WO2009153492A1 - Method for preparing fluorinated compounds - Google Patents
Method for preparing fluorinated compounds Download PDFInfo
- Publication number
- WO2009153492A1 WO2009153492A1 PCT/FR2009/050968 FR2009050968W WO2009153492A1 WO 2009153492 A1 WO2009153492 A1 WO 2009153492A1 FR 2009050968 W FR2009050968 W FR 2009050968W WO 2009153492 A1 WO2009153492 A1 WO 2009153492A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- carried out
- chromium
- alumina
- dehydrofluorination
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 title description 6
- DMUPYMORYHFFCT-UHFFFAOYSA-N 1,2,3,3,3-pentafluoroprop-1-ene Chemical compound FC=C(F)C(F)(F)F DMUPYMORYHFFCT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- SUAMPXQALWYDBK-UHFFFAOYSA-N 1,1,1,2,2,3-hexafluoropropane Chemical compound FCC(F)(F)C(F)(F)F SUAMPXQALWYDBK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000011651 chromium Substances 0.000 claims description 15
- 238000005796 dehydrofluorination reaction Methods 0.000 claims description 15
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- ZXVZGGVDYOBILI-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluoropropane Chemical compound FC(F)C(F)(F)C(F)F ZXVZGGVDYOBILI-UHFFFAOYSA-N 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 230000004913 activation Effects 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000002184 metal Substances 0.000 description 9
- -1 fire extinguishers Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000003682 fluorination reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FYIRUPZTYPILDH-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoropropane Chemical compound FC(F)C(F)C(F)(F)F FYIRUPZTYPILDH-UHFFFAOYSA-N 0.000 description 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- QCMJBECJXQJLIL-UHFFFAOYSA-L chromium(6+);oxygen(2-);difluoride Chemical compound [O-2].[O-2].[F-].[F-].[Cr+6] QCMJBECJXQJLIL-UHFFFAOYSA-L 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 229910001026 inconel Inorganic materials 0.000 description 2
- PLHASFSAGNOMLM-UHFFFAOYSA-N nickel(2+);oxido-(oxido(dioxo)chromio)oxy-dioxochromium Chemical compound [Ni+2].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O PLHASFSAGNOMLM-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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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Abstract
The invention relates to a method for dehydrofluorinating 1, 1, 1, 2, 2, 3-hexafluoropropane in 1, 2, 3, 3, 3-pentafluoropropene-1 in the presence of hydrogen.
Description
PROCEDE DE PREPARATION DE COMPOSES FLUORES PROCESS FOR THE PREPARATION OF FLUORINATED COMPOUNDS
DOMAINE DE L'INVENTIONFIELD OF THE INVENTION
L'invention a pour objet un procédé de préparation de composés fluorés, notamment le composé fluoré 1,2,3,3,3- pentafluoropropène-1 (1225ye) . ARRIERE-PLAN TECHNOLOGIQUEThe subject of the invention is a process for preparing fluorinated compounds, especially the 1,2,3,3,3-pentafluoropropene-1 (1225ye) fluorinated compound. BACKGROUND
Les hydrofluorocarbones (HFC) et en particulier les hydrofluorooléfines (HFOs) sont des composés connus pour leurs propriétés de réfrigérants et fluides caloporteurs, extinctrices, propulseurs, agents moussants, agents gonflants, diélectriques gazeux, milieu de polymérisation ou monomère, fluides supports, agents pour abrasifs, agents de séchage et fluides pour unité de production d'énergie. A la différence des CFC et des HCFC, qui sont potentiellement dangereux pour la couche d'ozone, les HFOs ne contiennent pas de chlore et donc ne posent pas de problème pour la couche d'ozone.Hydrofluorocarbons (HFCs) 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. Unlike CFCs and HCFCs, which are potentially hazardous to the ozone layer, HFOs do not contain chlorine and therefore do not pose a problem for the ozone layer.
