JP6742020B2 - Process for producing hydrocarbon composition and catalyst - Google Patents
Process for producing hydrocarbon composition and catalyst Download PDFInfo
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- JP6742020B2 JP6742020B2 JP2016173967A JP2016173967A JP6742020B2 JP 6742020 B2 JP6742020 B2 JP 6742020B2 JP 2016173967 A JP2016173967 A JP 2016173967A JP 2016173967 A JP2016173967 A JP 2016173967A JP 6742020 B2 JP6742020 B2 JP 6742020B2
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- hydrocarbon composition
- catalyst
- group
- producing
- hydrocarbon
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- 150000002430 hydrocarbons Chemical class 0.000 title claims description 168
- 229930195733 hydrocarbon Natural products 0.000 title claims description 165
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 148
- 239000000203 mixture Substances 0.000 title claims description 122
- 239000003054 catalyst Substances 0.000 title claims description 98
- 238000000034 method Methods 0.000 title claims description 23
- 230000008569 process Effects 0.000 title claims description 8
- 239000007788 liquid Substances 0.000 claims description 63
- 239000002994 raw material Substances 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 60
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 50
- 125000004432 carbon atom Chemical group C* 0.000 claims description 50
- 229910052760 oxygen Inorganic materials 0.000 claims description 50
- 239000001301 oxygen Substances 0.000 claims description 50
- 238000004519 manufacturing process Methods 0.000 claims description 43
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- 150000002148 esters Chemical class 0.000 claims description 26
- 125000005480 straight-chain fatty acid group Chemical group 0.000 claims description 23
- 239000011148 porous material Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 239000003921 oil Substances 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 238000005338 heat storage Methods 0.000 claims description 17
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 14
- 239000011232 storage material Substances 0.000 claims description 13
- 235000019871 vegetable fat Nutrition 0.000 claims description 12
- 238000004438 BET method Methods 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910021480 group 4 element Inorganic materials 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 41
- 239000000194 fatty acid Substances 0.000 description 41
- 229930195729 fatty acid Natural products 0.000 description 41
- 150000004665 fatty acids Chemical class 0.000 description 40
- 239000012071 phase Substances 0.000 description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 26
- 235000019198 oils Nutrition 0.000 description 19
- 239000003925 fat Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000007086 side reaction Methods 0.000 description 14
- 238000006606 decarbonylation reaction Methods 0.000 description 13
- 238000006114 decarboxylation reaction Methods 0.000 description 13
- 238000006317 isomerization reaction Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 150000003464 sulfur compounds Chemical class 0.000 description 13
- 239000010775 animal oil Substances 0.000 description 12
- 239000008158 vegetable oil Substances 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 238000005987 sulfurization reaction Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 235000019197 fats Nutrition 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 5
- 241000221089 Jatropha Species 0.000 description 4
- 235000019482 Palm oil Nutrition 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002540 palm oil Substances 0.000 description 4
- 229920001021 polysulfide Polymers 0.000 description 4
- 239000005077 polysulfide Substances 0.000 description 4
- 150000008117 polysulfides Polymers 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006324 decarbonylation Effects 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- -1 fatty acid glycerin ester Chemical class 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229910021476 group 6 element Inorganic materials 0.000 description 2
- 229910021472 group 8 element Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 125000005457 triglyceride group Chemical group 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 235000021360 Myristic acid Nutrition 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
- 235000021314 Palmitic acid Nutrition 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
- 235000021355 Stearic acid Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- LQJBNNIYVWPHFW-QXMHVHEDSA-N gadoleic acid Chemical compound CCCCCCCCCC\C=C/CCCCCCCC(O)=O LQJBNNIYVWPHFW-QXMHVHEDSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012782 phase change material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
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- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
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- 150000003573 thiols Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Description
本発明は、炭化水素組成物の製造方法及び触媒に関する。 The present invention relates to a method for producing a hydrocarbon composition and a catalyst.
従来より、天然油脂類又はその誘導体を、金属触媒又は合金触媒を用いて水素化処理することにより、炭化水素を含む組成物を製造する技術が知られている。 BACKGROUND ART Conventionally, there is known a technique of producing a composition containing a hydrocarbon by subjecting natural fats and oils or their derivatives to a hydrogenation treatment using a metal catalyst or an alloy catalyst.
例えば、天然油脂類あるいはその誘導体及び食用廃油等を原料とする炭化水素類の製造方法として、天然油脂、廃天然油脂またはその誘導体と、活性化した水素とを金属触媒、合金触媒、金属担持触媒および合金担持触媒からなる群より選ばれる触媒の存在下反応させることを特徴とする炭化水素類の製造方法が知られている(例えば、特許文献1参照)。 For example, as a method for producing hydrocarbons using natural fats and oils or their derivatives and edible waste oil as raw materials, natural fats and oils, waste natural fats and oils or their derivatives, and activated hydrogen are used as metal catalysts, alloy catalysts, and metal-supported catalysts. There is known a method for producing hydrocarbons, which comprises reacting in the presence of a catalyst selected from the group consisting of and an alloy-supported catalyst (see, for example, Patent Document 1).
また、動植物油脂および動植物油脂由来成分であるトリグリセリド含有炭化水素を原料として製造された環境低負荷型軽油基材を含有する軽油組成物として、動植物油脂および/または動物油脂由来成分を含有する原料油類を、周期律表第6A族および/または第8族金属と酸性質を有する無機酸化物を含有する水素化精製触媒と水素加圧下で接触させ、同時に/その後に結晶性モレキュラシーブを含有する担体に担持された周期律表第6A族および/または第8族金属を含有する異性化触媒と水素加圧下で接触させることにより得られる、炭素数15〜18の鎖状飽和炭化水素を50質量%以上含有し、炭素数15以上の側鎖を有する鎖状飽和炭化水素含有量を炭素数15以上の直鎖飽和炭化水素含有量で除した値が0.7以上、かつ特定の式を満たす軽油組成物が知られている(例えば、特許文献2参照)。 Further, as a light oil composition containing an environmentally low-loading diesel oil base material produced by using a triglyceride-containing hydrocarbon, which is a component derived from animal and vegetable oils and fats, as a raw material oil containing a component derived from animal and vegetable oils and/or animal fats and oils. Of the Periodic Table Group 6A and/or Group 8 metal with a hydrorefining catalyst containing an inorganic oxide having acidic properties under hydrogen pressure and at the same time/afterwards a carrier containing a crystalline molecular sieve. 50% by mass of a chain saturated hydrocarbon having 15 to 18 carbon atoms, which is obtained by contacting with an isomerization catalyst containing a metal of Group 6A and/or Group 8 of the periodic table supported under hydrogen pressure. Light oil containing the above and having a value of 0.7 or more obtained by dividing the chain saturated hydrocarbon content having a side chain of 15 or more carbon atoms by the linear saturated hydrocarbon content of 15 or more carbon atoms and satisfying a specific formula A composition is known (for example, refer to Patent Document 2).
再生可能な起源の留出物を優れた品質の燃料に転化するための触媒として、硫黄含有の第VIB族元素によって構成された活性相を含む担持型または非担持型の触媒であって、第VIB族元素はモリブデンであり、担持型触媒の場合、触媒の全質量に関して第VIB族元素の酸化物の重量で17〜35%の第VIB族元素含有量を有し、リン、ホウ素およびケイ素から選択されるドープ元素を前記担体に担持されてさらに含む、触媒が知られている(例えば、特許文献3参照)。 A supported or unsupported catalyst comprising an active phase constituted by a sulfur-containing Group VIB element as a catalyst for converting a distillate of a renewable origin into a fuel of excellent quality, comprising: The Group VIB element is molybdenum, which, in the case of supported catalysts, has a Group VIB element content of 17-35% by weight of the oxide of the Group VIB element with respect to the total mass of the catalyst, and from phosphorus, boron and silicon. There is known a catalyst that further includes a selected doping element supported on the carrier (see, for example, Patent Document 3).
軽油の収率を最大にし、カルボキシル基のアルキル基への水素化脱酸素メカニズムを促進する方法として、脱炭酸/脱カルボニルによる転化が多くとも10%に制限された、再生可能な供給源に由来する仕込原料の水素化脱酸素法であって、第VIB族からの少なくとも1種の元素と第VIII族からの少なくとも1種の元素とを含む活性相を含むバルク又は担持触媒を用い、前記元素は硫化物の形態であり、第VIB族からの金属(単数または複数)に対する第VIII族からの金属(単数または複数)の原子比は、厳密に0超かつ0.095未満であり、前記方法は、120〜450℃の範囲の温度、1〜10MPaの範囲の圧力、0.1〜10h−1の範囲の毎時液空間速度で、水素/仕込原料の比が仕込原料の容積(m3)当たり水素50〜3000Nm3となるように仕込原料と混合される水素の全量存在下に行われる、方法が知られている(例えば、特許文献4参照)。 As a way to maximize the yield of gas oil and accelerate the mechanism of hydrodeoxygenation of carboxyl groups to alkyl groups, it comes from renewable sources with decarboxylation/decarbonylation conversion limited to at most 10%. A method of hydrodeoxygenation of a feedstock using a bulk or supported catalyst comprising an active phase comprising at least one element from Group VIB and at least one element from Group VIII Is in the form of a sulphide and the atomic ratio of the metal(s) from Group VIII to the metal(s) from Group VIB is strictly greater than 0 and less than 0.095, Is a temperature in the range of 120 to 450° C., a pressure in the range of 1 to 10 MPa, an hourly liquid hourly space velocity in the range of 0.1 to 10 h −1 , and the hydrogen/feeding material ratio is the volume of the charging material (m 3 ). A method is known, which is carried out in the presence of the total amount of hydrogen mixed with the charged raw material so that the hydrogen content is 50 to 3000 Nm 3 per unit (for example, refer to Patent Document 4).
また、炭化水素を含む組成物を、潜熱を利用した蓄冷熱剤として用いることも検討されている。
例えば、炭素数がCnのノルマルパラフィン成分(A)および炭素数がCn+2のノルマルパラフィン成分(B)の2成分をそれぞれ10重量%以上含み、炭素数がCn+1のノルマルパラフィン成分(C)の含有量は10重量%未満で、(A)+(B)+(C)=100重量%であり、かつnは10から16の範囲である実質的に上記(A)および(B)のノルマルパラフィン成分の混合物からなる蓄冷熱剤が知られている(例えば、特許文献5参照)。
Also, the use of a composition containing a hydrocarbon as a cold heat storage agent utilizing latent heat has been studied.
For example, normal paraffin components with a carbon number C n (A) and comprising respectively 10 wt% or more of the two components of the carbon number of C n + 2 of the normal paraffin component (B), normal paraffin component of C n + 1 carbon atoms (C) Content of less than 10% by weight, (A)+(B)+(C)=100% by weight, and n is in the range of 10 to 16, substantially in the above (A) and (B). A cold storage heat agent composed of a mixture of normal paraffin components is known (see, for example, Patent Document 5).
また、動植物油脂を水素化処理するに際し、炭素原子奇数のn−パラフィン、及び分枝−パラフィンの両者を併せた副生物の生成を同時に抑え、炭素原子偶数のn−パラフィンを高収率で製造できる潜熱蓄熱基材炭化水素組成物の製造方法として、脱炭酸/脱カルボニルと分枝−パラフィンの生成を制限し、両者を併せた副生物が多くとも10%に制限された、動植物油脂由来の含酸素炭化水素化合物を含有する原料液の水素化脱酸素法であって、第6A族元素からの少なくとも1種の元素と第8族元素からの少なくとも1種の元素とを含む活性相を含むバルク又は担持触媒を用い、前記元素は硫化物の形態であり、第6A族元素からの金属(単数または複数)に対する第8族元素からの金属(単数または複数)の原子比は厳密に0を含み0.06未満であり、前記触媒はさらにリン及び/又はホウ素を、酸化物P2O5あるいはB2O3の重量で全触媒重量に対し1〜6%の量で含み、前記方法は原料液が、1〜250重量ppmの硫黄(硫黄元素として換算)を含有して、250〜350℃の範囲の温度、1〜10MPaの範囲の圧力、0.1〜10h−1の範囲の液空間速度で行われる潜熱蓄熱基材炭化水素組成物の製造方法が知られている(例えば、特許文献6参照)。 Moreover, when hydrogen-treating animal and vegetable oils and fats, the production of by-products including both n-paraffins with odd carbon atoms and branched-paraffins is suppressed at the same time, and n-paraffins with even carbon atoms are produced in high yield. As a method for producing a latent heat storage base hydrocarbon composition capable of producing a decarboxylation/decarbonylation and branched-paraffin production, a by-product combining both is limited to 10% at most, and derived from animal or vegetable oils and fats. A hydrodeoxygenation method of a raw material liquid containing an oxygen-containing hydrocarbon compound, comprising an active phase containing at least one element from a Group 6A element and at least one element from a Group 8 element Using a bulk or supported catalyst, the element is in the form of a sulphide and the atomic ratio of the metal(s) from the Group 8 element to the metal(s) from the Group 6A element is exactly 0. Less than 0.06, the catalyst further comprises phosphorus and/or boron in an amount of 1 to 6% by weight of the oxide P 2 O 5 or B 2 O 3 based on the total catalyst weight. The raw material liquid contains 1 to 250 ppm by weight of sulfur (calculated as elemental sulfur), a temperature in the range of 250 to 350° C., a pressure in the range of 1 to 10 MPa, and a liquid in the range of 0.1 to 10 h −1. A method for producing a latent heat storage base hydrocarbon composition that is performed at a space velocity is known (see, for example, Patent Document 6).
