JP5588171B2 - Method for producing hydrocarbon oil - Google Patents
Method for producing hydrocarbon oil Download PDFInfo
- Publication number
- JP5588171B2 JP5588171B2 JP2009519944A JP2009519944A JP5588171B2 JP 5588171 B2 JP5588171 B2 JP 5588171B2 JP 2009519944 A JP2009519944 A JP 2009519944A JP 2009519944 A JP2009519944 A JP 2009519944A JP 5588171 B2 JP5588171 B2 JP 5588171B2
- Authority
- JP
- Japan
- Prior art keywords
- oil
- fraction
- hydrocarbon oil
- hydrocarbon
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 150000002430 hydrocarbons Chemical class 0.000 title claims description 109
- 229930195733 hydrocarbon Natural products 0.000 title claims description 70
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 66
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000003921 oil Substances 0.000 claims description 192
- 235000019198 oils Nutrition 0.000 claims description 192
- 239000003054 catalyst Substances 0.000 claims description 103
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 64
- 229910052739 hydrogen Inorganic materials 0.000 claims description 64
- 239000001257 hydrogen Substances 0.000 claims description 64
- 229910052717 sulfur Inorganic materials 0.000 claims description 43
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 37
- 239000011593 sulfur Substances 0.000 claims description 37
- 229910052760 oxygen Inorganic materials 0.000 claims description 33
- 239000001301 oxygen Substances 0.000 claims description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 32
- 238000006317 isomerization reaction Methods 0.000 claims description 32
- 239000002994 raw material Substances 0.000 claims description 32
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 239000011148 porous material Substances 0.000 claims description 27
- 241001465754 Metazoa Species 0.000 claims description 23
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 21
- 239000008158 vegetable oil Substances 0.000 claims description 21
- 239000010775 animal oil Substances 0.000 claims description 20
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 20
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 17
- 239000000194 fatty acid Substances 0.000 claims description 17
- 229930195729 fatty acid Natural products 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 239000001569 carbon dioxide Substances 0.000 claims description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 15
- 150000002739 metals Chemical class 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- -1 fatty acid esters Chemical class 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000004665 fatty acids Chemical class 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229910021472 group 8 element Inorganic materials 0.000 claims description 6
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 238000004438 BET method Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims 1
- 239000011147 inorganic material Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 74
- 238000000034 method Methods 0.000 description 44
- 230000000694 effects Effects 0.000 description 31
- 239000000463 material Substances 0.000 description 16
- 239000002585 base Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 12
- 230000007423 decrease Effects 0.000 description 12
- 239000003925 fat Substances 0.000 description 12
- 235000019482 Palm oil Nutrition 0.000 description 11
- 235000019197 fats Nutrition 0.000 description 11
- 239000002540 palm oil Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 9
- 238000006114 decarboxylation reaction Methods 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 6
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 5
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 239000003350 kerosene Substances 0.000 description 5
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 4
- 208000016444 Benign adult familial myoclonic epilepsy Diseases 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 208000016427 familial adult myoclonic epilepsy Diseases 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- ZGNITFSDLCMLGI-UHFFFAOYSA-N flubendiamide Chemical compound CC1=CC(C(F)(C(F)(F)F)C(F)(F)F)=CC=C1NC(=O)C1=CC=CC(I)=C1C(=O)NC(C)(C)CS(C)(=O)=O ZGNITFSDLCMLGI-UHFFFAOYSA-N 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 229940024546 aluminum hydroxide gel Drugs 0.000 description 3
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 3
- 230000037361 pathway Effects 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 230000009471 action Effects 0.000 description 2
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- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
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- 238000004140 cleaning Methods 0.000 description 1
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
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- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 125000005457 triglyceride group Chemical group 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- 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
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
本発明は炭化水素油の製造方法に関する。 The present invention relates to a method for producing a hydrocarbon oil.
地球温暖化の防止対策としてバイオマスのもつエネルギーの有効利用に注目が集まっている。その中でも植物由来のバイオマスエネルギーは、植物の成長過程で光合成により大気中の二酸化炭素から固定化された炭素を有効利用できるため、ライフサイクルの観点からすると大気中の二酸化炭素の増加につながらない、所謂カーボンニュートラルという性質を持つ。 Attention has been focused on the effective use of biomass energy as a measure to prevent global warming. Among them, biomass energy derived from plants can effectively use carbon immobilized from carbon dioxide in the atmosphere by photosynthesis during the growth process of plants, so it does not lead to an increase in carbon dioxide in the atmosphere from the viewpoint of the life cycle, so-called It has the property of being carbon neutral.
このようなバイオマスエネルギーの利用は輸送用燃料の分野においても種々検討がなされている。例えば、ディーゼル燃料として動植物油由来の燃料を使用できれば、ディーゼルエンジンの高いエネルギー効率との相乗効果により、二酸化炭素の排出量削減において有効な役割を果たすと期待されている。動植物油を利用したディーゼル燃料としては、一般的には脂肪酸メチルエステル油（Ｆａｔｔｙ Ａｃｉｄ Ｍｅｔｈｙｌ Ｅｓｔｅｒ の頭文字から「ＦＡＭＥ」と略称される。）が知られている。ＦＡＭＥは動植物油の一般的な構造であるトリグリセリドを、アルカリ触媒等の作用によりメタノールとエステル交換反応に供することで製造される。 Various uses of such biomass energy have been studied in the field of transportation fuel. For example, if a fuel derived from animal and vegetable oils can be used as a diesel fuel, it is expected to play an effective role in reducing carbon dioxide emissions due to a synergistic effect with the high energy efficiency of a diesel engine. As diesel fuel using animal and vegetable oils, fatty acid methyl ester oil (abbreviated as “FAME” from the acronym of Fatty Acid Methyl Ester) is generally known. FAME is produced by subjecting triglyceride, which is a general structure of animal and vegetable oils, to transesterification with methanol by the action of an alkali catalyst or the like.