Le document WO 2008/040969 décrit la préparation de (hydro) fluoroalcène ayant de trois à six atomes de carbone par déhydrohalogénation d'un hydro (halo) fluoroalcane ayant de trois à six atomes de carbone en présence d'un catalyseur comprenant un composé de chrome et /ou de zinc. Ce document enseigne que la déhydrofluoration peut être mise en œuvre en l'absence de l'HF (acide fluorhydrique) mais il est préférable d'utiliser de l'HF pour éviter ou retarder la décomposition de la charge organique et/ou le cokage (encrassement par dépôt du coke) du catalyseur.The document 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. This document teaches that 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.
Le document WO 2008/008350 décrit la préparation d'un mélange d'isomères E et Z du 1, 2, 3, 3, 3-pentafluoropropène-1 (1225ye)à partir d'un hexafluoropropane, choisi parmi le 1, 1, 1,2, 3, 3-hexafluoropropane (HFC 236ea)et le 1,1,1,2,2,3- hexafluoropropane (HFC 236cb) , en présence d'un catalyseur d' oxyfluorure de chrome. L'exemple 1 de ce document illustre la réaction de déhydrofluoration de 1,1,1,2,2,3-
hexafluoropropane (HFC 236cb) en 1,2,3,3,3- pentafluoropropène-1 (1225ye) et montre qu'au bout de 26 heures de fonctionnement, la conversion du 236cb diminue fortement ainsi que la sélectivité en 1225ye. Pour rétablir l'activité catalytique ce document enseigne de régénérer le catalyseur par un traitement avec de l'air et de l'HF.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. To restore the catalytic activity this document teaches to regenerate the catalyst by treatment with air and HF.
Il existe donc un besoin d'un procédé de préparation de 1225ye à partir de 236cb permettant une stabilité dans le temps . RESUME DE L'INVENTIONThere is therefore a need for a process for preparing 1225ye from 236cb allowing stability over time. SUMMARY OF THE INVENTION
L'invention fournit donc un procédé de déhydrofluoration de 1, 1, 1, 2, 2, 3-hexafluoropropane en 1, 2, 3, 3, 3-pentafluoropropène-1, en présence d'hydrogène.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.
Selon des modes de réalisation : - la réaction est mise en œuvre en phase gazeuse avec un ratio molaire H2/I, 1,1,2,2, 3-hexafluoropropane compris entre 0,3 et 30. la réaction est mise en œuvre en phase gazeuse avec un ratio molaireAccording to embodiments: 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
H2/I, 1,1,2,2, 3-hexafluoropropane compris entre 0,5 et 20, avantageusement entre 1 et 10. le procédé est mis en œuvre en présence d'un catalyseur de déhydrofluoration . le catalyseur de déhydrofluoration est un catalyseur à base de chrome. le procédé est mis en œuvre à une température comprise entre 1500C et 5000C, de préférence entre 300 et 400°C. le procédé est mis en œuvre avec un temps de contact compris entre 0,1 et 100 secondes,
de préférence entre 1 et 50 secondes et avantageusement entre 5 et 40 secondes. DESCRIPTION DETAILLEE DE MODES DE REALISATIONH2 / I, 1,1,2,2, 3-hexafluoropropane of between 0.5 and 20, advantageously between 1 and 10. 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. DETAILED DESCRIPTION OF EMBODIMENTS
L'invention est basée sur la découverte que la réaction de déhydrofluoration du 236cb, lorsqu'elle est mise en œuvre en présence d'hydrogène, offre une stabilité dans le temps, tant au niveau conversion que sélectivité enThe 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
1225ye.1225ye.
En général, de l'hydrogène est injecté avec la charge de départ, par exemple en continu ou de façon alternée. Le ratio molaire H2/charge départ peut varier dans de grandes mesures, notamment entre 0,3 et 30, notamment entre 0,5 etIn general, 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
20, avantageusement entre 1 et 10.20, advantageously between 1 and 10.
La mise en œuvre de la réaction de déhydrofluoration en présence d'hydrogène permet une stabilité élevée dans le temps. La présence d'hydrogène permet aussi de réduire la production de lourds au cours de la réaction.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.
