forming 2,3,3,3-tetrafhioropropene, HCFO-1233xf is converted to HCFC-244bb. In one embodiment, this step may be performed in the liquid phase in a liquid phase reactor, which may be TFE or PFA-lined. Such a process may be performed in a temperature range of about 70-120°C and about 0.34-0.83 MPa gauge (50-120 psig).

    [0023] Any liquid phase fluorination catalyst may be used in the invention. A non-exhaustive list include Lewis acids, transition metal halides, transition metal oxides, Group IVb metal halides, a Group Vb metal halides, or combinations thereof. Nonexclusive examples of liquid phase fluorination catalysts are an antimony halide, a tin halide, a tantalum halide, a titanium halide, a niobium halide, and molybdenum halide, an iron halide, a fluorinated chrome halide, a fluorinated chrome oxide or combinations thereof. Specific non-exclusive examples of liquid phase fluorination catalysts are SbCl5, SbCl3, SbF5, SnCl4, TaCl5, TiCl4, NbCl5, MoCl6, FeCl3, a fluorinated species of SbCl5, a fluorinated species of SbCl3, a fluorinated species of SnCl4, a fluorinated species of TaCl5, a fluorinated species of TiCl4, a fluorinated species of NbCl5, a fluorinated species of MoCl6, a fluorinated species of FeCl3, or combinations thereof. Antimony pentachloride is most preferred.

    [0024] These catalysts can be readily regenerated by any means known in the art if they become deactivated. One suitable method of regenerating the catalyst involves flowing a stream of chlorine through the catalyst. For example, from about 0.9 to about 91 g (0.002 to about 0.2 lb) per hour of chlorine can be added to the liquid phase reaction for every 454 g (pound) of liquid phase fluorination catalyst. This may be done, for example, for from about 1 to about 2 hours or continuously at a temperature of from about 65°C to about 100°C.

    [0025] This second step of the reaction is not necessarily limited to a liquid phase reaction and may also be performed using a vapor phase reaction or a combination of liquid and vapor phases, such as that disclosed in U.S. Published Patent Application No. 20070197842, the contents of which are incorporated herein by reference. To this end, the HCFO-1233xf containing feed stream is preheated to a temperature of from about 50°C to about 400°C, and is contacted with a catalyst and fluorinating agent. Catalysts may include standard vapor phase agents used for such a reaction and fluorinating agents may include those generally known in the art, such as, but not limited to, hydrogen fluoride.

    [0026] In the third step of HFO-1234yf production, HCFC-244bb is fed to a second vapor phase reactor (dehydrochlorination reactor) to be dehydrochlorinated to make the desired product 2,3,3,3-tetrafluoropropene (HFO-1234yf). This reactor contains a catalyst that can catalytically dehydrochlorinate HCFC-244bb to make HFO-1234yf.

    [0027] The catalysts may be metal halides, halogenated metal oxides, neutral (or zero oxidation state) metal or metal alloy, or activated carbon in bulk or supported form. Metal halide or metal oxide catalysts may include, but are not limited to, mono-, bi-, and tri-valent metal halides, oxides and their mixtures/combinations, and more preferably mono-, and bi-valent metal halides and their mixtures/combinations. Component metals include, but are not limited to, Cr3+, Fe3+, Mg2+, Ca2+ , Ni2+, Zn2+ , Pd2+ , Li+, Na+, K+, and Cs+. Component halogens include, but are not limited to, F-, CI-, Br-, and I-. Examples of useful mono- or bi-valent metal halide include, but are not limited to, LiF, NaF, KF, CsF, MgF2, CaF2, LiCl, NaCl, KCl, and CsCl. Halogenation treatments can include any of those known in the prior art, particularly those that employ HF, F2, HCl, Cl2, HBr, Br2, HI, and I2 as the halogenation source.

    [0028] When neutral, i.e., zero valent, metals, metal alloys and their mixtures are used. Useful metals include, but are not limited to, Pd, Pt, Rh, Fe, Co, Ni, Cu, Mo, Cr, Mn, and combinations of the foregoing as alloys or mixtures. The catalyst may be supported or unsupported. Useful examples of metal alloys include, but are not limited to, SS 316, Monel 400, Inconel 825, Inconel 600, and Inconel 625. Such catalysts may be provided as discrete supported or unsupported elements and/or as part of the reactor and/or the reactor walls.