しかしながら、ＦＡＭＥを製造するプロセスにおいては、下記特許文献１に記載されている通り、副生するグリセリンの処理が必要であり、また生成油の洗浄などにコストやエネルギーを要する等の問題が指摘されている。 However, in the process for producing FAME, as described in Patent Document 1 below, it is necessary to treat glycerin produced as a by-product, and problems such as cost and energy are required for cleaning the produced oil. ing.
また、ＦＡＭＥは１分子中に２つの酸素原子を有することから、燃料としては極めて高い酸素含有量となり、従来の石油由来のディーゼル燃料に配合して使用する場合においてもなお、この酸素分がエンジン材質に与える悪影響が懸念されるとの問題もある。 Also, FAME has two oxygen atoms in one molecule, so it has an extremely high oxygen content as a fuel. Even when blended with conventional diesel fuel derived from petroleum, this oxygen content is still in the engine. There is also a problem that adverse effects on materials are concerned.
そこで、動植物に由来する含酸素炭化水素化合物を含む原料油を水素化触媒の存在下に水素化脱酸素処理して、実質的に酸素を含まない炭化水素からなる燃料油を製造する方法が検討されている（例えば下記特許文献２および３を参照。）。 Therefore, a method for producing a fuel oil composed of hydrocarbons substantially free of oxygen by hydrodeoxygenating raw material oils containing oxygenated hydrocarbon compounds derived from animals and plants in the presence of a hydrogenation catalyst is studied. (For example, see Patent Documents 2 and 3 below.)
しかしながら、上記従来の製造方法の場合、以下の点で改善の余地がある。 However, the conventional manufacturing method has room for improvement in the following points.
すなわち、動植物に由来する含酸素炭化水素化合物を含む原料油を水素化触媒の存在下に水素化脱酸素する反応は発熱反応であり、反応温度の上昇に対して反応器の耐熱性向上の必要性、高温副反応の増加及び高温に暴走反応の発生など問題があり、温度上昇を抑制する必要がある。なお、一般的な発熱反応においては、反応熱の除去のために反応器に冷却装置を設置する方法や不活性な物質（希釈媒）で原料を希釈する方法が採用されている。しかし、前者の方法は反応器が非常に高価となる。一方、後者の方法では十分な発熱抑制効果を得るためには不活性な物質を大量に用いる必要があり、装置の過度の大型化が必要などの制限がある。 In other words, the reaction of hydrodeoxygenating feedstock containing oxygenated hydrocarbon compounds derived from animals and plants in the presence of a hydrogenation catalyst is an exothermic reaction, and it is necessary to improve the heat resistance of the reactor as the reaction temperature increases. There is a problem such as increase in the temperature, side reaction at high temperature and occurrence of runaway reaction at high temperature, and it is necessary to suppress the temperature rise. In general exothermic reactions, a method of installing a cooling device in the reactor to remove reaction heat or a method of diluting the raw material with an inert substance (diluent) is employed. However, the former method makes the reactor very expensive. On the other hand, in the latter method, in order to obtain a sufficient heat generation suppressing effect, it is necessary to use a large amount of an inert substance, and there is a limitation that an excessively large apparatus is required.
また、二酸化炭素の排出量削減を目的として動植物に由来する含酸素炭化水素化合物を含む原料油を水素化触媒の存在下に水素化脱酸素してする炭化水素油を製造するには、除去された反応熱をエネルギーとして有効に回収することができなければ、そのエネルギーに相当する二酸化炭素の排出を削減できない。 In order to reduce hydrocarbon emissions, it is removed to produce hydrocarbon oils that hydrodeoxygenate feedstock containing oxygenated hydrocarbon compounds derived from animals and plants in the presence of hydrogenation catalysts. Unless the heat of reaction can be effectively recovered as energy, the emission of carbon dioxide corresponding to that energy cannot be reduced.
本発明は、上記従来技術の有する課題に鑑みてなされたものであり、反応による発熱量を抑制してエネルギー損失を抑えるとともに、希釈媒の使用量を低減することが可能な炭化水素油の製造方法を提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art, and is capable of producing hydrocarbon oil that can suppress the amount of heat generated by the reaction to suppress energy loss and reduce the amount of diluent used. It aims to provide a method.
上記課題を解決するために、本発明は、水素の存在下、動植物油に由来する含酸素炭化水素化合物を含有する原料油と、アルミニウム、ケイ素、ジルコニウム、ホウ素、チタン及びマグネシウムから選ばれる２種以上の元素を含んで構成される多孔性無機酸化物並びに該多孔性無機酸化物に担持された周期律表第６Ａ族及び第８族の元素から選ばれる１種以上の金属を含有する触媒とを、水素圧力２ＭＰａ以上４ＭＰａ以下で水素化処理し、得られる被処理物から水素、硫化水素、二酸化炭素及び水を除去して炭化水素油を得る工程を備え、前記原料油は、前記工程を経て得られた前記炭化水素油の一部を前記含酸素炭化水素化合物に対して０．５〜５質量倍となるようにリサイクル供給したリサイクル油と、前記含酸素炭化水素化合物に対して硫黄原子換算で１〜５０質量ｐｐｍの含硫黄炭化水素化合物と、を含有することを特徴とする、炭化水素油の製造方法を提供する。 In order to solve the above-mentioned problems, the present invention provides a raw material oil containing an oxygen-containing hydrocarbon compound derived from animal and vegetable oils in the presence of hydrogen, and two kinds selected from aluminum, silicon, zirconium, boron, titanium and magnesium. A porous inorganic oxide comprising the above elements, and a catalyst containing one or more metals selected from Group 6A and Group 8 elements of the periodic table supported on the porous inorganic oxide; And a hydrogen pressure treatment at a hydrogen pressure of 2 MPa or more and 4 MPa or less , and removing hydrogen, hydrogen sulfide, carbon dioxide and water from the treatment object to obtain a hydrocarbon oil, A part of the hydrocarbon oil obtained through recycle is supplied to the oxygenated hydrocarbon compound so as to be 0.5 to 5 times the mass of the oxygenated hydrocarbon compound. Characterized in that it contains and a sulfur-containing hydrocarbon compound having 1 to 50 mass ppm sulfur atom in terms Te, to provide a method for manufacturing a hydrocarbon oil.
