EP3641932A1 - Alpha-alumina-based catalyst and process for hydrogenation of an olefin in the presence thereof - Google Patents
Alpha-alumina-based catalyst and process for hydrogenation of an olefin in the presence thereofInfo
- Publication number
- EP3641932A1 EP3641932A1 EP18732066.8A EP18732066A EP3641932A1 EP 3641932 A1 EP3641932 A1 EP 3641932A1 EP 18732066 A EP18732066 A EP 18732066A EP 3641932 A1 EP3641932 A1 EP 3641932A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- catalyst
- less
- ppm
- total weight
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 150000001336 alkenes Chemical class 0.000 title claims description 23
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 21
- 238000000034 method Methods 0.000 title claims description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 8
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- -1 alkane compound Chemical class 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 6
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 claims description 5
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 claims description 5
- DMUPYMORYHFFCT-UPHRSURJSA-N (z)-1,2,3,3,3-pentafluoroprop-1-ene Chemical compound F\C=C(/F)C(F)(F)F DMUPYMORYHFFCT-UPHRSURJSA-N 0.000 claims description 5
- ZHJBJVPTRJNNIK-UPHRSURJSA-N (z)-1,2-dichloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(\Cl)=C\Cl ZHJBJVPTRJNNIK-UPHRSURJSA-N 0.000 claims description 5
- QAERDLQYXMEHEB-UHFFFAOYSA-N 1,1,3,3,3-pentafluoroprop-1-ene Chemical compound FC(F)=CC(F)(F)F QAERDLQYXMEHEB-UHFFFAOYSA-N 0.000 claims description 5
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims description 5
- OQISUJXQFPPARX-UHFFFAOYSA-N 2-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(Cl)=C OQISUJXQFPPARX-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000010948 rhodium Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 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 4
- 150000002739 metals Chemical class 0.000 description 3
- ZDCWZRQSHBQRGN-UHFFFAOYSA-N 1,1,1,2,3-pentafluoropropane Chemical compound FCC(F)C(F)(F)F ZDCWZRQSHBQRGN-UHFFFAOYSA-N 0.000 description 2
- INEMUVRCEAELBK-UHFFFAOYSA-N 1,1,1,2-tetrafluoropropane Chemical compound CC(F)C(F)(F)F INEMUVRCEAELBK-UHFFFAOYSA-N 0.000 description 2
- PFFGXVGPSGJOBV-UHFFFAOYSA-N 1,1,1,3-tetrafluoropropane Chemical compound FCCC(F)(F)F PFFGXVGPSGJOBV-UHFFFAOYSA-N 0.000 description 2
- QJMGASHUZRHZBT-UHFFFAOYSA-N 2,3-dichloro-1,1,1-trifluoropropane Chemical compound FC(F)(F)C(Cl)CCl QJMGASHUZRHZBT-UHFFFAOYSA-N 0.000 description 2
- ZPIFKCVYZBVZIV-UHFFFAOYSA-N 3-chloro-1,1,1-trifluoropropane Chemical compound FC(F)(F)CCCl ZPIFKCVYZBVZIV-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- VRVIDSRWPUGFBU-UHFFFAOYSA-N 2-chloro-1,1,1-trifluoropropane Chemical compound CC(Cl)C(F)(F)F VRVIDSRWPUGFBU-UHFFFAOYSA-N 0.000 description 1
- VLRGXXKFHVJQOL-UHFFFAOYSA-N 3-chloropentane-2,4-dione Chemical compound CC(=O)C(Cl)C(C)=O VLRGXXKFHVJQOL-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000004580 weight loss Effects 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/612—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/354—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by hydrogenation
Definitions
- the present invention relates to catalysts for the hydrogenation of olefins.
- the invention relates to supported catalysts for the hydrogenation of fluorinated olefins.
- Alumina is known as a support for these catalysts. Alumina has different phases: alpha, beta, gamma, delta, theta, eta, kappa. Knunyants et al.
- the present invention provides a catalyst comprising a) 90 to 99.99% by weight of alumina wherein said alumina is at least 90% by weight of the alpha-alumina; and b) from 0.01 to 10% by weight of at least one metal of valence O selected from the group consisting of Pd, Ru, Pt, Rh and Ir; characterized in that the chloride content of said catalyst is less than 500 ppm based on the total weight of the catalyst.
- the water content of said catalyst is less than 2% by weight based on the total weight of the catalyst.
