CN104726126A - 使用第一金属催化剂和第二经硫化的催化剂的来自可再生来源的进料的两步氢化处理 - Google Patents
使用第一金属催化剂和第二经硫化的催化剂的来自可再生来源的进料的两步氢化处理 Download PDFInfo
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- CN104726126A CN104726126A CN201410810495.4A CN201410810495A CN104726126A CN 104726126 A CN104726126 A CN 104726126A CN 201410810495 A CN201410810495 A CN 201410810495A CN 104726126 A CN104726126 A CN 104726126A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 59
- 239000002184 metal Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 35
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 238000011282 treatment Methods 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- -1 VIB metals Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 4
- 239000008158 vegetable oil Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 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
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 2
- 235000014593 oils and fats Nutrition 0.000 claims description 2
- 150000003626 triacylglycerols Chemical class 0.000 claims description 2
- 125000005457 triglyceride group Chemical group 0.000 claims description 2
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- 239000003925 fat Substances 0.000 description 4
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- 238000000926 separation method Methods 0.000 description 4
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241001133760 Acoelorraphe Species 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000020551 Helianthus annuus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000008116 organic polysulfides Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004313 potentiometry Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
- C07C1/2078—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)-O- moiety is eliminated
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
- C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating 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
- C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
- C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
-
- 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
-
- 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