ここで、上記原料油を水素化処理すると、動植物油に由来する含酸素炭化水素化合物の水素化脱酸素反応が進行し、炭化水素が生成する。本発明でいう「水素化脱酸素反応」とは、含酸素炭化水素化合物を構成する酸素原子を除去し、開裂した部分に水素を付加する反応を意味する。例えば脂肪酸トリグリセライドや脂肪酸は、それぞれエステル基、カルボキシル基等の含酸素基を有しているが、水素化脱酸素反応によって、これらの含酸素基に含まれる酸素原子が取り除かれ、含酸素炭化水素化合物は炭化水素に転換される。脂肪酸トリグリセライド等が有する含酸素基の水素化脱酸素には、主として二つの反応経路がある。第１の反応経路は、脂肪酸トリグリセライド等の含酸素基がそのまま二酸化炭素として脱離する脱炭酸経路であり、酸素原子は二酸化炭素として取り除かれる。第２の反応経路は、脂肪酸トリグリセライド等の炭素数を維持しながらアルデヒド、アルコールを経由して還元される水素化経路である。この場合、酸素原子は水に転換される。これらの反応が並列に進行した場合、炭化水素と水、二酸化炭素が生成する。 Here, when the said raw material oil is hydrotreated, the hydrodeoxygenation reaction of the oxygen-containing hydrocarbon compound derived from animal and vegetable oils proceeds to produce hydrocarbons. The “hydrodeoxygenation reaction” in the present invention means a reaction in which oxygen atoms constituting the oxygen-containing hydrocarbon compound are removed and hydrogen is added to the cleaved portion. For example, fatty acid triglycerides and fatty acids have oxygen-containing groups such as ester groups and carboxyl groups, respectively, but oxygen atoms contained in these oxygen-containing groups are removed by hydrodeoxygenation reaction, and oxygen-containing hydrocarbons. The compound is converted to a hydrocarbon. There are mainly two reaction pathways for hydrodeoxygenation of oxygen-containing groups of fatty acid triglycerides and the like. The first reaction pathway is a decarboxylation pathway in which oxygen-containing groups such as fatty acid triglycerides are eliminated as carbon dioxide as they are, and oxygen atoms are removed as carbon dioxide. The second reaction route is a hydrogenation route that is reduced via an aldehyde or alcohol while maintaining the number of carbon atoms such as fatty acid triglyceride. In this case, oxygen atoms are converted to water. When these reactions proceed in parallel, hydrocarbons, water, and carbon dioxide are generated.
ステアリン酸のアルキルエステルの場合を例とした水素化脱酸素の反応スキームを下記式（１）、（２）に示す。式（１）で表される反応スキームは上記第１の反応経路に相当するものであり、また、式（２）で示される反応スキームは上記第２の反応経路に相当するものである。また、式（１）、（２）中のＲはアルキル基を示す。
Ｃ１７Ｈ３５ＣＯＯＲ＋Ｈ２→Ｃ１７Ｈ３６＋ＣＯ２＋ＲＨ （１）
Ｃ１７Ｈ３５ＣＯＯＲ＋４Ｈ２→Ｃ１８Ｈ３８＋２Ｈ２Ｏ＋ＲＨ （２）The reaction scheme of hydrodeoxygenation taking the case of an alkyl ester of stearic acid as an example is shown in the following formulas (1) and (2). The reaction scheme represented by the formula (1) corresponds to the first reaction path, and the reaction scheme represented by the formula (2) corresponds to the second reaction path. In the formulas (1) and (2), R represents an alkyl group.
C 17 H 35 COOR + H 2 → C 17 H 36 + CO 2 + RH (1)
C 17 H 35 COOR + 4H 2 → C 18 H 38 + 2H 2 O + RH (2)
本発明の炭化水素油の製造方法においては、動植物油に由来する含酸素炭化水素化合物を含有する原料油を水素化処理するに際し、原料油に、上記工程で得られる被処理物及び／又は炭化水素油の一部であるリサイクル油と、含硫黄炭化水素化合物とをそれぞれ特定量含有せしめるとともに、上記特定の触媒及び反応条件を採用することによって、水素化脱酸素反応２つの経路のうち、反応熱がより低い上記第１の反応経路の占める割合を大きくすることができる。その結果、反応による発熱量自体を抑制するとともに、希釈媒の使用量を低減することが可能となる。 In the method for producing a hydrocarbon oil of the present invention, when a raw material oil containing an oxygen-containing hydrocarbon compound derived from an animal or vegetable oil is hydrotreated, the material to be treated and / or carbonized obtained in the above-described step is subjected to the raw material oil. Recycled oil, which is a part of hydrogen oil, and sulfur-containing hydrocarbon compounds are contained in specific amounts, and by adopting the above-mentioned specific catalyst and reaction conditions, reaction among the two hydrodeoxygenation reactions The proportion of the first reaction path with lower heat can be increased. As a result, the amount of heat generated by the reaction can be suppressed, and the amount of diluent used can be reduced.
本発明においては、上記工程で得られた炭化水素油を、軽質留分、中間留分及び重質留分に分留し、軽質留分と中間留分とのカット温度を１００〜２００℃、中間留分と重質留分とのカット温度を３００〜４００℃とすることが好ましい。 In the present invention, the hydrocarbon oil obtained in the above step is fractionated into a light fraction, a middle fraction and a heavy fraction, and the cut temperature of the light fraction and the middle fraction is 100 to 200 ° C., It is preferable that the cut temperature of the middle distillate and the heavy distillate is 300 to 400 ° C.
