WO2004035204A1 - Nickel catalyst for hydrogenation reactions - Google Patents
Nickel catalyst for hydrogenation reactions Download PDFInfo
- Publication number
- WO2004035204A1 WO2004035204A1 PCT/NL2003/000705 NL0300705W WO2004035204A1 WO 2004035204 A1 WO2004035204 A1 WO 2004035204A1 NL 0300705 W NL0300705 W NL 0300705W WO 2004035204 A1 WO2004035204 A1 WO 2004035204A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- nickel
- atomic ratio
- magnesium
- oil
- Prior art date
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 138
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011777 magnesium Substances 0.000 claims abstract description 34
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 19
- 239000003921 oil Substances 0.000 claims description 19
- 235000019198 oils Nutrition 0.000 claims description 19
- 230000001681 protective effect Effects 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 239000011241 protective layer Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012018 catalyst precursor Substances 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 9
- 235000021323 fish oil Nutrition 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000003549 soybean oil Substances 0.000 claims description 7
- 235000012424 soybean oil Nutrition 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 4
- 235000019482 Palm oil Nutrition 0.000 claims description 3
- 235000019486 Sunflower oil Nutrition 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000002540 palm oil Substances 0.000 claims description 3
- 239000002600 sunflower oil Substances 0.000 claims description 3
- 239000002385 cottonseed oil Substances 0.000 claims 1
- 235000012343 cottonseed oil Nutrition 0.000 claims 1
- 239000003925 fat Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 235000019197 fats Nutrition 0.000 description 11
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 235000010469 Glycine max Nutrition 0.000 description 5
- 244000068988 Glycine max Species 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011253 protective coating Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000010685 fatty oil Substances 0.000 description 3
- 235000021588 free fatty acids Nutrition 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000007420 reactivation Effects 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- -1 AICI3 Chemical class 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 235000021081 unsaturated fats Nutrition 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
- C11C3/123—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on nickel or derivates
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- 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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- 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
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J37/03—Precipitation; Co-precipitation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/392—Metal surface area
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- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/615—100-500 m2/g
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- 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
- B01J35/635—0.5-1.0 ml/g
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- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- 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
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1018—Biomass of animal origin
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/703—Activation
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- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Definitions
- the invention relates to a catalyst comprising nickel, alumina magnesium and silica, to a method for preparing such a catalyst and to a process for hydrogenating unsaturated organic compounds.
- Nickel/alumina catalysts with a nickel/aluminium ratio of 2-20 are known to be active catalysts for the hydrogenation of unsaturated organic compounds from EP-A 0 167 201.
- the catalysts claimed in EP-A 0 167 201 further comprise silica in a nickel/silica ratio of 1-20.
- the disclosed catalysts are prepared in a process wherein first a nickel hydroxide/carbonate is precipitated and thereafter aluminium nitrate and silicate are added. The resulting precipitate is thereafter activated with hydrogen.
- the examples show catalysts comprising at least 85 wt. % Ni that are used in the hydrogenation of fish oil. It is reported that they may retain their activity for a prolonged period and tend to show a high poison resistance.
- EP-A 1 101 530 describes a nickel-iron catalyst for use in the hydrogenation of resins. Magnesium (oxide) may be present. This publication does not recognise the relevance of the particle size with respect to the hydrogenation of unsaturated compounds and the working examples do not mention the particle size of the used catalyst. It is not suggested to use the catalyst in the hydrogenation of fatty substances, such as vegetable or animal oils.
- US-A 5 493 037 relates to a fixed bed process for hydrogenating fatty acids, comprising the use of a formed nickel catalyst with a relatively low nickel content. Contents of 10-50 wt. % are mentioned, without specifying how the weight percentage is defined.
- a magnesium salt may be present as a support or in the binder (clay). The publication is silent about suitable pore volumes and nickel surface areas.
- the present invention relates to a catalyst comprising nickel, silica, alumina and magnesium, wherein the nickel to magnesium atomic ratio is 5-75, preferably 5-50.