La réaction de déhydrofluoration est mise en œuvre avec un catalyseur de déhydrofluoration . Ce catalyseur est par exemple un catalyseur à base d'un métal notamment d'un métal de transition ou un dérivé oxyde ou halogénure ou oxyhalogénure d'un tel métal. Des catalyseurs sont par exemple FeCl3, oxyfluorure de chrome, Ni (incluant les treillis de Ni), NiCl2, CrF3, et leurs mélanges. D'autres catalyseurs possibles sont les catalyseurs supportés sur carbone, les catalyseurs à base d'antimoine, les catalyseurs à base d'aluminium (tel que AlF3 et Al2O3 et oxyfluorure d'aluminium et alumine fluorée), de palladium, de platine, de rhodium et de ruthénium. On pourra se référer à la liste donnée dans le document US-P-5396000, colonne 1, ligne 50 à colonne 2, ligne 2 ou à la liste donnée dans WO2007/056194, page 16, lignes 13-23.
Selon une variante, on utilise un catalyseur mixte, contenant à la fois du chrome et du nickel. Le ratio molaire Cr:Ni, par rapport à l'élément métallique, est généralement compris entre 0,5 et 5, par exemple entre 0,7 et 2, notamment voisin de 1. Le catalyseur peut contenir en poids de 0,5 à 20% de chrome et de 0,5 à 20% de nickel et, de préférence, entre 2 et 10% de chacun des métaux.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. Reference may be made to the list given in US-P-5396000, column 1, line 50 to column 2, line 2 or to the list given in WO2007 / 056194, page 16, lines 13-23. According to one variant, 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.
Le métal peut être présent sous forme métallique ou sous forme de dérivés, notamment oxyde, halogénure ou oxyhalogénure, ces dérivés, notamment halogénure et oxyhalogénure, étant obtenus par activation du métal catalytique. Bien que l' activation du métal ne soit pas nécessaire, elle est préférée.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.
Le support est à base d'aluminium. On peut citer plusieurs supports possibles comme l'alumine, l'alumine activée ou les dérivés d'aluminium. Ces dérivés d'aluminium sont notamment des halogénures ou oxyhalogénures d'aluminium, décrits par exemple dans US-P-4902838, ou obtenus par le procédé d' activation décrit ci-dessous. Le catalyseur peut comprendre le chrome et du nickel sous une forme non-activée ou sous forme activée, sur un support qui a subi aussi l' activation du métal ou non.The support is based on aluminum. There may be mentioned several possible supports such as alumina, activated alumina or aluminum derivatives. These 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.
Le catalyseur peut être préparé à partir d'alumine (en général une alumine dite activée ; cette alumine activée est une alumine à porosité élevée, et est distincte de l'alumine ayant subi le traitement d'activation du métal) . Dans une première étape l'alumine est transformée en fluorure d'aluminium ou en mélange de fluorure d'aluminium et d'alumine, par fluoration à l'aide d'air et d'acide fluorhydrique, le taux de transformation de l'alumine en fluorure d'aluminium dépendant essentiellement de la température à laquelle est effectuée la fluoration de l'alumine (en général entre 2000C et 4500C, de préférence
entre 250°C et 4000C) . Le support est ensuite imprégné à l'aide de solutions aqueuses de sels de chrome et de nickel ou à l'aide de solutions aqueuses d'acide chromique, de sel de nickel et de méthanol (servant de réducteur au chrome) . Comme sels de chrome et de nickel, on peut employer des chlorures, ou d'autres sels tels que, par exemple, les oxalates, formiates, acétates, nitrates et sulfates ou le bichromate de nickel, pour autant que ces sels soient solubles dans la quantité d'eau susceptible d'être absorbée par le support. Le catalyseur peut aussi être préparé par imprégnation directe de l'alumine (qui en général est activée) à l'aide des solutions des composés de chrome et de nickel ci-dessus mentionnées. Dans ce cas, la transformation d'au moins une partie (par exemple 70% ou plus) de l'alumine en fluorure d'aluminium ou oxyfluorure d'aluminium s'effectue lors de l'étape d'activation du métal du catalyseur.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). In a first step, 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). As 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.