また、上記工程で得られた炭化水素油又は該炭化水素油から分留された中間留分について異性化処理を施すことが好ましい。 Moreover, it is preferable to subject the hydrocarbon oil obtained in the above step or the middle fraction fractionated from the hydrocarbon oil to isomerization.
また、上記工程で得られた炭化水素油又は該炭化水素油から分留された中間留分について異性化処理を施し、得られた異性化処理油を軽質留分、中間留分及び重質留分に分留し、軽質留分と中間留分とのカット温度を１００〜２００℃、中間留分と重質留分とのカット温度を３００〜４００℃とすることが好ましい。 In addition, the hydrocarbon oil obtained in the above step or the middle distillate fractionated from the hydrocarbon oil is subjected to isomerization treatment, and the obtained isomerized oil is mixed with a light fraction, a middle fraction and a heavy fraction. It is preferable that the cut temperature of the light fraction and the middle fraction is 100 to 200 ° C., and the cut temperature of the middle fraction and the heavy fraction is 300 to 400 ° C.
また、リサイクル油は、炭化水素油の一部を含有することが好ましい。さらに、炭化水素油から分留された前記中間留分の一部、炭化水素油又は炭化水素油から分留された中間留分について異性化処理したものの一部、あるいは、炭化水素油又は炭化水素油から分留された中間留分について異性化処理したものから分留された中間留分の一部を含有することが好ましい。 Moreover, it is preferable that recycled oil contains a part of hydrocarbon oil. Further, a part of the middle fraction fractionated from hydrocarbon oil, a part of the middle fraction fractionated from hydrocarbon oil or hydrocarbon oil, a part of the isomerization treatment, or a hydrocarbon oil or hydrocarbon It is preferable to contain a portion of the middle distillate fraction obtained by isomerization of the middle distillate fraction from the oil.
また、原料油に含まれる含酸素炭化水素化合物は、脂肪酸類及び脂肪酸エステル類から選ばれる１種以上の化合物であることが好ましく、脂肪酸のトリグリセライドであることがより好ましい。 The oxygen-containing hydrocarbon compound contained in the raw oil is preferably one or more compounds selected from fatty acids and fatty acid esters, and more preferably triglycerides of fatty acids.
また、水素化処理に使用される触媒は、その窒素吸着ＢＥＴ法による細孔容積が０．３０〜０．８５ｍｌ／ｇであり、平均細孔直径が５〜１１ｎｍであり、全細孔容積に占める細孔直径３ｎｍ以下の細孔に由来する細孔容積の割合が３５容量％以下であることが好ましい。 Moreover, the catalyst used for the hydrotreatment has a pore volume of 0.30 to 0.85 ml / g according to the nitrogen adsorption BET method, an average pore diameter of 5 to 11 nm, and a total pore volume of It is preferable that the proportion of the pore volume derived from pores having a pore diameter of 3 nm or less is 35% by volume or less.
さらに、触媒に含まれる多孔性無機酸化物はリン元素を含有することが好ましい。 Furthermore, the porous inorganic oxide contained in the catalyst preferably contains a phosphorus element.
以上の通り、本発明によれば、反応による発熱量を抑制してエネルギー損失を抑えるとともに、希釈媒の使用量を低減することが可能な炭化水素油の製造方法が提供される。 As described above, according to the present invention, there is provided a method for producing a hydrocarbon oil capable of suppressing the amount of heat generated by a reaction to suppress energy loss and reducing the amount of diluent used.
以下、本発明の好適な実施形態について詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail.
（原料油）
本発明においては、動植物油に由来する含酸素化合物と、特定のリサイクル油と、含硫黄炭化水素化合物とを含有する原料油が用いられる。なお、水素化処理のスタートアップ時には、リサイクル油に相当する脂肪族炭化水素化合物を予め用意し、該炭化水素化合物を原料油に含有させたものを水素化処理に供してもよい。(Raw oil)
In the present invention, a raw material oil containing an oxygen-containing compound derived from animal and vegetable oils, a specific recycled oil, and a sulfur-containing hydrocarbon compound is used. At the time of start-up of the hydrotreatment, an aliphatic hydrocarbon compound corresponding to the recycled oil may be prepared in advance, and the hydrocarbon compound contained in the feed oil may be subjected to the hydrotreatment.
動植物油に由来する含酸素化合物としては、動植物油由来の油脂成分やその誘導品が、脱炭酸反応が起きやすいことから好適である。ここで油脂成分には、天然もしくは人工的に生産、製造される動植物油脂及び動植物油成分及び／又はこれらの油脂を由来して生産、製造される成分及びこれらの油脂製品の性能を維持、向上させる目的で添加される成分が包含される。また油脂成分の誘導体には、上記油脂製品を製造する過程で副生される成分や、意図的に誘導品へ加工された成分が包含される。 As the oxygen-containing compounds derived from animal and vegetable oils, oil and fat components derived from animal and vegetable oils and derivatives thereof are preferable because decarboxylation reaction easily occurs. Here, the oil and fat component maintains and improves the performance of natural and artificially produced and manufactured animal and vegetable oils and animal and vegetable oil components and / or components derived and produced from these oils and fats and these oil and fat products. The component added for the purpose of making it included is included. In addition, the derivative of the fat and oil component includes a component that is by-produced in the process of producing the fat and oil product and a component that is intentionally processed into a derivative.
