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WO1999007470A1 - Catalyseur de fluoration et procede de preparation correspondant - Google Patents

Catalyseur de fluoration et procede de preparation correspondant Download PDF

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Publication number
WO1999007470A1
WO1999007470A1 PCT/US1997/013941 US9713941W WO9907470A1 WO 1999007470 A1 WO1999007470 A1 WO 1999007470A1 US 9713941 W US9713941 W US 9713941W WO 9907470 A1 WO9907470 A1 WO 9907470A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
fluorination
chlorine
reaction
fluorination catalyst
Prior art date
Application number
PCT/US1997/013941
Other languages
English (en)
Inventor
John Stephen Bass
Addison Miles Smith
Paul Gene Clemmer
Mark Kaiser
Li Wang
Original Assignee
Alliedsignal Inc.
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 Alliedsignal Inc. filed Critical Alliedsignal Inc.
Priority to AU39123/97A priority Critical patent/AU3912397A/en
Priority to PCT/US1997/013941 priority patent/WO1999007470A1/fr
Publication of WO1999007470A1 publication Critical patent/WO1999007470A1/fr

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Classifications

    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/22—Halogenating
    • B01J37/24—Chlorinating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to vapor phase fluorination catalysts and processes for their preparation and use.
  • the invention relates to fluorination catalysts which are pretreated with chlorine in order to maintain catalyst life and improve product yields and selectivity.
  • the invention relates to a process for the production of hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, and fluorocarbons by vapor phase fluorination of hydrocarbons, halocarbons, or hydrohalocarbons with hydrogen fluoride in the presence of a chlorine pretreated fluorination catalyst.
  • the disclosed process is disadvantageous because it requires temperatures, during catalyst regeneration, which may be detrimental to fluorination catalysts other than chromic fluoride, such as chromia. Additionally, the disclosed process is disadvantageous because catalyst regeneration is preferably carried out at superatmospheric pressures.
  • the present invention provides a fluorination catalyst that has improved performance in that it has an improved life, good selectivity, and good fluorination process yields.
  • the present invention provides processes for the preparation of fluorination catalysts with improved performance in fluorination reactions and use of the catalysts.
  • the catalysts of this invention are prepared by contacting the catalysts with chlorine. It has been discovered that this chlorine treatment improves the fluorination catalysts' performance in fluorination reactions in that catalyst deactivation is substantially reduced while at the same time, product yields and selectivity are good compared to catalysts untreated with chlorine.
  • the fluorination catalysts useful in the present invention may be any one of the vapor phase fluorination catalysts known in the art.
  • exemplary fluorination catalysts include, without limitation, metal based catalysts such as metal oxides, metal fluorides and halides, and lanthanide and actinide catalysts.
  • the fluorination catalyst is a chromium based catalyst such as chromium oxide, also known as chromia, halogenated chromium catalysts such as chromium fluoride and chromium oxyfluoride, or chromium based catalysts containing other metals.
  • the catalyst is chromia catalyst.
  • Amounts of the catalysts of this invention useful in fluorination reactions are readily ascertainable by those of ordinary skill in the art.
  • the amount of catalyst used will be an amount effective to drive the reaction to completion, which amount will be a function of the desired, or required, productivity, e ⁇ , the amount of product to be formed.
  • the fluorination catalyst useful in this invention may be in bulk form or may be supported on any known support system.
  • Exemplary support systems include, without limitation, activated carbon, alumina, aluminum fluoride, aluminum oxyfluoride, and other oxides such as titania and magnesia.
  • a catalyst promoter may be used in conjunction with the catalyst. Any of the known promoters may be used, including a metal or metals from groups VIII, VIIB, IIIB, LB and/or a metal having an atomic number of 58 through 71 as disclosed in US Patent No. 4,922,037 which is incorporated herein by reference in its entirety.
  • chromia catalysts may be made by any number of processes such as heating Cr(OH) 3 or chromium oxide gel precipitated from an aqueous solution of Cr(III) compounds by the addition of base.