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
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Abstract
本发明描述一种来自可再生来源的进料的两步氢化处理方法，包括：a)第一步，称作温和预氢化步骤，在第一金属催化剂存在下进行，所述第一金属催化剂包括由至少一种VIII族金属和/或至少一种VIB族金属构成的活性氢化脱氢相和无定形无机载体；和b)第二步，称作第二处理步骤，在第二经硫化的催化剂存在下进行，所述第二经硫化的催化剂包括由至少一种VIII族非贵金属和/或至少一种VIB族金属构成的活性氢化脱氢相和无定形无机载体。
Description
本申请是申请日为2008年6月3日，申请号为200880019801.5，发明名称为“使用第一金属催化剂和第二经硫化的催化剂的来自可再生来源的进料的两步氢化处理”的发明专利的分案申请。
技术领域
石油产品的稀缺和成本的增加驱使对取代物的追寻。本文中，来自生物质的产品占据入选位置。目前，生物质的使用主要采取两个途径：生物酯途径，在加入汽油库(gas oil pool)之前将植物油转化为甲酯；和乙醇途径，在加入汽油库之前将糖和淀粉转化为乙醇或ETBE(乙基叔丁基醚)。
目前，与化石燃料相比，这种生物产品的生产成本仍然较高，并且由于显著的财政激励，它们仅具有经济利益。
此外，据专家所说，可耕种土地的可用性将不能允许超过待生产的燃料的当前消耗的10％。
相反，可以在各种工业，例如食品工业或石化工业中使用的高纯度正链烷的生产涉及吨位比燃料所需的那些低得多。此外，这种产品的生产可以证明是比对于燃料更加有利。
因此，在此所述的本发明属于生产碳原子数为6至25，优选10至24并且优选用于生产汽油或煤油的高纯度正链烷的范围。
一方面，本发明提供一种两步氢化处理来自可再生来源的进料的方法，包括：
a)第一步，称作温和预氢化步骤，其在第一金属催化剂存在下进行，所述第一金属催化剂包括由至少一种VIII族金属和/或至少一种VIB族金属构成的活性氢化脱氢相(phase active hydrodeshydrogenante)和无定形无机载体，其在50℃至300℃的温度、0.1至10MPa的氢分压和0.1h-1至10h-1对催化剂的时空速率下进行；和
b)第二步，称作第二处理步骤，其在第二经硫化的催化剂存在下进行，所述第二经硫化的催化剂包括由至少一种VIII族非贵金属和/或至少一种VIB族金属构成的活性氢化脱氢相和无定形无机载体，其在200℃至450℃的温度、1MPa至10MPa的压力、0.1h-1至10h-1对催化剂的时空速率下进行，其中与进料混合的氢气的总量使得氢气对进料比率为每m3进料有50至1000Nm3的氢气。
本发明的一个优点为可以提供由氢化的选择活性更高并允许该步在较低温度进行的第一金属催化剂，随后可使氢化产率最大的第二经硫化的催化剂构成的串联方法。
发明描述
现已找到一种氢化处理来自可再生来源的进料的两步方法，包括：
a)第一步，称作温和预氢化步骤，其在第一金属催化剂存在下进行，所述第一金属催化剂包括由至少一种VIII族金属和/或至少一种VIB族金属构成的活性氢化脱氢相和无定形无机载体，其在50℃至300℃的温度、0.1至10MPa的氢分压和0.1h-1至10h-1对催化剂的时空速率下进行；和
b)第二步，称作第二处理步骤，其在第二经硫化的催化剂存在下进行，所述第二经硫化的催化剂包括由至少一种VIII族非贵金属和/或至少一种VIB族金属构成的活性氢化脱氢相和无定形无机载体，其在200℃至450℃的温度、1MPa至10MPa的压力、0.1h-1至10h-1对催化剂的时空速率下进行，其中与进料混合的氢气的总量使得氢气对进料比率为每m3进料有50至1000Nm3的氢气。
根据本发明方法的步骤a)，第一金属催化剂包括由至少一种VIII族金属和/或至少一种VIB族金属构成的活性氢化脱氢相，VIII族金属优选选自镍和钴，钯和铂；更优选VIII族金属为镍，VIB族金属优选选自钼和钨；更优选VIB族金属为钼。
有利地使用以下金属的组合：镍-钼和钴-钼。
根据本发明方法的步骤a)的高度优选实施方案，在被称为温和预氢化步骤的第一步中使用的所述第一金属催化剂包括无定形无机载体和由至少一种VIII族金属构成的活性氢化脱氢相，该VIII族金属为镍。
VIII族贵金属或非贵金属的量有利地为0.5重量％至20重量％，优选为5重量％至10重量％，相对于催化剂的总质量。VIB族金属的量有利地为0.5重量％至20重量％，优选为7重量％至17重量％，相对于催化剂的总质量。
根据本发明方法的步骤a)的高度优选实施方案，在被称为温和预氢化步骤的第一步中使用的所述第一金属催化剂包括选自氧化铝、二氧化硅和二氧化硅-氧化铝的无定形无机载体。
根据本发明的方法，第一步，称作温和预氢化步骤，其在第一金属催化剂存在下进行，所述第一金属催化剂包括由至少一种VIII族金属和/或至少一种VIB族金属构成的活性氢化脱氢相和无定形无机载体，该第一步之后为第二步，称作第二处理步骤，其在第二经硫化的催化剂存在下进行，所述第二经硫化的催化剂包括由至少一种VIII族非贵金属和/或至少一种VIB族金属构成的活性氢化脱氢相和无定形无机载体。