動植物油に由来する油脂成分としては、例えば、牛脂、トウモロコシ油、菜種油、大豆油、パーム油などが挙げられる。本発明においては動植物油に由来する油脂成分として、いかなる油脂を用いてもよく、これら油脂を使用した後の廃油でもよい。ただし、カーボンニュートラルの観点からは植物油脂が好ましく、脂肪酸アルキル鎖炭素数及びその反応性の観点から、菜種油、大豆油及びパーム油がより好ましい。なお、上記の油脂は１種を単独で又は２種以上を混合して用いてもよい。 Examples of the oil and fat component derived from animal and vegetable oils include beef tallow, corn oil, rapeseed oil, soybean oil, and palm oil. In the present invention, any fats and oils derived from animal and vegetable oils may be used, and waste oil after using these fats and oils may be used. However, vegetable oils and fats are preferable from the viewpoint of carbon neutral, and rapeseed oil, soybean oil, and palm oil are more preferable from the viewpoint of the number of fatty acid alkyl chain carbons and their reactivity. In addition, you may use said fats and oils individually by 1 type or in mixture of 2 or more types.
動植物油に由来する油脂成分の誘導体としては、上記油脂成分の脂肪酸トリグリセリドを構成する脂肪酸やそれらのメチルエステルなどのエステル体に加工されている成分を含んでいてもよい。これらの脂肪酸トリグリセリドを構成する脂肪酸の代表的例としては、飽和脂肪酸と称する分子構造中に不飽和結合を有しない脂肪酸である酪酸（Ｃ３Ｈ７ＣＯＯＨ）、カプロン酸（Ｃ５Ｈ１１ＣＯＯＨ）、カプリル酸（Ｃ７Ｈ１５ＣＯＯＨ）、カプリン酸（Ｃ９Ｈ１９ＣＯＯＨ）、ラウリン酸（Ｃ１１Ｈ２３ＣＯＯＨ）、ミリスチン酸（Ｃ１３Ｈ２７ＣＯＯＨ）、パルミチン酸（Ｃ１５Ｈ３１ＣＯＯＨ）、ステアリン酸（Ｃ１７Ｈ３５ＣＯＯＨ）、及び不飽和結合を１つもしくは複数有する不飽和脂肪酸であるオレイン酸（Ｃ１７Ｈ３３ＣＯＯＨ）、リノール酸（Ｃ１７Ｈ３１ＣＯＯＨ）、リノレン酸（Ｃ１７Ｈ２９ＣＯＯＨ）、リシノレン酸（Ｃ１７Ｈ３２（ＯＨ）ＣＯＯＨ）等が挙げられるDerivatives of fat and oil components derived from animal and vegetable oils may include components processed into ester bodies such as fatty acids constituting the fatty acid triglycerides of the fat and oil components and methyl esters thereof. Typical examples of fatty acids constituting these fatty acid triglycerides include butyric acid (C 3 H 7 COOH) and caproic acid (C 5 H 11 COOH), which are fatty acids having no unsaturated bond in the molecular structure called saturated fatty acid. , Caprylic acid (C 7 H 15 COOH), capric acid (C 9 H 19 COOH), lauric acid (C 11 H 23 COOH), myristic acid (C 13 H 27 COOH), palmitic acid (C 15 H 31 COOH) , Stearic acid (C 17 H 35 COOH), and oleic acid (C 17 H 33 COOH), linoleic acid (C 17 H 31 COOH), linolenic acid (C), which are unsaturated fatty acids having one or more unsaturated bonds 17 H 29 COOH), ricinolenic acid (C 17 H 32 (OH) COOH) and the like.
リサイクル油は、水素化処理における反応熱による温度上昇を抑制する役割を担っている。本発明においては、該リサイクル油として、水素化処理により得られる該被処理物から水素、硫化水素、二酸化炭素及び水を除去した炭化水素油（留出油）の一部が、原料油にリサイクル供給される。 Recycled oil plays a role of suppressing temperature rise due to reaction heat in hydroprocessing. In the present invention, as the recycled oil, a part of hydrocarbon oil (distilled oil) obtained by removing hydrogen, hydrogen sulfide, carbon dioxide and water from the material to be processed obtained by hydroprocessing is recycled to the raw material oil. Supplied.
リサイクル油は、上記炭化水素油の一部を含有することが好ましい。さらに、炭化水素油から分留された中間留分の一部、炭化水素油又は炭化水素油から分留された中間留分について異性化処理したものの一部、あるいは、炭化水素油又は炭化水素油から分留された中間留分について異性化処理したものから分留された中間留分の一部を含有することが好ましい。これらの成分を原料油にリサイクル供給する際には、当該成分を冷却しておくことが好ましい。 The recycled oil preferably contains a part of the hydrocarbon oil. Furthermore, a part of middle fraction fractionated from hydrocarbon oil, a part of isomerized portion of middle fraction fractionated from hydrocarbon oil or hydrocarbon oil, or hydrocarbon oil or hydrocarbon oil It is preferable to contain a part of the middle distillate fraction obtained from the isomerization treatment of the middle distillate fraction obtained from 1). When these components are recycled to the feedstock, it is preferable to cool the components.
原料油におけるリサイクル油の含有量は、動植物油に由来する含酸素炭化水素化合物に対して０．５〜５質量倍であり、反応器の最高使用温度に応じて前記の範囲内で比率が定められる。これは、両者の比熱が同じであると仮定した場合に、両者を１対１で混合すると温度上昇は動植物油に由来する物質を単独で反応させる場合の半分となることから、上記範囲内であれば反応熱を十分に低下させることができるとの理由による。なお、リサイクル油の含有量が含酸素炭化水素化合物の５質量倍より大きいと、含酸素炭化水素化合物の濃度が低下して反応性が低下し、また、配管等の流量が増加して負荷が増大する。他方、リサイクル油の含有量が含酸素炭化水素化合物の０．５質量倍より低い場合は温度上昇を十分に抑制できない。 The content of the recycled oil in the raw material oil is 0.5 to 5 times the mass of the oxygen-containing hydrocarbon compound derived from the animal and vegetable oil, and the ratio is determined within the above range according to the maximum use temperature of the reactor. It is done. Assuming that the specific heat of the two is the same, if the two are mixed one-on-one, the temperature rise will be half that when the substance derived from animal and vegetable oils is reacted alone. If it exists, it is because the reaction heat can fully be reduced. If the content of the recycled oil is larger than 5 times the mass of the oxygen-containing hydrocarbon compound, the concentration of the oxygen-containing hydrocarbon compound is lowered and the reactivity is lowered, and the flow rate of the piping is increased and the load is increased. Increase. On the other hand, when the content of the recycled oil is lower than 0.5 times the mass of the oxygen-containing hydrocarbon compound, the temperature rise cannot be sufficiently suppressed.