  • mixtures of urea and Cr(III) salts in aqueous form may be heated to form a hydrated chromium oxide gel which, in turn, may be heated to provide chromia catalysts.
  • reacting of CrO 3 with a reducing agent such as alcohol to form a chromia catalyst.
  • Further exemplary methods for the preparation of chromia catalysts include the oxidation of chromium oxalate or chromium acetate and the thermal decomposition of compounds such as
  • pretreat is meant to chemically or physically alter a catalyst in order to create active sites on the catalyst at which a reaction may occur.
  • the precise pretreatment used will depend on the specific reaction that the catalyst will be used in.
  • the catalyst may be calcined under a flow of inert gas at temperatures from about 200° C to about 450° C for from about 2 to about 100 hours.
  • the catalyst may be exposed to hydrogen fluoride, either alone or mixed with up to about 5 to about 95 weight percent of an inert gas at temperatures from about 200° C to about 450° C for about 1 to about 50 hours.
  • pretreatment methods such as standard calcination and fluorination treatments, well known to those ordinarily skilled in the art, may be used.
  • the chlorine may be introduced at any point in the pretreatment process used.
  • the catalyst is contacted with the chlorine after the catalyst has been dried under an inert gas or vacuum and after it has been contacted with hydrogen fluoride
  • the chlorine may be introduced, either in liquid or gaseous form, into the pretreatment process and may be added at conditions appropriate to the pretreatment process being utilized.
  • the chlorine is diluted with from about 60 to about 75 percent hydrogen fluoride and/or from about 20 to about 30 percent of an inert gas. Dilution may occur prior to, or simultaneously with, the chlorine being passed over the catalyst.
  • the chlorine may be passed over the catalyst at a total volume of chlorine to total volume of catalyst of from about 1 to about 3,000 v/v. More preferably, the chlorine to catalyst volume is from about 10 to about 1,000 v/v, most preferably from about 50 to about 500 v/v.
  • the chlorine may be exposed over a period of time that is convenient for the equipment being utilized. Generally, the chlorine exposure may be for a period of time from about 1 to about 200 hours, more preferably from about 5 to about 70 hours, and most preferably from about 10 to about 30 hours.
  • Chlorine exposure may be conducted at any temperature and pressure convenient to the fluorination process to be used.
  • the temperature of exposure is identical to the temperature of the fluorination reaction, typically from about 100° C to about 400° C.
  • exposure pressures range from atmospheric to the pressure of the fluorination reaction, typically up to about 500 psig, for which the catalyst will be used.
  • the feed material Following pretreatment of the catalyst with chlorine, the flow of chlorine is discontinued and the feed material, along with hydrogen fluoride, can be introduced and the fluorination reaction initiated.
  • the catalyst of this invention may be used to produce any fluorinated product.
  • the feed material used in the fluorination reaction will depend on the desired fluorinated product.
  • the feed material may be any hydrocarbon, halocarbon, or hydrohalocarbon of from 1 to 6 carbon atoms, both saturated and olefinic.
  • Exemplary feed materials include, without limitation, methylene chloride, chloroform, tetrachloroethylene, trichloroethylene, vinyl chloride, 1, 1, 1-trichloroethane, acetylene, 1, 1-dichloroethane, vinylidene chloride, 1,1, 1 ,3 ,3 ,3-hexachloroethane, 1 , l-dichloro-2,2,2-trifluoroethane, 1 -chloro- 1 ,2,2,2- tetrafluoroethane, l-chloro-2,2,2-trifluoroethane, l-fluoro-l, l-dichloroethane, and 1 -chloro- 1, 1-difluoroethane.
  • the need for the continuous addition of any material that is typically used to extend catalyst life during the fluorination reaction is eliminated.
  • the catalyst may be regenerated, preferably by the non-continuous addition of chlorine to the reactants.
  • “regenerate” is meant to restore reaction sites to the catalyst.
  • the non-continuous addition, or addition that does not proceed uninterrupted for the duration of the fluorination reaction, of chlorine may be at flows of from about 0.1 to about 10 mol percent based on organic content. More preferably, the amount of chlorine is from about 2 to about 8 mol percent.
  • the flow of feed materials may be discontinued and the fluorination catalyst contacted with chlorine, either alone or in dilute form.