しかし、含酸素炭化水素組成物を水素化脱酸素処理して炭化水素組成物を製造するにあたり、副反応である、脱炭酸/脱カルボニル反応と異性化反応とが抑制され、主反応である水素化脱酸素反応の選択性に優れる炭化水素組成物の製造方法として、特許文献6に記載された方法以外の方法が提供されることが望ましい。 However, when producing a hydrocarbon composition by hydrodeoxygenating an oxygen-containing hydrocarbon composition, decarboxylation/decarbonylation reactions and isomerization reactions, which are side reactions, are suppressed, and hydrogen, which is a main reaction, is suppressed. It is desirable that a method other than the method described in Patent Document 6 be provided as a method for producing a hydrocarbon composition having excellent selectivity for chemical deoxygenation reaction.
本発明の一態様の課題は、含酸素炭化水素組成物を水素化脱酸素処理して炭化水素組成物を製造するにあたり、副反応である、脱炭酸/脱カルボニル反応と異性化反応とが抑制され、主反応である水素化脱酸素反応の選択性に優れる炭化水素組成物の製造方法並びに触媒を提供することである。 An object of one embodiment of the present invention is to suppress a decarboxylation/decarbonylation reaction and an isomerization reaction, which are side reactions in producing a hydrocarbon composition by hydrodeoxygenating an oxygen-containing hydrocarbon composition. The present invention provides a method for producing a hydrocarbon composition and a catalyst which are excellent in selectivity of the hydrodeoxygenation reaction which is a main reaction.
上記課題を解決するための具体的手段には、以下の態様が含まれる。
<1> 炭素数が偶数である直鎖脂肪酸及び前記炭素数が偶数である直鎖脂肪酸に由来するエステルからなる群から選択される少なくとも1種を含む含酸素炭化水素組成物を含有する原料液を準備する工程と、
BET法による比表面積が100m2/g〜400m2/gである多孔質材料を含有する担体と、前記担体に担持された活性相であって、第6族の元素からなる群から選択される少なくとも1種の元素X1と第8族〜第10族の元素からなる群から選択される少なくとも1種の元素X2とを含有し、前記元素X1に対する前記元素X2の原子数比が0.06〜0.30である活性相と、を含む触媒を準備する工程と、
前記触媒を、硫化処理する工程と、
硫化処理された前記触媒と前記原料液と水素とを接触させ、前記原料液中の前記含酸素炭化水素組成物を水素化脱酸素処理することにより、炭素数が偶数である直鎖炭化水素を含む炭化水素組成物を製造する工程と、
を有する炭化水素組成物の製造方法。
<2> 前記元素X1が、Mo及びWの少なくとも一方であり、
前記元素X2が、Coである<1>に記載の炭化水素組成物の製造方法。
<3> 前記担体が、更に、第4族の元素からなる群から選択される少なくとも1種の元素X3の酸化物を、前記担体の全量に対して1質量%〜30質量%含有する<1>又は<2>に記載の炭化水素組成物の製造方法。
<4> 前記元素X3が、Ti及びZrの少なくとも一方である<3>に記載の炭化水素組成物の製造方法。
<5> 前記多孔質材料が、γ−アルミナである<1>〜<4>のいずれか1つに記載の炭化水素組成物の製造方法。
<6> 前記炭化水素組成物を製造する工程は、硫化処理された前記触媒と前記原料液と水素とを、温度200℃〜450℃、圧力0.1MPa〜10MPa、液空間速度0.1h−1〜10h−1の条件で接触させる<1>〜<5>のいずれか1つに記載の炭化水素組成物の製造方法。
<7> 前記含酸素炭化水素組成物が、動植物油脂に由来する組成物である<1>〜<6>のいずれか1つに記載の炭化水素組成物の製造方法。
<8> 前記炭化水素組成物が、潜熱蓄熱材料として用いられる<1>〜<7>のいずれか1つに記載の炭化水素組成物の製造方法。
<9> 前記触媒中におけるP2O5及びB2O3の総含有量が、前記触媒全量に対し、1質量%未満である<1>〜<8>のいずれか1つに記載の炭化水素組成物の製造方法。
<10> BET法による比表面積が100m2/g〜400m2/gである多孔質材料を含有する担体と、
前記担体に担持された活性相であって、第6族の元素からなる群から選択される少なくとも1種の元素X1と第8族〜第10族の元素からなる群から選択される少なくとも1種の元素X2とを含有し、前記元素X1に対する前記元素X2の原子数比が0.06〜0.30である活性相と、
を含む触媒。
Specific means for solving the above problems include the following aspects.
<1> A raw material liquid containing an oxygen-containing hydrocarbon composition containing at least one selected from the group consisting of straight-chain fatty acids having an even number of carbon atoms and esters derived from straight-chain fatty acids having an even number of carbon atoms. And the step of preparing
A carrier having a specific surface area by BET method contains a porous material which is 100m 2 / g~400m 2 / g, a supported active phase on the support is selected from the group consisting of elements of Group 6 At least one element X1 and at least one element X2 selected from the group consisting of Group 8 to Group 10 elements are contained, and the atomic ratio of the element X2 to the element X1 is 0.06 to Providing an active phase that is 0.30, and a catalyst comprising:
A step of sulfiding the catalyst,
By contacting the sulfur-treated catalyst with the raw material liquid and hydrogen, and subjecting the oxygen-containing hydrocarbon composition in the raw material liquid to hydrodeoxygenation, a straight-chain hydrocarbon having an even number of carbon atoms is obtained. Producing a hydrocarbon composition comprising
A method for producing a hydrocarbon composition having:
<2> The element X1 is at least one of Mo and W,
The method for producing a hydrocarbon composition according to <1>, wherein the element X2 is Co.
<3> The carrier further contains an oxide of at least one element X3 selected from the group consisting of Group 4 elements in an amount of 1% by mass to 30% by mass based on the total amount of the carrier <1. > Or <2>, the method for producing the hydrocarbon composition.
<4> The method for producing a hydrocarbon composition according to <3>, wherein the element X3 is at least one of Ti and Zr.
<5> The method for producing a hydrocarbon composition according to any one of <1> to <4>, wherein the porous material is γ-alumina.
<6> In the step of producing the hydrocarbon composition, the sulfurating treatment of the catalyst, the raw material liquid, and hydrogen are performed at a temperature of 200° C. to 450° C., a pressure of 0.1 MPa to 10 MPa, and a liquid space velocity of 0.1 h −. The method for producing the hydrocarbon composition according to any one of <1> to <5>, which is brought into contact under the condition of 1 to 10 h −1 .
<7> The method for producing a hydrocarbon composition according to any one of <1> to <6>, wherein the oxygen-containing hydrocarbon composition is a composition derived from animal and vegetable fats and oils.
<8> The method for producing a hydrocarbon composition according to any one of <1> to <7>, in which the hydrocarbon composition is used as a latent heat storage material.
<9> The carbonization according to any one of <1> to <8>, in which the total content of P 2 O 5 and B 2 O 3 in the catalyst is less than 1 mass% with respect to the total amount of the catalyst. Method for producing hydrogen composition.
A carrier having a specific surface area by <10> BET method contains a porous material which is 100m 2 / g~400m 2 / g,
An active phase supported on the carrier, which is at least one element X1 selected from the group consisting of elements of Group 6 and at least one selected from the group consisting of elements of Groups 8 to 10 An active phase containing the element X2 and the atomic ratio of the element X2 to the element X1 is 0.06 to 0.30,
A catalyst containing.
本発明の一態様によれば、含酸素炭化水素組成物を水素化脱酸素処理して炭化水素組成物を製造するにあたり、副反応である、脱炭酸/脱カルボニル反応と異性化反応とが抑制され、主反応である水素化脱酸素反応の選択性に優れる炭化水素組成物の製造方法並びに触媒が提供される。 According to one embodiment of the present invention, when producing a hydrocarbon composition by hydrodeoxygenating an oxygen-containing hydrocarbon composition, side reactions such as decarboxylation/decarbonylation reaction and isomerization reaction are suppressed. A method for producing a hydrocarbon composition and a catalyst having excellent selectivity in the hydrodeoxygenation reaction, which is a main reaction, are provided.
本明細書において、「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
本明細書において、「工程」との用語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の目的が達成されれば、本用語に含まれる。
In the present specification, the numerical range represented by "to" means a range including the numerical values before and after "to" as the lower limit value and the upper limit value.
In the present specification, the term “step” is included in this term as long as the intended purpose of the step is achieved not only as an independent step but also when it cannot be clearly distinguished from other steps. Be done.
本開示の炭化水素組成物の製造方法(以下、「本開示の製造方法」ともいう)は、
炭素数が偶数である直鎖脂肪酸及び前記炭素数が偶数である直鎖脂肪酸に由来するエステルからなる群から選択される少なくとも1種を含む含酸素炭化水素組成物を含有する原料液を準備する工程(以下、「原料液準備工程」ともいう)と、
BET法による比表面積が100m2/g〜400m2/gである多孔質材料を含有する担体と、前記担体に担持された活性相であって、第6族の元素からなる群から選択される少なくとも1種の元素X1と第8族〜第10族の元素からなる群から選択される少なくとも1種の元素X2とを含有し、前記元素X1に対する前記元素X2の原子数比が0.06〜0.30である活性相と、を含む触媒を準備する工程(以下、「触媒準備工程」ともいう)と、
前記触媒を、硫化処理する工程(以下、「硫化処理工程」ともいう)と、
硫化処理された前記触媒と前記原料液と水素とを接触させ、前記原料液中の前記含酸素炭化水素組成物を水素化脱酸素処理することにより、炭素数が偶数である直鎖炭化水素を含む炭化水素組成物を製造する工程(以下、「水素化脱酸素処理工程」ともいう)と、
を有する。
本開示の触媒は、上記担体と上記活性相とを含む。
The production method of the hydrocarbon composition of the present disclosure (hereinafter, also referred to as “production method of the present disclosure”) is
A raw material liquid containing an oxygen-containing hydrocarbon composition containing at least one selected from the group consisting of straight-chain fatty acids having an even number of carbon atoms and esters derived from straight-chain fatty acids having an even number of carbon atoms is prepared. Process (hereinafter, also referred to as "raw material liquid preparation process"),
A carrier having a specific surface area by BET method contains a porous material which is 100m 2 / g~400m 2 / g, a supported active phase on the support is selected from the group consisting of elements of Group 6 At least one element X1 and at least one element X2 selected from the group consisting of Group 8 to Group 10 elements are contained, and the atomic ratio of the element X2 to the element X1 is 0.06 to A step of preparing a catalyst containing an active phase of 0.30 (hereinafter, also referred to as “catalyst preparation step”),
A step of subjecting the catalyst to sulfurization treatment (hereinafter, also referred to as “sulfurization treatment step”);
By contacting the sulfur-treated catalyst with the raw material liquid and hydrogen, and subjecting the oxygen-containing hydrocarbon composition in the raw material liquid to hydrodeoxygenation, a straight-chain hydrocarbon having an even number of carbon atoms is obtained. A step of producing a hydrocarbon composition containing (hereinafter, also referred to as “hydrodeoxygenation treatment step”),
Have.
The catalyst of the present disclosure includes the carrier and the active phase.