原料油とリサイクル油の混合方法は特に限定されないが、例えば予め混合してその混合物を水素化処理装置の反応器に導入してもよく、あるいは原料油を反応器に導入する際に、反応器の前段において供給してもよい。さらに、反応器を複数直列に繋げて反応器間に導入する、あるいは単独の反応器内で触媒層を分割して触媒層間に導入することも可能である。 The mixing method of the raw material oil and the recycled oil is not particularly limited. For example, the raw material oil may be mixed in advance and the mixture may be introduced into the reactor of the hydrotreating apparatus. Alternatively, when the raw material oil is introduced into the reactor, the reactor You may supply in the front | former stage. Further, a plurality of reactors can be connected in series and introduced between the reactors, or the catalyst layer can be divided and introduced between the catalyst layers in a single reactor.
また、含硫黄炭化水素化合物は、水素化処理における脱酸素活性を向上させる役割を担っている。含硫黄炭化水素化合物としては、特に制限されないが、具体的には、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及びこれらの誘導体などが挙げられる。原料油に含まれる含硫黄炭化水素化合物は単一の化合物であってもよく、あるいは２種以上の混合物であってもよい。さらに、硫黄分を含有する石油系炭化水素留分を原料油に添加してもよい。 Further, the sulfur-containing hydrocarbon compound plays a role of improving the deoxygenation activity in the hydrotreatment. Although it does not restrict | limit especially as a sulfur-containing hydrocarbon compound, Specifically, sulfide, disulfide, polysulfide, thiol, thiophene, benzothiophene, dibenzothiophene, these derivatives, etc. are mentioned. The sulfur-containing hydrocarbon compound contained in the feedstock oil may be a single compound or a mixture of two or more. Furthermore, you may add the petroleum-type hydrocarbon fraction containing a sulfur content to raw material oil.
硫黄分を含有する石油系炭化水素留分としては、一般的な石油精製工程で得られる留分を用いることができる。例えば、常圧蒸留装置や減圧蒸留装置から得られる所定の沸点範囲に相当する留分、あるいは、水素化脱硫装置、水素化分解装置、残油直接脱硫装置、流動接触分解装置などから得られる、所定の沸点範囲に相当する留分を使用してもよい。なお、上記の各装置から得られる留分は１種を単独で又は２種以上を混合して用いてもよい。 As the petroleum hydrocarbon fraction containing sulfur, a fraction obtained in a general petroleum refining process can be used. For example, a fraction corresponding to a predetermined boiling range obtained from an atmospheric distillation apparatus or a vacuum distillation apparatus, or obtained from a hydrodesulfurization apparatus, a hydrocracking apparatus, a residual oil direct desulfurization apparatus, a fluid catalytic cracking apparatus, etc. A fraction corresponding to a predetermined boiling range may be used. In addition, you may use the fraction obtained from each said apparatus individually by 1 type or in mixture of 2 or more types.
含硫黄炭化水素化合物の含有量は、動植物油に由来する含酸素炭化水素化合物に対して硫黄原子換算として１〜５０質量ｐｐｍが必要であり、好ましくは５〜３０質量ｐｐｍ、より好ましくは１０〜２０質量ｐｐｍである。硫黄原子換算として含有量が１質量ｐｐｍ未満であると、脱酸素活性を安定的に維持することが困難となる傾向にある。他方、５０質量ｐｐｍを超えると、水素化処理工程で排出される軽質ガス中の硫黄濃度が増加するのに加え、被処理油又は炭化水素油に含まれる硫黄分含有量が増加する傾向にあり、ディーゼルエンジン等の燃料として用いる場合にエンジン排ガス浄化装置への悪影響が懸念される。なお、本発明における硫黄分は、ＪＩＳ Ｋ ２５４１「硫黄分試験方法」又はＡＳＴＭ−５４５３に記載の方法に準拠して測定される硫黄分の質量含有量を意味する。 The content of the sulfur-containing hydrocarbon compound needs to be 1 to 50 mass ppm, preferably 5 to 30 mass ppm, more preferably 10 to 10 ppm in terms of sulfur atom with respect to the oxygen-containing hydrocarbon compound derived from animal and vegetable oils. 20 ppm by mass. When the content is less than 1 ppm by mass in terms of sulfur atom, it tends to be difficult to stably maintain the deoxygenation activity. On the other hand, if it exceeds 50 ppm by mass, the sulfur content in the light gas discharged in the hydrotreating process will increase, and the sulfur content in the oil to be treated or hydrocarbon oil will tend to increase. When used as a fuel for a diesel engine or the like, there is a concern about an adverse effect on the engine exhaust gas purification device. In addition, the sulfur content in this invention means the mass content of the sulfur content measured based on the method of JISK2541 "Sulfur content test method" or ASTM-5453.
