WO1993016798A1 - Catalyseur de fluorination et procede - Google Patents

Catalyseur de fluorination et procede Download PDF

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Publication number
WO1993016798A1
WO1993016798A1 PCT/GB1993/000244 GB9300244W WO9316798A1 WO 1993016798 A1 WO1993016798 A1 WO 1993016798A1 GB 9300244 W GB9300244 W GB 9300244W WO 9316798 A1 WO9316798 A1 WO 9316798A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
zinc
weight
alumina
chloro
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Application number
PCT/GB1993/000244
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English (en)
Inventor
John David Scott
Michael John Watson
Original Assignee
Imperial Chemical Industries Plc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Imperial Chemical Industries Plc filed Critical Imperial Chemical Industries Plc
Priority to BR9305966A priority Critical patent/BR9305966A/pt
Priority to EP93904165A priority patent/EP0627961A1/fr
Priority to KR1019940702982A priority patent/KR100255872B1/ko
Priority to JP5514609A priority patent/JPH07504353A/ja
Publication of WO1993016798A1 publication Critical patent/WO1993016798A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms

Definitions

  • This invention relates to an improved fluorination catalyst and to a process for the production of fluorinated hydrocarbons by the catalysed reaction of hydrocarbons and halogenated hydrocarbons with hydrogen fluoride.
  • the invention relates in particular to a promoted alumina, halogenated alumina or aluminium oxyhalide catalyst and relates in a particular embodiment to a process for the production of 1,1 ,1,2-tetrafluoroethane by the catalysed reaction of l-chloro-2,2,2-tetrafluoroethane with hydrogen fluoride .
  • chromia or a halogenated chromia may be used in the vapour-phase reaction of trichloroethylene with hydrogen fluoride to produce l-chloro-2,2,2-trifluoroethane as described in GB Patent 1,307,224 and in the vapour-phase reaction of l-chloro-2,2, 2-trifluoroethane with hydrogen fluoride to produce 1,1,1,2-tetrafluoroethane as described in GB Patent 1,589,924.
  • the same catalyst may be used for the fluorination of chlorodifluorethylene to l-chloro-2 ,2,2-trifluoroethane .
  • GB Patent 1,589,924 describes the removal of chlorodifluoroethylene impurity from 1,1,1 ,2-tetrafluoroethane by reacting the impurity with hydrogen fluoride.
  • Catalysts may also comprise chromium upon a metal oxide, halogenated oxide or oxyfluoride support, for example alumina or magnesia, and during the fluorination process in which the catalyst is employed, the chromium may be
  • a chromium-free fluorination catalyst comprising an activity-promoting amount of zinc or a compound of zinc supported on an alumina, halogenated alumina or aluminium
  • a process for the production of fluorinated hydrocarbons which comprises reacting a hydrocarbon or a halogenated hydrocarbon with hydrogen fluoride in the vapour phase in the presence of a fluorination catalyst as defined in the
  • the amount of zinc incorporated in the catalyst is such as to result in promotion of the activity of the alumina, halogenated alumina or aluminium oxyhalide into which the zinc promoter is incorporated.
  • the amount is important since
  • the incorporation of too much of the zinc promoter may result in a decrease rather than an increase in catalyst activity when compared to the activity of the catalyst when the optimum amount of zinc promoter is incorporated and it is only when the zinc promoter is present in the correct
  • the amount of zinc promoter incorporated in the catalyst to achieve significant activity promotion will depend upon the basic support employed, in particular the surface area of the support and upon the method used to
  • the optimum amount of zinc promoter is readily determined by simple routine experiment. Overall, the amount of zinc will usually be in the range from about 0.52 to about 302, and preferably from about 1.52 to about 252 by weight of the catalyst.
  • the optimum amount of zinc incorporated depends on the surface area of the catalyst, in particular the 'working" surface area of the catalyst".
  • the working surface area of the catalyst is the surface area of the catalyst measured after catalyst preparation and pre-treatment with hydrogen fluoride (as described hereafter) or, if the catalyst is not pre-treated with hydrogen fluoride, after the catalyst has been employed in a vapour phase fluorination reaction in which hydrogen fluoride is employed.
  • the working ⁇ urface area of the catalyst may be in the range from about 10 to about 100m /g, typically from about 10 to about 50 m 2 /g.
  • the catalyst is prepared from alumina
  • alumina with a surface area of from about 50m /g to about 400m 2 /g gives a catalyst after preparation and pre-treatment with a working surface area in the defined range.
  • the catalyst may be prepared from starting aluminas having a surface area from about 50m /g to about 250m /g and preferably from about 150m 2 /g to about 250m 2 /g.
  • the amount of promoter incorporated in the catalyst also depends upon the catalyst preparation employed.
  • the effective part of the catalyst is believed to be the surface of the support containing zinc promoter cations located in an alumina, halogenated alumina or aluminium oxyhalide lattice and it is the amount of such surface zinc promoter which determines the activity of the catalyst.