Les alumines activées susceptibles d'être utilisées pour la préparation du catalyseur sont des produits bien connus, disponibles dans le commerce. Elles sont généralement préparées par calcination d'hydrates d'alumine (hydroxydes d'aluminium) à une température comprise entre 300°C et 8000C.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.
De préférence, mais sans que cela soit nécessaire, le catalyseur est conditionné ou activé, c'est-à-dire transformé en constituants actifs et stables (aux conditions réactionnelles) par une opération préalable dite d'activation. Ce traitement peut être réalisé soit "in situ" (dans le réacteur de déhydrofluoration) ou bien dans un appareillage adéquat conçu pour résister aux conditions d' activation .Preferably, but without this being necessary, 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.
Cette étape d'activation comprend en général les étapes suivantes :
Une étape de séchage. Cette étape de séchage est effectuée à haute température (2500C à 4500C, de préférence 3000C à 3500C) en général sous courant d'azote ou d'air. Cette étape peut être éventuellement précédée dans un premier temps d'une première étape de séchage à basse température (100°C à 150°C, de préférence 1100C à 1200C) en présence d'air ou d'azote. La durée de l'étape de séchage peut être comprise entre 1 et 50 heures.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.
Une étape de fluoration. Cette étape de fluoration est mise en œuvre à basse températureA fluorination step. This fluorination step is carried out at low temperature
(1800C à 3500C) au moyen d'un mélange d'acide fluorhydrique et d'azote, en contrôlant la teneur en HF de façon que la température ne dépasse pas(180 ° C. to 350 ° C.) using a mixture of hydrofluoric acid and nitrogen, controlling the HF content so that the temperature does not exceed
3500C. La durée de l'étape de fluoration peut être comprise entre 1 et 50 heures.350 ° C. The duration of the fluorination step may be between 1 and 50 hours.
Eventuellement une étape de finition sous courant d'acide fluorhydrique pur ou dilué par de l'azote à une température pouvant aller jusqu'à 4500C. La durée de l'étape de finition peut être comprise entre 1 et 15 heures.Optionally a 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.
Pendant cette opération, les précurseurs catalytiquesDuring this operation, catalytic precursors
(par exemple halogénures de nickel et de chrome, chromate ou bichromate de nickel, oxyde de chrome) sont transformés en fluorures et/ou oxyfluorures correspondants, ce qui entraîne un dégagement d'eau et/ou d'acide chlorhydrique .(For example, 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.
L'analyse chimique des éléments (chrome, nickel, fluor, aluminium, oxygène) , après cette activation, permet de vérifier la composition minérale du catalyseur.The chemical analysis of the elements (chromium, nickel, fluorine, aluminum, oxygen), after this activation, makes it possible to check the mineral composition of the catalyst.
Un tel catalyseur est décrit dans EP-A-486333, en particulier page 3, lignes 11-48, exemples IA, 2A et 4A, passages auxquels il est renvoyé.
La réaction de déhydrofluoration est mise en œuvre en général en phase gazeuse.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.
Le catalyseur peut être présent sous toute forme appropriée, par exemple sous forme de lit fixe ou fluidisé, de préférence en lit fixe. La direction de flux peut être de haut en bas ou de bas en haut.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.
La température peut être comprise entre 1500C et 6000C, de préférence entre 300 et 5000C et avantageusement entre 300 et 450°C. La pression peut être atmosphérique, ou inférieure ou supérieure à cette pression atmosphérique.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.
Le temps de contact (rapport entre le volume de catalyseur et le flux total de la charge) est en général compris entre 0,1 et 100 secondes, de préférence entre 1 et 50 secondes et avantageusement entre 5 et 40 secondes.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.