本発明において、リサイクル油及び含硫黄炭化水素化合物の原料油への添加は同時に行っても別々に行ってもよいが、リサイクル油を原料油に添加した後、含硫黄化合物を更に添加することが好ましい。また、含硫黄炭化水素化合物は、原料油とリサイクル油の混合油に予め混合してその混合物を水素化処理装置の反応器に導入してもよく、あるいは原料油とリサイクル油の混合油を反応器に導入する際に、反応器の前段において供給してもよい。 In the present invention, the recycle oil and the sulfur-containing hydrocarbon compound may be added to the feedstock oil at the same time or separately, but after the recycle oil is added to the feedstock oil, the sulfur-containing compound may be further added. preferable. In addition, the sulfur-containing hydrocarbon compound may be mixed in advance with a mixed oil of raw material oil and recycled oil, and the mixture may be introduced into the reactor of the hydrotreating apparatus, or the mixed oil of raw material oil and recycled oil may be reacted. When it is introduced into the reactor, it may be supplied before the reactor.
（水素化処理）
本発明にかかる水素化処理においては、アルミニウム、ケイ素、ジルコニウム、ホウ素、チタン及びマグネシウムから選ばれる２種以上の元素を含んで構成される多孔性無機酸化物並びに該多孔性無機酸化物に担持された周期律表第６Ａ族及び第８族の元素から選ばれる１種以上の金属を含有する触媒が用いられる。(Hydrogenation treatment)
In the hydrogenation treatment according to the present invention, a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and the porous inorganic oxide are supported. In addition, a catalyst containing one or more metals selected from Group 6A and Group 8 elements of the periodic table is used.
本発明で用いられる触媒の担体としては、上述のようにアルミニウム、ケイ素、ジルコニウム、ホウ素、チタン及びマグネシウムから選ばれる２種以上を含んで構成される多孔性無機酸化物が用いられる。かかる多孔性無機酸化物としては、脱酸素活性及び脱硫活性を一層向上できる点から、アルミニウム、ケイ素、ジルコニウム、ホウ素、チタン及びマグネシウムから選ばれる２種以上であることが好ましく、アルミニウムと他の元素とを含む無機酸化物（酸化アルミニウムと他の酸化物との複合酸化物）が更に好ましい。 As the catalyst carrier used in the present invention, a porous inorganic oxide comprising two or more selected from aluminum, silicon, zirconium, boron, titanium and magnesium as described above is used. The porous inorganic oxide is preferably at least two selected from aluminum, silicon, zirconium, boron, titanium and magnesium from the viewpoint that the deoxygenation activity and desulfurization activity can be further improved. Aluminum and other elements And an inorganic oxide (a composite oxide of aluminum oxide and another oxide) is more preferable.
多孔性無機酸化物が構成元素としてアルミニウムを含有する場合、アルミニウムの含有量は、多孔性無機酸化物全量を基準として、アルミナ換算で、好ましくは１〜９７質量％、より好ましくは１０〜９７質量％、更に好ましくは２０〜９５質量％である。アルミニウムの含有量がアルミナ換算で１質量％未満であると、担体酸性質などの物性が好適でなく、十分な脱酸素活性及び脱硫活性が発揮されない傾向にある。他方、アルミニウムの含有量がアルミナ換算で９７質量％を超えると、触媒表面積が不十分となり、活性が低下する傾向にある。 When the porous inorganic oxide contains aluminum as a constituent element, the aluminum content is preferably 1 to 97% by mass, more preferably 10 to 97% by mass in terms of alumina, based on the total amount of the porous inorganic oxide. %, More preferably 20 to 95% by mass. When the aluminum content is less than 1% by mass in terms of alumina, physical properties such as carrier acid properties are not suitable, and sufficient deoxidation activity and desulfurization activity tend not to be exhibited. On the other hand, when the aluminum content exceeds 97% by mass in terms of alumina, the catalyst surface area becomes insufficient and the activity tends to decrease.
アルミニウム以外の担体構成元素である、ケイ素、ジルコニウム、ホウ素、チタン及びマグネシウムを担体に導入する方法は特に制限されず、これらの元素を含有する溶液などを原料として用いればよい。例えば、ケイ素については、ケイ素、水ガラス、シリカゾルなど、ホウ素についてはホウ酸など、リンについては、リン酸やリン酸のアルカリ金属塩など、チタンについては硫化チタン、四塩化チタンや各種アルコキサイド塩など、ジルコニウムについては硫酸ジルコニウムや各種アルコキサイド塩などを用いることができる。 The method for introducing silicon, zirconium, boron, titanium and magnesium, which are carrier constituent elements other than aluminum, is not particularly limited, and a solution containing these elements may be used as a raw material. For example, for silicon, silicon, water glass, silica sol, etc., for boron, boric acid, etc., for phosphorus, phosphoric acid and alkali metal salts of phosphoric acid, etc., for titanium, titanium sulfide, titanium tetrachloride and various alkoxide salts, etc. As for zirconium, zirconium sulfate and various alkoxide salts can be used.
さらに、多孔性無機酸化物は、構成元素としてリンを含有することが好ましい。リンの含有量は、多孔性無機酸化物全量を基準として、好ましくは０．１〜１０質量％、より好ましくは０．５〜７質量％、更に好ましくは２〜６質量％である。リンの含有量が０．１質量％未満の場合には十分な脱酸素活性及び脱硫活性が発揮されない傾向にあり、また、１０質量％を超えると過度の分解が進行して目的とする炭化水素油の収率が低下する恐れがある。 Furthermore, the porous inorganic oxide preferably contains phosphorus as a constituent element. The phosphorus content is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, and still more preferably 2 to 6% by mass, based on the total amount of the porous inorganic oxide. When the phosphorus content is less than 0.1% by mass, sufficient deoxygenation activity and desulfurization activity tend not to be exhibited, and when it exceeds 10% by mass, excessive decomposition proceeds and the target hydrocarbon Oil yield may be reduced.