本発明者は鋭意検討した結果、上記含酸素炭化水素組成物を、元素X1と元素X2とを含有する活性相を含む触媒によって水素化脱酸素(Hydrodeoxygenation;HDO)処理するにあたり、上記触媒として、元素X1に対する元素X2の原子数比が0.06〜0.30である触媒を用いると、副反応である脱炭酸/脱カルボニル反応と異性化反応とが抑制され、主反応である水素化脱酸素反応の選択性が向上することを見出した。
即ち、本開示の製造方法及び本開示の触媒によれば、副反応である、脱炭酸/脱カルボニル反応と異性化反応とが抑制され、主反応である水素化脱酸素反応の選択性が向上する。
詳細には、水素化脱酸素反応(主反応)によれば、原料としての、炭素数が偶数である直鎖脂肪酸及び/又は炭素数が偶数である直鎖脂肪酸に由来するエステルから、原料中の直鎖脂肪酸(又は、上記エステルを形成するための直鎖脂肪酸)の炭素数と同数の炭素原子を有する(即ち、炭素数が偶数の)直鎖炭化水素が生成される。
脱炭酸/脱カルボニル反応(副反応)によれば、上記原料から、上記原料中の直鎖脂肪酸(又は、上記エステルを形成するための直鎖脂肪酸)の炭素数よりも1つ少ない数の炭素原子を有する(即ち、炭素数が奇数の)炭化水素が生成される。
異性化反応(副反応)によれば、上記原料から、分岐鎖炭化水素が生成される。
As a result of intensive studies by the present inventor, the oxygen-containing hydrocarbon composition was treated as a catalyst by hydrodeoxygenation (HDO) treatment with a catalyst containing an active phase containing an element X1 and an element X2. When a catalyst in which the atomic ratio of the element X2 to the element X1 is 0.06 to 0.30 is used, the decarboxylation/decarbonylation reaction which is a side reaction and the isomerization reaction are suppressed, and the hydrogenation desorption which is a main reaction is suppressed. It was found that the selectivity of oxygen reaction was improved.
That is, according to the production method of the present disclosure and the catalyst of the present disclosure, the decarboxylation/decarbonylation reaction and the isomerization reaction that are side reactions are suppressed, and the selectivity of the hydrodeoxygenation reaction that is the main reaction is improved. To do.
More specifically, according to the hydrodeoxygenation reaction (main reaction), a linear fatty acid having an even number of carbon atoms and/or an ester derived from a linear fatty acid having an even number of carbons is used as a raw material in the raw material. A straight-chain hydrocarbon having the same number of carbon atoms as the straight-chain fatty acid of (or the straight-chain fatty acid for forming the ester) (that is, an even number of carbon atoms) is produced.
According to the decarboxylation/decarbonylation reaction (side reaction), the number of carbon atoms from the above raw material is one less than the number of carbon atoms of the straight chain fatty acid (or the straight chain fatty acid for forming the above ester) in the above raw material. Hydrocarbons having atoms (ie, having an odd number of carbon atoms) are produced.
According to the isomerization reaction (side reaction), branched chain hydrocarbons are produced from the above raw materials.
以下、本開示の製造方法の各工程について説明する。 Hereinafter, each step of the manufacturing method of the present disclosure will be described.
<触媒準備工程>
触媒準備工程は、本開示の触媒を準備する工程である。
本開示の触媒は、
BET法による比表面積が100m2/g〜400m2/gである多孔質材料を含有する担体と、
担体に担持された活性相であって、第6族の元素からなる群から選択される少なくとも1種の元素X1と第8族〜第10族の元素からなる群から選択される少なくとも1種の元素X2とを含有し、元素X1に対する元素X2の原子数比(以下、「原子数比〔元素X2/元素X1〕」ともいう)が0.06〜0.30である活性相と、
を含む。
触媒準備工程は、便宜上の工程である。
即ち、触媒準備工程は、本開示の触媒を製造する工程であってもよいし、予め製造した本開示の触媒を単に準備する工程であってもよい。
<Catalyst preparation step>
The catalyst preparation step is a step of preparing the catalyst of the present disclosure.
The catalyst of the present disclosure is
A carrier having a specific surface area by BET method contains a porous material which is 100m 2 / g~400m 2 / g,
An active phase supported on a carrier, which is at least one element X1 selected from the group consisting of Group 6 elements and at least one element selected from the group consisting of Group 8 to Group 10 elements An active phase containing the element X2 and having an atomic ratio of the element X2 to the element X1 (hereinafter, also referred to as “atomic ratio [element X2/element X1]”) of 0.06 to 0.30;
including.
The catalyst preparation step is a step for convenience.
That is, the catalyst preparation step may be a step of producing the catalyst of the present disclosure or may be a step of simply preparing a catalyst of the present disclosure produced in advance.
(活性相)
本開示の触媒は、後述する担体に担持された活性相であって、元素X1と元素X2とを含有し原子数比〔元素X2/元素X1〕が0.06〜0.30である活性相を含む。
触媒の活性相において、原子数比〔元素X2/元素X1〕が0.06〜0.30であると、原子数比〔元素X2/元素X1〕が0.06未満である場合及び原子数比〔元素X2/元素X1〕が0.30超である場合と比較して、副反応である、脱炭酸/脱カルボニル反応と異性化反応とが抑制され、主反応である水素化脱酸素反応の選択性が向上する。
水素化脱酸素反応の選択性を更に向上させる観点から、原子数比〔元素X2/元素X1〕としては、0.06〜0.25が好ましく、0.06〜0.20がより好ましい。
(Active phase)
The catalyst of the present disclosure is an active phase supported on a carrier described later, which contains the elements X1 and X2 and has an atomic number ratio [element X2/element X1] of 0.06 to 0.30. including.
In the active phase of the catalyst, when the atomic ratio [element X2/element X1] is 0.06 to 0.30, the atomic ratio [element X2/element X1] is less than 0.06 and the atomic ratio Compared with the case where [element X2/element X1] is more than 0.30, side reactions such as decarboxylation/decarbonylation reaction and isomerization reaction are suppressed, and the main reaction of hydrodeoxygenation reaction is suppressed. Selectivity is improved.
From the viewpoint of further improving the selectivity of the hydrodeoxygenation reaction, the atomic ratio [element X2/element X1] is preferably 0.06 to 0.25, and more preferably 0.06 to 0.20.
元素X1は、第6族の元素からなる群から選択される少なくとも1種の元素である。
元素X1は、水素化脱酸素反応の選択性をより向上させる観点から、Mo、W、及びCrからなる群から選択される少なくとも1種であることが好ましく、Mo及びWの少なくとも一方であることがより好ましく、Moであることが特に好ましい。
The element X1 is at least one element selected from the group consisting of Group 6 elements.
From the viewpoint of further improving the selectivity of the hydrodeoxygenation reaction, the element X1 is preferably at least one selected from the group consisting of Mo, W, and Cr, and is at least one of Mo and W. Is more preferable, and Mo is particularly preferable.
元素X2は、第8族〜第10族の元素からなる群から選択される少なくとも1種の元素である。
元素X2は、水素化脱酸素反応の選択性をより向上させる観点から、
Co、Rh、Tr、Fe、Ru、Os、Ni、Pd、及びPtからなる群から選択される少なくとも1種であることが好ましく、
Co、Fe、Ni、Pd、及びPtからなる群から選択される少なくとも1種であることがより好ましく、
Co、Fe、及びNiからなる群から選択される少なくとも1種であることが更に好ましく、
Co及びNiの少なくとも一方であることが更に好ましく、
Coであることが特に好ましい。
The element X2 is at least one element selected from the group consisting of elements of Group 8 to Group 10.
From the viewpoint of further improving the selectivity of the hydrodeoxygenation reaction, the element X2 is
It is preferably at least one selected from the group consisting of Co, Rh, Tr, Fe, Ru, Os, Ni, Pd, and Pt,
More preferably, it is at least one selected from the group consisting of Co, Fe, Ni, Pd, and Pt,
More preferably at least one selected from the group consisting of Co, Fe, and Ni,
More preferably at least one of Co and Ni,
Particularly preferred is Co.
水素化脱酸素反応の選択性をより向上させる観点から、元素X1と元素X2との組み合わせとして、特に好ましくは、元素X1がMo及びWの少なくとも一方であり、元素X2がCoである組み合わせである。 From the viewpoint of further improving the selectivity of the hydrodeoxygenation reaction, the combination of the element X1 and the element X2 is particularly preferably a combination in which the element X1 is at least one of Mo and W and the element X2 is Co. ..
元素X1は、活性相の製造適性の観点から、活性相中に元素X1の酸化物の形態で含まれることが好ましい。
元素X1の酸化物の含有量には特に制限はないが、触媒の全量(即ち、担体及び活性相の合計量)に対し、1質量%〜50質量%が好ましく、5質量%〜40質量%がより好ましく、10質量%〜30質量%が更に好ましい。
The element X1 is preferably contained in the active phase in the form of an oxide of the element X1 from the viewpoint of the suitability for production of the active phase.
The content of the oxide of the element X1 is not particularly limited, but is preferably 1% by mass to 50% by mass, and 5% by mass to 40% by mass, based on the total amount of the catalyst (that is, the total amount of the carrier and the active phase). Is more preferable and 10 mass%-30 mass% is still more preferable.
元素X2は、活性相の製造適性の観点から、活性相中に元素X2の酸化物の形態で含まれることが好ましい。
元素X2の酸化物の含有量には特に制限はなく、元素X1の酸化物の含有量、及び、原子数比〔元素X2/元素X1〕を考慮して、適宜調整できる。
The element X2 is preferably contained in the active phase in the form of an oxide of the element X2 from the viewpoint of the suitability for production of the active phase.
The content of the oxide of the element X2 is not particularly limited, and can be appropriately adjusted in consideration of the content of the oxide of the element X1 and the atomic ratio [element X2/element X1].
後述する担体(例えば、多孔質材料からなる担体、多孔質材料と元素X3の酸化物とを含む担体、等)に活性相を担持させる方法としては、
(1)後述する担体に対して、元素X1の酸化物の前駆体及び元素X2の酸化物を含む溶液を含浸させ、得られた複合体を焼成することにより、担体に対し、元素X1の酸化物及び元素X2の酸化物を含む活性相を担持させる方法、
(2)後述する担体に対して、元素X1の酸化物の前駆体の溶液及び元素X2の酸化物を含む溶液の一方を含浸させ、次いで他方を含浸させ、得られた複合体を焼成することにより、担体に対し、元素X1の酸化物及び元素X2の酸化物を含む活性相を担持させる方法、
(3)後述する担体に対して、元素X1(又はその酸化物)及び元素X2(又はその酸化物)を、それぞれ、蒸着、CVD(chemical vapor deposition;化学気相成長)、又はスパッタリングによって付着させる方法、
(4)後述する担体と、元素X1(又はその酸化物)と、元素X2(又はその酸化物)と、を混合する方法、
等が挙げられる。
中でも、触媒活性に優れる活性相を形成できる観点、及び、活性相の製造適性の観点から、上記(1)又は上記(2)の方法が好ましい。
元素X1の酸化物の前駆体としては、元素X1及び酸素原子を含む塩が挙げられる。
元素X2の酸化物の前駆体としては、元素X2及び酸素原子を含む塩が挙げられる。
元素X1の酸化物の前駆体及び/又は元素X2の酸化物を含む溶液としては、水溶液又はアルコール溶液が好ましく、水溶液が特に好ましい。
Examples of a method for supporting an active phase on a carrier described later (for example, a carrier made of a porous material, a carrier containing a porous material and an oxide of the element X3, etc.)
(1) The carrier described below is impregnated with a solution containing a precursor of the oxide of the element X1 and an oxide of the element X2, and the resulting composite is baked to oxidize the element X1 to the carrier. And an active phase containing an oxide of the element X2,
(2) The carrier described below is impregnated with one of the precursor solution of the oxide of the element X1 and the solution containing the oxide of the element X2, and then with the other, and the resulting composite is fired. A method of supporting an active phase containing an oxide of the element X1 and an oxide of the element X2 on the carrier by
(3) The element X1 (or its oxide) and the element X2 (or its oxide) are attached to the carrier described later by vapor deposition, CVD (chemical vapor deposition), or sputtering, respectively. Method,
(4) A method of mixing a carrier to be described later, the element X1 (or its oxide), and the element X2 (or its oxide),
Etc.
Above all, the method of (1) or (2) above is preferable from the viewpoint of forming an active phase having excellent catalytic activity and the suitability for producing the active phase.
Examples of the oxide precursor of the element X1 include a salt containing the element X1 and an oxygen atom.
Examples of the oxide precursor of the element X2 include salts containing the element X2 and an oxygen atom.