- magnesium is thought to act as a catalyst promotor in the hydrogenation of unsaturated hydrocarbons, in particular fatty substances, as is indicated by the Examples 1 and 2, below.
- the present invention relates to a catalyst comprising nickel, silica, alumina and magnesium, wherein the nickel to silicium atomic ratio (Ni/Si) is 2 to 30, the nickel to aluminium atomic ratio (Ni/Al) is 9 to 40 and the nickel to magnesium atomic ratio (Ni/Mg) is 5-75.
- a catalyst according to the present invention shows a very high activity for the hydrogenation of unsaturated compounds, in particular unsaturated fatty substances, such as fatty oils including unsaturated fats. These oils typically mainly comprise glycerides, in particular triglycerides.
- the invention may very suitably be employed for the hydrogenation of fatty substances of vegetable and/or animal origin for food grade applications.
- a catalyst according to the invention has been found to have a very high activity as a hydrogenation catalyst.
- a catalyst according to the invention is found to be highly active for relatively clean oils - i.e. oils with a relatively low sulphur content - like soy bean, as well as for more contaminated oils, like fish oil, having a high sulphur content.
- a catalyst according to the invention may very suitably be used in a slurry process. Accordingly the present invention also relates to a slurry comprising a catalyst according to the invention.
- the skilled person will know how to make a suitable slurry based upon common general knowledge and the information disclosed herein. For instance, as a liquid phase the feed stock to be processed is very suitable.
- the total weight percentage of Ni in the reduced catalyst may be chosen in a wide range, as defined by the Ni Si, Ni/Al and Ni/Mg ranges.
- the amount of nickel is at least 50 wt. % and not higher than 80 wt. %, more preferably 51-80 wt. %. Even more preferably the amount of nickel is 55-75 wt.%. Very good results have been achieved with an amount of nickel of 65-72 wt.%.
- Ni/Si is at least about 2.5, more preferably at least about 3. Very good results have been achieved with a Ni/Si of at least 6.5.
- Ni/Si is preferably about 22 or less, more preferably about 15 or less. Very good results have been achieved with a Ni/Si of up to about 7.5. Ni/Al is preferably about 10 to about 35, more preferably about 10- 30, even more preferably about 15-25. Very good results have been achieved with a catalyst having a Ni/Al of more than 20, e.g. up to 22.
- Ni/Mg may preferably be chosen in the range of about 5-50, more preferably 5-30, even more preferably about 6 to about 20. Very suitable is a catalyst with a Ni/Mg of about 7.5-12.5, e.g. about 10.
- a catalyst of the invention which is essentially free of iron (typically having less than 0.1 % Fe).
- the protective layer may have any form, wherein at least the catalytically active sites of the catalyst are essentially covered with a protective material. Protection of the catalyst is in principle possible by applying a layer of oxide on the catalyst, in particular on the nickel (crystallites).
- a method for applying a suitable film of oxide is known in generally known in the art, and may be based on DE19909175.
- the oxide may suitably be removed shortly before use. The skilled person will know how to remove (e.g. by reactivation) the oxide, based upon a known method for reactivating known nickel catalysts on a support (e.g. on alumina, silica or a combination thereof).
- a highly suitable protective material for protecting a catalyst is a material comprising a fatty substance, preferably a hardened oil or fat, more preferably a hardened vegetable oil or fat. Very good results have been achieved with a catalyst coated with hardened soy bean fat. Other highly preferred examples of fatty substances include hardened palm oil fat, hardened sunflower oil and hardened rapeseed oil. A mixture comprising a number of fatty substances may very suitably be used.
- An advantage of a protective material comprising a fatty substance instead of a thin film of oxide on the catalyst is that the catalyst does not need to be re-activated before use. At a high temperature (e.g.
- re-activation of a catalyst with a protective oxide film may take a relatively long time, resulting in a longer overall reaction time, or may not take place to a sufficient extent at all.
- the protective material forming a protective layer may be provided around individualised particles, or at least on the catalytically active part thereof (in particular in case a layer of oxide).