  • the activity-promoting effect of the zinc promoter per unit weight of the zinc promoter is generally higher for catalysts made by impregnation than for catalysts made by other methods and containing the zinc promoter in non-surface locations.
  • optimum activity promotion results when the amount of zinc is within the range of about 0.52 by weight to about 102 by weight of the catalyst, preferably within the range from about 0.52 to about 62, more preferably in the range from about 1.52 to about 42 and especially in the range from about 1.52 to about 3.52; less than 0.52 by weight of zinc may be insufficient to result in significant promotion of catalyst activity whilst more than about 82 by weight of zinc may result in no significant increase in cat ⁇ alyst activity when compared to the activity promotion provided by the above optimum ranges of zinc.
  • the amount of zinc may be within the range from about 32 to about 302 by weight of the catalyst, preferably from about 42 to about 252 by weight of the catalyst, especially from about 52 to about 152 by weight of the catalyst.
  • the zinc promoter may be incorporated in the catalyst in the form of a compound, for example a halide, oxyhalide, oxide or hydroxide depending at least to some extent upon the catalyst preparation technique employed.
  • the compound is preferably a water-soluble salt, for example a halide, nitrate or acetate, and is employed as its aqueous solution.
  • the hydroxides of the promoter and aluminium may be co-precipitated and then converted to the oxides to prepare the catalyst.
  • Mixing and milling of insoluble zinc compounds with the basic catalyst provides a further method of preparing the catalyst.
  • a method for making catalysts based on aluminium oxyhalide comprises adding a compound of the promoter to hydrated aluminium fluoride and calcining the mixture.
  • the fluorination catalyst will usually be subjected to a prefluorination treatment with hydrogen fluoride and optionally an inert diluent prior to use in the catalysis of fluorination reactions.
  • a typical pretreatment comprises heating the catalyst at 250°C to 450°C in contact with hydrogen fluoride, or a mixture of hydrogen fluoride and air. Consequently the working catalyst is believed to be at least partially zinc fluoride supported on fluorinated alumina or aluminium oxyfluoride.
  • the catalyst may be used in the form of pellets or granules of appropriate size for use in a fixed bed or a fluidised bed. It may be regenerated or reactivated periodically by heating in air at a temperature of from about 300°C to about 500°C. Air may be used as a mixture with an inert gas such as nitrogen or with hydrogen fluoride which emerges hot from the catalyst treatment process and may be used directly in vapour phase fluorination processes.
  • an inert gas such as nitrogen or with hydrogen fluoride which emerges hot from the catalyst treatment process and may be used directly in vapour phase fluorination processes.
  • the activity of the base (unpromoted) alumina, halogenated alumina or aluminium oxyhalide catalyst is enhanced by the incorporation of the promoter.
  • the selectivity of the reaction catalysed by the catalyst towards the production of 1 ,1,1 ,2-tetrafluoroethane from l-chloro-2,2 ,2-trifluoroethane and hydrogen fluoride may be at least as high as that using the corresponding unpromoted catalysts, typically in excess of 852.
  • the catalyst may contain one or more metals other than zinc, for example nickel, copper, manganese, cobalt, and iron, and in particular iron, cobalt and copper since the presence of one or more of these metals may enhance the extent to which catalyst activity may be restored by regeneration of the catalyst.
  • metals other than zinc for example nickel, copper, manganese, cobalt, and iron, and in particular iron, cobalt and copper since the presence of one or more of these metals may enhance the extent to which catalyst activity may be restored by regeneration of the catalyst.
  • metals other than zinc for example nickel, copper, manganese, cobalt, and iron, and in particular iron, cobalt and copper since the presence of one or more of these metals may enhance the extent to which catalyst activity may be restored by regeneration of the catalyst.
  • the catalyst comprises a relatively high loading of zinc, say for example in the case of a catalyst prepared by impregnation, greater than about 32, preferably greater than about 42 and especially greater than about 52 by weight zinc
  • the ratio (wt2 based on the weight of the catalyst) of zinc to iron is preferably in the range from about 80:1 to about 2:1, more preferably in the range from about 16:1 to about 2:1. This ratio is preferred irrespective of the absolute amounts of zinc and iron in the catalyst.
  • the absolute amounts of zinc and iron may be higher, for example at least 62, preferably at least 102 zinc by weight of the catalyst, and an amount of iron in the range from about 0.22 to about 122, preferably from about 0.42 to about 4.52 by weight of the catalyst, in respect of catalysts prepared by methods, for example co-precipitation, which lead to significant amounts of zinc and iron being incorporated in the catalyst in non- ⁇ urface locations, the relative amounts of zinc and iron (wt2 based on the weight of the catalyst) is also preferably within the ranges given above .
