EP2285489A1 - Verfahren zur herstellung fluorierter verbindungen - Google Patents
Verfahren zur herstellung fluorierter verbindungenInfo
- 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- Withdrawn
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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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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 |
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EP2285489A1 true EP2285489A1 (de) | 2011-02-23 |
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EP09766054A Withdrawn EP2285489A1 (de) | 2008-06-18 | 2009-05-26 | Verfahren zur herstellung fluorierter verbindungen |
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EP (1) | EP2285489A1 (de) |
CN (1) | CN102065999A (de) |
FR (1) | FR2932798B1 (de) |
WO (1) | WO2009153492A1 (de) |
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GB0808836D0 (en) | 2008-05-15 | 2008-06-18 | Ineos Fluor Ltd | Process |
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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 |
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2008
- 2008-06-18 FR FR0854008A patent/FR2932798B1/fr not_active Expired - Fee Related
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2009
- 2009-05-26 CN CN2009801233114A patent/CN102065999A/zh active Pending
- 2009-05-26 WO PCT/FR2009/050968 patent/WO2009153492A1/fr active Application Filing
- 2009-05-26 EP EP09766054A patent/EP2285489A1/de not_active Withdrawn
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Also Published As
Publication number | Publication date |
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WO2009153492A1 (fr) | 2009-12-23 |
FR2932798A1 (fr) | 2009-12-25 |
FR2932798B1 (fr) | 2010-08-13 |
CN102065999A (zh) | 2011-05-18 |
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