- a multiplicity of catalyst particles may be incorporated (in particular dispersed) into the protective material forming the protective layer.
- the protective material with catalyst particles incorporated therein may very suitably be in the form of a p articulate material.
- Such particulate material is also referred to herein as matrix particles.
- the size of the matrix particles is not particularly critical. Conveniently, matrix particles may for instance have a size (as defined by the diameter of the enveloping circle) in the range of about 1 to about 12 mm, more in particular in the range of about 2-10 mm.
- the size of the catalyst particles incorporated therein is usually at least about one or two orders of magnitude less than the matrix particles.
- a preferred size of the catalyst particles is as the preferred particle diameters defined below .
- the amount of protective material is preferably at least about 40 wt. %, more preferably at least about 55 wt. % even more preferably at least about 60 wt. %. Very good results have been achieved with an amount of at least 65 wt. %. (All wt. %'s based upon the total weight of catalyst plus protective material).
- the amount of protective material is less than about 95 wt. %, more preferably less than about 90 wt.%, even more preferably less than about 85 wt. %. Very good results have been achieved with a weight percentage of up to about 82 wt. % (All wt. %'s based upon the total weight of catalyst plus protective material).
- the melting temperature of the protective material with which the catalyst is coated is preferably less than the temperature at which the hydrogenation is carried out, in order to facilitate dissolution of the protective material at the beginning of a hydrogenation process in accordance with the invention.
- Good results have inter alia been achieved with a protective material have a melting temperature of less than about 90 °C, more in particular of less than about 85 °C. Very good results have been achieved with a melting temperature of less than 80 °C.
- the minimum melting temperature of the protective material is in general higher than the temperature at which the catalyst is stored before use.
- the melting temperature is at least about 40 °C, more preferably at least about 50 °C.
- the protective coating when the catalyst is used in a slurry process, the protective coating will preferably dissolve in the feedstock. Else, the coating may be removed from the process, shortly before using the catalyst in a hydrogenation process. The coating may very suitably be removed by contacting the catalyst with a solvent, such as a feedstock, preferably at a temperature higher than the melting point of the coating fat.
- the pore volume (as measured by N 2 desorption, 20-600 A, on a Quantachrome Autosorb 6) is preferably at least 0.4 ml/g, more I preferably at least 0.5 ml g, even more preferably at least 0.55 ml g.
- the upper limit is not particularly critical. Very good results have been achieved in the range of 0.4 to 1 ml/g. More preferably, the pore volume is up to about 0.75 ml/g, e.g. 0.6-0.7 ml/g.
- the volume average particle size (D(v.0,5)) of a catalyst according to the invention may be chosen in a wide range, inter alia depending upon the intended use, in particular if the catalyst is provided with a protective coating.
- a catalyst with a D(v.0,5) of less than about 20 ⁇ m.
- the volume average particle size is preferably at least about 1 ⁇ m, more preferably at least about 2 ⁇ m, even more preferably at least about 3.
- a volume average particle size in the range of about 3 to about 8 ⁇ m has been found to be highly advantageous.
- a catalyst with a higher average particle size e.g. 8.6 ⁇ m
- such a catalyst has been found to have a higher activity with respect to hydrogenation of a unsaturated organic compound, especially a fatty substance.
- Very good results have been achieved with a catalyst having a volume average particle size of about 4 to about 7 ⁇ m.
- D(v.0,5) is the value as measured by LASER diffraction with a Malvern MS 1002, lens 45 mm - which corresponds to a measuring range of 0.1-100 ⁇ m - using "Independent" as the model for calculating the particle size.
- the (D(v.0,5)) as used herein is the diameter of the catalyst . per se, i.e. without a protective coating.
- the catalyst preferably comprises nickel crystallites.
- the majority of the nickel crystallites preferably has a diameter of less than 60 A, more preferably of about 20-50 A, even more preferably of about 20-40 A.
- the size as used herein is the value as determinable by XRD on the reduced catalyst protected by a coating of a fatty substance (such as hardened soybean fat) (See also Examples).