  • a further feature of the invention resides in use of the promoted catalyst in fluorination processes comprising reaction of a hydrocarbon or halogenated hydrocarbon with hydrogen fluoride in the vapour-phase.
  • Alkene ⁇ (unsaturated hydrocarbons) and in particular halogenated alkenes, for example trichloroethylene or halogenated alkanes of 1-4C atoms preferably containing at least one chlorine atom may be fluorinated and examples of specific fluorinations which may be effected are the production of 1,1,1,2-tetrafluoroethane from l-chloro-2,2,2-trifluoroethane , the production of l-chloro-2,2,2-trifluoroethane from trichloroethylene and the conversion of l-chloro-2,2-difluoroethylene to l-chloro-2 ,2,2-trifluoroethane.
  • Examples of other fluorination reactions in which the catalyst is useful are the reaction of perchloroethylene with hydrogen fluoride in vapour phase to produce dichlorotrifluoroethane (123), chlorotetrafluoroethane (124) and/or pentafluoroethane (125), and the reaction of perchloroethylene with chlorine and hydrogen fluoride in vapour phase to produce trichlorotrifluoroethane (113), dichlorotetrafluoroethane (114/114a) and/or chloropentafluorothane (115).
  • the fluorination conditions employed may be those known to be useable when employing chromia or halogenated chromia as the catalyst, for example atmospheric or superatmospheric pressure, hydrogen fluoride and temperatures in the range of 180°C to about 500°C depending upon the particular fluorination reaction being carried out.
  • the increased activity of the promoted catalyst permits reactions to be carried out without loss of efficiency at significantly lower temperatures than those required to achieve similar activity using the unpromoted alumina.
  • yields of only 0.52 1, 1 ,1 ,2-tetrafluoroethane from l-chloro-2 ,2 ,2-trifluoroethane may be achieved at atmospheric pressure when using the relatively high temperature of 360°C or above when using unpromoted alumina
  • a lower temperature of say 280°C is sufficient to achieve greater reaction efficiency using a zinc-promoted alumina.
  • the temperature is the same, say 300°C, a shorter contact time is required using the promoted catalyst.
  • a preferred embodiment of the process of the invention resides in a process for the preparation of 1,1,1,2-tetrafluoroethane which comprises reacting l-chloro-2,2,2-trifluoroethane with hydrogen fluoride in the vapour phase in the presence of the promoted catalyst of the invention.
  • This process may be carried out under atmospheric or superatmospheric pressure at a temperature of from about 280°C to 500°C.
  • the process may be one stage of a two or three-stage process, for example it may be the second stage of a process for the production of 1,1,1,2-tetrafluoroethane from trichloroethylene, the first stage being the vapour-phase fluorination of trichloroethylene with hydrogen fluoride in the presence of a fluorination catalyst to produce l-chloro-2,2,2-trifluoroethane .
  • the promoted catalyst of the invention may be used in the first stage as well as in the second stage of this two-stage process.
  • Typical reaction conditions for the the first stage are atmospheric or superatmospheric pressure and a temperature in the range of about 180°C to about 400°C.
  • 1,1,1,2-tetrafluoroethane from l-chloro-2,2,2-trifluoroethane results in a product stream containing the toxic impurity l-chloro-2,2,-difluoroethylene .
  • This impurity can be removed by reacting it with hydrogen fluoride in the vapour phase in the presence of a fluorination catalyst at a temperature below about 270°C, for example 150°C to 270°C.
  • the promoted catalyst of the invention may be employed in this reaction, thus providing a three-stage process for the preparation of 1 ,1 ,1,2-tetrafluoroethane essentially free from l-chloro-2,2-difluoroethylene from trichloroethylene using the promoted catalyst in one or more of each of the three reaction stages.
  • a particularly preferred embodiment of the above-described two-stage process for preparing 1,1,1,2-tetrafluoroethane from trichloroethylene comprises the steps of:
  • step B passing product of step A together with trichloroethylene to a second reaction zone containing a fluorination catalyst at a temperature in the range from about 180°C to about 400°C but lower than the temperature in step A to form a product containing l-chloro-2,2,2-trifluoroethane , 1,1,1, 2-tetrafluoroethane , hydrogen chloride and unreacted trichloroethylene and hydrogen fluoride ,
  • step B treating product of step B to separate hydrogen chloride and 1 ,1, 1,2-tetrafluoroethane from l-chloro-2,2 ,2-trifluoroethane , unreacted hydrogen fluoride and unreacted trichloroethylene;
  • step D feeding l-chloro-2,2,2-trifluoroethane obtained from step C together with hydrogen fluoride to said first reaction zone step (A), wherein a chromium-free fluorination catalyst as previously described herein is employed in at least one of steps (A) and (B) .
  • At least the ⁇ toichiometric amount of hydrogen fluoride is usually employed in step A of the preferred embodiment.
  • Typical amounts include from 1 to 10 moles, and preferably from 1 to 6 moles, of hydrogen fluoride per mole of l-chloro-2,2,2-trifluoroethane .
  • the product of this reaction step will usually contain unreacted hydrogen fluoride in addition to 1,1,1,2- tetra luoroethane, hydrogen chloride and by-products.