- the carbon mass content is less than 500 ppm based on the total weight of the catalyst.
- the mass content of sodium is less than 100 ppm based on the total weight of the catalyst.
- the mass content of antimony is less than 20 ppm based on the total weight of the catalyst. According to a preferred embodiment, in said catalyst:
- the mass content of gold is less than 100 ppm based on the total weight of the catalyst, and / or
- the mass content of lead is less than 50 ppm based on the total weight of the catalyst, and / or
- the mass content of zinc is less than 250 ppm based on the total weight of the catalyst, and / or
- the mass content of iron is less than 50 ppm based on the total weight of the catalyst, and / or
- the mass content of copper is less than 50 ppm based on the total weight of the catalyst, and / or
- the mass content of magnesium is less than 50 ppm based on the total weight of the catalyst, and / or
- the mass content of calcium is less than 50 ppm based on the total weight of the catalyst, and / or
- the mass content of nickel is less than 50 ppm based on the total weight of the catalyst, and / or
- the mass content of chromium is less than 10 ppm based on the total weight of the catalyst, and / or
- the mass content of cobalt is less than 10 ppm based on the total weight of the catalyst, and / or
- the mass content of manganese is less than 10 ppm based on the total weight of the catalyst.
- the present invention provides a process for the hydrogenation of an olefin comprising at least one fluorine atom comprising contacting said olefin with hydrogen in the gas phase in the presence of the catalyst according to the present invention for forming an alkane compound derived from the hydrogenation of said olefin.
- said olefin is selected from the group consisting of 1,1,2,3,3,3-hexafluoropropene, 1,2,3,3,3-pentafluoropropene, 1,1,3,3, 3- pentafluoropropene, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,2-dichloro-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene and 2-chloro-3,3,3-trifluoropropene.
- the present invention also provides a catalyst comprising a) 90 to 99.99% by weight of alumina wherein said alumina is at least 90% by weight of the alpha-alumina; and b) 0.01 to 10% by weight of at least one metal of valency 0 selected from the group consisting of Pd, Ru, Pt, Rh and Ir; characterized in that the carbon content of said catalyst is less than 500 ppm based on the total weight of the catalyst.
- a catalyst is provided.
- said catalyst comprises from 90 to 99.99% by weight of alumina and from 0.01 to 10% by weight of at least one metal of valency 0 based on the total weight of the catalyst.
- the alumina used is an alumina comprising at least 90% by weight of alumina-alpha based on the total weight of the alumina.
- the alumina used is an alumina comprising at least 91% by weight of alumina-alpha, preferably at least 92% by weight, more preferably at least 93% by weight, in particular at least 94% by weight, more especially at least 95% by weight, preferably at least 96% by weight, more preferably at least 97% by weight, preferably at least 98% by weight, particularly preferably at least 99% by weight of alumina-alpha based on the total weight of the alumina.
- the alumina consists of alumina-alpha.
- said catalyst comprises at least 0.025% by weight of at least one metal of valency 0, advantageously at least 0.05% by weight, preferably at least 0.075% by weight, more preferably at least 0 , 1% by weight, in particular at least 0.125% by weight, more particularly at least 0.15% by weight, preferably at least 0.175% by weight of at least one metal of valence 0 based on the total weight of the catalyst.
- said catalyst comprises at most 10% by weight of at least one metal of valence 0, advantageously at most 9% by weight, preferably at most 8% by weight, more preferably at most 7% by weight. weight, in particular at most 6% by weight, more particularly at most 5% by weight, preferably at most 4% by weight, more preferably at most 3% by weight, particularly preferably at most 2% by weight. weight of at least one metal of valency 0 based on the total weight of the catalyst.
- said catalyst may comprise at least 0.025% by weight of at least one metal of valency 0, advantageously at least 0.05% by weight, preferably at least 0.075% by weight, more preferably at least 0.1% by weight. weight, in particular at least 0.125% by weight, more particularly at least 0.15% by weight, preferably at least 0.175% by weight at least one metal of valency 0; and at most 10% by weight of at least one metal of valence 0, advantageously at most 9% by weight, preferably at most 8% by weight, more preferably at most 7% by weight, in particular at most 6% by weight. weight, more particularly at most 5% by weight, preferably at most 4% by weight, more preferably at most 3% by weight, particularly preferably at most 2% by weight of at least one valence metal 0 based on the total weight of the catalyst.