    [0029] Preferred, but non-limiting, catalysts include activated carbon, stainless steel (e.g., SS 316), austenitic nickel-based alloys (e.g., Inconel 625), nickel, fluorinated 10% CsCl/MgO, and 10% CsCl/MgF2. A suitable reaction temperature is about 300-550°C and a suitable reaction pressure may be between about 0-1.03 MPa gauge (0-150 psig). The reactor effluent may be fed to a caustic scrubber or to a distillation column to remove the byproduct of HCl to produce an acid-free organic product which, optionally, may undergo further purification using one or any combination of purification techniques that are known in the art.

    [0030] The reaction may be carried out at a temperature range of from about 200°C to about 800°C, from about 300°C to about 600°C, or from about 400°C to about 500°C. Suitable reactor pressures range from about 0 MPa gauge to about 1.38 MPa gauge (0 psig to about 200 psig), from about 0.069 to about 0.69 MPa gauge (10 psig to about 100 psig), or from about 0.14 to about 0.48 MPa gauge (20 to about 70 psig).

    [0031] In vapor-phase HCFC-244bb dehydrochlorination, HCFC-244bb feed, which can be formed from HCFO-1233xf hydrofluorination as described in US20090240090, is fed continuously to a vaporizer and the vaporized feed to a reactor. Due to incomplete conversion of HCFO-1233xf and its close boiling point to HCFC-244bb as well as the formation of azeotrope or azeotrope-like composition of HCFC-244bb and HCFO-1233xf under certain conditions, the separation of these two compounds is difficult. For this reason, the HCFC-244bb feed generally contains certain amount of HCFO-1233xf. The dehydrochlorination reaction may be carried out under conditions to attain a HCFC-244bb conversion of about 5% or higher, about 20% or higher, or about 30% or higher. The reaction may be carried out at a temperature in the range of from about 200°C to about 800° C, from about 300°C to about 600°C, or from about 400°C to about 500° C; the reactor pressure may be in the range of from about 0 MPa gauge to about 1.38 MPa gauge (0 psig to about 200 psig), from about 0.069 to about 0.69 MPa gauge (10 psig to about 100 psig), or from about 0.14 to about 0.48 MPa gauge (20 to about 70 psig).

    [0032] In general, the effluent from the dehydrochlorination reactor may be processed to achieve desired degrees of separation and/or other processing. Besides HFO-1234yf produced, the effluent generally contains HCl, unconverted HCFC-244bb, and HCFO-1233xf (which is mainly carried over from the previous step of HCFO-1233xf hydrofluorination). Optionally, HCl is then recovered from the result of the dehydrochlorination reaction. Recovery of HCl is conducted by conventional distillation where it is removed from the distillate. Alternatively, HCl can be recovered or removed by using water or caustic scrubbers. When a water extractor is used HCl is removed as an aqueous solution. When a caustic solution is used, HCl is removed from system as a chloride salt in aqueous solution. After the recovery or removal of HCl, the organic stream may be sent to a distillation column for separation. HFO-1234yf, collected from the overhead of the column, may be sent to another column for further purification, while a fraction of the mixture of HCFO-1233xf and HCFC-244bb, accumulated in the reboiler, may be sent back to the dehydrochlorination reactor for the recycle of HCFC-244bb, and the rest to the HCFO-1233xf hydrofluorination reactor for the recycle of HCFO-1233xf.

    [0033] Applicants have surprisingly discovered that, after one or more cycles of the foregoing, the reactor used in the dehydrochlorination of HCFC-244bb to form HFO-1234yf will contain impurities such as metal halides. Such impurities, if left in the reactor during the next dehydrochlorination cycle, will decrease the selectivity to HFO-1234yf and increase selectivity toward HCFO-1233xf - an undesired byproduct. While not intending to be bound by theory, it is believed that metal halides such as NiX2 (X = F, or CI) CrX3, FeX3, MoX3, NbX3, CoX2, and the like, are incidentally formed by halogenation of the metal components of the reactor (e.g., Inconel 625). These metal halides, especially trivalent metal halides, act as dehydrofluorination catalysts converting HCFC-244bb to HCFO-1233xf. The present invention provides a solution to this problem by reducing the content of impurities in the reactor during shut-down and/or maintenance of the reactor, thereby improving HFO-1234yf selectivity and similarly reducing the formation of HCFO-1233xf