  • the addition or contacting of chlorine is carried out for a period of time sufficient to regenerate the catalyst, preferably from about 1 to about 50 hours, more preferably from about 10 to about 25 hours.
  • the vapor phase fluorination reactions in which the catalysts of this invention are used are generally known.
  • the reaction will be carried out in a corrosion resistant reactor at temperatures from about 100° C to about 450° C, preferably, from about 250° C to about 400° C and at a pressure from about 0 psig to about 300 psig, preferably from about 50 psig to about 200 psig depending on the specific reaction and productivity requirements.
  • the mole ratio of HF/feed will be from about 50/1 to about 1/1, preferably about 10/1 to about 2/1.
  • the liquid hourly space velocity for a fixed bed reactor will be about 0.5 to about 5.0 hr "1 , preferably from about 0.75 to about 2 hr '1 based on the feed material.
  • product will be separated from the byproduct by distillation and purified as required depending on the end use.
  • Suitable reaction conditions are determinable by those ordinarily skilled in the art by a consideration of the feed material as well as the desired conversion of the feed consistent with a high selectivity.
  • the catalysts of this invention may be advantageously used to produce any of a wide variety of fluorinated hydrocarbons, halocarbons, or hydrohalocarbon products including, without limitation, difluoromethane, pentafluoroethane, and 1,2,2,2-tetrafluoroethane.
  • fluorinated hydrocarbons halocarbons, or hydrohalocarbon products
  • hydrohalocarbon products including, without limitation, difluoromethane, pentafluoroethane, and 1,2,2,2-tetrafluoroethane.
  • difluoromethane pentafluoroethane
  • 1,2,2,2-tetrafluoroethane 1,2,2,2-tetrafluoroethane.
  • the catalyst of this invention may be used in this reaction to increase yields and provide improved selectivity.
  • Example 1 An INCONELTM reactor was charged with 60 cc chromia catalyst and heated to 350° C under a 550 seem flow of dry nitrogen over a period of 5 hours and then held for 12 hours. The pressure was maintained at atmospheric pressure. The temperature was then reduced to 200° C and the nitrogen flow decreased to 275 seem. Anhydrous hydrogen fluoride was added to the nitrogen flow at 33 g/hr and the rate maintained until the initial exotherm subsided. The temperature was then raised to 350° C over a period of 3 hours and the hydrogen fluoride feed rate increased to 43 g/hr. Both temperature and feed rates were held for 9 hours.
  • Example 2 An INCONELTM reactor was charged with 60 cc chromia catalyst pretreated as in Example 1. The feeds were started and reaction run as described in Example 1 except that air was added to the reaction mixture at a flow rate of 10 seem. This resulted in an oxygen:CH 2 Cl 2 ratio of 0.012. Results are listed on Table II Table II
  • Example 3 An TNCONELTM reactor was charged with 285 cc chromia catalyst and the catalyst heated to 350° C under a 350 seem flow of nitrogen over a period of 7 hours. The pressure was maintained at atmospheric pressure and catalyst held at 350° C for 8 hours. The reactor temperature was reduced to 200° C and anhydrous hydrogen fluoride added to the nitrogen flow at 50 g/hr. The temperature was increased to 350° C over a period of 5 hours and held at that temperature for 2 hours. The reactor temperature was reduced to 250° C and chlorine gas added to the mixture at 50 seem. The chlorine pretreatment was continued for 13 hours after which the chlorine flow was discontinued and CH 2 C1 was added to the HF/N 2 mixture.
  • Example 3 demonstrates that catalyst regeneration is achieved readily by the subsequent, non-continuous addition of chlorine to the deactivated catalyst.
  • Example 4 An INCONELTM reactor was charged with 60 cc chromia catalyst pretreated as in Example 1. The feeds were started and reaction run as for Example 1 except that chorine gas was added to the reaction mixture at a flow rate sufficient to equal a Cl 2 : CH 2 C1 2 mole ratio of 0.100. After 88 hours on stream, the chlorine cofeed was discontinued and the reaction allowed to proceed for an additional 66 hours with no oxidant cofeed. The results are listed on Table VI.
  • Example 4 illustrates that the continuous addition of chlorine during the fluorination reaction is inferior in performance to the catalyst of this invention in both reaction yield and selectivity. Notably, yield and selectivity markedly improved after discontinuation of the chlorine flow in Example 4.