Un gaz diluant (azote, hélium ou argon) peut être utilisé dans la réaction.A diluent gas (nitrogen, helium or argon) can be used in the reaction.
La réaction est mise en œuvre dans un réacteur dédié aux réactions impliquant des halogènes. De tels réacteurs sont connus de l'homme du métier, et peuvent comprendre des revêtements intérieurs à base par exemple de Hastelloy®, Inconel®, Monel® ou de fluoropolymères . Le réacteur peut aussi comprendre des moyens d'échange de chaleur, si besoin . Le produit final de la réaction est séparé de façon classique, et les réactifs n'ayant pas réagi sont avantageusement recyclés dans le procédé. On rappellera que : le taux de conversion est le % du produit de départ ayant réagi (nombre mole de produit départ ayant réagi/nombre mole produit départ introduit) ;
la sélectivité en produit recherché est le ratio nombre de mole de produit recherché formé/nombre mole produit départ ayant réagi ; le rendement en produit recherché est le ratio nombre de mole de produit recherché formé/nombre mole produit départ introduit, le rendement en produit recherché pouvant encore être défini comme le produit de la conversion et de la sélectivité . - le temps de contact est l'inverse de la vitesse spatiale VVH (ou GHSV en langue anglaise) . la vitesse spatiale est le rapport entre le débit volumique total sur le volume du lit catalytique, dans les conditions normales de température et de pression.The reaction is carried out in a reactor dedicated to reactions involving halogens. Such 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. It will be recalled that: 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.
La productivité est exprimée en masse de produit recherché obtenu par unité de temps et par unité de catalyseur (masse ou volume) ; cette productivité est liée au temps de contact. EXEMPLESProductivity is expressed as the mass of desired product obtained per unit of time and per unit of catalyst (mass or volume); this productivity is related to the contact time. EXAMPLES
Les exemples suivants illustrent l'invention sans la limiter . Exemple 1. Préparation du catalyseur.The following examples illustrate the invention without limiting it. Example 1. Preparation of the catalyst
Le catalyseur utilisé est un catalyseur Ni-Cr/A1F3 préparé comme suit.The catalyst used is a Ni-Cr / AlF 3 catalyst prepared as follows.
Dans un évaporateur rotatif, on place 343g d'un support obtenu dans une étape précédente par fluoration d'alumine GRACE HSA en lit fixe vers 2800C à l'aide d'air et d'acide fluorhydrique (concentration volumique de 5 à 10 % de cet acide dans l'air) . L'alumine GRACE HSA de départ présente les caractéristiques physicochimiques suivantes : forme : billes de 0,5-2 mm de diamètre
surface BET : 220 m2 /g volume poreux : 1,3 cm /g On prépare par ailleurs deux solutions aqueuses séparées :In a rotary evaporator, 343 g of 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:
(a) solution chromique additionnée de chlorure de nickel contenant :(a) Chromium solution containing nickel chloride containing:
- anhydride chromique 55 g- chromic anhydride 55 g
- chlorure de nickel hexahydraté 130 g- nickel chloride hexahydrate 130 g
- eau 63 g- water 63 g
(b) Solution méthanolique contenant
Ces deux solutions sont introduites simultanément à une température de 400C sous pression atmosphérique et en 2 heures environ, sur le support en agitation. Après une étape de maturation sous azote, le catalyseur est séché sous azote, puis sous vide à 65°C puis vers 900C pendant 6 heures.(b) Methanolic solution containing These two solutions are simultaneously introduced at a temperature of 40 ° C. under atmospheric pressure and in approximately 2 hours, on the stirring support. After a maturation step under nitrogen, the catalyst is dried under nitrogen and then under vacuum at 65 ° C. and then at 90 ° C. for 6 hours.