    [0034] To this end, the impurities in the reactor are removed such that the reactor is substantially free of impurities. As used herein, the term "impurities" includes any compound or combination of compounds that reduce the selectivity of HCFC-244bb to HFO-1234yf and/or increase selectivity changeover from HFO-1234yf to HCFO-1233xf. Such impurities may include, but are not limited to, metal halides, metal oxides, and carbonaceous materials. As used herein, the definition of "substantially free" means that the amount of impurities is reduced in the reactor so as to measurably improve selectivity of the conversion of HCFC-244bb to HFO-1234yf and/or decrease selectivity in the conversion of HCFC-244bb to HCFO-1233xf. While the definition of "substantially free" may be as defined herein, in one aspect, the removal of impurities to a "substantially free level" improves selectivity of HCFC-244bb to HFO-1234yf to at least 90% or higher, 95% or higher, or 97% or higher, or 99% or higher, or 99.5% or higher. Selectivity may be calculated by number of moles of product (HFO-1234yf) formed divided by number of moles of reactant consumed or, otherwise, using standard methods known in the art.

    [0035] The step of removing impurities from the reactor may be accomplished after the dehydrochlorination reaction of HCFC-244bb is discontinued by subjecting the metal alloy reactor to the following treatments: (1) purging the reactor with an inert gas; (2) optionally, oxidizing the impurities in the reactor by introducing an oxidizing agent into the reactor under conditions effective to oxidize the impurities; (3) reducing the impurities in the reactor by introducing a reducing agent into the reactor under conditions effective to reduce the impurities; (4) cooling the reactor to an ambient temperature while passing the reducing agent and/or inert gas through the reactor; and (5) maintaining a positive pressure in the reactor with the reducing agent and/or the inert gas. In certain embodiments the impurities include, but are not limited to, metal halides, metal oxides, and carbonaceous materials. The metal halides may include, for example, halides of Ni, Cr, Fe, Cu, Mo, Nb, and Co.

    [0036] The inert gas introduced into the reactor in the purging step may include, but is not limited to, He, Ar, N2, and combinations of these. The purging step may be carried out at a temperature range of from about 100°C to about 700°C, about 200°C to about 600°C, about 300°C to about 500°C, or about 400°C to about 500°C.

    [0037] The oxidizing agent may be introduced into the reactor under conditions effective to burn off the carbonaceous materials in the reactor. To this end, the oxidizing agent may include, but is not limited to, H2O, CO2, O2, air, O3, Cl2, N2O, and combinations of these. Such oxidizing agents may be pure or diluted with an inert gas such as N2, Ar, and He. In one practice of this embodiment, the oxidizing agent is oxygen and is diluted with nitrogen. The dilution can be as high as practically possible, for example, about 0.1% volume of oxidizing agent. In a preferred embodiment, the concentration of oxidizing agent after dilution ranges from about 0.5 to about 21 vol%, preferably from about 1 to about 5 vol%, and more preferably from about 2 to about 3 vol%. The oxidizing step may be carried out at a temperature range of from about 100°C to about 700°C, about 200°C to about 600°C, about 300°C to about 500°C, or about 400°C to about 500°C. In another preferred embodiment, air is used as oxygen source and diluted air is used. In yet another preferred embodiment, air is used together with steam in a steam-air decoking process, in which air is used to burn off the carbonaceous materials and steam is used to keep the burning temperatures low such that they do not exceed the maximum tolerable temperatures.

    [0038] The reducing agent may be introduced into the reactor under conditions effective to convert any metal halides or metal oxides into metallic metals. To this end, the reducing agent may include, but is not limited to, H2, NH3, and C1-C12 hydrocarbons. In certain embodiments, the reducing agent is diluted or provided in diluted form. Suitable diluents include inert gases such as N2, Ar, and He. In one practice of this embodiment, the reducing agent is hydrogen and is diluted with nitrogen. The dilution can be as high as practically possible, for example, about 0.1% volume of reducing agent. In a preferred embodiment, the concentration of reducing agent after dilution ranges from about 0.5 to about 20 vol%, preferably from about 1 to about 5 vol%, and more preferably from about 2 to about 2.5 vol%. The reducing step may be carried out at a temperature range of from about 100°C to about 700°C, about 200°C to about 600°C, about 300°C to about 500°C, or about 400°C to about 500°C.