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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)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un catalyseur de fluoration en phase vapeur, sa régénération et son utilisation. Le catalyseur de l'invention s'obtient en mettant en contact un catalyseur de fluoration avec du chlore pendant le prétraitement du catalyseur, lequel prétraitement sert à préserver la durée de vie du catalyseur. Le catalyseur de l'invention convient à la fluoration en phase vapeur d'hydrocarbures, d'halocarbures et d'hydrohalocarbures en vue de la préparation de produits fluorés, et ce, avec un rendement accru et une meilleure sélectivité.
PCT/US1997/013941 1997-08-08 1997-08-08 Catalyseur de fluoration et procede de preparation correspondant WO1999007470A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU39123/97A AU3912397A (en) 1997-08-08 1997-08-08 Fluorination catalysts and process for their preparation
PCT/US1997/013941 WO1999007470A1 (fr) 1997-08-08 1997-08-08 Catalyseur de fluoration et procede de preparation correspondant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1997/013941 WO1999007470A1 (fr) 1997-08-08 1997-08-08 Catalyseur de fluoration et procede de preparation correspondant

Publications (1)

Publication Number Publication Date
WO1999007470A1 true WO1999007470A1 (fr) 1999-02-18

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WO (1) WO1999007470A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7285261B2 (en) 2005-10-28 2007-10-23 Honeywell International Inc Preparation and application of novel chromium based nanocatalyst for gas-phase fluorination and hydrofluorination reactions
JP2017501992A (ja) * 2013-12-04 2017-01-19 アルケマ フランス １−クロロ−２，２−ジフルオロエタンの製造方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49134612A (fr) * 1973-05-08 1974-12-25
US4155881A (en) * 1978-03-08 1979-05-22 E. I. Du Pont De Nemours And Company Activation of chromic fluoride catalyst with hydrogen chloride and chlorine
US4465786A (en) * 1982-09-27 1984-08-14 General Electric Company Catalyst composition for the preparation of 3,3,3-trifluoropropene
USH1129H (en) * 1989-02-24 1993-01-05 E. I. Du Pont De Nemours And Company Process for manufacture of 1,1,1,2-tetrafluoroethane
JPH06228021A (ja) * 1993-01-29 1994-08-16 Central Glass Co Ltd １，１−ジフルオロエタンの製造法
EP0751108A1 (fr) * 1995-06-29 1997-01-02 Elf Atochem S.A. Procédé de fabrication du difluorométhane

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49134612A (fr) * 1973-05-08 1974-12-25
US4155881A (en) * 1978-03-08 1979-05-22 E. I. Du Pont De Nemours And Company Activation of chromic fluoride catalyst with hydrogen chloride and chlorine
US4465786A (en) * 1982-09-27 1984-08-14 General Electric Company Catalyst composition for the preparation of 3,3,3-trifluoropropene
USH1129H (en) * 1989-02-24 1993-01-05 E. I. Du Pont De Nemours And Company Process for manufacture of 1,1,1,2-tetrafluoroethane
JPH06228021A (ja) * 1993-01-29 1994-08-16 Central Glass Co Ltd １，１−ジフルオロエタンの製造法
EP0751108A1 (fr) * 1995-06-29 1997-01-02 Elf Atochem S.A. Procédé de fabrication du difluorométhane

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 7514, Derwent World Patents Index; Class E16, AN 75-23265W, XP002058514 *
DATABASE WPI Section Ch Week 9437, Derwent World Patents Index; Class E16, AN 94-299714, XP002058515 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7285261B2 (en) 2005-10-28 2007-10-23 Honeywell International Inc Preparation and application of novel chromium based nanocatalyst for gas-phase fluorination and hydrofluorination reactions
JP2017501992A (ja) * 2013-12-04 2017-01-19 アルケマ フランス １−クロロ−２，２−ジフルオロエタンの製造方法
US9981891B2 (en) * 2013-12-04 2018-05-29 Arkema France Process for producing 1-chloro-2,2-difluoroethane

Also Published As

Publication number Publication date
AU3912397A (en) 1999-03-01

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