根据本发明方法的步骤b)的优选实施方案，所述第二经硫化的催化剂包括由至少一种VIII族非贵金属和/或至少一种VIB族金属构成的活性氢化脱氢相，VIII族非贵金属优选选自镍和钴，优选VIII族非贵金属为镍，以及VIB族金属优选选自钼和钨；优选VIB族金属为钼。
根据本发明方法的步骤b)的高度优选实施方案，在被称作第二处理步骤的第二步中使用的所述第二经硫化的催化剂包括无定形无机载体和由至少一种VIII族非贵金属和至少一种VIB族金属构成的活性氢化脱氢相，该VIII族非贵金属为镍，VIB族金属为钼。
所述第二经硫化的催化剂中的VIB族金属和VIII族金属的氧化物的总量有利地为5重量％至40重量％，和优选7重量％至30重量％，相对于催化剂的总质量。
在所述第二经硫化的催化剂中的一种或多种VIB族金属比一种或多种VIII族金属之间的以金属氧化物表示的重量比有利地为20比1，和优选为10比2。
本发明方法的步骤b)中使用的优选的第二经硫化的催化剂有利地包括，在无定形无机载体上，0.5重量％至10重量％，优选1重量％至5重量％的氧化镍(NiO)含量，和1重量％至30重量％，优选5重量％至25重量％的氧化钼(MoO3)含量，所述百分比用相对于催化剂总质量的重量％来表示。
根据本发明方法的步骤b)的优选实施方案，所述第二经硫化的催化剂包括至少一种选自磷、硅、氟和硼的掺杂元素，所述元素的氧化物的掺杂元素量按重量计低于20％，优选低于10％，相对于催化剂总质量。
该掺杂元素可以有利地被引入基体中，或者优选沉积在载体上。也可以将硅单独地或者与磷和/或硼和/或氟一起沉积在载体上。
根据本发明方法的步骤b)的优选实施方案，所述第二经硫化的催化剂包括选自单独使用的或以混合物形式使用的氧化铝、二氧化硅、二氧化硅氧化铝、氧化镁和粘土的无定形无机载体。所述载体也可以有利地包括其它化合物，例如选自单独使用的或以混合物形式使用的氧化硼、氧化锆、氧化钛和磷酸酐的氧化物。
高度优选使用氧化铝载体，和更优选使用η、δ或γ氧化铝载体。
根据本发明方法的步骤b)，所述第二催化剂为经硫化的催化剂；因此建议使其与在反应温度下在氢气存在下足以防止脱硫的分压的H2S保持接触。为此目的，和在常规方式中，将硫化氢或在第二步条件下分解成为H2S的至少一种含硫化合物加入到进料中或者直接加入到反应器中。
可以列举的含硫化合物的实例为二甲基二硫化物(DMDS)、二硫化碳(CS2)、有机多硫化合物、硫醇、硫化物、二硫化物、含氧硫化合物和溶解的和/或部分悬浮的元素硫。
根据本发明方法的优选实施方案，第一步，称作温和预氢化步骤，其在第一金属催化剂存在下进行，所述第一金属催化剂包括氧化铝载体和由至少一种VIII族金属构成的活性氢化脱氢相，该VIII族金属为镍，和第二步，称作第二处理步骤，其在第二经硫化的催化剂存在下进行，所述第二经硫化的催化剂包括氧化铝载体和由至少一种VIII族非贵金属和至少一种VIB族金属构成的活性氢化脱氢相，该VIII族非贵金属为镍，VIB族金属为钼。
本发明氢化处理方法中使用的来自可再生来源的进料有利地由动物或植物来源的油和脂肪，或此类进料的混合物构成，其包含甘油三酸酯和/或脂肪酸和/或酯。可以被包括的可能植物油为来自以下植物的未精制的或者完全或部分精制油：油菜籽、葵花、大豆、棕榈、棕榈-坚果、橄榄、椰子；该名单并非限制性的。可以列举的可能脂肪为任何动物脂肪，例如猪油或者由来自食品工业的剩余物组成的脂肪或来自餐馆业的脂肪。
在此定义进料包含甘油三酸酯结构和/或脂肪酸及其酯，具有包含6至25个碳原子的脂肪链。
这些进料实际上或完全不含有含硫和含氮化合物并且不含芳族烃。
有利地，在本发明的两步氢化处理方法之前，进料可以经历预处理或预精制步骤，以便通过适当的处理消除例如在离子交换树脂上的污染物，例如金属、碱性化合物、碱土和磷。
适当处理的实例为本领域技术人员公知的热处理和/或化学处理。
根据本发明的氢化处理方法的一个优选实施方案，所述方法的第一步，所述温和预氢化步骤包括温和预氢化所述进料的脂肪酸烃链中包含的双键的至少50％，优选至少80％，更优选至少90％，随后为第二处理步骤，包括氢化所述进料的脂肪酸烃链中包含的酯官能团的至少50％，优选至少80％的双键，更优选至少90％的酯官能团和更优选至少99％的酯官能团。
烃链的双键可以使用一些分析方法分析：
·测量碘值，包括测量能够键合至烃链不饱和键的二碘(I2)的量。测量值因此用键合至100g产物的I2的mg来表示。应用于脂肪酸，碘值例如对于油酸为90，对于亚油酸为181，和对于亚麻酸为274。使用标准方法EN 14111测量植物油的甲基酯(MEVO)的碘值。可以列举的其它标准方法为ASTM D 1959和ASTM D 5554法。
·使用电位测定法测量溴指数或溴值。溴指数适用于含量低于1000mg/100g的产物，其使用标准的ASTM D 2710。溴值关注使用标准ASTM D 1159，用电位测定法分析含量超过1g/100g的产物。
使用红外光谱法证明酯官能团的存在。该方法的原理在于存在对于酯官能团特定的红外谱带。酯官能团的氢化由此导致在红外线中检测的特定谱带消失。