The solution containing the oxide precursor of the element X1 and/or the oxide of the element X2 is preferably an aqueous solution or an alcohol solution, and particularly preferably an aqueous solution.
(担体)
本開示の触媒は、BET法による比表面積(以下、単に「比表面積」ともいう)が100m2/g〜400m2/gである多孔質材料を含有する担体を含む。
多孔質材料の比表面積が100m2/g以上であると、本開示の担体を含む触媒の活性(以下、単に「触媒活性」ともいう)が向上する。
多孔質材料の比表面積が400m2/g以下であると、担体の強度、担体の製造適性等の点で有利である。
多孔質材料の比表面積は、100m2/g〜350m2/gであることが好ましく、150m2/g〜300m2/gであることがより好ましい。
(Carrier)
The catalyst of the present disclosure comprises a carrier having a specific surface area by BET method (hereinafter, simply referred to as "specific surface area") contains a porous material which is 100m 2 / g~400m 2 / g.
When the specific surface area of the porous material is 100 m 2 /g or more, the activity of the catalyst containing the carrier of the present disclosure (hereinafter, also simply referred to as “catalytic activity”) is improved.
When the specific surface area of the porous material is 400 m 2 /g or less, it is advantageous in terms of strength of the carrier, suitability for manufacturing the carrier, and the like.
The specific surface area of the porous material is preferably 100m 2 / g~350m 2 / g, and more preferably 150m 2 / g~300m 2 / g.
上記多孔質材料は、1種のみであっても2種以上であってもよい。
上記多孔質材料としては、触媒活性を効果的に発現させる観点から、アルミナ、シリカ、シリカ−アルミナ、ジルコニア、セリア、ゼオライト、粘土、活性炭、等が挙げられ、アルミナが好ましい。
アルミナとしては、η−アルミナ、δ−アルミナ、又はγ−アルミナが好ましく、γ−アルミナが特に好ましい。
The above-mentioned porous material may be only one kind or two or more kinds.
Examples of the porous material include alumina, silica, silica-alumina, zirconia, ceria, zeolite, clay and activated carbon from the viewpoint of effectively exhibiting catalytic activity, and alumina is preferred.
As alumina, η-alumina, δ-alumina, or γ-alumina is preferable, and γ-alumina is particularly preferable.
担体中における上記多孔質材料の含有量は、担体の全量に対し、60質量%〜100質量%が好ましく、70質量%〜100質量%であることがより好ましく、80質量%〜100質量%であることが特に好ましい。 The content of the porous material in the carrier is preferably 60% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and 80% by mass to 100% by mass with respect to the total amount of the carrier. It is particularly preferable that
担体は、更に、第4族の元素からなる群から選択される少なくとも1種の元素X3の酸化物を含むことが好ましい。
担体が、更に元素X3の酸化物を含む場合、水素化脱酸素反応の選択性がより向上する。この理由は明らかではないが、担体が更に元素X3の酸化物を含む場合には、触媒の酸性度がより低減され、その結果、副反応(特に異性化反応)をより低減できるため、と考えられる。
It is preferable that the carrier further contains an oxide of at least one element X3 selected from the group consisting of Group 4 elements.
When the carrier further contains the oxide of the element X3, the selectivity of the hydrodeoxygenation reaction is further improved. The reason for this is not clear, but it is considered that when the carrier further contains an oxide of the element X3, the acidity of the catalyst is further reduced, and as a result, side reactions (particularly isomerization reaction) can be further reduced. To be
担体が元素X3の酸化物を含有する場合、元素X3の酸化物の含有量は、担体の全量に対して、1質量%〜30質量%であることが好ましく、3質量%〜30質量%であることがより好ましく、5質量%〜30質量%であることが更に好ましく、10質量%〜30質量%であることが特に好ましい。
元素X3の酸化物の含有量が1質量%以上であると、上述した元素X3の酸化物による効果がより効果的に発揮され、水素化脱酸素反応の選択性がより向上する。
元素X3の酸化物の含有量が30質量%以下であると、担体の生産性(例えば、原料コスト、担体の製造工程の簡略化、等)の点で有利である。
When the carrier contains an oxide of the element X3, the content of the oxide of the element X3 is preferably 1% by mass to 30% by mass, and 3% by mass to 30% by mass with respect to the total amount of the carrier. It is more preferable that the amount is 5% by mass to 30% by mass, further preferably 10% by mass to 30% by mass.
When the content of the oxide of the element X3 is 1% by mass or more, the effect of the oxide of the element X3 described above is more effectively exhibited, and the selectivity of the hydrodeoxygenation reaction is further improved.
When the content of the oxide of the element X3 is 30% by mass or less, it is advantageous in terms of carrier productivity (for example, raw material cost, simplification of carrier manufacturing process, etc.).
元素X3は、上述した元素X3の酸化物による効果をより効果的に発揮させ、水素化脱酸素反応の選択性をより向上させる観点から、Ti、Zr、及びHfからなる群から選択される少なくとも1種であることが好ましく、Ti及びZrの少なくとも一方であることがより好ましく、Tiであることが特に好ましい。 The element X3 is at least selected from the group consisting of Ti, Zr, and Hf from the viewpoint of more effectively exerting the effect of the oxide of the element X3 described above and further improving the selectivity of the hydrodeoxygenation reaction. It is preferably one kind, more preferably at least one of Ti and Zr, and particularly preferably Ti.
多孔質材料と元素X3の酸化物とを含む担体の製造方法としては、
(1)多孔質材料に対して、元素X3の酸化物の前駆体を含む溶液を含浸させ、得られた複合体を焼成することにより、多孔質材料と元素X3の酸化物とを含む担体を製造する方法、
(2)多孔質材料に対して元素X3の酸化物を、蒸着、CVD、又はスパッタリングによって付着させる方法、
(3)多孔質材料と元素X3の酸化物とを混合する方法、
等が挙げられる。
中でも、本開示の製造方法の効果がより効果的に奏される点で、上記(1)の方法が好ましい。
元素X3の酸化物の前駆体としては、元素X3のアルコキシドが好ましい。
元素X3の酸化物の前駆体を含む溶液としては、アルコール溶液が好ましい。
As a method of producing a carrier containing a porous material and an oxide of the element X3,
(1) A carrier containing a porous material and an oxide of the element X3 is obtained by impregnating a porous material with a solution containing a precursor of an oxide of the element X3 and firing the obtained composite. How to manufacture,
(2) A method of attaching an oxide of the element X3 to the porous material by vapor deposition, CVD, or sputtering,
(3) A method of mixing the porous material and the oxide of the element X3,
Etc.
Above all, the method of (1) above is preferable because the effects of the manufacturing method of the present disclosure are more effectively exhibited.
As the precursor of the oxide of the element X3, the alkoxide of the element X3 is preferable.
As the solution containing the oxide precursor of the element X3, an alcohol solution is preferable.
本開示の触媒(担体及び/又は活性相)は、上述した成分以外の成分を含んでいてもよい。
本開示の触媒は、例えば、特開2015−30822号公報に記載のP2O5及びB2O3を含んでいてもよい。
但し、本開示の触媒によれば、原子数比〔元素X2/元素X1〕を0.06〜0.30としたことにより、水素化脱酸素反応の選択性が向上する。このため、本開示の触媒では、触媒中におけるP2O5及びB2O3の総含有量が、触媒の全量に対し、1質量%未満である場合においても、優れた水素化脱酸素反応の選択性が維持される。触媒中におけるP2O5及びB2O3の総含有量が触媒の全量に対して1質量%未満であることは、触媒の生産性(例えば、生産工程の簡略化、原料コスト)の面で有利である。
触媒中におけるP2O5及びB2O3の総含有量は、触媒の全量に対し、0.5質量%未満であってもよく、0.1質量%未満であってもよく、0質量%であってもよい(即ち、触媒がP2O5及びB2O3を含有しなくてもよい)。
The catalyst (support and/or active phase) of the present disclosure may include components other than the components described above.
The catalyst of the present disclosure may include P 2 O 5 and B 2 O 3 described in JP-A-2015-30822, for example.
However, according to the catalyst of the present disclosure, the selectivity of the hydrodeoxygenation reaction is improved by setting the atomic ratio [element X2/element X1] to 0.06 to 0.30. Therefore, in the catalyst of the present disclosure, even when the total content of P 2 O 5 and B 2 O 3 in the catalyst is less than 1% by mass with respect to the total amount of the catalyst, an excellent hydrodeoxygenation reaction is achieved. The selectivity of is maintained. The fact that the total content of P 2 O 5 and B 2 O 3 in the catalyst is less than 1% by mass with respect to the total amount of the catalyst means that the productivity of the catalyst (for example, simplification of the production process, raw material cost) is reduced. Is advantageous.
The total content of P 2 O 5 and B 2 O 3 in the catalyst may be less than 0.5% by mass, may be less than 0.1% by mass, and may be 0% by mass, based on the total amount of the catalyst. % (Ie the catalyst may be free of P 2 O 5 and B 2 O 3 ).
<原料液準備工程>
原料液準備工程は、炭素数が偶数である直鎖脂肪酸及び前記炭素数が偶数である直鎖脂肪酸に由来するエステルからなる群から選択される少なくとも1種を含む含酸素炭化水素組成物を含有する原料液を準備する工程である。
原料液準備工程は、便宜上の工程である。
即ち、原料液準備工程は、原料液を製造する工程であってもよいし、予め製造した原料液を単に準備する工程であってもよい。
<Raw material liquid preparation process>
The raw material liquid preparation step includes an oxygen-containing hydrocarbon composition containing at least one selected from the group consisting of straight-chain fatty acids having an even number of carbons and esters derived from straight-chain fatty acids having an even number of carbons. This is a step of preparing a raw material liquid to be used.
The raw material liquid preparation step is a step for convenience.
That is, the raw material liquid preparation step may be a step of producing the raw material liquid, or may be a step of simply preparing a preliminarily produced raw material liquid.
(含酸素炭化水素組成物)
原料液のうち、上記含酸素炭化水素組成物は、目的物である、炭素数が偶数である直鎖炭化水素を含む炭化水素組成物の実質的な原料である。
即ち、本開示の製造方法では、上記含酸素炭化水素組成物が水素化脱酸素処理されて、炭素数が偶数である直鎖炭化水素を含む炭化水素組成物が製造される。
(Oxygen-containing hydrocarbon composition)
Among the raw material liquids, the oxygen-containing hydrocarbon composition is a substantial raw material of a target hydrocarbon composition containing a straight-chain hydrocarbon having an even number of carbon atoms.
That is, in the production method of the present disclosure, the oxygen-containing hydrocarbon composition is hydrodeoxygenated to produce a hydrocarbon composition containing a straight-chain hydrocarbon having an even number of carbon atoms.
含酸素炭化水素組成物が、炭素数が偶数である直鎖脂肪酸を含む場合、含酸素炭化水素組成物に含まれる炭素数が偶数である直鎖脂肪酸は、1種のみであっても2種以上であってもよい。
また、この場合、含酸素炭化水素組成物は、炭素数14の直鎖脂肪酸、炭素数16の直鎖脂肪酸、及び炭素数18の直鎖脂肪酸からなる群から選択される少なくとも1種(好ましくは2種以上)を含むことが好ましい。
When the oxygen-containing hydrocarbon composition contains a straight-chain fatty acid having an even number of carbon atoms, the number of straight-chain fatty acids having an even-number of carbon atoms contained in the oxygen-containing hydrocarbon composition is two, if only one. It may be more.
Further, in this case, the oxygen-containing hydrocarbon composition is at least one selected from the group consisting of linear fatty acids having 14 carbon atoms, linear fatty acids having 16 carbon atoms, and linear fatty acids having 18 carbon atoms (preferably, It is preferable to include two or more kinds).
以下、炭素数n(例えば、炭素数18)を、「Cn」(例えば「C18」)と表記することがある。 Hereinafter, the carbon number n (for example, carbon number 18) may be referred to as “Cn” (for example, “C18”).
含酸素炭化水素組成物に含まれ得る炭素数が偶数である直鎖脂肪酸は、飽和脂肪酸であっても不飽和脂肪酸であってもよい。
含酸素炭化水素組成物に含まれ得る炭素数が偶数である直鎖脂肪酸の炭素数は、12、14、16、18、又は20であることが好ましい。
含酸素炭化水素組成物に含まれ得る炭素数が偶数である直鎖脂肪酸としては、ラウリン酸(C12:0)、ミリスチン酸(C14:0)、パルミチン酸(C16:0)、ステアリン酸(C18:0)、オレイン酸(C18:1)、リノール酸(C18:2)、アラキジン酸(C20:0)、ガドレイン酸(C20:1)、等が挙げられる。
ここで、「Cn:m」(例えば「C18:1」)との表記は、炭素数がn(例えば18)であり不飽和結合の数がm(例えば1)であることを意味する。
The linear fatty acid having an even number of carbon atoms that can be contained in the oxygen-containing hydrocarbon composition may be a saturated fatty acid or an unsaturated fatty acid.