On charge 500g de solide imprégné dans un réacteur tubulaire en inconel. Le catalyseur est tout d'abord séché sous balayage d'azote à basse température puis jusqu'à 3200C, à pression atmosphérique. Il est ensuite fluoré en présence d'un mélange acide fluorhydrique / azote500 g of impregnated solid are loaded into a tubular reactor in inconel. The catalyst is first dried under nitrogen sweep at low temperature and then up to 320 0 C, at atmospheric pressure. It is then fluorinated in the presence of a hydrofluoric acid / nitrogen mixture
(concentration volumique de 5 à 10 % de cet acide dans l'azote) à 320°C puis jusqu'à 390°C. L'alimentation d' HF est alors coupée. Le balayage à l'azote est maintenu pendant 15 minutes à 3900C puis le catalyseur est refroidi jusqu'à 60°C sous balayage d'azote.(volume concentration of 5 to 10% of this acid in nitrogen) at 320 ° C and then up to 390 ° C. The supply of HF is then cut off. The nitrogen sweep is maintained for 15 minutes at 390 ° C. and then the catalyst is cooled to 60 ° C. under a nitrogen sweep.
Les caractéristiques du catalyseur après activation sont les suivantes : surface BET : 40 m2 /g volume poreux : 0,4 cm /g
composition chimique pondérale :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:
- Al : 25 %- Al: 25%
- F : 58 %- F: 58%
- Cr : 5,3 % " Ni : 6,4 %- Cr: 5.3% "Ni: 6.4%
Exemple 2. Déhydrofluoration de 236cb en 1225ye.Example 2. Dehydrofluorination of 236cb in 1225ye.
On utilise un réacteur d'un volume de 50cm et de 2,1 cm de diamètre, contenant 20g de catalyseur sous forme d'un lit fixe d'une hauteur de 6,6 cm. La pression est de 1 bar. La température est de 375°C.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.
On y introduit 100 mmol de 236cb par heure et 450 mmol d'hydrogène par heure, soit un ratio molaire hydrogène/ 236cb = 4,5.It introduces 100 mmol of 236cb per hour and 450 mmol of hydrogen per hour, a molar ratio hydrogen / 236cb = 4.5.
Le temps de contact est de 6,7 secondes. Au bout de 100 heures de fonctionnement, la conversion de 236cb et la sélectivité en 1225ye restent constantes.
The contact time is 6.7 seconds. After 100 hours of operation, 236cb conversion and 1225ye selectivity remain constant.
Claims
1. Procédé de déhydrofluoration de 1,1,1,2,2,3- hexafluoropropane en 1, 2, 3, 3, 3-pentafluoropropène-1, en présence d'hydrogène.1. Process for the dehydrofluorination of 1,1,1,2,2,3-hexafluoropropane to 1, 2,3,3,3-pentafluoropropene-1 in the presence of hydrogen.
2. Procédé selon la revendication 1, dans lequel la réaction est mise en œuvre en phase gazeuse avec un ratio molaire H2/l, 1, 1, 2, 3, 3-hexafluoropropane compris entre 0,3 et 30.2. The method of claim 1, wherein the reaction is carried out in the gas phase with a molar ratio H 2 / l, 1, 1, 2, 3, 3-hexafluoropropane between 0.3 and 30.
3. Procédé selon la revendication 1 ou 2, dans lequel la réaction est mise en œuvre en phase gazeuse avec un ratio molaire H2/l, 1, 1, 2, 2, 3-hexafluoropropane compris entre 0,5 et 20, avantageusement entre 1 et 10.3. The method of claim 1 or 2, wherein the reaction is carried out in the gas phase with a molar ratio H 2 / l, 1, 1, 2, 2, 3-hexafluoropropane between 0.5 and 20, preferably between 1 and 10.
4. Procédé selon l'une des revendications 1 à 3, mis en œuvre en présence d'un catalyseur de déhydrofluoration .4. Method according to one of claims 1 to 3, implemented in the presence of a dehydrofluorination catalyst.
5. Procédé selon la revendication 4, dans lequel le catalyseur de déhydrofluoration est un catalyseur mixte à base de chrome et de nickel sur un support à base d ' aluminium.5. The process according to claim 4, wherein the dehydrofluorination catalyst is a mixed catalyst based on chromium and nickel on an aluminum-based support.