- said catalyst may comprise at least 0.01% by weight or at least 0.0125% by weight or at least 0.015% by weight or at least 0.0175% by weight or at least 0.02% by weight. % by weight or at least 0.0225% by weight or at least 0.025% by weight or at least 0.0275% by weight or at least 0.03% by weight or at least 0.0325% by weight or at least 0.035% % by weight or at least 0.0375% by weight or at least 0.04% by weight or at least 0.0425% by weight or at least 0.045% by weight or at least 0.0475% by weight or at least 0% by weight , 05% by weight or at least 0.0525% by weight or at least 0.055% by weight or at least 0.0575% by weight or at least 0.06% by weight or at least 0.0625% by weight or at less than 0,065% by weight or at least 0,0675% by weight or at least 0,07% by weight or at least 0,0725% by weight or at least 0,075% by weight or at least at least 0,075%
- said catalyst may comprise at most 10% by weight or at most 10% by weight or at most 9.5% by weight or at most 9% by weight or at most 8.5% by weight or not more than 8% by weight or not more than 7,5% by weight or not more than 7% by weight or not more than 6,5% by weight or not more than 6% by weight or not more than 5,5% by weight or not more 5% by weight or not more than 4,5% by weight or not more than 4% by weight or not more than 3,5% by weight or not more than 3% by weight or not more than 2,5% by weight or not more than 2% by weight of at least one metal of valency 0 based on the total weight of the catalyst.
- said catalyst may comprise at least 0.01% by weight or at least 0.0125% by weight or at least 0.015% by weight or at least 0.0175% by weight or at least 0.02% by weight or at least less than 0,0225% by weight or at least 0,025% by weight or at least 0,0275% by weight or at least 0,03% by weight or at least 0,0325% by weight or at least 0,035% by weight or at less than 0.0375% by weight or at least 0.04% by weight or at least 0.0425% by weight or at least 0.045% by weight or at least 0.0475% by weight or at least 0.05% by weight or at least 0.0525% by weight or at least 0.055% by weight or at least 0.0575% by weight; at least 0.06% by weight or at least 0.0625% by weight or at least 0.065% by weight or at least 0.0675% by weight or at least 0.07% by weight or at least 0.0725% by weight weight or at least 0.075% by weight or at least 0.0775% by weight or at least 0.08% by weight
- said at least one metal of valency 0 is selected from the group consisting of Pd, Ru, Pt, Rh and Ir.
- said at least one metal of valency 0 is selected from the group consisting of Pd and Rh.
- said at least one metal of valency 0 is palladium.
- the carbon content of said catalyst is less than 900 ppm based on the total weight of the catalyst, advantageously less than 800 ppm, preferably less than 700 ppm, more preferably less than 600 ppm, in particular less than 500 ppm, more particularly less than 400 ppm, preferably less than 300 ppm, advantageously preferred less than 200 ppm, preferentially preferred less than 100 ppm, more preferentially preferred less than 50 ppm, particularly preferred at less than 10 ppm based on the total weight of the catalyst, more particularly preferred said catalyst is free of carbon.
- the water content of said catalyst is less than 5% by weight based on the total weight of the catalyst, advantageously less than 4% by weight, preferably less than 3% by weight, more preferably less than 2% by weight.
- % by weight in particular less than 1% by weight, more particularly less than 0.5% by weight, so preferred less than 0.1% by weight, more preferably less than 0.05% by weight based on the total weight of the catalyst.
- the mass content of chloride is less than 1000 ppm based on the total weight of the catalyst, preferably less than 900 ppm, preferably less than 800 ppm, more preferably less than 700 ppm, in particular less than 600 ppm. ppm, more preferably less than 500 ppm, preferably less than 400 ppm, more preferably less than 300 ppm, advantageously preferred less than 200 ppm, preferably less than 100 ppm based on the total weight of the catalyst .
- the mass content of sodium is less than
- ppm based on the total weight of the catalyst, preferably less than 900 ppm, preferably less than 800 ppm, more preferably less than 700 ppm, in particular less than 600 ppm, more particularly less than 500 ppm, preferably less than 400 ppm.
- ppm more preferably less than 300 ppm, advantageously preferred less than 200 ppm, preferably preferred less than 100 ppm based on the total weight of the catalyst.