The straight-chain fatty acid having an even number of carbon atoms that can be contained in the oxygen-containing hydrocarbon composition preferably has 12, 14, 16, 18, or 20 carbon atoms.
Examples of the straight-chain fatty acid having an even number of carbon atoms that can be contained in the oxygen-containing hydrocarbon composition include lauric acid (C12:0), myristic acid (C14:0), palmitic acid (C16:0), and stearic acid (C18). :0), oleic acid (C18:1), linoleic acid (C18:2), arachidic acid (C20:0), gadoleic acid (C20:1), and the like.
Here, the expression "Cn:m" (for example, "C18:1") means that the number of carbon atoms is n (for example, 18) and the number of unsaturated bonds is m (for example, 1).
含酸素炭化水素組成物が、炭素数が偶数である直鎖脂肪酸に由来するエステルを含む場合、含酸素炭化水素組成物に含まれる炭素数が偶数である直鎖脂肪酸に由来するエステルは、1種のみであっても2種以上であってもよい。
また、この場合、含酸素炭化水素組成物は、C14の直鎖脂肪酸に由来するエステル、C16の直鎖脂肪酸に由来するエステル、及びC18の直鎖脂肪酸に由来するエステルからなる群から選択される少なくとも1種(好ましくは2種以上)を含むことが好ましい。
ここで、「炭素数が偶数である直鎖脂肪酸に由来するエステル」とは、炭素数が偶数である直鎖脂肪酸と、アルコールと、の反応によって形成されたエステルを意味する。
アルコールとして、好ましくは、グリセリン又はメタノールである。即ち、「炭素数が偶数である直鎖脂肪酸に由来するエステル」として、好ましくは、脂肪酸グリセリンエステル(例えば、脂肪酸トリグリセリド)又は脂肪酸メチルエステルである。
When the oxygen-containing hydrocarbon composition contains an ester derived from a straight-chain fatty acid having an even number of carbon atoms, the ester derived from a straight-chain fatty acid having an even number of carbon atoms contained in the oxygen-containing hydrocarbon composition is 1 There may be only one kind or two or more kinds.
Further, in this case, the oxygen-containing hydrocarbon composition is selected from the group consisting of an ester derived from a C14 linear fatty acid, an ester derived from a C16 linear fatty acid, and an ester derived from a C18 linear fatty acid. It is preferable to contain at least one type (preferably two or more types).
Here, the "ester derived from a straight-chain fatty acid having an even number of carbon atoms" means an ester formed by the reaction of a straight-chain fatty acid having an even number of carbon atoms and an alcohol.
The alcohol is preferably glycerin or methanol. That is, the “ester derived from a straight-chain fatty acid having an even number of carbon atoms” is preferably a fatty acid glycerin ester (eg, fatty acid triglyceride) or a fatty acid methyl ester.
炭素数が偶数である直鎖脂肪酸に由来するエステルにおける直鎖脂肪酸の好ましい態様は、前述した、含酸素炭化水素組成物に含まれ得る炭素数が偶数である直鎖脂肪酸の好ましい態様と同様である。 The preferred embodiment of the linear fatty acid in the ester derived from the linear fatty acid having an even number of carbon atoms is the same as the preferred embodiment of the linear fatty acid having an even number of carbon atoms that can be contained in the oxygen-containing hydrocarbon composition described above. is there.
含酸素炭化水素組成物は、炭素数が偶数である直鎖脂肪酸及び炭素数が偶数である直鎖脂肪酸に由来するエステル以外の成分(例えば、炭素数が奇数である直鎖脂肪酸、炭素数が奇数である直鎖脂肪酸に由来するエステル、分岐鎖脂肪酸、分岐鎖脂肪酸に由来するエステル、等)を含んでいてもよい。
但し、本開示の製造方法の効果をより効果的に得る観点から、含酸素炭化水素組成物において、炭素数が偶数である直鎖脂肪酸及び炭素数が偶数である直鎖脂肪酸に由来するエステルの総含有量は、含酸素炭化水素組成物の全量に対し、90質量%以上であることが好ましく、95質量%以上であることがより好ましく、97質量%以上であることが特に好ましい。
The oxygen-containing hydrocarbon composition is a component other than an ester derived from a linear fatty acid having an even number of carbons and a linear fatty acid having an even number of carbons (for example, a linear fatty acid having an odd number of carbons, a carbon number of An ester derived from an odd-numbered linear fatty acid, a branched chain fatty acid, an ester derived from a branched chain fatty acid, and the like) may be included.
However, from the viewpoint of more effectively obtaining the effect of the production method of the present disclosure, in an oxygen-containing hydrocarbon composition, a linear fatty acid having an even number of carbons and an ester derived from a linear fatty acid having an even number of carbons The total content is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 97% by mass or more, based on the total amount of the oxygen-containing hydrocarbon composition.
更に、後述する水素化脱酸素処理工程において、C16の直鎖炭化水素及びC18の直鎖炭化水素を含む炭化水素組成物を製造する場合には、含酸素炭化水素組成物における、C16の直鎖脂肪酸、C16の直鎖脂肪酸に由来するエステル、C18の直鎖脂肪酸、及びC18の直鎖脂肪酸に由来するエステルの総含有量は、含酸素炭化水素組成物の全量に対し、90質量%以上であることが好ましく、95質量%以上であることがより好ましく、97質量%以上であることが特に好ましい。 Further, in the hydrodeoxygenation treatment step described below, when a hydrocarbon composition containing a C16 straight chain hydrocarbon and a C18 straight chain hydrocarbon is produced, the C16 straight chain in the oxygen-containing hydrocarbon composition is used. The total content of the fatty acid, the ester derived from the C16 linear fatty acid, the C18 linear fatty acid, and the ester derived from the C18 linear fatty acid is 90% by mass or more based on the total amount of the oxygen-containing hydrocarbon composition. It is preferably present, more preferably 95% by mass or more, and particularly preferably 97% by mass or more.
含酸素炭化水素組成物は、バイオマス利用の観点から、動植物油脂に由来する組成物であることが好ましい。
動植物油脂に由来する組成物としては、動植物油脂、動植物油脂を精製(例えば蒸留)した組成物、動植物油脂を使用した後の廃油、などが挙げられる。
動植物油脂としては、ココナッツ油、ヒマワリ油、大豆油、オリーブ油、綿実油、菜種油、パーム油、ジャトロファ油、等が挙げられる。
含酸素炭化水素組成物は、1種の動植物油脂に由来する組成物であってもよいし、2種以上の動植物油脂に由来する組成物であってもよい。
含酸素炭化水素組成物として、好ましくは、パーム油、ジャトロファ油、又はPFAD(Palm Fatty Acid Distillate;パーム脂肪酸蒸留物)である。
From the viewpoint of biomass utilization, the oxygen-containing hydrocarbon composition is preferably a composition derived from animal and vegetable oils and fats.
Examples of the composition derived from animal and vegetable oils and fats include animal and vegetable oils and fats, compositions obtained by refining (for example, distilling) animal and vegetable oils and fats, waste oil after using animal and vegetable oils, and the like.
Examples of animal and vegetable oils and fats include coconut oil, sunflower oil, soybean oil, olive oil, cottonseed oil, rapeseed oil, palm oil, jatropha oil, and the like.
The oxygen-containing hydrocarbon composition may be a composition derived from one type of animal or vegetable oil or fat, or may be a composition derived from two or more types of animal or vegetable oil or fat.
The oxygen-containing hydrocarbon composition is preferably palm oil, jatropha oil, or PFAD (Palm Fatty Acid Distillate).
(硫黄元素)
原料液は、硫黄元素を含有することが好ましい。これにより、後述する水素化脱酸素処理工程において、触媒の活性をより高めることができる。
原料液が硫黄元素を含有する場合、硫黄元素は、原料液中に、硫黄単体の形態で含有されてもよいし、硫黄化合物の形態で含有されてもよいし、硫黄単体の形態及び硫黄化合物の形態で含有されてもよい。原料液に含有され得る硫黄化合物は、1種のみであってもよいし、2種以上であってもよい。
ここでいう硫黄化合物の具体例及び好ましい態様は、後述する、硫化処理に用い得る硫黄化合物の具体例及び好ましい態様と同様である。
(Sulfur element)
The raw material liquid preferably contains elemental sulfur. As a result, the activity of the catalyst can be further increased in the hydrodeoxygenation treatment step described below.
When the raw material liquid contains elemental sulfur, the elemental sulfur may be contained in the raw material liquid in the form of a simple substance of sulfur, may be contained in the form of a sulfur compound, or may be contained in the form of a simple substance of sulfur and a sulfur compound. May be contained in the form of The sulfur compound that may be contained in the raw material liquid may be only one kind or two or more kinds.
The specific examples and preferred embodiments of the sulfur compound here are the same as the specific examples and preferred embodiments of the sulfur compound that can be used in the sulfurization treatment described later.
原料液が硫黄元素を含有する場合、原料液全量に対する硫黄元素の含有量は、1質量ppm以上であることが好ましい。
硫黄元素の含有量が1質量ppm以上であると、後述する水素化脱酸素処理工程において、触媒活性を十分に発現させることができ、その結果、水素化脱酸素反応の選択性が寄り向上する。硫黄元素の含有量は、好ましくは5質量ppm以上、より好ましくは10質量ppm以上である。
また、原料液が硫黄元素を含有する場合、原料液全量に対する硫黄元素の含有量は、1000質量ppm以下であることが好ましい。
硫黄元素の含有量が1000質量ppm以下であると、炭化水素組成物(目的物)の生産性が向上する。硫黄元素の含有量は、より好ましくは500質量ppm以下、更に好ましくは400質量ppm以下、更に好ましくは300質量ppm以下、特に好ましくは250質量ppm以下である。
When the raw material liquid contains elemental sulfur, the content of elemental sulfur relative to the total amount of the raw material liquid is preferably 1 mass ppm or more.
When the content of the elemental sulfur is 1 mass ppm or more, the catalytic activity can be sufficiently expressed in the hydrodeoxygenation treatment step described later, and as a result, the selectivity of the hydrodeoxygenation reaction is improved. .. The content of elemental sulfur is preferably 5 mass ppm or more, more preferably 10 mass ppm or more.
When the raw material liquid contains elemental sulfur, the content of elemental sulfur relative to the total amount of the raw material liquid is preferably 1000 mass ppm or less.
When the content of the elemental sulfur is 1000 mass ppm or less, the productivity of the hydrocarbon composition (target product) is improved. The content of elemental sulfur is more preferably 500 mass ppm or less, further preferably 400 mass ppm or less, further preferably 300 mass ppm or less, and particularly preferably 250 mass ppm or less.
<硫化処理工程>
硫化処理工程は、前述した触媒を、硫化処理する工程である。
これにより、触媒(好ましくは活性相)中の金属が硫化され、その結果、触媒が水素化脱酸素反応の活性を発揮する。
<Sulfidation process>
The sulfurating treatment step is a step of subjecting the above-mentioned catalyst to sulfurizing treatment.
This causes the metal in the catalyst (preferably the active phase) to be sulphided so that the catalyst exhibits hydrodeoxygenation reaction activity.
硫化処理は、前述した触媒と、硫黄元素と、を接触させることにより行うことができる。
硫化処理では、硫黄元素を、硫黄単体の形態で用いてもよいし、硫黄化合物の形態で用いてもよいし、硫黄単体の形態及び硫黄化合物の形態で用いてもよい。硫化処理に用い得る硫黄化合物は、1種のみであってもよいし、2種以上であってもよい。
硫化処理に用い得る硫黄化合物としては特に制限されないが、含硫黄炭化水素化合物が好ましく、スルフィド、ジスルフィド、ポリスルフィド、チオール、チオフェン、ベンゾチオフェン、ジベンゾチオフェン、ジベンジルポリスルフィド、若しくはこれらの誘導体、又は、硫黄分を含有する石油系炭化水素留分が好ましい。
The sulfurating treatment can be performed by bringing the above-mentioned catalyst into contact with elemental sulfur.