    [0039] In certain embodiments, the cooling step is carried out in the presence of an inert gas including, but not limited to, He, Ar, N2, and combinations of these. Similarly, the step of maintaining a positive pressure in the reactor until the next reaction is carried out may be with an inert gas including, but not limited to, He, Ar, N2, and combinations of these. In embodiments in which a reducing agent is used to maintain a positive pressure, the reducing agent may include, but is not limited to, H2, NH3, C1-C12 hydrocarbons, and combinations of these. In certain embodiments, the step of maintaining positive pressure in the reactor may be carried out with a reducing agent diluted with an inert gas.

    [0040] The following are examples of the invention and are not to be construed as limiting.

    EXAMPLES


    Example 1



    [0041] This example illustrates the performance of an Inconel 625 reactor which had been used for HCFC-244bb dehydrochlorination for over 1000 hours and exposed to air at room temperature for about two months after shut-down.

    [0042] The cylindrical Inconel 625 reactor of 19 mm (¾") diameter was immersed into a 3-zone electrical furnace. Process temperatures were recorded using a multi-point thermocouple placed inside the reactor. A feed containing 99.1 GC area% HCFC-244bb and 0.6 GC area% HCFO-1233xf was fed into the bottom of the vertically mounted reactor and was vaporized before reaching reaction zone. The reaction was conducted under conditions of 480°C, 0 MPa gauge (0 psig), and 12 g-organic/h. Effluent gases were passed through a gas sampling tube so that the progress of the reaction was monitored periodically via GC analysis of the contents of the gas sampling tube. The results show during the period of 10 hours on stream, the averaged HCFC-244bb conversion, HFO-1234yf selectivity, and HCFO-1233xf were 99.7%, 5.3%, and 92.4%, respectively, indicating the un-treated reactor after the initial 1000 hours on stream was more active for HCFC-244bb dehydrofluorination than for dehydrochlorination.

    Example 2



    [0043] This example illustrates the performance of an Inconel 625 reactor which has been used for HCFC-244bb dehydrochlorination for over 1000 hours and treated in hydrogen flow for two hours at 480°C and then kept in nitrogen (never exposed to air) at room temperature for about two months after shut-down.

    [0044] The cylindrical Inconel 625 reactor of 19 mm (¾") diameter is immersed into a 3-zone electrical furnace. Process temperatures are recorded using a multi-point thermocouple placed inside the reactor. A feed containing 99.1 GC area% HCFC-244bb and 0.6 GC area% HCFO-1233xf is fed into the bottom of the vertically mounted reactor and is vaporized before reaching reaction zone. The reaction is conducted under conditions of 480°C, 0 MPa gauge (0 psig), and 12 g-organic/h. Effluent gases are passed through a gas sampling tube so that the progress of the reaction is monitored periodically via GC analysis of the contents of the gas sampling tube. The results show during the period of 10 hours on stream, the averaged HCFC-244bb conversion, HFO-1234yf selectivity, and HCFO-1233xf are 30.0%, 99.5%, and 0.4%, respectively, indicating hydrogen-treated reactor after the initial 1000 hours on stream is more active for HCFC-244bb dehydrochlorination than for dehydrofluorination.


    Claims

    1. A process for removing impurities from a dehydrochlorination reactor comprising an inner metal alloy surface in which a dehydrochlorination reaction of 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) to 2,3,3,3-tetrafluoropropene (HFO-1234yf) takes place, comprising the steps of:

    (a) purging the reactor with an inert gas;

    (b) optionally, oxidizing the impurities in the reactor by introducing an oxidizing agent into the reactor under conditions effective to oxidize the impurities;

    (c) reducing the impurities in the reactor by introducing a reducing agent into the reactor under conditions effective to reduce the impurities;

    (d) cooling the reactor to an ambient temperature while passing the reducing agent and/or inert gas through the reactor; and

    (e) maintaining a positive pressure in the reactor with the reducing agent and/or the inert gas, wherein the impurities in the reactor comprise metal halides, metal oxides or carbonaceous materials.