  • Preferred reaction temperatures for this stage of the process are in the range from 325°C to 385°C with contact times of from 1 to 100 and preferably from 5 to 30 seconds at 5 to 20 bars pressure.
  • Step B From 10 to 100, preferably from 15 to 60, moles of hydrogen fluoride per mole of trichloroethylene are typically employed in Step B. Again, the reaction product of this stage will normally contain unreacted hydrogen fluoride. Contact times of 1 to 100 seconds, preferably 5 to 30 seconds may be used, typically at 220-350°C and 5 to 20 bars pressure.
  • the process according to the invention is operated continuously.
  • catalyst deactivation necessitating periodic catalyst regeneration or reactivation may interrupt continuous operation of the process.
  • the feeding of air to the catalyst during operation of the process may counter catalyst deactivation and reduce the frequency of process interruption for catalyst regeneration or reactivation.
  • the fluorination activities of the zinc promoted aluminas were measured using an atmospheric pressure microreactor.
  • Catalysts (2g) were charged to a 1/4' diameter microreactor and were conditioned in a stream of HF at 300°C for 1 hour and then heated to 350°C and further conditioned in an air/HF (ratio 1:20) stream for approximately 15hrs.
  • microreactor was then fed with a mixed l-chloro-2,2, 2-trifluoroethane (133a) and HF feed using a molar feed ratio of 1.0:3.5, which gave a 2 second contact time at 300°C.
  • the activity of the zinc-impregnated alumina catalyst reached a peak at a zinc content in the range of about 22 to about 32 w/w.
  • the activity of catalysts comprising 22 and 3.82 by weight nickel on alumina, prepared from an aqueous solution of nickel (II) chloride as described above were also measured.
  • the atomic loading of the 3.82 nickel on alumina catalyst is the same as that of the catalyst containing 22 zinc and 22 nickel.
  • the results of the study are shown as 2 yields of 1 ,1,1,2-tetrafluoroethane in Table 2 and demonstrate the beneficial effect of zinc/nickel addition to alumina compared to alumina alone, but nevertheless inferior effect of zinc/nickel addition compared to zinc addition alone and the even poorer effect of nickel addition alone.
  • catalysts comprising 22 and 3.682 by weight manganese on alumina, prepared from an aqueous solution of manganese (II) chloride as described above, were also measured.
  • the atomic loading of the 3.682 manganese on alumina catalyst is the same as that of the catalyst containing 22 zinc and 22 manganese.
  • the activity of a catalyst comprising 22 by weight iron on alumina prepared from an aqueous solution of iron (III) chloride as described above, was also measured.
  • the atomic loading of the 62 w/w zinc and 0.5Z w/w iron on alumina is equal to that of the 6.62 w/w zinc on alumina catalyst (example 7) and the activity of the catalyst of example 7 and examples 3, 5 and 6 are also shown below for the purposes of comparison.
  • the catalysts were prepared according to the method described previously for examples 1 to 12 except that the solutions to which the alumina was added were as follows:
  • Example 21 same as example 12.
  • Example 22 4.07g of alumina added to an aqueous solution of 0.63g of ZnCl ⁇ and 0.3g of CoCl ⁇ hexahydrate in 10 ml of water.
  • Example 23 4.07g of alumina added to an aqueous solution of 0.63g of Z Cl2 and 0.3g of iCl2 hexahydrate in 10 ml of water.
  • Example 24 4.04g of alumina added to an aqueous solution of 0.63g of ZnCl 2 and 0.34g of Mn(CH 3 C0 2 )2 tetrahydrate in 10ml of water.
  • Example 25 4.17g of alumina added to an aqueous solution of 0.63g of Z Cl2 and 0.2g of CuCl2 dihydrate in 10 ml of water.
  • aluminium fluoride prepared by the reaction of alumina (supplied by Harshaw Ltd) with hydrogen fluoride at 340°C for 48 hours, in the form of granules of size 0.5-1.4mm and having a surface area of 13m 2 /g was added to an aqueous solution of zinc (II) chloride (0.02g) in distilled water (5ml) and stirred to ensure thorough wetting of the solid by the solution. The mixture was then dried by direct heating and the resultant solid sieved to give particles of size 0.5-1.4mm of a finished catalyst comprising 0.22 w/w zinc on aluminium fluoride.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention se rapporte à un catalyseur de fluorination sans chrome comportant une quantité de zinc stimulant l'activité, supportée par un oxyde d'aluminium, un oxyde d'aluminium hydrogéné ou un oxyhalogénure d'aluminium, et à l'utilisation du catalyseur pour produire des hydrocarbones fluorinés en faisant réagir un hydrocarbone ou un hydrocarbone halogéné avec du fluorure d'hydrogène dans la phase vapeur en présence du catalyseur.
PCT/GB1993/000244 1992-02-26 1993-02-05 Catalyseur de fluorination et procede WO1993016798A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR9305966A BR9305966A (pt) 1992-02-26 1993-02-05 Catalisador de fluoração isento de cromo e processo para a produção de um hidrocarboneto fluorado
EP93904165A EP0627961A1 (fr) 1992-02-26 1993-02-05 Catalyseur de fluorination et procede
KR1019940702982A KR100255872B1 (ko) 1992-02-26 1993-02-05 플루오르화 촉매 및 플루오르화 방법
JP5514609A JPH07504353A (ja) 1992-02-26 1993-02-05 弗素化触媒及び弗素化方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9204072.4 1992-02-26
GB929204072A GB9204072D0 (en) 1992-02-26 1992-02-26 Fluorination catalyst and process