- said catalyst may have:
- a mass content of gold is less than 100 ppm, preferably less than 50 ppm based on the total weight of the catalyst, and / or
- a mass content of lead is less than 50 ppm, preferably less than 25 ppm, based on the total weight of the catalyst, and / or
- a mass content of zinc is less than 250 ppm, preferably less than 100 ppm, based on the total weight of the catalyst, and / or
- a mass content of iron is less than 50 ppm, preferably less than 25 ppm, based on the total weight of the catalyst, and / or
- a mass content of copper is less than 50 ppm, preferably less than 25 ppm, based on the total weight of the catalyst, and / or
- a mass content of magnesium is less than 50 ppm, preferably less than 25 ppm, based on the total weight of the catalyst, and / or
- a calcium content by weight is less than 50 ppm, preferably less than 25 ppm, based on the total weight of the catalyst, and / or a mass content of nickel is less than 50 ppm, preferably less than 25 ppm, based on the total weight of the catalyst, and / or
- a mass content of chromium is less than 10 ppm based on the total weight of the catalyst, and / or
- a mass content of cobalt is less than 10 ppm based on the total weight of the catalyst, and / or
- a mass content of manganese is less than 10 ppm based on the total weight of the catalyst, and / or
- a mass content of antimony is less than 20 ppm, preferably less than 10 ppm, based on the total weight of the catalyst.
- the platinum mass content is less than 100 ppm, preferably less than 50 ppm, based on the total weight of the catalyst, and / or
- the mass content of rhodium is less than 100 ppm, preferably less than 50 ppm, based on the total weight of the catalyst, and / or
- the mass content of ruthenium is less than 100 ppm, preferably less than 50 ppm, based on the total weight of the catalyst, and / or
- the mass content of iridium is less than 100 ppm, preferably less than 50 ppm, based on the total weight of the catalyst.
- the specific surface area of said catalyst is between 0.1 and 150 m 2 / g.
- the specific surface area of said catalyst is between 0.3 and 140 m 2 / g, preferably between 1 and 130 m 2 / g, more preferably between 2 and 120 m 2 / g, more particularly between 3 and 110 m 2. / g, preferably between 4 and 100 m 2 / g.
- Said catalyst can be obtained by mixing the various constituents thereof in the indicated mass proportions.
- the present invention provides a process for the hydrogenation of an olefin comprising at least one fluorine atom comprising contacting said olefin with hydrogen in the gas phase in the presence of the catalyst according to the present invention.
- said olefin is selected from the group consisting of 1,1,2,3,3,3-hexafluoropropene, 1,2,3,3,3-pentafluoropropene, 1,1,3,3, 3- pentafluoropropene, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,2-dichloro-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene and 2-chloro-3,3,3-trifluoropropene.
- the hydrogenation step can be carried out in the presence of a hh / olefin molar ratio of between 1 and 40, preferably of between 2 and 15.
- the hydrogenation step can be carried out at a pressure of between 0.5 and 20 bara and preferably between 1 and 5 bara.
- the catalyst may be present in any suitable form, extruded, pellets or beads.
- the hydrogenation step can be carried out under conditions such that the temperature at the inlet of the reactor is between 30 ° C. and 200 ° C., preferably between 40 ° C. and 140 ° C., and that at the outlet. the reactor is between 50 ° C and 250 ° C, preferably between 80 ° C and 160 ° C.
- the contact time (ratio between the volume of catalyst and the total gaseous flow under normal conditions of temperature and pressure) is advantageously between 0.1 and 60 seconds, preferably between 0.2 and 45 seconds, more preferably between 0.2 and 30 seconds, in particular between 0.2 and 10 seconds and more particularly between 1 and 5 seconds.
- the reactor is an adiabatic reactor.
- This hydrogenation step may be carried out in a multi-stage adiabatic reactor.
- the present process allows the formation of an alkane compound derived from the hydrogenation of the olefin comprising at least one fluorine atom, i.e. an alkane compound comprising at least one fluorine atom.
- the present process allows the formation of a stream comprising said alkane compound comprising at least one fluorine atom, unreacted olefin, unreacted hydrogen.
- the olefin can be 1,1,2,3,3,3-hexafluoropropene, 1,2,3,3,3-pentafluoropropene, 1,1,3,3,3-pentafluoropropene, 1 , 3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,2-dichloro-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene or 2-chloro-3 , 3,3-trifluoropropene.