- the nickel surface area is preferably 75 to 200 m 2 /g of nickel, more preferably approximately 100-175 m 2 /g of nickel, even more preferably approximately 100-150 m 2 /g of nickel. Very good results have been achieved with a catalyst having a nickel surface area of 110-145 m 2 /g of nickel.
- the nickel surface area as used herein is the value as can be determined by hydrogen chemisorption at 50 °C, after in situ reduction with hydrogen (60 ml/min) for 2 hours at 400 °C and subsequently degassing for 14 hours at 350 °C in a Carlo Erba Sorptomatic 1900. The amount of adsorbed hydrogen is determined by extrapolation of the reduction isotherm to zero pressure and the nickel surface area is calculated assuming a site density of 6.77 A 2 /atom.
- the BET surface area preferably is about 300 to about 450 m 2 /g catalyst, more preferably about 350 to about 400 m 2 /g catalyst.
- the BET surface area as used herein is the value that can be measured by determining the amount of nitrogen adsorbed at 77 K and P/Po of approximately 0.3 and assuming a nitrogen cross sectional area of 16.2 A 2 , after degassing the catalyst sample at 180 °C.
- the catalyst is made from a catalyst precursor that is prepared by co-precipitation, of which it will be clear to the skilled professional how to choose suitable method conditions.
- nickel, alumina, silica and magnesium are precipitated together (i.e. without forming intermediate precipitates of only one or some of the components).
- a nickel source, a silica source, an alumina source and a magnesium source may be mixed in a liquid (e.g. water or an aqueous solution) to form a precipitate (a catalyst precursor), comprising all four said components.
- the co-precipitation is carried out with the aid of a precipitant, e.g. an alkali metal carbonate (such as Na 2 CO3) or an alkali metal hydroxide (such as NaOH).
- a precipitant e.g. an alkali metal carbonate (such as Na 2 CO3) or an alkali metal hydroxide (such as NaOH).
- the precipitation is carried out at a temperature in the range of 20-100 °C .
- Very good results have been achieved at a temperature in the range of 50-100 °C, in particular at a temperature in the range of 75-98 °C.
- the catalyst precursor may thereafter be isolated, e.g. by filtration, from the liquid and calcined, e.g. at a temperature of 200-750 °C for 1-5 hours.
- the catalyst may very suitably be activated by reduction with hydrogen, e.g. at a temperature of 250-600 °C, e.g. for 1-5 hours.
- the nickel, silica, alumina and magnesium sources may be chosen from sources commonly used to prepare catalysts.
- Suitable nickel sources include inorganic nickel salts, preferably Ni(NO 3 )2, NiCl 2 , NiSO , and organic nickel salts, preferably nickel acetate.
- the nickel source is a solution or suspension of any of these salts.
- Suitable silica sources include water glass, sodium silicate (Na2Si0 3 ) and colloidal silica.
- the silica source is a solution or suspension of any of these components.
- Suitable alumina sources include aluminium salts, preferably inorganic salts such as AICI3, A1(N0 3 )3 and sodium aluminate (NaAl ⁇ 2).
- the alumina source is a solution or suspension of any of these salts.
- Suitable magnesium sources include magnesium salts, preferably inorganic salts such as Mg(NO 3 )2 , MgC , and MgSO .
- the magnesium source is a solution or suspension of any of these salts.
- the catalyst may be coated with a protective layer, e.g. a fatty substance such as hardened soy bean fat, hardened palm oil fat, hardened sun flower oil fat or a combination thereof, which may serve to avoid oxidation of (parts of) the catalyst (see also above).
- a protective coating based upon common general knowledge and the information disclosed herein. This may for example be done by blending a (reduced) catalyst powder into the molten coating material (such as the molten fat) and subsequently solidifying the resulting suspension to form flakes or droplets of coated catalyst particles. For instance, one may let droplets of the suspension fall on a surface having a temperature below the melting temperature of the fatty substance (such as a cooled plate) thereby solidifying the droplets to form matrix particles. Such method is very suitable for preparing particles generally having an essentially hemispherical shape. Another way to produce matrix particles is to let the droplets fall in a fluid (generally cooled fluid) wherein the particles solidify. Thus more or less spherical matrix particles may be formed. It is also an option to flake the suspension to flakes of a suitable thickness.
