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WO1993008146A1 - Procede de fabrication de 1,1,1,2-tetrafluoroethane - Google Patents

Procede de fabrication de 1,1,1,2-tetrafluoroethane Download PDF

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Publication number
WO1993008146A1
WO1993008146A1 PCT/US1992/008924 US9208924W WO9308146A1 WO 1993008146 A1 WO1993008146 A1 WO 1993008146A1 US 9208924 W US9208924 W US 9208924W WO 9308146 A1 WO9308146 A1 WO 9308146A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
fluorination
hfc
cfc
boehmite
Prior art date
Application number
PCT/US1992/008924
Other languages
English (en)
Inventor
Li Wang
Timothy J. Barder
Mark Kaiser
Russell W. Johnson
Blaise J. Arena
Original Assignee
Allied-Signal 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 Allied-Signal Inc. filed Critical Allied-Signal Inc.
Publication of WO1993008146A1 publication Critical patent/WO1993008146A1/fr

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Classifications

    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • 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

Definitions

  • Fiel of the Ipverfcion This invention relates generally to the fluorination of halogenated hydrocarbons. More specifically, it relates to the fluorination with HF of l,l,l-trifluoro-2-chloroethane (CFC-133a) to produce 1,1,1,2-tetrafluoroethane (HFC-134a) , a compound likely to replace CFC-12 (dichlorodifluoromethane) in certain applications.
  • CFC-133a l,l,l-trifluoro-2-chloroethane
  • HFC-134a 1,1,1,2-tetrafluoroethane
  • Prior Art CFC-12 is widely used in air conditioning equipment and other applications, but its use is being limited because of concern about depletion of the atmospheric ozone layer.
  • Alumina is used as a support for a metal fluoride which may include chromium in O8910341-A. Chromium salts are impregnated on gamma-alumina in J02/157235A for a vapor phase reaction which produces CFC * -23 rather than HFC-134a.
  • a supported chromium oxide or halide is used to make HFC-134a in J02/172933A. Chromium is supported on A1F 3 for preparation of HFC-134a in U.S. Pat. No. 4,766,260 and U.S. Pat. 5,008,475.
  • the present invention particularly relates to a catalyst for such an improved process.
  • the catalyst of the invention has application to other related fluorinations.
  • Vaporphase fluorination of hydrocarbons and/or halogenated hydrocarbons and in particular fluorination of l,l,l-trifluoro-2-chloroethane (CFC-133a) to 1,1,1,2- tetrafluoroethane (HFC-134a) , may be carried out at fluorination conditions in the presence of HF over a catalyst produced by mixing an acidic chromium compound, preferably a chromium hydroxy chloride, Cr(OH)Cl 2 »2H 2 0 with an aluminum oxide hydrate, preferably boehmite and water, then extruding pellets and heating in nitrogen (not air) .
  • an acidic chromium compound preferably a chromium hydroxy chloride, Cr(OH)Cl 2 »2H 2 0
  • an aluminum oxide hydrate preferably boehmite and water
  • the catalyst is prepared by mixing 95 to 9 wt.% of a finely powdered boehmite
  • particles of about 10 to 75 microns with 5 to 91 wt.% of Cr(OH)Cl 2 '2H 2 0 and water to form a dough, which is then extruded to form particles suitable for use in a fixed bed reactor.
  • the particles may be dried at a temperature of about 20"C to 120*C in air, preferably 70*C to 100 ⁇ C, and thereafter, heated in nitrogen at 300*C to 650°C, preferably 400"C to 550*C, and held at the maximum temperature for about 2 to 12 hours, preferably about 4 hours.
  • the process may be carried out in the vapor phase with a mole ratio of HF to CFC-133a of 10/1 to 1/1.
  • the mole ratio would be about 5/1 to 2/1.
  • the reaction conditions include a temperature in the range of about 300*c to 450*C, preferably a temperature of about 325*C to 400*C, and a pressure in the range of 100 to 2,000 kPa, preferably about 172 to 517 kPa gauge.
  • the liquid hourly space velocity will be about 0.5 to 5.0 hr * , preferably about 0.75 to 2 hr "1 . based on the feedstock.
  • Figures l and 2 show the activity and selectivity of catalysts of the invention in converting CFC-133a to HFC-134a.
  • the Catalyst is made from an aluminum oxide hydrate, preferably boehmite (alpha alumina monohydrate i.e., AIO(OH) or A1 2 0 3 «H 2 0) and an acidic chromium compound, preferably Cr(OH)Cl 2 »2H 2 0 since the combination has been found to provide performance similar to the CF 3 or Cr 2 0 3 catalysts of the prior art, but at substantially lower cost.