由温和预氢化组成的处理所述进料的第一步是用来使进料的脂肪酸烃链中包含的双键饱和，以避免双键的副反应，例如导致形成焦炭或胶的聚合反应。该第一预氢化步骤有利地在上述第一金属催化剂存在下，在50℃至300℃的温度，优选50℃至200℃，和更优选100℃至200℃和0.1MPa至10MPa的氢分压下进行。对催化剂的时空速率为0.1h-1至10h-1。
该温和预氢化步骤期间消耗的氢气量为相对于进料的0.5重量％至1重量％的氢气。
该第一温和预氢化步骤的流出液然后在所述进料的第二处理步骤中与上述第二经硫化的催化剂接触，所述第二处理步骤在200℃至450℃，优选220℃至350℃的温度下进行。压力为1MPa至10MPa，优选2MPa至6MPa。对催化剂的时空速率为0.1h-1至10h-1。进料在氢气存在下与催化剂接触。与进料混合的氢气的总量使得氢气对进料的比率为每m3进料有50至1000Nm3氢气，优选每m3进料有100至500Nm3氢气。第二步骤期间的氢气消耗一般为2重量％至3重量％，相对于初始进料。
所述处理进料的第二步在比所述温和预氢化的第一步更严格的工作条件下进行，有利地完成进料的脂肪酸的烃链中包含的酯官能团的至少50％，优选至少80％，更优选至少90％和更优选至少99％。
使用上述红外光谱法证明酯官能团的存在。
来自本发明的两步氢化处理方法的至少一部分，优选全部经氢化处理的流出液然后经历一个或多个分离步骤。
这一步骤的目的是将气体与液体分离，以及特别是回收还可能包含例如一氧化碳(CO)、二氧化碳(CO2)和丙烷的气体的富氢气体，以及由至少50重量％，优选至少80重量％，更优选至少90重量％以及更优选至少98重量％的直链正链烷烃构成并具有6至25的碳原子数的至少一种液态烃流出液。
使用层析法测量链烷烃(正链烷烃和异链烷烃)的量。其与质谱仪联用。这一方法还提供定量烯烃、环烷烃和芳烃的量的途径(PONA分析)。
本发明方法的来自可再生来源的进料的两步氢化处理法期间，形成的水的一部分被包含在液态烃流出液中，其至少一部分，优选全部有利地与液态烃流出液分离。因此，分离之后可以为去除水的步骤。
分离的氢气(H2)、一氧化碳(CO)、二氧化碳(CO2)和丙烷的混合物然后可以有利地经历本领域技术人员已知的处理，以去除一氧化碳(CO)和二氧化碳(CO2)并将氢气与丙烷分离，后者可以有利地被输送到提供蒸汽裂解液化气的蒸汽裂解熔炉中。
实施例1
步骤a)来自可再生来源的进料的两步氢化处理
1)第一温和预氢化步骤
向由已经调整至提供等温操作的反应器构成的第一阶段中加入40g温和预氢化催化剂的固定床，所述预氢化催化剂基于在氧化铝上的镍，其包含15重量％镍(以镍计算)并被预还原。向该固定床输送具有如下组成的100g/h预精制菜籽油。
表2：来自可再生来源的进料的组成
在150℃、4MPa的压力下引入每升进料为100∶1NTP的氢气(NTP＝常温常压)。分离出过量氢气之后，以极轻微超过100％的产率获得甘油酯的混合物。预氢化流出液包含与起始进料相同的链，其中双键已经几乎完全氢化。所得氢气消耗为大约0.9重量％，相对于进料。
2)第二进料处理步骤
来自第一步的预氢化混合物全部直接输送到第二反应器中，所述第二反应器在等温条件下工作并具有装有89g用于第二进料处理步骤的催化剂的固定床，所述催化剂包括氧化铝载体上的由镍和钼构成并具有4.3重量％氧化镍含量和21.5重量％氧化钼含量的氢化脱氢相，该催化剂已经被硫化。将每升进料为150∶1NTP的H2引入到保持在300℃、4MPa压力的反应器中。
步骤b)：分离来自步骤a)的流出液
分离全部来自本发明方法的步骤a)的经氢化处理的流出液，以便回收富氢气体和与产生的水分离的液态链烷烃流出液。获得的产率在以下表格中示出：
表3
使用与质谱仪联用的气相色谱法分析如此获得的液态链烷烃流出液：其由98重量％的碳原子数为6至25的正链烷烃和2重量％的C17至C21异链烷烃构成。超过95％的正链烷烃为C16至C22。
Claims (8)
1.来自可再生来源的进料的两步氢化处理方法，包括：
a) 第一步，称作温和预氢化步骤，其在第一金属催化剂存在下进行，所述第一金属催化剂包括无定形无机载体氧化铝和由至少一种VIII族金属构成的活性氢化脱氢相，所述VIII族金属是镍，其在50℃至300℃的温度、0.1至10 MPa的氢分压和0.1 h-1至10 h-1对催化剂的时空速率下进行；和
b) 第二步，称作第二处理步骤，其在第二经硫化的催化剂存在下进行，所述第二经硫化的催化剂包括由至少一种VIII族非贵金属和/或至少一种VIB族金属构成的活性氢化脱氢相和无定形无机载体，其在200℃至450℃的温度、1 MPa至10 MPa的压力、0.1 h-1至10 h-1对催化剂的时空速率下进行，其中与进料混合的氢气的总量使得氢气对进料的比率为每m3进料有50至1000 Nm3的氢气，
其中来自可再生来源的进料为动物或植物来源的油和脂肪，或此类进料的混合物，其包含甘油三酸酯和/或脂肪酸和/或酯，所述植物油可以为未精制的或完全或部分精制的，所述进料包含甘油三酸酯结构和/或脂肪酸结构及其酯，其脂肪链包含6至25的碳原子数。
2.根据权利要求1的方法，其中所述第二经硫化的催化剂包括由至少一种VIII族非贵金属和/或至少一种VIB族金属构成的活性氢化脱氢相，该VIII族非贵金属选自镍和钴，VIB族金属选自钼和钨。
3.根据权利要求2的方法，其中VIII族非贵金属为镍，VIB族金属为钼。