- a (reduced) catalyst powder into the molten coating material (such as the molten fat) and subsequently solidifying the resulting suspension to form flakes or droplets of coated
- a catalyst according to the present invention may be used for a variety of applications, and in particular for catalytic hydrogenation.
- the catalyst may be employed in a process for hydrogenating organic compounds wherein said compound is contacted with hydrogen in the presence of the catalyst.
- the process conditions may be chosen from the processes typically used for the hydrogenation of a particular compound.
- the process may be a batch or a continuous process.
- the process is a slurry-process.
- An important advantage of a hydrogenation process according to the invention is the possibility to decrease the dosage of catalyst in order to achieve a particular conversion within the same hydrogenation time (contact time of feed (substrate) and catalyst) or to reduce the hydrogenation time at a particular catalyst dosage.
- a process according to the invention has been found to be particularly suitable for the hydrogenation of a relatively clean oil (e.g. soy bean oil) and/or a more contaminated oil (e.g. fish oil or rape seed oil).
- a relatively clean oil e.g. soy bean oil
- a more contaminated oil e.g. fish oil or rape seed oil
- a fatty substance hydrogenated in accordance with the present invention preferably mainly comprises triglycerides, such that the content of free fatty acids is quite low.
- a preferred feed stock hydrogenated in accordance with the invention such as a fully refined vegetable or animal oils
- usually less than about 0.1 wt.% free fatty acids and preferably less than 0.05 wt.% is present. Since high concentrations of free fatty acids may deactivate the catalyst by nickel soap formation, their presence is preferably below said levels.
- contaminations such as sulphur in the contaminated oil.
- the selectivity has been found to remain high enough to achieve a favourable conversion of the unsaturated compounds.
- the present invention also offers a considerable advantage since it offers the advantage that a single type of catalyst can very favourably be used in the hydrogenation of contaminated oil and also in the hydrogenation of clean oil. Thus a single stock of catalyst may be kept for the conversion of either of these products.
- a metal solution (1000 ml) containing 95 g Ni/1 and 5g Mg/1 was prepared from a NiCk solution (198 g Ni/1) and MgC . ⁇ EbO.
- the base solution was prepared by dissolving 183 g Na 2 CO3 and 44.4 g Na2Si ⁇ 3.5H2 ⁇ in 1000 ml of demineralised water.
- the metal and base solution were injected at equal flow rates (1000 ml/hr) into a well stirred precipitation vessel containing 1725 ml of demineralised water and 3.8 g of AI2O3 as sodium aluminate.
- the temperature during precipitation was maintained at 95 °C while the pH was between 7.5 and 8.5.
- the precipitate was washed with demineralised water and dried overnight at 110 °C.
- the dried catalyst was calcined for 1.5 hours at 375 °C and subsequently activated by reduction in hydrogen for 2 hours at 400 °C.
- the reduced catalyst powder was protected from air oxidation by dispersing it in an inert atmosphere in molten, hardened soybean fat at 80- 100 °C. Catalyst flakes were formed by solidifying the blend of reduced catalyst powder and coating fat on a cooling plate.
- the catalyst properties of the calcined sample are as summarised in Table 1.
- the catalyst of Example 2 was prepared according the procedure as described in Example 1, except that no magnesium was added.
- Example 3 The catalyst of Example 3 was prepared according the procedure as described in Example 1, except that no alumina was added. Examples 4 and 5
- Example 4 The catalysts of Examples 4 and 5 were prepared according to the procedure as described in Example 1, except that variations were made in the amount of starting materials resulting in catalyst properties as indicated in Table 1.
- the catalyst of Examples 6 and 7 were prepared according to the procedure as described with example 1, except that magnesium was replaced by copper and cobalt respectively.