  • the catalyst is the product resulting from calcining a mixture of about 95 to 9 wt.% boehmite and about 5 to 91 wt.% of Cr(OH)Cl 2 «2H 2 0.
  • the mixture will contain about 90 to 65 wt.% boehmite and about .. ⁇ > to 10 wt.% of Cr(OH)Cl 2 »2H 2 0, along with sufficient watei- to bind the mixture.
  • Aluminum oxide hydrates such as beta aluminum oxide monohydrate or alpha or beta alumina trihydrate may be substituted for boehmite, although not necessarily with equivalent results.
  • acid chromium compounds may be substituted for Cr(OH)Cl 2 »2H 2 0, such as CrCl 3 , Cr(N0 3 ) 3 , Cr(OH) (CH j COO) ⁇ Cr(CH 3 COO) 3 , and Cr 3 (OH) 2 (CH 3 COO) 7 , although not necessarily with equivalent results.
  • the acid chromium compounds are believed to peptize the aluminum oxide hydrate particles, resulting in a strong extrudate or pellet.
  • the catalyst precursor may be prepared by extrusion, pelletizing or other methods of compacting the mixture.
  • an extrudable dough is formed by mixing a finely divided boehmite powder, preferably about 10 to 75 microns in size, with Cr(OH)Cl 2 »2H 2 0 and water until a mixture suitable for extrusion results.
  • a finely divided boehmite powder preferably about 10 to 75 microns in size
  • Cr(OH)Cl 2 »2H 2 0 a finely divided boehmite powder
  • Cr(OH)Cl 2 »2H 2 0 preferably about 10 to 75 microns in size
  • Cr(OH)Cl 2 »2H 2 0 preferably about 10 to 75 microns in size
  • Cr(OH)Cl 2 »2H 2 0 preferably about 10 to 75 microns in size
  • Cr(OH)Cl 2 »2H 2 0 preferably about 10 to 75 microns in size
  • Cr(OH)Cl 2 »2H 2 0
  • Such extruded particles typically will have a diameter in the range of about 1.5 to 2 mm and have a length of about 1 to 3 times the diameter.
  • the particles After being extruded the particles will be dried in air at temperatures in the range of about 20"C to 120*C, preferably 80*C to 100 * C, and then heated in nitrogen (not air) at about 300*C to 650'C, preferably 400'C to 550*C, for a suitable period of about 2 to 12 hours, preferably about 4 hours.
  • the calcining operation serves to convert boehmite to A1 2 ° 3 and to convert Cr(OH)Cl 2 »2H,0 to surface amorphous Cr 2 0 3 .
  • the calcined particles are then ready to be used in the fluorination of CFC-133a to HFC-134a. As will be seen below, heating the catalyst in nitrogen provides improved performance relative to heating the same catalyst in air.
  • Fluorination of hydrocarbons and partially halogenated hydrocarbons may be carried out using the catalyst of the invention.
  • Hydrogen atoms or halogen atoms are replaced by fluorine atoms by reaction with HF.
  • HF fluorine atoms
  • CFC-133a hydrogen fluoride
  • HFC-134a 1,1,1,2- tetrafluoroethane
  • halogenated hydrocarbons may be fluorinated with the catalyst of the invention, including such compounds as perchloroethylene (CC1 2 CC1 2 ) , partially chlorinated ethylenes, and chloro- and chlorofluoromethanes.
  • perchloroethylene CC1 2 CC1 2
  • partially chlorinated ethylenes ethylenes
  • chloro- and chlorofluoromethanes chloro- and chlorofluoromethanes.
  • 300*C to 450'C preferably about 325 ⁇ C to 400'C and at pressures in the range of 100 to 2,000 kPa, preferably about 172 to 517 kPa (gauge) .
  • the mole ratio of HF/feed will be in the range of about 10/1 to 1/1, preferably 5/1 to 2/1.
  • the liquid hourly space velocity for a fixed bed reactor will be about 0.5 to 5.0 hr "1 , preferably about
  • HFC-134a in the feed is typically converted with a selectivity to HFC-134a of about 90 to 99%.
  • Example 1 The catalyst prepared in Example 1 were tested by grinding the extrudates of Example 1 to 20-40 mesh size and then placing 30 mL of the particles in a 0.5 inch diameter i.d. (12.7 mm) reactor and then passing HF and CFC-133a (2.5/1 mol ratio) over the catalysts at a liquid hourly space velocity of 1.0 hr *1 (based on CFC- 133a) at a temperature of 350 * C and a pressure of 45 psig (310 kPa gauge) .
  • the results showed the superiority of the extrudates which had been heated in nitrogen, as will be seen in Figures 1 and 2.
  • the performance of the catalyst of the invention was equivalent to that of prior art catalysts consisting solely of Cr 2 0 3 and superior to the extrudate calcined in air instead of nitrogen with respect to both activity and selectivity. Since the catalyst of the invention is significantly less expensive than the conventional catalyst containing only chromium oxides, the catalyst of the invention provides an advantage to the user while retaining the performance of the conventional catalyst.