- said alkane compound may be 1,1,1,2,3,3-hexafluoropropane, 1,1,1,2,3-pentafluoropropane, 1,1,1,3,3-pentafluoropropane, 1,1, 1,3-tetrafluoropropane, 1,1,1,2-tetrafluoropropane, 2,3-dichloro-1,1,1-trifluoropropane, 3-chloro-1,1,1-trifluoropropane or 2-chloro-1, 1, l-trifluoropropane.
- said process allows the hydrogenation of 1,1,2,3,3,3-hexafluoropropene by 1,1,1,2,3,3-hexafluoropropane or the hydrogenation of 1,2,3,3, 3-pentafluoropropene in 1,1,1,2,3-pentafluoropropane or the hydrogenation of 1,1,3,3,3-pentafluoropropene in 1,1,1,3,3-pentafluoropropane or the hydrogenation of 1, 3,3,3-tetrafluoropropene at 1,1,1,3-tetrafluoropropane or the hydrogenation of 2,3,3,3-tetrafluoropropene at 1,1,1,2- tetrafluoropropane or the hydrogenation of 1,2-dichloro-3,3,3-trifluoropropene to 2,3-dichloro-1,1,1-trifluoropropane or the hydrogenation of 1-chloro-3,3,3-trifluoropropene to 3-chloro-1,1,1,2,3,
- the present method can be implemented in continuous or discontinuous mode.
- the conversion of the olefin may be greater than 90%, advantageously greater than 91%, preferably greater than 92%, more preferably greater than 93%, in particular greater than 94%, more particularly greater than 95%, so preferred greater than 96%, more preferred greater than 97%, preferentially preferred greater than 98%, particularly preferred greater than 99%.
- the present process allows the preparation of an alkane compound comprising at least one fluorine atom and derived from said olefin comprising at least one fluorine atom with a very good selectivity.
- the alkane compound selectivity comprising at least one fluorine atom and derived from said olefin is greater than 98%, preferably greater than 98.5%, in particular greater than 99%.
- the contents of H2O, sodium, carbon, chloride, metals and the specific surface are determined by the analysis methods known to those skilled in the art.
- the water content can for example be determined by the weight loss of the catalyst at 100 ° C.
- the content of chloride, sodium and metals can be determined by ICP-OES or ICP-MS.
- the specific surface is determined by the BET method according to the common practice of those skilled in the art.
- the carbon content can be measured according to ASTM D2866.
- a stainless steel tubular reactor with an internal diameter of 2.1 cm and a length of 120 cm containing 330 cm 3 of catalyst in the form of a fixed bed is used.
- the pressure is 2 bara.
- the hydrogen / HFP molar ratio at the inlet of the reactor is 6.
- the temperature at the reactor inlet is 39.7 ° C. and the maximum temperature reached during the reaction is 110.3 ° C.
- the contact time according to the definition given above is 10.8 s. In this example, two catalysts were tested.
- the catalyst used in Example 1-1 contains 0.2% by weight of Pd / alpha-alumina and less than 100 ppm of carbon and has a specific surface area of> 4 m 2 / g.
- the catalyst used in the example 1-2 contains 0.2% by weight of Pd / alpha-alumina and 1500 ppm of carbon and has a specific surface area> 4 m 2 / g.
- Table 1 The results are shown in Table 1 below. A conversion of 100% HFP with a HFC-236ea selectivity of 99.5% in the presence of a catalyst according to the present invention is obtained against a selectivity of 98.9% with a catalyst comprising a carbon content greater than 1500. ppm. In addition, deactivation of the catalyst used in Example 1-2 is observed.
- Example 1 is repeated with a catalyst comprising 0.2% by weight of palladium supported on alpha alumina, less than 100 ppm of carbon, 50 ppm of sodium and 0.1% by weight of water. A 99.8% conversion to HFP is obtained with a HFC-236ea selectivity of 99.3%.