6. Procédé selon l'une des revendications 1 à 5, mis en œuvre à une température comprise entre 1500C et 5000C, de préférence entre 300 et 400°C.6. Method according to one of claims 1 to 5, implemented at a temperature between 150 0 C and 500 0 C, preferably between 300 and 400 ° C.
7. Procédé selon l'une des revendications 1 à 6, mis en œuvre avec un temps de contact compris entre 0,1 et 100 secondes, de préférence entre 1 et 50 secondes et avantageusement entre 5 et 40 secondes. 7. Method according to one of claims 1 to 6, implemented with a contact time of between 0.1 and 100 seconds, preferably between 1 and 50 seconds and preferably between 5 and 40 seconds.
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CN2009801233114A CN102065999A (en) | 2008-06-18 | 2009-05-26 | Method for preparing fluorinated compounds |
EP09766054A EP2285489A1 (en) | 2008-06-18 | 2009-05-26 | Method for preparing fluorinated compounds |
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FR0854008A FR2932798B1 (en) | 2008-06-18 | 2008-06-18 | PROCESS FOR THE PREPARATION OF FLUORINATED COMPOUNDS |
FRFR08.54008 | 2008-06-18 |
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PCT/FR2009/050968 WO2009153492A1 (en) | 2008-06-18 | 2009-05-26 | Method for preparing fluorinated compounds |
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CN (1) | CN102065999A (en) |
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Cited By (1)
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US9162948B2 (en) | 2008-05-15 | 2015-10-20 | Mexichem Amanco Holding S.A. De C.V. | Process for the preparation of 2, 3, 3, 3-tetrafluoropropene |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0974571B1 (en) * | 1998-07-21 | 2003-04-23 | Atofina Chemicals, Inc. | Preparation of 1,1,1,3-tetrafluoropropene( 1234ze ) |
WO2008030440A2 (en) * | 2006-09-05 | 2008-03-13 | E. I. Du Pont De Nemours And Company | Process to manufacture 2,3,3,3-tetrafluoropropene |
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 |
-
2008
- 2008-06-18 FR FR0854008A patent/FR2932798B1/en not_active Expired - Fee Related
-
2009
- 2009-05-26 CN CN2009801233114A patent/CN102065999A/en active Pending
- 2009-05-26 WO PCT/FR2009/050968 patent/WO2009153492A1/en active Application Filing
- 2009-05-26 EP EP09766054A patent/EP2285489A1/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0974571B1 (en) * | 1998-07-21 | 2003-04-23 | Atofina Chemicals, Inc. | Preparation of 1,1,1,3-tetrafluoropropene( 1234ze ) |
WO2008030440A2 (en) * | 2006-09-05 | 2008-03-13 | E. I. Du Pont De Nemours And Company | Process to manufacture 2,3,3,3-tetrafluoropropene |
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 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9162948B2 (en) | 2008-05-15 | 2015-10-20 | Mexichem Amanco Holding S.A. De C.V. | Process for the preparation of 2, 3, 3, 3-tetrafluoropropene |
US9957210B2 (en) | 2008-05-15 | 2018-05-01 | Mexichem Amanco Holdings S.A. De C.V. | Process for the preparation of 2,3,3,3-tetrafluoropropene |
US10683248B2 (en) | 2008-05-15 | 2020-06-16 | Mexichem Amanco Holding S.A. De C.V. | Process for the preparation of 2,3,3,3-tetrafluoropropene |
US11267772B2 (en) | 2008-05-15 | 2022-03-08 | Mexichem Amanco Holding S.A. De C.V. | Process for the preparation of 2,3,3,3-tetrafluoropropene |
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EP2285489A1 (en) | 2011-02-23 |
FR2932798A1 (en) | 2009-12-25 |
FR2932798B1 (en) | 2010-08-13 |
CN102065999A (en) | 2011-05-18 |
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