4.根据权利要求1至3任一项的方法，其中所述第二经硫化的催化剂包括无定形无机载体和由至少一种VIII族非贵金属和至少一种VIB族金属构成的活性氢化脱氢相，该VIII族非贵金属为镍，VIB族金属为钼。
5.根据权利要求1至4任一项的方法，其中在所述第二经硫化的催化剂中VIB族金属和VIII族金属的氧化物的总量为相对于催化剂总质量的5重量%至40重量%。
6.根据权利要求1至5任一项的方法，其中所述第二经硫化的催化剂在无定形无机载体上包括相对于催化剂总质量的0.5重量%至10重量%的量的氧化镍(NiO)，和相对于催化剂总质量的1重量%至30重量%的量的氧化钼(MoO3)。
7.根据权利要求1至6任一项的方法，其中所述第二经硫化的催化剂包括选自单独使用的或作为混合物使用的氧化铝、二氧化硅、二氧化硅-氧化铝、氧化镁和粘土的无定形无机载体。
8.根据权利要求7的方法，其中所述载体为氧化铝载体。
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| FR2917424B1 (fr) | 2007-06-12 | 2012-10-19 | Inst Francais Du Petrole | Production de charges de vapocraquage a haut rendement en ethylene, propylene et polymeres resultants par hydrotraitement d'huile vegetales |
| US8231804B2 (en) | 2008-12-10 | 2012-07-31 | Syntroleum Corporation | Even carbon number paraffin composition and method of manufacturing same |
| FR2943071B1 (fr) | 2009-03-10 | 2011-05-13 | Inst Francais Du Petrole | Procede d'hydrodesoxygenation de charges issues de sources renouvelables avec conversion limitee en decarboxylation mettant en oeuvre un catalyseur a base de nickel et de molybdene |
| FR2949475B1 (fr) * | 2009-09-02 | 2012-04-20 | Inst Francais Du Petrole | Procede de conversion de charges issues de sources renouvelables en co-traitement avec une charge petroliere mettant en oeuvre un catalyseur a base de molybdene |
| FR2949476B1 (fr) * | 2009-09-02 | 2012-08-03 | Inst Francais Du Petrole | Procede de conversion de charges issues de sources renouvelables en co-traitement avec une charge petroliere mettant en oeuvre un catalyseur a base de nickel et de molybdene |
| FR2951734B1 (fr) | 2009-10-27 | 2012-08-03 | Inst Francais Du Petrole | Procede d'hydrotraitement de charges issues de sources renouvelables avec chauffe indirecte |
| FR2951733B1 (fr) * | 2009-10-27 | 2012-08-10 | Inst Francais Du Petrole | Procede d'hydrotraitement de charges issues de sources renouvelables avec chauffe indirecte mettant en oeuvre un catalyseur a base de molybdene |
| FR2951732B1 (fr) * | 2009-10-27 | 2012-08-03 | Inst Francais Du Petrole | Procede d'hydrotraitement de charges issues de sources renouvelables avec chauffe indirecte mettant en oeuvre un catalyseur a base de nickel et de molybdene presentant un rapport atomique particulier |