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WO1993016798A1 true WO1993016798A1 (fr) 1993-09-02

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EP (1) EP0627961A1 (fr)
JP (1) JPH07504353A (fr)
KR (1) KR100255872B1 (fr)
CN (2) CN1050776C (fr)
BR (1) BR9305966A (fr)
CA (1) CA2128434A1 (fr)
GB (2) GB9204072D0 (fr)
TW (1) TW253842B (fr)
WO (1) WO1993016798A1 (fr)

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EP0733613A1 (fr) * 1993-12-09 1996-09-25 Daikin Industries, Limited Procede de production du difluoromethane et du 1,1,1,2-tetrafluoroethane
US7053252B2 (en) 2001-08-03 2006-05-30 Atofina Process for preparing 1,1,1-trifluoro-2,2-dichloroethane
JP2014534899A (ja) * 2011-10-12 2014-12-25 バイエル・インテレクチユアル・プロパテイー・ゲー・エム・ベー・ハー １−クロロ−２，２−ジフルオロエタンを製造するための１，１，２−トリクロロエタン及び／又は１，２−ジクロロエテンの触媒的気相フッ素化
US8921625B2 (en) 2007-02-05 2014-12-30 Reaction35, LLC Continuous process for converting natural gas to liquid hydrocarbons
US9133078B2 (en) 2010-03-02 2015-09-15 Gtc Technology Us, Llc Processes and systems for the staged synthesis of alkyl bromides
US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
US10087125B2 (en) * 2013-12-12 2018-10-02 Xi'an Modern Chemistry Research Institute Chromium-free catalyst for gas-phase fluorination and application thereof
US20220331790A1 (en) * 2018-09-27 2022-10-20 Chevron Phillips Chemical Company Lp Processes for Producing Fluorided Solid Oxides and Uses Thereof in Metallocene-Based Catalyst Systems

