EP2285489A1 - Verfahren zur herstellung fluorierter verbindungen - Google Patents

Verfahren zur herstellung fluorierter verbindungen

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Publication number
EP2285489A1
EP2285489A1 EP09766054A EP09766054A EP2285489A1 EP 2285489 A1 EP2285489 A1 EP 2285489A1 EP 09766054 A EP09766054 A EP 09766054A EP 09766054 A EP09766054 A EP 09766054A EP 2285489 A1 EP2285489 A1 EP 2285489A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
carried out
chromium
alumina
dehydrofluorination
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP09766054A
Other languages
English (en)
French (fr)
Inventor
Michel Devic
Anne Pigamo
Laurent Wendlinger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
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 Arkema France SA filed Critical Arkema France SA
Publication of EP2285489A1 publication Critical patent/EP2285489A1/de
Withdrawn legal-status Critical Current

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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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/22—Halogenating
    • B01J37/26—Fluorinating
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/866—Nickel and chromium
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the subject of the invention is a process for preparing fluorinated compounds, especially the 1,2,3,3,3-pentafluoropropene-1 (1225ye) fluorinated compound.
  • Hydrofluorocarbons and in particular hydrofluoroolefins (HFOs) are compounds known for their properties as coolants and heat transfer fluids, fire extinguishers, propellants, foaming agents, blowing agents, gaseous dielectrics, polymerization medium or monomer, carrier fluids, agents for abrasives, drying agents and fluids for power generation unit.
  • HFCs hydrofluorocarbons
  • HFOs hydrofluoroolefins
  • WO 2008/040969 describes the preparation of (hydro) fluoroalkene having from three to six carbon atoms by dehydrohalogenation of a hydro (halo) fluoroalkane having from three to six carbon atoms in the presence of a catalyst comprising a compound of chromium and / or zinc.
  • dehydrofluorination can be carried out in the absence of HF (hydrofluoric acid) but it is preferable to use HF to avoid or delay decomposition of the organic charge and / or coking ( fouling by coke deposition) of the catalyst.
  • WO 2008/008350 describes the preparation of a mixture of E and Z isomers of 1,2,3,3,3-pentafluoropropene-1 (1225ye) from hexafluoropropane, selected from 1, 1, 1,2,3,3,3-hexafluoropropane (HFC 236ea) and 1,1,1,2,2,3-hexafluoropropane (HFC 236cb) in the presence of a chromium oxyfluoride catalyst.
  • Example 1 of this document illustrates the dehydrofluorination reaction of 1,1,1,2,2,3- hexafluoropropane (HFC 236cb) in 1,2,3,3,3-pentafluoropropene-1 (1225ye) and shows that after 26 hours of operation, the conversion of 236cb decreases sharply and selectivity to 1225ye.
  • HFC 236cb 1,1,1,2,2,3- hexafluoropropane
  • the invention therefore provides a process for the dehydrofluorination of 1, 1, 1, 2, 2, 3-hexafluoropropane in 1, 2, 3, 3, 3-pentafluoropropene-1, in the presence of hydrogen.
  • the reaction is carried out in the gaseous phase with a molar ratio H 2 / I, 1,1,2,2,3-hexafluoropropane of between 0.3 and 30; the reaction is carried out in gas phase with a molar ratio
  • the process is carried out in the presence of a dehydrofluorination catalyst.
  • the dehydrofluorination catalyst is a chromium-based catalyst.
  • the process is carried out at a temperature of between 150 ° C. and 500 ° C., preferably between 300 ° and 400 ° C.
  • the process is carried out with a contact time of between 0.1 and 100 seconds, preferably between 1 and 50 seconds and advantageously between 5 and 40 seconds.
  • the invention is based on the discovery that the 236cb dehydrofluorination reaction, when carried out in the presence of hydrogen, provides stability over time, both in terms of conversion and selectivity to
  • hydrogen is injected with the feedstock, for example continuously or alternately.
  • the molar ratio H 2 / feedstock can vary widely, especially between 0.3 and 30, in particular between 0.5 and
  • the implementation of the dehydrofluorination reaction in the presence of hydrogen allows a high stability over time.
  • the presence of hydrogen also reduces the production of heavy during the reaction.
  • the dehydrofluorination reaction is carried out with a dehydrofluorination catalyst.
  • This catalyst is, for example, a catalyst based on a metal, especially a transition metal, or an oxide or halide or oxyhalide derivative of such a metal.
  • Catalysts are, for example, FeCl 3, chromium oxyfluoride, Ni (including Ni lattice), NiCl 2 , CrF 3 , and mixtures thereof.
  • Other possible catalysts are carbon supported catalysts, antimony catalysts, aluminum catalysts (such as AlF 3 and Al 2 O 3 and aluminum oxyfluoride and fluorinated alumina), palladium, platinum, rhodium and ruthenium.
  • a mixed catalyst containing both chromium and nickel is used.
  • the molar ratio Cr: Ni with respect to the metallic element, is generally between 0.5 and 5, for example between 0.7 and 2, in particular close to 1.
  • the catalyst may contain by weight from 0.5 to 20% of chromium and 0.5 to 20% of nickel and, preferably, between 2 and 10% of each of the metals.
  • the metal may be present in metallic form or in the form of derivatives, in particular oxide, halide or oxyhalide, these derivatives, in particular halide and oxyhalide, being obtained by activation of the catalytic metal. Although activation of the metal is not necessary, it is preferred.
  • the support is based on aluminum.
  • supports such as alumina, activated alumina or aluminum derivatives.
  • aluminum derivatives are in particular aluminum halides or oxyhalides, for example described in US-P-4902838, or obtained by the activation method described below.
  • the catalyst may comprise chromium and nickel in a non-activated form or in activated form, on a support which has also undergone activation of the metal or not.
  • the catalyst can be prepared from alumina (generally so-called activated alumina, this activated alumina is a high porosity alumina, and is distinct from the alumina having undergone the metal activation treatment).