     
    2. A process for preparing 2,3,3,3-tetrafluoropropene comprising:

    (a) removing impurities from a reactor such that the reactor is substantially free of impurities comprising the steps of:

    (i) purging the reactor with an inert gas;

    (ii) optionally, oxidizing the impurities in the reactor by passing an oxidizing agent through the reactor at a temperature that is sufficiently high to oxidize the impurities;

    (iii) reducing the impurities in the reactor by passing a reducing agent through the reactor at a temperature that is sufficiently high to reduce the impurities;

    (iv) cooling the reactor to an ambient temperature while passing the reducing agent and/or inert gas through the reactor; and

    (v) maintaining a positive pressure in the reactor with the reducing agent and/or the inert gas; and

    (b) providing a starting composition comprising 2-chloro-1,1,1,2-tetrafluoropropane in the reactor; and

    contacting the starting composition in the reactor under conditions effective to produce a final composition comprising 2,3,3,3-tetrafluoropropene, wherein the impurities in the reactor comprise metal halides, metal oxides or carbonaceous materials.
     
    3. The process of claim 1 or claim 2, wherein the metal halides comprise halides of Ni, Cr, Fe, Mo, Nb, Cu, or Co.
     
    4. The process of any one of claims 1-3, wherein the inert gas introduced into the reactor in the purging step comprises a gas selected from the group consisting of He, Ar, N2, and combinations of these, and preferably N2.
     
    5. The process of any one of claims 1-4, wherein the purging step is carried out at a temperature of from 100°C to 700°C, preferably from 200°C to 600°C, and more preferably from 300°C to 500°C, and most preferably from 400°C to 500°C.
     
    6. The process of any one of claims 1-5 wherein the impurities are oxidized with an oxidizing agent and the oxidizing agent is introduced into the reactor under conditions effective to burn off the carbonaceous materials in the reactor.
     
    7. The process of claim 6, wherein the oxidizing agent introduced into the reactor in the oxidizing step comprises a gas selected from the group consisting of H2O, CO2, O2, air, O3, Cl2, N2O, and combinations of these, and more preferably air.
     
    8. The process of claim 7, wherein the oxidizing step is carried out at a temperature of from 100°C to 700°C, preferably from 200°C to 600°C, more preferably from 300°C to 500°C, and most preferably from 400°C to 500°C.
     
    9. The process of any one of claims 1-8, wherein the reducing agent is introduced into the reactor under conditions effective to convert metal halides or metal oxides into metallic metals.
     
    10. The process of any one of claims 1-9, wherein the reducing agent introduced into the reactor in the reducing step comprises a gas selected from the group consisting of H2, NH3, and C1-C12 hydrocarbons, and more preferably H2.
     
    11. The process of any one of claims 1-10, wherein the reducing step is carried out at a temperature of from 100°C to 700°C, preferably from 200°C to 600°C, more preferably from 300°C to 500°C, and most preferably from 400°C to 500°C.
     


    Ansprüche

    1. Verfahren zum Entfernen von Verunreinigungen aus einem Dehydrochlorierungsreaktor, der eine innere Metalllegierungsoberfläche umfasst, und in dem eine Dehydrochlorierungsreaktion von 2-Chlor-1,1,1,2-Tetrafluorpropan (HCFC-244bb) zu 2,3,3,3-Tetrafluorpropen (HFO-1234yf) stattfindet, umfassend die Schritte:

    (a) Spülen des Reaktors mit einem Inertgas,

    (b) gegebenenfalls Oxidieren der Verunreinigungen im Reaktor durch Einführen eines Oxidationsmittels in den Reaktor unter Bedingungen, die wirksam sind, um die Verunreinigungen zu oxidieren,

    (c) Reduzieren der Verunreinigungen im Reaktor durch Einführen eines Reduktionsmittels in den Reaktor unter Bedingungen, die wirksam sind, um die Verunreinigungen zu reduzieren,

    (d) Kühlen des Reaktors auf Umgebungstemperatur, während das Reduktionsmittel und/oder das Inertgas durch den Reaktor geleitet wird, und

    (e) Aufrechterhaltung eines Überdrucks im Reaktor mit dem Reduktionsmittel und/oder dem Inertgas, wobei die Verunreinigungen im Reaktor Metallhalogenide, Metalloxide oder kohlenstoffhaltige Materialien umfassen.