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US20100016607A1 (en) * 2006-12-11 2010-01-21 University Of Florida Research Foundation Inc. Process for the Synthesis of Highly Active Binary Metal Fluoride as a Fluorinating Agent for Aromatics
US8158549B2 (en) * 2009-09-04 2012-04-17 Honeywell International Inc. Catalysts for fluoroolefins hydrogenation
CN102491871B (zh) * 2011-12-12 2013-12-18 南京信息工程大学 一种七氟丙烷的制备方法
CN102698779B (zh) * 2012-06-15 2013-11-06 浙江师范大学 用于联产hcfc-123、hcfc-124和hfc-125的催化剂及制备方法
CN104803823A (zh) * 2014-01-24 2015-07-29 上海汇友精密化学品有限公司 一种三氟甲烷的制备方法
CN105399598A (zh) * 2015-11-23 2016-03-16 淄博澳宏化工科技有限公司 一种1,1,1,3,3-五氟丙烷的制备装置及制备方法
CN109516895B (zh) * 2016-08-17 2022-01-07 山东东岳化工有限公司 一种氯氟烃资源化利用的方法

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EP0733613A1 (fr) * 1993-12-09 1996-09-25 Daikin Industries, Limited Procede de production du difluoromethane et du 1,1,1,2-tetrafluoroethane
EP0733613A4 (fr) * 1993-12-09 1996-12-11 Daikin Ind Ltd Procede de production du difluoromethane et du 1,1,1,2-tetrafluoroethane
US5849963A (en) * 1993-12-09 1998-12-15 Daikin Industries, Ltd. Method for producing difluoromethane and 1,1,1,2-tetrafluoroethane
US7053252B2 (en) 2001-08-03 2006-05-30 Atofina Process for preparing 1,1,1-trifluoro-2,2-dichloroethane
US7176338B2 (en) 2001-08-03 2007-02-13 Atofina Process for preparing 1,1,1-trifluoro-2, 2-dichloroethane
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
US8921625B2 (en) 2007-02-05 2014-12-30 Reaction35, LLC Continuous process for converting natural gas to liquid hydrocarbons
US9133078B2 (en) 2010-03-02 2015-09-15 Gtc Technology Us, Llc Processes and systems for the staged synthesis of alkyl bromides
JP2014534899A (ja) * 2011-10-12 2014-12-25 バイエル・インテレクチユアル・プロパテイー・ゲー・エム・ベー・ハー １−クロロ−２，２−ジフルオロエタンを製造するための１，１，２−トリクロロエタン及び／又は１，２−ジクロロエテンの触媒的気相フッ素化
US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems
US10087125B2 (en) * 2013-12-12 2018-10-02 Xi'an Modern Chemistry Research Institute Chromium-free catalyst for gas-phase fluorination and application thereof
US20220331790A1 (en) * 2018-09-27 2022-10-20 Chevron Phillips Chemical Company Lp Processes for Producing Fluorided Solid Oxides and Uses Thereof in Metallocene-Based Catalyst Systems
US11731122B2 (en) * 2018-09-27 2023-08-22 Chevron Phillips Chemical Company Lp Processes for producing fluorided solid oxides and uses thereof in metallocene-based catalyst systems

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KR950700117A (ko) 1995-01-16
KR100255872B1 (ko) 2000-05-01
TW253842B (fr) 1995-08-11
GB9204072D0 (en) 1992-04-08
EP0627961A1 (fr) 1994-12-14
CN1111606A (zh) 1995-11-15
CN1078172A (zh) 1993-11-10
CN1050776C (zh) 2000-03-29
BR9305966A (pt) 1997-10-21
CA2128434A1 (fr) 1993-09-02
JPH07504353A (ja) 1995-05-18
GB9302144D0 (en) 1993-03-24
CN1049419C (zh) 2000-02-16

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