  • the alumina is converted into aluminum fluoride or a mixture of aluminum fluoride and alumina, by fluorination with air and hydrofluoric acid, the conversion rate of the alumina aluminum fluoride depending essentially on the temperature at which the fluorination of the alumina is carried out (generally between 200 0 C and 450 0 C, preferably between 250 ° C. and 400 ° C.).
  • the support is then impregnated with aqueous solutions of chromium and nickel salts or with aqueous solutions of chromic acid, nickel salt and methanol (used as a chromium reducing agent).
  • chromium and nickel salts chlorides, or other salts such as, for example, oxalates, formates, acetates, nitrates and sulphates or nickel dichromate may be employed, provided that these salts are soluble in the amount of water that can be absorbed by the support.
  • the catalyst can also be prepared by direct impregnation of alumina (which in general is activated) using the solutions of the chromium and nickel compounds mentioned above. In this case, the transformation of at least a portion (for example 70% or more) of the alumina into aluminum fluoride or aluminum oxyfluoride is carried out during the activation step of the catalyst metal.
  • the activated aluminas that can be used for catalyst preparation are well known, commercially available products. They are generally prepared by calcining alumina hydrates (aluminum hydroxides) at a temperature of between 300 ° C. and 800 ° C.
  • the catalyst is conditioned or activated, that is to say transformed into active and stable constituents (at the reaction conditions) by a prior operation called activation.
  • This treatment can be carried out either "in situ” (in the dehydrofluorination reactor) or in a suitable apparatus designed to withstand the conditions of activation.
  • This activation step generally comprises the following steps: A drying step. This drying step is carried out at high temperature (250 ° C. to 450 ° C., preferably 300 ° C. to 350 ° C.), generally under a stream of nitrogen or air. This step may optionally be preceded, in a first step, by a first drying step at low temperature (100 ° C. to 150 ° C., preferably 110 ° C. to 120 ° C.) in the presence of air or nitrogen. The duration of the drying step can be between 1 and 50 hours.
  • a fluorination step is carried out at low temperature
  • the duration of the fluorination step may be between 1 and 50 hours.
  • finishing step under current of pure hydrofluoric acid or diluted with nitrogen at a temperature up to 450 ° C.
  • the duration of the finishing step may be between 1 and 15 hours.
  • nickel and chromium halides, chromate or nickel dichromate, chromium oxide are converted to the corresponding fluorides and / or oxyfluorides, resulting in the evolution of water and / or hydrochloric acid.
  • Such a catalyst is described in EP-A-486333, in particular page 3, lines 11-48, Examples IA, 2A and 4A, passages to which it is referred.
  • the dehydrofluorination reaction is generally carried out in the gas phase.
  • the catalyst may be present in any suitable form, for example in the form of a fixed or fluidized bed, preferably in a fixed bed.
  • the direction of flow can be from top to bottom or from bottom to top.
  • the temperature may be between 150 ° C. and 600 ° C., preferably between 300 and 500 ° C. and advantageously between 300 and 450 ° C.
  • the pressure may be atmospheric, or lower or higher than this atmospheric pressure.
  • the contact time (ratio between the volume of catalyst and the total flow of the charge) is generally between 0.1 and 100 seconds, preferably between 1 and 50 seconds and advantageously between 5 and 40 seconds.
  • a diluent gas nitrogen, helium or argon
  • nitrogen, helium or argon can be used in the reaction.
  • the reaction is carried out in a reactor dedicated to reactions involving halogens.
  • reactors are known to those skilled in the art, and may include interior coatings based for example on Hastelloy®, Inconel®, Monel® or fluoropolymers.
  • the reactor may also include heat exchange means, if necessary.
  • the final product of the reaction is separated in a conventional manner, and unreacted reagents are advantageously recycled to the process.
  • the conversion ratio is the% of the reacted starting material (number of mole of reacted starting material / mole number of feedstock introduced);
  • the desired product selectivity is the ratio of the number of moles of desired product formed to the number of moles of product that has reacted;
  • the desired product yield is the ratio of the number of moles of desired product formed to the number of mole products introduced, the yield of the desired product being able to be further defined as the product of conversion and selectivity.
  • the contact time is the inverse of the space velocity VVH (or GHSV in English). Spatial velocity is the ratio of the total volume flow to the volume of the catalytic bed under normal conditions of temperature and pressure.
  • the catalyst used is a Ni-Cr / AlF 3 catalyst prepared as follows.
  • a support obtained in a previous step is placed by fluorination of GRACE HSA alumina in a fixed bed at 280 ° C. using air and hydrofluoric acid (concentration of 5 to 10 vol. % of this acid in the air).
  • the starting GRACE HSA alumina has the following physicochemical characteristics: shape: beads of 0.5-2 mm in diameter BET surface: 220 m 2 / g pore volume: 1.3 cm / g Two separate aqueous solutions are also prepared:
  • the characteristics of the catalyst after activation are as follows: BET surface: 40 m 2 / g pore volume: 0.4 cm / g chemical weight composition:
  • a reactor with a volume of 50 cm and 2.1 cm in diameter is used, containing 20 g of catalyst in the form of a fixed bed having a height of 6.6 cm.
  • the pressure is 1 bar.
  • the temperature is 375 ° C.
  • the contact time is 6.7 seconds. After 100 hours of operation, 236cb conversion and 1225ye selectivity remain constant.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP09766054A 2008-06-18 2009-05-26 Verfahren zur herstellung fluorierter verbindungen Withdrawn EP2285489A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0854008A FR2932798B1 (fr) 2008-06-18 2008-06-18 Procede de preparation de composes fluores
PCT/FR2009/050968 WO2009153492A1 (fr) 2008-06-18 2009-05-26 Procede de preparation de composes fluores