     
    2. Verfahren zur Herstellung von 2,3,3,3-Tetrafluorpropen, umfassend:

    (a) Entfernen von Verunreinigungen aus einem Reaktor, so dass der Reaktor im Wesentlichen frei von Verunreinigungen ist, umfassend die Schritte:

    (i) Spülen des Reaktors mit einem Inertgas,

    (ii) gegebenenfalls Oxidieren der Verunreinigungen im Reaktor durch Hindurchleiten eines Oxidationsmittels durch den Reaktor bei einer Temperatur, die ausreichend hoch ist, um die Verunreinigungen zu oxidieren,

    (iii) Reduzieren der Verunreinigungen im Reaktor durch Durchleiten eines Reduktionsmittels durch den Reaktor bei einer Temperatur, die ausreichend hoch ist, um die Verunreinigungen zu reduzieren,

    (iv) Kühlen des Reaktors auf Umgebungstemperatur, während das Reduktionsmittel und/oder Inertgas durch den Reaktor geleitet wird, und

    (v) Aufrechterhalten eines Überdrucks im Reaktor mit dem Reduktionsmittel und/oder dem Inertgas, und

    (b) Bereitstellen einer Ausgangszusammensetzung, die 2-Chlor-1,1,1,2-tetrafluorpropan enthält, im Reaktor, und

    Kontaktieren der Ausgangszusammensetzung im Reaktor unter Bedingungen, die wirksam sind, um eine Endzusammensetzung herzustellen, die 2,3,3,3-Tetrafluorpropen umfasst, wobei die Verunreinigungen im Reaktor Metallhalogenide, Metalloxide oder kohlenstoffhaltige Materialien umfassen.
     
    3. Verfahren nach Anspruch 1 oder Anspruch 2, wobei die Metallhalogenide Halogenide von Ni, Cr, Fe, Mo, Nb, Cu oder Co umfassen.
     
    4. Verfahren nach einem der Ansprüche 1 bis 3, wobei das in den Reaktor in der Spülstufe eingeleitete Inertgas ein Gas, ausgewählt aus der Gruppe bestehend aus He, Ar, N2 und Kombinationen davon, vorzugsweise N2, umfasst.
     
    5. Verfahren nach einem der Ansprüche 1-4, wobei der Spülschritt bei einer Temperatur von 100°C bis 700°C, vorzugsweise von 200°C bis 600°C und besonders bevorzugt von 300°C bis 500°C und meist bevorzugt von 400°C bis 500°C durchgeführt wird.
     
    6. Verfahren nach einem der Ansprüche 1-5, wobei die Verunreinigungen mit einem Oxidationsmittel oxidiert werden und das Oxidationsmittel in den Reaktor unter Bedingungen eingeführt wird, die wirksam sind, um die kohlenstoffhaltigen Materialien im Reaktor abzubrennen.
     
    7. Verfahren nach Anspruch 6, wobei das in den Reaktor im Oxidationsschritt eingeführte Oxidationsmittel ein Gas, ausgewählt aus der Gruppe, bestehend aus H2O, CO2, O2, Luft, O3, Cl2, N2O und Kombinationen davon, vorzugsweise Luft, umfasst.
     
    8. Verfahren nach Anspruch 7, wobei der Oxidationsschritt bei einer Temperatur von 100°C bis 700°C, vorzugsweise von 200°C bis 600°C, besonders bevorzugt von 300°C bis 500°C und meist bevorzugt von 400°C bis 500°C durchgeführt wird.
     
    9. Verfahren nach einem der Ansprüche 1-8, bei dem das Reduktionsmittel in den Reaktor unter Bedingungen eingeführt wird, die wirksam sind, um Metallhalogenide oder Metalloxide in metallische Metalle umzuwandeln.
     
    10. Verfahren nach einem der Ansprüche 1-9, wobei das im Reduktionsschritt in den Reaktor eingeführte Reduktionsmittel ein Gas, ausgewählt aus der Gruppe bestehend aus H2, NH3 und C1-C12-Kohlenwasserstoffen, vorzugsweise H2, umfasst.
     
    11. Verfahren nach einem der Ansprüche 1-10, wobei der Reduktionsschritt bei einer Temperatur von 100°C bis 700°C, vorzugsweise von 200°C bis 600°C, besonders bevorzugt von 300°C bis 500°C und meist bevorzugt von 400°C bis 500°C durchgeführt wird.
     