| FR2953854B1 (fr) * | 2009-12-16 | 2012-12-28 | Inst Francais Du Petrole | Procede de conversion de charges issues de sources renouvelables avec pretraitement des charges par dephosphatation a chaud |
| JP5864946B2 (ja) * | 2010-08-04 | 2016-02-17 | 新日鐵住金株式会社 | アルミニウム合金板の温間成形用潤滑油、アルミニウム合金板及びその温間成形方法 |
| CO6620012A1 (es) * | 2011-08-09 | 2013-02-15 | Ecopetrol Sa | Método mejorado para la obtención de diesel a partir de fuentes renovables mediante el control del nivel de insaturación |
| PL221207B1 (pl) * | 2012-11-26 | 2016-03-31 | Inst Chemii Przemysłowej Im Prof Ignacego Mościckiego | Sposób otrzymywania węglowodorów parafinowych z tłuszczów pochodzenia naturalnego |
| US9540390B2 (en) * | 2013-01-24 | 2017-01-10 | Fundacion Technalia Research & Innovation | Method for manufacturing 1,4:3,6-dianhydrohexitol di(alkyl carbonate)s |
| US20150005551A1 (en) * | 2013-07-01 | 2015-01-01 | Syntroleum Corporation | Method of processing adulterated biomass feedstocks |
| WO2016064362A1 (en) | 2014-10-20 | 2016-04-28 | Netaş Telekomüni̇kasyon Anoni̇m Şi̇rketi̇ | Encrypted messaging method over the smart cards |
| CN104673352B (zh) * | 2015-01-30 | 2016-09-14 | 浙江大学 | 一种以地沟油为原料低氢耗制备长链烷烃的方法 |
| CN104610004B (zh) * | 2015-01-30 | 2016-08-24 | 浙江大学 | 一种以微藻油为原料低氢耗制备长链烷烃的方法 |
| PL233307B1 (pl) | 2015-08-28 | 2019-09-30 | Inst Chemii Przemyslowej Im Prof Ignacego Moscickiego | Sposób otrzymywania biowęglowodorów ciekłych z olejów pochodzenia naturalnego |
| US10876050B2 (en) * | 2019-03-01 | 2020-12-29 | Uop Llc | Process for producing diesel fuel from a biorenewable feed |
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| MY157822A (en) | 2016-07-29 |
| KR101509272B1 (ko) | 2015-04-06 |
| WO2009004180A3 (fr) | 2009-02-26 |
| JP2010529981A (ja) | 2010-09-02 |
| JP5337797B2 (ja) | 2013-11-06 |
| FR2917423B1 (fr) | 2012-11-30 |
| FR2917423A1 (fr) | 2008-12-19 |
| US20100292518A1 (en) | 2010-11-18 |
| WO2009004180A2 (fr) | 2009-01-08 |
| KR20100040719A (ko) | 2010-04-20 |
| US8674151B2 (en) | 2014-03-18 |
| EP2167614A2 (fr) | 2010-03-31 |
| CN101679875A (zh) | 2010-03-24 |
| BRPI0813931A2 (pt) | 2015-08-25 |
| CA2689990A1 (fr) | 2009-01-08 |
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