In the sulfurating treatment, elemental sulfur may be used in the form of simple substance of sulfur, in the form of sulfur compound, or in the form of simple substance of sulfur and in the form of sulfur compound. Only one sulfur compound may be used in the sulfurization treatment, or two or more sulfur compounds may be used.
The sulfur compound that can be used in the sulfurization treatment is not particularly limited, but a sulfur-containing hydrocarbon compound is preferable, and sulfide, disulfide, polysulfide, thiol, thiophene, benzothiophene, dibenzothiophene, dibenzyl polysulfide, or a derivative thereof, or sulfur. Petroleum hydrocarbon fractions containing fractions are preferred.
硫化処理に用い得る硫黄化合物としては、下記式(S1)で表される化合物も好ましい。
R−Sn−R’ … 式(S1)
式(S1)中、nは、1〜10を表し、R及びR’は、それぞれ独立に有機基を表す。
As the sulfur compound that can be used in the sulfurating treatment, a compound represented by the following formula (S1) is also preferable.
R-S n -R '... formula (S1)
In formula (S1), n represents 1 to 10, and R and R′ each independently represent an organic group.
式(S1)中、nとしては、2〜7が好ましく、4〜6がより好ましい。
式(S1)中、Rで表される有機基の炭素数及びR’で表される有機基の炭素数の合計は、2〜150であることが好ましく、2〜60であることがより好ましく、2〜20であることが特に好ましい。
R及びR’は、それぞれ独立に、直鎖若しくは分岐鎖の炭化水素基(好ましくはアルキル基)、アリール基、アルキルアリール基、又はアリールアルキル基が好ましい。
In formula (S1), n is preferably 2 to 7, and more preferably 4 to 6.
In the formula (S1), the total number of carbon atoms of the organic group represented by R and the number of carbon atoms of the organic group represented by R′ is preferably 2 to 150, more preferably 2 to 60. , 2 to 20 is particularly preferable.
R and R′ are each independently preferably a linear or branched hydrocarbon group (preferably an alkyl group), an aryl group, an alkylaryl group, or an arylalkyl group.
式(S1)で表される化合物の具体例としては、C8H17−S4.8−C8H17(ジ(1,1,3,3−テトラメチルブチル)ポリスルフィド;DIC社製CS−40)、ジメチルジスルフィド(DMDS)、などが挙げられる。 Specific examples of the compound represented by formula (S1), C 8 H 17 -S 4.8 -C 8 H 17 ( di (1,1,3,3-tetramethylbutyl) polysulfide; DIC Corp. CS -40), dimethyl disulfide (DMDS), and the like.
触媒の硫化処理は、現場(in situ)で行ってもよいし、現場外(ex situ)で行ってもよい。 The sulfurization treatment of the catalyst may be performed in situ or ex situ.
<水素化脱酸素処理工程>
水素化脱酸素処理工程は、硫化処理された上記触媒と上記原料液と水素とを接触させ、上記原料液中の前記含酸素炭化水素組成物を水素化脱酸素処理することにより、炭素数が偶数である直鎖炭化水素を含む炭化水素組成物を製造する工程である。
<Hydrodeoxidation process>
In the hydrodeoxygenation treatment step, the catalyst that has been subjected to sulfurization, the raw material liquid and hydrogen are brought into contact with each other, and the oxygen-containing hydrocarbon composition in the raw material liquid is hydrodeoxygenated to have a carbon number of A step of producing a hydrocarbon composition containing an even number of straight-chain hydrocarbons.
水素化脱酸素処理工程において、硫化処理された上記触媒と上記原料液と水素とを接触させる際の条件としては、一般的な条件を適用できるが、特に好ましい条件は、温度200℃〜450℃、圧力1MPa〜100MPa、液空間速度0.1h−1〜10h−1の条件である。 In the hydrodeoxygenation treatment step, general conditions can be applied as conditions for contacting the sulfurized catalyst, the raw material liquid, and hydrogen, but particularly preferable conditions are a temperature of 200°C to 450°C. , Pressure 1 MPa to 100 MPa, and liquid space velocity 0.1 h −1 to 10 h −1 .
硫化処理された上記触媒と上記原料液と水素とを接触させる際の温度(以下、「反応温度」ともいう)は、上述のとおり、200℃〜450℃であることが好ましい。
反応温度が200℃以上であると、水素化脱酸素処理(水素化脱酸素反応)がより効果的に進行する。
反応温度が450℃以下であると、副反応(脱炭酸/脱カルボニル反応、異性化反応等)をより抑制できる。
反応温度は、200℃〜400℃であることがより好ましく、250℃〜350℃であることが特に好ましい。
As described above, the temperature (hereinafter, also referred to as "reaction temperature") at which the sulfurating catalyst is brought into contact with the raw material liquid and hydrogen is preferably 200°C to 450°C.
When the reaction temperature is 200° C. or higher, the hydrodeoxygenation treatment (hydrodeoxygenation reaction) proceeds more effectively.
When the reaction temperature is 450° C. or lower, side reactions (decarboxylation/decarbonylation reaction, isomerization reaction, etc.) can be further suppressed.
The reaction temperature is more preferably 200°C to 400°C, particularly preferably 250°C to 350°C.
硫化処理された上記触媒と上記原料液と水素とを接触させる際の圧力(以下、「反応圧力」ともいう)は、上述のとおり、0.1MPa〜10MPaであることが好ましい。
反応圧力が0.1MPa以上であると、水素化脱酸素処理(水素化脱酸素反応)が効果的に進行し、かつ、副反応(脱炭酸/脱カルボニル反応、異性化反応等)が抑制される。
反応圧力が10MPa以下であると、水素化脱酸素処理を行う反応器を安価な材料で製造でき、また、上記反応器の構造を簡易化できるので、生産性に優れる。
反応圧力は、1MPa〜10MPaであることが好ましい。
The pressure (hereinafter, also referred to as “reaction pressure”) for bringing the sulfurized catalyst, the raw material liquid, and hydrogen into contact with each other is preferably 0.1 MPa to 10 MPa, as described above.
When the reaction pressure is 0.1 MPa or more, the hydrodeoxygenation treatment (hydrodeoxygenation reaction) effectively proceeds, and side reactions (decarboxylation/decarbonylation reaction, isomerization reaction, etc.) are suppressed. It
When the reaction pressure is 10 MPa or less, a reactor for performing hydrodeoxygenation treatment can be manufactured with an inexpensive material, and the structure of the reactor can be simplified, resulting in excellent productivity.
The reaction pressure is preferably 1 MPa to 10 MPa.
硫化処理された上記触媒と上記原料液と水素とを接触させる際の液空間速度は、上述のとおり、0.1h−1〜10h−1であることが好ましい。
上記液空間速度が0.1h−1以上であると、反応器の容積をより小さくすることができるので、生産性に優れる。
上記液空間速度が10h−1以下であると、水素化脱酸素処理(水素化脱酸素反応)が効果的に進行する。
As described above, the liquid hourly space velocity at the time of contacting the sulfurized catalyst, the raw material liquid, and hydrogen is preferably 0.1 h −1 to 10 h −1 .
When the liquid hourly space velocity is 0.1 h −1 or more, the volume of the reactor can be further reduced, and therefore the productivity is excellent.
When the liquid hourly space velocity is 10 h -1 or less, the hydrodeoxygenation treatment (hydrodeoxygenation reaction) effectively proceeds.
また、硫化処理された上記触媒と上記原料液と水素とを接触させる際、原料液の流量に対する水素の流量の比〔水素の流量/原料液の流量〕は、50Nm3/m3〜3000Nm3/m3が好ましく、70Nm3/m3〜2000Nm3/m3がより好ましく、150Nm3/m3〜1500Nm3/m3が更に好ましく、300Nm3/m3〜1000Nm3/m3が特に好ましい。 Further, when the catalyst subjected to the sulfurization treatment and the raw material liquid and hydrogen are brought into contact with each other, the ratio of the flow rate of hydrogen to the flow rate of the raw material liquid [hydrogen flow rate/raw material solution flow rate] is 50 Nm 3 /m 3 to 3000 Nm 3 / m 3 are preferred, more preferably 70Nm 3 / m 3 ~2000Nm 3 / m 3, more preferably 150Nm 3 / m 3 ~1500Nm 3 / m 3, particularly preferably 300 Nm 3 / m 3 1000 nm 3 / m 3 ..
水素化脱酸素処理工程では、硫化処理された上記触媒と上記原料液と水素とを接触させることにより、上記原料液中の含酸素炭化水素組成物を水素化脱酸素処理する。
上記接触(即ち、水素化脱酸素処理)は、固定床反応器又は沸騰床反応器にて行うことができるが、固定床反応器にて行うことが好ましい。
In the hydrodeoxygenation treatment step, the oxygen-containing hydrocarbon composition in the raw material liquid is hydrodeoxygenated by contacting the sulfurized catalyst, the raw material liquid and hydrogen.
The above contact (that is, hydrodeoxygenation treatment) can be performed in a fixed bed reactor or a boiling bed reactor, but is preferably performed in a fixed bed reactor.
水素化脱酸素処理工程では、原料液中の含酸素炭化水素組成物を水素化脱酸素処理することにより、目的物として、炭素数が偶数である直鎖炭化水素を含む炭化水素組成物を製造する。
詳細には、本工程では、含酸素炭化水素組成物に含まれる、炭素数が偶数である直鎖脂肪酸及び/又は炭素数が偶数である直鎖脂肪酸に由来するエステルが、水素化脱酸素処理され、目的物として、炭素数が偶数である直鎖炭化水素を含む炭化水素組成物を製造する。
この際、前述した触媒の作用により、副反応(脱炭酸/脱カルボニル反応、及び、異性化反応)が抑制され、水素化脱酸素処理における主反応(水素化脱酸素反応)が高選択で進行する。
このため、本工程によれば、原料液中の上記直鎖脂肪酸及び/又は上記エステルの炭素数と、同じ炭素数の直鎖炭化水素を含む炭化水素組成物を容易に製造できる。
例えば、原料液として、C16の直鎖脂肪酸又はそのエステル、及び、C18の直鎖脂肪酸又はそのエステルを含む原料液を用いた場合には、C16の直鎖炭化水素及びC18の直鎖炭化水素を含む炭化水素組成物を容易に製造できる。
In the hydrodeoxygenation treatment process, the oxygen-containing hydrocarbon composition in the raw material liquid is hydrodeoxygenated to produce a hydrocarbon composition containing a straight-chain hydrocarbon having an even number of carbon atoms as a target product. To do.
Specifically, in this step, the linear fatty acid having an even number of carbon atoms and/or the ester derived from the linear fatty acid having an even number of carbons contained in the oxygen-containing hydrocarbon composition is hydrodeoxygenated. As a result, a hydrocarbon composition containing a straight-chain hydrocarbon having an even number of carbon atoms is produced.
At this time, by the action of the catalyst described above, side reactions (decarboxylation/decarbonylation reaction and isomerization reaction) are suppressed, and the main reaction (hydrodeoxygenation reaction) in the hydrodeoxygenation process proceeds with high selectivity. To do.
Therefore, according to this step, a hydrocarbon composition containing a linear hydrocarbon having the same carbon number as the carbon number of the linear fatty acid and/or the ester in the raw material liquid can be easily produced.
For example, when a raw material liquid containing a C16 straight-chain fatty acid or an ester thereof and a C18 straight-chain fatty acid or an ester thereof is used as a raw material liquid, a C16 straight-chain hydrocarbon and a C18 straight-chain hydrocarbon are used. A hydrocarbon composition containing the same can be easily produced.
目的物(炭素数が偶数である直鎖炭化水素を含む炭化水素組成物)の用途には特に制限はない。
目的物の用途として、軽油又は潜熱蓄熱材(PCM;phase change material)が挙げられるが、潜熱蓄熱材が特に好ましい。
ここで、潜熱蓄熱材とは、相転移に伴う潜熱(例えば、液相から固相への相転移時に放出する凝固熱及び/又は固相から液相への相転移時に吸収する融解熱)を利用した蓄熱材である。潜熱蓄熱材は、顕熱を利用した蓄熱材と比較して、蓄熱材容積の縮小化、熱損失低減などの点で優れている。近年、潜熱蓄熱材を利用した、蓄熱式空調機器、蓄熱式建材、各種保温器具、装置等が数多く提案されている。潜熱蓄熱材については、特開2015−30822号公報の段落0001〜0005の記載を参照できる。
即ち、本開示の製造方法は、潜熱蓄熱材としての、炭素数が偶数である直鎖炭化水素を含む炭化水素組成物を、簡単な製造工程にて製造する方法として特に好適である。
There is no particular limitation on the use of the target product (hydrocarbon composition containing a straight-chain hydrocarbon having an even number of carbon atoms).