    Revendications

    1. Procédé pour éliminer les impuretés d'un réacteur de déshydrochloration ayant une surface interne en alliage métallique sur laquelle se produit une réaction de déshydrochloration du 2-chloro-1,1,1,2-tétrafluoropropane (HCFC-244bb) en 2,3,3,3-tétrafluoropropène (HFO-1234yf) consistant à :

    (a) purger le réacteur avec un gaz inerte,

    (b) éventuellement, oxyder des impuretés dans le réacteur en y introduisant un agent oxydant dans des conditions efficaces pour oxyder les impuretés,

    (c) réduire les impuretés dans le réacteur en y introduisant un agent réducteur dans des conditions efficaces pour réduire les impuretés,

    (d) refroidir le réacteur à une température ambiante en y faisant passer l'agent réducteur et/ou un gaz inerte, et

    (e) maintenir une pression positive dans le réacteur avec l'agent réducteur et/ou le gaz inerte, les impuretés dans le réacteur comprenant des halogénures métalliques, des oxydes métalliques ou des matières carbonées.


     
    2. Procédé de préparation du 2,3,3,3-tétrafluoropropène consistant à :

    (a) éliminer des impuretés d'un réacteur pour que le réacteur soit sensiblement exempt d'impuretés, et consistant à :

    (i) purger le réacteur avec un gaz inerte,

    (ii) éventuellement, oxyder les impuretés dans le réacteur en y faisant passer un agent oxydant à une température suffisamment élevée pour oxyder les impuretés,

    (iii) réduire les impuretés dans le réacteur en y faisant passer un agent réducteur à une température suffisamment élevée pour réduire les impuretés,

    (iv) refroidir le réacteur à une température ambiante tout en y faisant passer l'agent réducteur et/ou un gaz inerte, et

    (v) y maintenir à une pression positive avec l'agent réducteur et/ou le gaz inerte, et

    (b) fournir au réacteur une composition de départ comprenant du 2-chloro-1,1,1,2-tétrafluoropropane, et

    mettre en contact la composition de départ dans le réacteur dans des conditions efficaces pour produire une composition finale comprenant du 2,3,3,3-tétrafluoropropène, les impuretés dans le réacteur comprenant des halogénures métalliques, des oxydes métalliques ou des matériaux carbonés.
     
    3. Procédé selon la revendication 1 ou la revendication 2, selon lequel les halogénures métalliques comprennent des halogénures de Ni, Cr, Fe, Mo, Nb, Cu ou Co.
     
    4. Procédé selon l'une quelconque des revendications 1 à 3, selon lequel le gaz inerte introduit dans le réacteur dans l'étape de purge comprend un gaz choisi dans le groupe : He, Ar, N2 et leurs combinaisons, et de préférence N2.
     
    5. Procédé selon l'une quelconque des revendications 1 à 4, selon lequel l'étape de purge est effectuée à une température de 100°C à 700°C, de préférence de 200°C à 600°C, et plus préférablement de 300°C à 500°C, et plus préférablement de 400°C à 500°C.
     
    6. Procédé selon l'une quelconque des revendications 1 à 5, selon lequel on oxyde les impuretés avec un agent oxydant introduit dans le réacteur dans des conditions efficaces pour en éliminer les matières carbonées.
     
    7. Procédé selon la revendication 6, selon lequel
    on introduit dans le réacteur lors de l'étape d'oxydation un agent oxydant comprenant un gaz choisi dans le groupe : H2O, CO2, O2, air, O3, Cl2, N2O, et leurs combinaisons, et plus préférablement l'air.
     
    8. Procédé selon la revendication 7, selon lequel
    on effectue l'étape d'oxydation à une température de 100°C à 700°C, de préférence de 200°C à 600°C, plus préférablement de 300°C à 500°C, et de préférence de 400°C à 500°C.
     
    9. Procédé de l'une des revendications 1-8, selon lequel
    on introduit l'agent réducteur dans le réacteur dans des conditions efficaces pour convertir les halogénures métalliques ou les oxydes métalliques en métaux.
     
    10. Procédé selon l'une quelconque des revendications 1 à 9, selon lequel l'agent réducteur introduit dans le réacteur lors de l'étape de réduction comprend : un gaz choisi dans le groupe constitué par les hydrocarbures, H2, NH3 et C1-C12, et plus préférablement H2.
     
    11. Procédé selon l'une quelconque des revendications 1 à 10, selon lequel on réduit à une température comprise entre 100°C et 700°C, de préférence entre 200°C et 600°C, plus préférablement entre 300°C à 500°C, et de préférence de 400°C à 500°C.
     






    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description




    Non-patent literature cited in the description