- the catalyst of Example 8 was prepared according to the procedure as describedin Example 1 except that a different agitation speed was used during the precipitation, (an agitation speed of 400 instead of 475 rpm was used).
- the pore volume and BET surface area of the catalysts were measured by nitrogen adsorption/desorption using a Quantachrome Autosorb-6. Particle size was determined by laser diffraction using a Malvern Mastersizer 1002. The nickel surface area was measured by hyrogen chemisorption with a Carlo Erba Sorptometic 1900.
- the nickel crystallite size was measured with a Phillips DW1820 rontgen diffractometer using the Ni(lll) peak (d-value 2.06 A).
- the soy bean oil (SBO) hydrogenating activity of the catalysts was determined by the hydrogenation of 500 g of soybean oil (iodine value 130) and measuring the time needed to reach an iodine value of 70.
- the catalyst loading was 0.0075% as nickel, the hydrogen pressure was 0.7 bar and the temperature was 204 °C.
- the iodine value was measured by the Wijs method as described in A.O.C.S. Official Method Cd 1-25 (1990).
- the fish oil (FO) hydrogenation activity of the catalysts was determined by the hydrogenation of 500 g of fish oil (iodine value 160) at 180 °C, 2 bar hydrogen pressure and a nickel loading of 0.031%. The activity is expressed as the time in minutes required to reach an iodine value (IV) of 115. The iodine value was measured by the Wijs method.
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Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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US10/531,782 US7528092B2 (en) | 2002-10-18 | 2003-10-17 | Nickel catalyst for hydrogenation reactions |
AU2003272148A AU2003272148A1 (en) | 2002-10-18 | 2003-10-17 | Nickel catalyst for hydrogenation reactions |
BR0315407-6A BR0315407A (en) | 2002-10-18 | 2003-10-17 | Catalyst, method for preparing same, and processes for hydrogenating an unsaturated organic compound and an unsaturated grease |
MXPA05003990A MXPA05003990A (en) | 2002-10-18 | 2003-10-17 | Nickel catalyst for hydrogenation reactions. |
CA2502579A CA2502579C (en) | 2002-10-18 | 2003-10-17 | Nickel catalyst for hydrogenation reactions |
EP03754310A EP1551550A1 (en) | 2002-10-18 | 2003-10-17 | Nickel catalyst for hydrogenation reactions |
US12/411,484 US8207083B2 (en) | 2002-10-18 | 2009-03-26 | Nickel catalyst for hydrogenation reactions |
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EP02079362 | 2002-10-18 | ||
EP02079362.6 | 2002-10-18 |
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US12/411,484 Division US8207083B2 (en) | 2002-10-18 | 2009-03-26 | Nickel catalyst for hydrogenation reactions |
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US (2) | US7528092B2 (en) |
EP (2) | EP3195931A1 (en) |
KR (1) | KR20050072109A (en) |
CN (1) | CN1705514A (en) |
AU (1) | AU2003272148A1 (en) |
BR (1) | BR0315407A (en) |
CA (1) | CA2502579C (en) |
MX (1) | MXPA05003990A (en) |
PE (1) | PE20040285A1 (en) |
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Also Published As
Publication number | Publication date |
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RU2330718C2 (en) | 2008-08-10 |
AU2003272148A1 (en) | 2004-05-04 |
US7528092B2 (en) | 2009-05-05 |
US8207083B2 (en) | 2012-06-26 |
US20090182181A1 (en) | 2009-07-16 |
CA2502579C (en) | 2011-09-20 |
BR0315407A (en) | 2005-08-16 |
US20060100452A1 (en) | 2006-05-11 |
CA2502579A1 (en) | 2004-04-29 |
KR20050072109A (en) | 2005-07-08 |
RU2005115095A (en) | 2006-01-20 |
CN1705514A (en) | 2005-12-07 |
EP3195931A1 (en) | 2017-07-26 |
EP1551550A1 (en) | 2005-07-13 |
PE20040285A1 (en) | 2004-07-16 |
MXPA05003990A (en) | 2005-08-03 |
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