Examples of the intended use of the object include light oil or a latent heat storage material (PCM; phase change material), and the latent heat storage material is particularly preferable.
Here, the latent heat storage material means latent heat associated with phase transition (for example, heat of solidification released during phase transition from liquid phase to solid phase and/or heat of fusion absorbed during phase transition from solid phase to liquid phase). The heat storage material used. The latent heat storage material is superior to the heat storage material that uses sensible heat in that the volume of the heat storage material is reduced and the heat loss is reduced. In recent years, a large number of heat storage type air conditioners, heat storage type building materials, various heat retaining devices, devices, and the like have been proposed that utilize latent heat storage materials. Regarding the latent heat storage material, the description in paragraphs 0001 to 0005 of JP-A-2015-30822 can be referred to.
That is, the production method of the present disclosure is particularly suitable as a method for producing a hydrocarbon composition containing a straight-chain hydrocarbon having an even number of carbon atoms as a latent heat storage material by a simple production process.
以下、本発明を実施例により更に具体的に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples.
〔実施例1〕
<触媒の作製>
触媒の担体としてアルミナ担体(γ−アルミナ担体、日本ケッチェン社製、比表面積275m2/g)を準備した。このアルミナ担体(50g)をナス型フラスコに入れた。
アルミナ担体(50g)を入れたナス型フラスコに、モリブデン酸アンモニウム4水和物((NH4)6Mo7O24・4H2O)及び硝酸コバルト6水和物(Co(NO3)2・6H2O)を含む水溶液を注入し、アルミナ担体に含浸させた。
得られた複合体を加熱しながら、ロータリーエバポレーターによって上記複合体から水分を蒸発させた。得られた固体を120℃で1時間乾燥させ、次いで500℃で焼成した。
以上により、アルミナ担体(50g)に、酸化モリブデン(MoO3)及び酸化コバルト(CoO)からなる活性相が担持された構造を有する触媒を得た。
蛍光X線分析(XRF;X-ray Fluorescence Analysis)の結果、得られた触媒において、酸化モリブデンの含有量は、触媒の全量(即ち、担体と活性相との合計量)に対して20質量%であり、活性相における原子数比〔Co/Mo〕は表4に示すように0.06であった。
[Example 1]
<Preparation of catalyst>
As a catalyst carrier, an alumina carrier (γ-alumina carrier, manufactured by Nippon Ketjen Co., Ltd., specific surface area 275 m 2 /g) was prepared. This alumina carrier (50 g) was placed in an eggplant-shaped flask.
In an eggplant-shaped flask containing an alumina carrier (50 g), ammonium molybdate tetrahydrate ((NH 4 ) 6 Mo 7 O 24 ·4H 2 O) and cobalt nitrate hexahydrate (Co(NO 3 ) 2 · An aqueous solution containing 6H 2 O) was injected to impregnate the alumina carrier.
While heating the obtained composite, water was evaporated from the composite by a rotary evaporator. The solid obtained was dried at 120° C. for 1 hour and then calcined at 500° C.
As described above, a catalyst having a structure in which an active phase composed of molybdenum oxide (MoO 3 ) and cobalt oxide (CoO) was supported on the alumina carrier (50 g) was obtained.
As a result of X-ray fluorescence analysis (XRF), in the obtained catalyst, the content of molybdenum oxide was 20% by mass with respect to the total amount of the catalyst (that is, the total amount of the carrier and the active phase). The atomic number ratio [Co/Mo] in the active phase was 0.06 as shown in Table 4.
<原料液の作製>
含酸素炭化水素組成物として、下記表1に示す脂肪酸組成のPFAD(Palm Fatty Acid Distillate;パーム脂肪酸蒸留物)を準備した。
<Preparation of raw material liquid>
As the oxygen-containing hydrocarbon composition, PFAD (Palm Fatty Acid Distillate) having a fatty acid composition shown in Table 1 below was prepared.
表1に示す各脂肪酸は、PFAD中に、80質量%程度が脂肪酸の形態で、20質量%程度が脂肪酸トリグリセリドの形態で、それぞれ含有されている。 Each of the fatty acids shown in Table 1 is contained in PFAD in the amount of about 80% by mass in the form of fatty acid and about 20% by mass in the form of fatty acid triglyceride.
上記PFADに対し、硫黄化合物であるジ(1,1,3,3−テトラメチルブチル)ポリスルフィド(CS−40;DIC(株))を、作製される原料液の全量に対する硫黄元素の含有量が50質量ppmとなるように添加することにより、原料液を得た。 Di(1,1,3,3-tetramethylbutyl)polysulfide (CS-40; DIC Co., Ltd.), which is a sulfur compound, was added to the above-mentioned PFAD in such a manner that the content of elemental sulfur relative to the total amount of the raw material liquid produced was A raw material liquid was obtained by adding 50 mass ppm.
<硫化処理及び水素化脱酸素処理>
上記で作製された触媒を固定床反応器に収容した。
次いで、2質量%のCS−40を含む、軽油留分に相当する炭化水素混合物を固定床反応器に供給することにより、固定床反応器中の触媒を5時間硫化処理した。硫化処理の条件は、温度350℃、圧力1MPa、及び液空間速度5.0h−1とした。
次に、固定床反応器に供給する物質を、上記軽油留分に相当する炭化水素混合物から、上記原料液(即ち、PFADとCS-40との混合物)に切り替えて水素化脱酸素処理を行い、液体生成物を得た。水素化脱酸素処理の条件は、反応温度300℃、反応圧力3MPa、液空間速度1.0h−1、及び、水素ガス流量と原料液流量との比率(水素ガス流量/原料液流量)1000Nm3/m3とした。
<Sulfidation treatment and hydrodeoxygenation treatment>
The catalyst prepared above was placed in a fixed bed reactor.
Next, the catalyst in the fixed bed reactor was subjected to sulfurization treatment for 5 hours by supplying a hydrocarbon mixture containing 2 mass% of CS-40 corresponding to a gas oil fraction to the fixed bed reactor. The conditions of the sulfurization treatment were a temperature of 350° C., a pressure of 1 MPa, and a liquid space velocity of 5.0 h −1 .
Next, the substance supplied to the fixed bed reactor is switched from the hydrocarbon mixture corresponding to the above gas oil fraction to the above raw material liquid (that is, the mixture of PFAD and CS-40) for hydrodeoxygenation treatment. , A liquid product was obtained. The conditions of the hydrodeoxygenation treatment are a reaction temperature of 300° C., a reaction pressure of 3 MPa, a liquid space velocity of 1.0 h −1 , and a ratio of a hydrogen gas flow rate to a raw material liquid flow rate (hydrogen gas flow rate/raw material liquid flow rate) 1000 Nm 3 /M 3 .
水素化脱酸素処理後の液体生成物を回収し、油水分離を行った後、油分(即ち、目的物である炭化水素組成物)をガスクロマトグラフで分析した。
その結果、原料液中の含酸素炭化水素組成物(PFAD)中の酸素原子は、水素化脱酸素反応によってほぼ除去されていた。また、得られた炭化水素組成物(目的物)中、C14以下の炭化水素及びC19以上の炭化水素は少なく、炭化水素組成物中のほとんどがC15〜C18の炭化水素であった。詳細には、酸素を含む生成物、C14以下の炭化水素、及びC19以上の炭化水素の総含有量が、炭化水素組成物(目的物)の全量に対して10質量%未満であり、C15〜C18の炭化水素の総含有量が、炭化水素組成物(目的物)の全量に対して90質量%超であった。
The liquid product after the hydrodeoxygenation treatment was recovered, oil-water separation was performed, and then the oil content (that is, the target hydrocarbon composition) was analyzed by gas chromatography.
As a result, the oxygen atoms in the oxygen-containing hydrocarbon composition (PFAD) in the raw material liquid were almost removed by the hydrodeoxygenation reaction. Further, in the obtained hydrocarbon composition (target product), there were few hydrocarbons having a C14 or less and hydrocarbons having a C19 or more, and most of the hydrocarbon compositions were C15 to C18 hydrocarbons. Specifically, the total content of the product containing oxygen, the hydrocarbon of C14 or less, and the hydrocarbon of C19 or more is less than 10 mass% with respect to the total amount of the hydrocarbon composition (object), and C15 to The total content of C18 hydrocarbons was more than 90% by mass with respect to the total amount of the hydrocarbon composition (object).
次に、炭化水素組成物中のC15〜C18の炭化水素の内訳として、
水素化脱酸素反応(即ち、主反応)によって生成したC16の直鎖炭化水素及びC18の直鎖炭化水素中の炭素原子の合計モル数Pe、
脱炭酸/脱カルボニル反応(即ち、副反応)によって生成したC15の直鎖炭化水素及びC17の直鎖炭化水素中の炭素原子の合計モル数Po、及び
異性化反応(即ち、副反応)によって生成したC15〜C18の分岐鎖炭化水素中の炭素原子の合計モル数Piをそれぞれ求め、下記式(1)によって水素化脱酸素反応の選択性を求めた。
結果を表4に示す。
水素化脱酸素反応の選択性(モル%)=(Pe/(Pe+Po+Pi))×100 … 式(1)
Next, as a breakdown of C15 to C18 hydrocarbons in the hydrocarbon composition,
The total number of moles Pe of carbon atoms in the C16 linear hydrocarbon and the C18 linear hydrocarbon produced by the hydrodeoxygenation reaction (that is, the main reaction) Pe,
The total number of moles Po of carbon atoms in the C15 straight chain hydrocarbon and the C17 straight chain hydrocarbon produced by the decarboxylation/decarbonylation reaction (ie, side reaction), and the isomerization reaction (ie, side reaction) The total number of moles Pi of carbon atoms in the C15 to C18 branched chain hydrocarbon was determined, and the selectivity of the hydrodeoxygenation reaction was determined by the following formula (1).
The results are shown in Table 4.
Selectivity of hydrodeoxygenation reaction (mol %)=(Pe/(Pe+Po+Pi))×100 Formula (1)
式(1)によって求められる水素化脱酸素反応の選択性は、C15〜C18の炭化水素における、水素化脱酸素反応の主反応の生成物(即ち、C16の直鎖炭化水素及びC18の直鎖炭化水素)の割合(モル%)を意味する。
水素化脱酸素反応の選択性の数値が高い程、水素化脱酸素反応の選択性に優れることを意味する。
The selectivity of the hydrodeoxygenation reaction obtained by the formula (1) is determined by the products of the main reaction of the hydrodeoxygenation reaction (that is, the C16 straight chain hydrocarbon and the C18 straight chain hydrocarbon) in the C15 to C18 hydrocarbon. (Hydrocarbon) means the ratio (mol %).
The higher the selectivity of the hydrodeoxygenation reaction, the better the selectivity of the hydrodeoxygenation reaction.
〔実施例2〜5、比較例1〜2〕
触媒の作製において、硝酸コバルト6水和物(Co(NO3)2・6H2O)の量を変更することにより、活性相中の原子数比〔Co/Mo〕を表4に示すように変更したこと以外は実施例1と同様の操作を行った。
結果を表4に示す。
[Examples 2-5, Comparative Examples 1-2]
In the preparation of the catalyst, by changing the amount of cobalt nitrate hexahydrate (Co (NO 3) 2 · 6H 2 O), the atomic ratio of the active phase in the [Co / Mo] As shown in Table 4 The same operation as in Example 1 was performed except that the changes were made.
The results are shown in Table 4.
また、いずれの例においても、酸素を含む生成物、C14以下の炭化水素、及びC19以上の炭化水素の総含有量が、炭化水素組成物(目的物)の全量に対して10質量%未満であり、C15〜C18の炭化水素の総含有量が、炭化水素組成物(目的物)の全量に対して90質量%超であった。 Further, in any of the examples, the total content of the product containing oxygen, the hydrocarbon of C14 or less, and the hydrocarbon of C19 or more is less than 10 mass% with respect to the total amount of the hydrocarbon composition (target product). Yes, the total content of C15 to C18 hydrocarbons was more than 90 mass% with respect to the total amount of the hydrocarbon composition (object).