Publications (1)

Publication Number Publication Date
EP2285489A1 true EP2285489A1 (de) 2011-02-23

Family

ID=39951436

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09766054A Withdrawn EP2285489A1 (de) 2008-06-18 2009-05-26 Verfahren zur herstellung fluorierter verbindungen

Country Status (4)

Country Link
EP (1) EP2285489A1 (de)
CN (1) CN102065999A (de)
FR (1) FR2932798B1 (de)
WO (1) WO2009153492A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0808836D0 (en) 2008-05-15 2008-06-18 Ineos Fluor Ltd Process

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6124510A (en) * 1998-07-21 2000-09-26 Elf Atochem North America, Inc. 1234ze preparation
WO2008030444A2 (en) * 2006-09-05 2008-03-13 E. I. Du Pont De Nemours And Company Process for producing 1,2,3,3,3-pentafluoropropene and related azeotropic compositions
ES2447037T3 (es) * 2006-09-05 2014-03-11 E.I. Du Pont De Nemours And Company Procedimiento de fabricación de 2,3,3,3-tetrafluoropropeno

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009153492A1 *

Also Published As

Publication number Publication date
WO2009153492A1 (fr) 2009-12-23
FR2932798A1 (fr) 2009-12-25
FR2932798B1 (fr) 2010-08-13
CN102065999A (zh) 2011-05-18

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