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

Abstract

On décrit un procédé amélioré de fluoration en phase vapeur, notamment un procédé de fluoration de 1,1,1-trifluoro-2-chloroéthane (CFC-133a) par l'acide fluorhydrique (HF) afin d'obtenir 1,1,1,2-tétrafluoroéthane (HFC-134a). Pour cela, on utilise un catalyseur qui se compose de préférence essentiellement de boehmite et de Cr(OH)Cl2.2H2O, combiné et extrudé pour former des matières particulaires et chauffé ensuite dans l'azote.
PCT/US1992/008924 1991-10-25 1992-10-19 Procede de fabrication de 1,1,1,2-tetrafluoroethane WO1993008146A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US78292891A 1991-10-25 1991-10-25
US782,928 1991-10-25

Publications (1)

Publication Number Publication Date
WO1993008146A1 true WO1993008146A1 (fr) 1993-04-29

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PCT/US1992/008924 WO1993008146A1 (fr) 1991-10-25 1992-10-19 Procede de fabrication de 1,1,1,2-tetrafluoroethane

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AU (1) AU2892292A (fr)
WO (1) WO1993008146A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001017676A1 (fr) * 1999-09-09 2001-03-15 Basell Polyolefine Gmbh Procede de preparation de catalyseurs phillips pour la polymerisation d'olefines avec des productivites ameliorees lors de la mise en oeuvre du procede de formage de particules
RU2179885C1 (ru) * 2001-04-24 2002-02-27 Открытое акционерное общество "Галоген" Катализатор для синтеза хладонов
US9771309B2 (en) 2005-04-08 2017-09-26 Mexichem Amanco Holding S.A. De C.V. Chromia based fluorination catalyst

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2252126A1 (en) * 1973-11-22 1975-06-20 Instititul Central Cercetari C Chrome-alumina extruded catalysts - of increased strength by impregnating mixed easily and difficultly peptized alumina particles with aq. chromic acid
EP0417680A1 (fr) * 1989-09-13 1991-03-20 Hoechst Aktiengesellschaft Procédé pour la fabrication de 1,1,1,2-tétrafluoroéthane
US5155082A (en) * 1991-04-12 1992-10-13 Allied-Signal Inc. Catalyst for the manufacture of chlorofluorocarbons, hydrochlorofluorocarbons and hydrofluorocarbons
EP0408005B1 (fr) * 1989-07-12 1994-03-02 AUSIMONT S.p.A. Procédé pour préparer du 1,1,1,2-tétrafluoroéthane

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2252126A1 (en) * 1973-11-22 1975-06-20 Instititul Central Cercetari C Chrome-alumina extruded catalysts - of increased strength by impregnating mixed easily and difficultly peptized alumina particles with aq. chromic acid
EP0408005B1 (fr) * 1989-07-12 1994-03-02 AUSIMONT S.p.A. Procédé pour préparer du 1,1,1,2-tétrafluoroéthane
EP0417680A1 (fr) * 1989-09-13 1991-03-20 Hoechst Aktiengesellschaft Procédé pour la fabrication de 1,1,1,2-tétrafluoroéthane
US5155082A (en) * 1991-04-12 1992-10-13 Allied-Signal Inc. Catalyst for the manufacture of chlorofluorocarbons, hydrochlorofluorocarbons and hydrofluorocarbons

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001017676A1 (fr) * 1999-09-09 2001-03-15 Basell Polyolefine Gmbh Procede de preparation de catalyseurs phillips pour la polymerisation d'olefines avec des productivites ameliorees lors de la mise en oeuvre du procede de formage de particules
US6699947B1 (en) 1999-09-09 2004-03-02 Basell Polyolefine Gmbh Method for producing Phillips catalysts for polymerizing olefins with better productivity rates in the particle-form process
RU2179885C1 (ru) * 2001-04-24 2002-02-27 Открытое акционерное общество "Галоген" Катализатор для синтеза хладонов
US9771309B2 (en) 2005-04-08 2017-09-26 Mexichem Amanco Holding S.A. De C.V. Chromia based fluorination catalyst
US10189757B2 (en) 2005-04-08 2019-01-29 Mexichem Amanco Holding S.A. De C.V. Chromia based fluorination catalyst

Also Published As

Publication number Publication date
AU2892292A (en) 1993-05-21

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