〔実施例6〕
原料油中の含酸素炭化水素組成物(PFAD)を、表2に示すトリグリセリドの脂肪酸組成のジャトロファ油に変更し、活性化処理及び水素化脱離処理に用いる硫黄化合物(CS−40)をジメチルジスルフィド(DMDS)に変更し、水素化脱酸素処理の条件(反応温度、反応圧力、及び液空間速度)を表4に示すように変更したこと以外は実施例1と同様の操作を行った。
結果を表4に示す。
[Example 6]
The oxygen-containing hydrocarbon composition (PFAD) in the feedstock was changed to jatropha oil having the fatty acid composition of triglyceride shown in Table 2, and the sulfur compound (CS-40) used in the activation treatment and the hydrodesorption treatment was dimethyl. The same operation as in Example 1 was carried out except that the disulfide (DMDS) was changed and the hydrodeoxygenation conditions (reaction temperature, reaction pressure, and liquid hourly space velocity) were changed as shown in Table 4.
The results are shown in Table 4.
また、実施例6において、酸素を含む生成物、C14以下の炭化水素、及びC19以上の炭化水素の総含有量が、炭化水素組成物(目的物)の全量に対して10質量%未満であり、C15〜C18の炭化水素の総含有量が、炭化水素組成物(目的物)の全量に対して90質量%超であった。 Moreover, in Example 6, the total content of the product containing oxygen, the hydrocarbon of C14 or less, and the hydrocarbon of C19 or more is less than 10% by mass with respect to the total amount of the hydrocarbon composition (target product). , The total content of C15 to C18 hydrocarbons was more than 90% by mass with respect to the total amount of the hydrocarbon composition (object).
表2に示す各脂肪酸は、実際には、脂肪酸トリグリセリドの形態でジャトロファ油に含有されている。 Each fatty acid shown in Table 2 is actually contained in jatropha oil in the form of fatty acid triglyceride.
〔実施例7〕
原料油中の含酸素炭化水素組成物を、表3に示すトリグリセリドの脂肪酸組成を有するパーム油に変更し、かつ、水素化脱酸素処理の条件(反応温度、反応圧力、及び液空間速度)を表4に示すように変更したこと以外は実施例1と同様の操作を行った。
結果を表4に示す。
[Example 7]
The oxygen-containing hydrocarbon composition in the feedstock was changed to palm oil having the fatty acid composition of triglyceride shown in Table 3, and the conditions for the hydrodeoxygenation treatment (reaction temperature, reaction pressure, and liquid hourly space velocity) were changed. The same operation as in Example 1 was performed except that the changes were made as shown in Table 4.
The results are shown in Table 4.
また、実施例7において、酸素を含む生成物、C14以下の炭化水素、及びC19以上の炭化水素の総含有量が、炭化水素組成物(目的物)の全量に対して10質量%未満であり、C15〜C18の炭化水素の総含有量が、炭化水素組成物(目的物)の全量に対して90質量%超であった。 Moreover, in Example 7, the total content of the product containing oxygen, the hydrocarbon of C14 or less, and the hydrocarbon of C19 or more is less than 10% by mass with respect to the total amount of the hydrocarbon composition (object). , The total content of C15 to C18 hydrocarbons was more than 90% by mass with respect to the total amount of the hydrocarbon composition (object).
表3に示す各脂肪酸は、実際には、脂肪酸トリグリセリドの形態でパーム油に含有されている。 Each fatty acid shown in Table 3 is actually contained in palm oil in the form of fatty acid triglyceride.
〔実施例8〜10〕
触媒の作製において、アルミナ担体を、以下のようにして作製されたチタニア添加アルミナ担体に変更した(即ち、チタニア添加アルミナ担体に活性相を担持させた)こと以外は実施例1と同様の操作を行った。
結果を表4に示す。
[Examples 8 to 10]
In the production of the catalyst, the same operation as in Example 1 was carried out except that the alumina support was changed to the titania-added alumina support produced as follows (that is, the active phase was loaded on the titania-added alumina support). went.
The results are shown in Table 4.
また、いずれの例においても、酸素を含む生成物、C14以下の炭化水素、及びC19以上の炭化水素の総含有量が、炭化水素組成物(目的物)の全量に対して10質量%未満であり、C15〜C18の炭化水素の総含有量が、炭化水素組成物(目的物)の全量に対して90質量%超であった。 Further, in any of the examples, the total content of the product containing oxygen, the hydrocarbon of C14 or less, and the hydrocarbon of C19 or more is less than 10 mass% with respect to the total amount of the hydrocarbon composition (target product). Yes, the total content of C15 to C18 hydrocarbons was more than 90 mass% with respect to the total amount of the hydrocarbon composition (object).
<チタニア添加アルミナ担体の作製(実施例8〜10)>
実施例8〜10において、チタニア添加アルミナ担体は、以下のようにして作製した。
チタンイソプロポキシド(Ti(OCH(CH3)4))のエタノール溶液を調製し、ナスフラスコにいれた。ここに、実施例1で用いたアルミナ担体(50g)を入れ、室温で2時間放置することにより、チタンイソプロポキシドのエタノール溶液をアルミナ担体に含浸させた。
次に、ロータリーエバポレーターにより、上記エタノール溶液を含浸させたアルミナ担体からエタノールを蒸発させ、次いでここに適量の水を添加し、室温で12時間チタンイソプロポキシドの加水分解を行った。
得られた生成物からロータリーエバポレーターによって水を蒸発させ、次いで120℃で2時間乾燥させ、その後、600℃で4時間焼成することにより、チタニア(TiO2)が添加されたアルミナ担体(即ち、チタニア添加アルミナ担体)を得た。
上述したチタンイソプロポキシドのエタノール溶液の濃度は、最終的に得られるチタニア添加アルミナ担体の全体に対するチタニアの含有量が、5質量%(実施例8)、15質量%(実施例9)、及び20質量%(実施例10)の各含有量となるように調整した。チタニア添加アルミナ担体の全体に対するチタニアの含有量は、蛍光X線分析(XRF)によって確認した。
<Preparation of titania-added alumina carrier (Examples 8 to 10)>
In Examples 8 to 10, the titania-added alumina carrier was prepared as follows.
An ethanol solution of titanium isopropoxide (Ti (OCH (CH 3) 4)) were prepared and placed in a recovery flask. The alumina carrier (50 g) used in Example 1 was put therein and left standing at room temperature for 2 hours to impregnate the alumina carrier with an ethanol solution of titanium isopropoxide.
Next, ethanol was evaporated from the alumina carrier impregnated with the above ethanol solution by a rotary evaporator, and then an appropriate amount of water was added thereto, and titanium isopropoxide was hydrolyzed at room temperature for 12 hours.
Water was evaporated from the obtained product by a rotary evaporator, then dried at 120° C. for 2 hours, and then calcined at 600° C. for 4 hours to obtain an alumina carrier to which titania (TiO 2 ) was added (that is, titania). (Added alumina carrier) was obtained.
Regarding the concentration of the ethanol solution of titanium isopropoxide described above, the content of titania with respect to the entire titania-added alumina carrier finally obtained is 5% by mass (Example 8), 15% by mass (Example 9), and The content was adjusted to 20% by mass (Example 10). The content of titania in the entire titania-added alumina carrier was confirmed by fluorescent X-ray analysis (XRF).
表4に示すように、触媒の活性相における原子数比〔Co/Mo〕が0.06〜0.30である実施例1〜10では、C15〜C18の炭化水素におけるC16の直鎖炭化水素及びC18の直鎖炭化水素の割合(Pe/(Pe+Po+Pi))×100)(モル%)が90.3モル%以上であり、水素化脱酸素反応の選択性に優れていた。
これに対し、触媒の活性相における原子数比〔Co/Mo〕が0.06未満である比較例1では、C15〜C18の炭化水素におけるC16の直鎖炭化水素及びC18の直鎖炭化水素の割合(Pe/(Pe+Po+Pi))×100)(モル%)が88.5モル%であり、水素化脱酸素反応の選択性に劣っていた。
また、触媒の活性相における原子数比〔Co/Mo〕が0.30超である比較例2では、C15〜C18の炭化水素におけるC16の直鎖炭化水素及びC18の直鎖炭化水素の割合(Pe/(Pe+Po+Pi))×100)(モル%)が84.8モル%であり、水素化脱酸素反応の選択性に劣っていた。
As shown in Table 4, in Examples 1 to 10 in which the atom number ratio [Co/Mo] in the active phase of the catalyst is 0.06 to 0.30, the straight chain hydrocarbon of C16 in the hydrocarbon of C15 to C18. And the proportion (Ce/(Pe+Po+Pi))×100) of C18 straight-chain hydrocarbons (mol %) was 90.3 mol% or more, and the selectivity of the hydrodeoxygenation reaction was excellent.
On the other hand, in Comparative Example 1 in which the atom number ratio [Co/Mo] in the active phase of the catalyst is less than 0.06, the C16 linear hydrocarbon and the C18 linear hydrocarbon in the C15 to C18 hydrocarbons are The ratio (Pe/(Pe+Po+Pi))×100) (mol %) was 88.5 mol %, and the selectivity of the hydrodeoxygenation reaction was poor.
Further, in Comparative Example 2 in which the atomic ratio [Co/Mo] in the active phase of the catalyst is more than 0.30, the proportion of the C16 linear hydrocarbon and the C18 linear hydrocarbon in the C15 to C18 hydrocarbons ( Pe/(Pe+Po+Pi))×100) (mol %) was 84.8 mol %, and the selectivity of the hydrodeoxygenation reaction was poor.
また、実施例1及び8〜10の対比より、TiO2(チタニア)添加アルミナ担体を用いると(実施例8〜10)、水素化脱酸素反応の選択性がより向上することがわかる。 Further, from the comparison between Examples 1 and 8 to 10, it is understood that the use of the TiO 2 (titania)-added alumina carrier (Examples 8 to 10) further improves the selectivity of the hydrodeoxygenation reaction.
Claims (9)
BET法による比表面積が100m2/g〜400m2/gである多孔質材料を含有する担体と、前記担体に担持された活性相であって、第6族の元素からなる群から選択される少なくとも1種の元素X1と第8族〜第10族の元素からなる群から選択される少なくとも1種の元素X2とを含有し、前記元素X1に対する前記元素X2の原子数比が0.06〜0.20である活性相と、を含む触媒を準備する工程と、
前記触媒を硫化処理する工程と、
硫化処理された前記触媒と前記原料液と水素とを接触させ、前記原料液中の前記含酸素炭化水素組成物を水素化脱酸素処理することにより、炭素数が偶数である直鎖炭化水素を含む炭化水素組成物を製造する工程と、
を有し、
前記元素X1が、Moであり、
前記元素X2が、Coである、
炭化水素組成物の製造方法。 A raw material liquid containing an oxygen-containing hydrocarbon composition containing at least one selected from the group consisting of straight-chain fatty acids having an even number of carbon atoms and esters derived from straight-chain fatty acids having an even number of carbon atoms is prepared. Process,
A carrier having a specific surface area by BET method contains a porous material which is 100m 2 / g~400m 2 / g, a supported active phase on the support is selected from the group consisting of elements of Group 6 At least one element X1 and at least one element X2 selected from the group consisting of Group 8 to Group 10 elements are contained, and the atomic ratio of the element X2 to the element X1 is 0.06 to Providing a catalyst comprising an active phase of 0.20 ,
A step of sulfiding the catalyst,
By contacting the sulfurized catalyst and the raw material liquid and hydrogen, and hydrodeoxygenating the oxygen-containing hydrocarbon composition in the raw material liquid, a straight-chain hydrocarbon having an even number of carbon atoms is obtained. Producing a hydrocarbon composition comprising
Have
The element X1 is Mo ,
The element X2 is Co,
Process for producing hydrocarbon composition.
BET法による比表面積が100m2/g〜400m2/gである多孔質材料を含有する担体と、
前記担体に担持された活性相であって、第6族の元素からなる群から選択される少なくとも1種の元素X1と第8族〜第10族の元素からなる群から選択される少なくとも1種の元素X2とを含有し、前記元素X1に対する前記元素X2の原子数比が0.06〜0.20である活性相と、
を含み、
前記元素X1が、Moであり、
前記元素X2が、Coである、
触媒。 A catalyst used in a reaction for producing a hydrocarbon composition by hydrodeoxygenating an oxygen-containing hydrocarbon composition,
A carrier having a specific surface area by BET method contains a porous material which is 100m 2 / g~400m 2 / g,
An active phase supported on the carrier, which is at least one element X1 selected from the group consisting of elements of Group 6 and at least one selected from the group consisting of elements of Groups 8 to 10 An active phase containing the element X2 and the atomic ratio of the element X2 to the element X1 is 0.06 to 0.20 ,
Only including,
The element X1 is Mo ,
The element X2 is Co,
catalyst.
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