Abstract
Description
Claims
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FR1755585A FR3067617B1 (en) | 2017-06-20 | 2017-06-20 | ALPHA ALUMINA CATALYST AND PROCESS FOR HYDROGENATING AN OLEFIN IN THE PRESENCE THEREOF |
PCT/EP2018/066162 WO2018234261A1 (en) | 2017-06-20 | 2018-06-19 | Alpha-alumina-based catalyst and process for hydrogenation of an olefin in the presence thereof |
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EP18732066.8A Pending EP3641932A1 (en) | 2017-06-20 | 2018-06-19 | Alpha-alumina-based catalyst and process for hydrogenation of an olefin in the presence thereof |
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US (1) | US11291977B2 (en) |
EP (1) | EP3641932A1 (en) |
CN (1) | CN110769928A (en) |
FR (1) | FR3067617B1 (en) |
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US2995510A (en) * | 1958-07-10 | 1961-08-08 | Standard Oil Co | Purification of alumina |
JPS5037806A (en) * | 1973-06-27 | 1975-04-08 | ||
US5015614A (en) * | 1989-07-03 | 1991-05-14 | Exxon Research And Engineering Company | Novel alumina support materials |
US6521203B1 (en) * | 1992-06-02 | 2003-02-18 | Sumitomo Chemical Co., Ltd. | Process for producing α-alumina |
JP3605831B2 (en) * | 1992-10-05 | 2004-12-22 | ダイキン工業株式会社 | Method for fluorinating halogenated hydrocarbons |
IL109236A (en) * | 1993-04-13 | 1998-01-04 | Sumitomo Chemical Co | Alpha-alumina powder and its production |
JP3733599B2 (en) * | 1993-08-11 | 2006-01-11 | 住友化学株式会社 | Metal oxide powder and method for producing the same |
JP3632243B2 (en) * | 1994-07-28 | 2005-03-23 | 旭硝子株式会社 | Method for producing difluoroacetic acid fluoride and difluoroacetic acid ester |
AU699077B2 (en) * | 1995-02-21 | 1998-11-19 | Sumitomo Chemical Company, Limited | Alpha-alumina and method for producing the same |
FR2735487B1 (en) * | 1995-06-16 | 1997-08-22 | Inst Francais Du Petrole | PROCESS FOR THE CATALYTIC TRANSFORMATION OF HYDROCARBONS INTO AROMATIC COMPOUNDS WITH A CATALYST CONTAINING ALKALINE OR ALKALINO-EARTH METALS |
US6583328B1 (en) * | 1999-04-05 | 2003-06-24 | Pcbu Services, Inc. | Method for the preparation of 1,1,1,3,3-pentafluoropropene and 1,1,1,3,3-pentafluoropropane |
DE102005029294A1 (en) * | 2005-06-22 | 2007-01-04 | Basf Ag | New heterogeneous ruthenium catalyst comprising amorphous silicon dioxide, useful in the hydrogenation of a carbocyclic aromatic group to the corresponding carbocyclic aliphatic group |
DE102005040286A1 (en) * | 2005-08-25 | 2007-03-01 | Basf Ag | Mechanically stable catalyst based on alpha-alumina |
CN101516782B (en) * | 2006-09-19 | 2011-11-16 | 住友化学株式会社 | Alpha-alumina powder |
TW200837036A (en) * | 2006-11-15 | 2008-09-16 | Du Pont | Process for producing 2,3,3,3-tetrafluoropropene |
JP4997953B2 (en) * | 2006-12-15 | 2012-08-15 | 日本軽金属株式会社 | Method for producing high purity α-alumina |
FR2946645B1 (en) * | 2009-06-12 | 2011-07-01 | Arkema France | PROCESS FOR PRODUCING HEXAFLUOROPROPANE |
FR2946644B1 (en) * | 2009-06-12 | 2011-10-14 | Arkema France | PROCESS FOR PRODUCING PENTAFLUOROPROPANE |
US20110028770A1 (en) * | 2009-08-03 | 2011-02-03 | Honeywell International Inc. | Hydrogenation catalyst |
US8158549B2 (en) * | 2009-09-04 | 2012-04-17 | Honeywell International Inc. | Catalysts for fluoroolefins hydrogenation |
RU2562460C2 (en) * | 2010-07-20 | 2015-09-10 | Басф Се | Method of obtaining acetylene by sachsse-bartholomé method |
TW201247315A (en) * | 2011-05-16 | 2012-12-01 | Du Pont | Catalytic hydrogenation of fluoroolefins, alpha-alumina supported palladium compositions and their use as hydrogenation catalysts |
CN104945221B (en) * | 2015-06-11 | 2017-07-18 | 浙江衢州巨新氟化工有限公司 | A kind of method of the tetrafluoropropene of coproduction 2,3,3,3 and 1,3,3,3 tetrafluoropropenes |
-
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US11291977B2 (en) | 2022-04-05 |
FR3067617B1 (en) | 2019-07-19 |
US20200206720A1 (en) | 2020-07-02 |
CN110769928A (en) | 2020-02-07 |
WO2018234261A1 (en) | 2018-12-27 |
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