上記の酸化アルミニウム以外の担体構成成分の原料は、担体の焼成より前の工程において添加することが好ましい。例えば、アルミニウム水溶液に予め上記原料を添加した後、これらの構成成分を含む水酸化アルミニウムゲルを調製してもよく、調合した水酸化アルミニウムゲルに対して上記原料を添加してもよい。あるいは、市販の酸化アルミニウム中間体やベーマイトパウダーに水もしくは酸性水溶液を添加して混練する工程において上記原料を添加してもよいが、水酸化アルミニウムゲルを調合する段階で共存させることがより好ましい。酸化アルミニウム以外の担体構成成分の効果発現機構は必ずしも解明されたわけではないが、アルミニウムと複合的な酸化物状態を形成していると推察され、このことが担体表面積の増加や活性金属との相互作用を生じることにより、活性に影響を及ぼしていると考えられる。 It is preferable to add the raw materials for the carrier constituents other than the above-described aluminum oxide in the step prior to the firing of the carrier. For example, after adding the said raw material previously to aluminum aqueous solution, the aluminum hydroxide gel containing these structural components may be prepared, and the said raw material may be added with respect to the prepared aluminum hydroxide gel. Alternatively, the above raw materials may be added in a step of adding water or an acidic aqueous solution to a commercially available aluminum oxide intermediate or boehmite powder and kneading them, but it is more preferable to coexist at the stage of preparing aluminum hydroxide gel. Although the mechanism of the effect of the carrier constituents other than aluminum oxide has not necessarily been elucidated, it is presumed that it forms a complex oxide state with aluminum, which increases the surface area of the carrier and the interaction with the active metal. It is considered that the activity is affected by producing the action.
担体としての上記多孔性無機酸化物には、周期律表第６Ａ族及び第８族の元素から選ばれる１種以上の金属が担持される。これらの金属の中でも、コバルト、モリブデン、ニッケル及びタングステンから選ばれる２種以上の金属を組み合わせて用いることが好ましい。好適な組み合せとしては、例えば、コバルト−モリブデン、ニッケル−モリブデン、ニッケル−コバルト−モリブデン、ニッケル−タングステンが挙げられる。これらのうち、ニッケル−モリブデン、ニッケル−コバルト−モリブデン及びニッケル−タングステンの組み合せがより好ましい。水素化処理に際しては、これらの金属を硫化物の状態に転換して使用する。 The porous inorganic oxide as a carrier carries one or more metals selected from Group 6A and Group 8 elements of the periodic table. Among these metals, it is preferable to use a combination of two or more metals selected from cobalt, molybdenum, nickel and tungsten. Examples of suitable combinations include cobalt-molybdenum, nickel-molybdenum, nickel-cobalt-molybdenum, and nickel-tungsten. Of these, combinations of nickel-molybdenum, nickel-cobalt-molybdenum, and nickel-tungsten are more preferred. In the hydrotreatment, these metals are used after being converted to a sulfide state.
触媒質量を基準とする活性金属の含有量としては、タングステン及びモリブデンの合計担持量の範囲は、酸化物換算で１２〜３５質量％が好ましく、１５〜３０質量％がより好ましい。タングステン及びモリブデンの合計担持量が１２質量％未満であると、活性点が少なくなり、十分な活性が得られなくなる傾向がある。他方、３５質量％を越えると、金属が効果的に分散せず、十分な活性が得られなくなる傾向がある。コバルト及びニッケルの合計担持量の範囲は、酸化物換算で１．０〜１５質量％が好ましく、１．５〜１２質量％がより好ましい。コバルト及びニッケルの合計担持量が１．０質量％未満であると、十分な助触媒効果が得られず、活性が低下する傾向がある。他方、１５質量％を越えると、金属が効果的に分散せず、十分な活性が得られなくなる傾向がある。 As the content of the active metal based on the catalyst mass, the range of the total supported amount of tungsten and molybdenum is preferably 12 to 35% by mass in terms of oxide, and more preferably 15 to 30% by mass. If the total supported amount of tungsten and molybdenum is less than 12% by mass, the active sites tend to decrease and sufficient activity cannot be obtained. On the other hand, if it exceeds 35% by mass, the metal is not effectively dispersed and sufficient activity tends not to be obtained. The range of the total supported amount of cobalt and nickel is preferably 1.0 to 15% by mass and more preferably 1.5 to 12% by mass in terms of oxide. When the total supported amount of cobalt and nickel is less than 1.0% by mass, a sufficient promoter effect cannot be obtained and the activity tends to decrease. On the other hand, if it exceeds 15% by mass, the metal is not effectively dispersed and sufficient activity tends not to be obtained.
これらの活性金属を触媒に含有させる方法は特に限定されず、通常の脱硫触媒を製造する際に適用される公知の方法を用いることができる。通常、活性金属の塩を含む溶液を触媒担体に含浸する方法が好ましく採用される。また、平衡吸着法、Ｐｏｒｅ−ｆｉｌｌｉｎｇ法、Ｉｎｃｉｐｉｅｎｔ−ｗｅｔｎｅｓｓ法なども好ましく採用される。例えば、Ｐｏｒｅ−ｆｉｌｌｉｎｇ法は、担体の細孔容積を予め測定しておき、これと同じ容積の金属塩溶液を含浸する方法である。なお、含浸方法は特に限定されるものではなく、金属担持量や触媒担体の物性に応じて適当な方法で含浸することができる。 The method for incorporating these active metals into the catalyst is not particularly limited, and a known method applied when producing an ordinary desulfurization catalyst can be used. Usually, a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed. In addition, an equilibrium adsorption method, a pore-filling method, an incident-wetness method, and the like are also preferably employed. For example, the pore-filling method is a method in which the pore volume of the carrier is measured in advance and impregnated with a metal salt solution having the same volume. The impregnation method is not particularly limited, and it can be impregnated by an appropriate method according to the amount of metal supported and the physical properties of the catalyst carrier.
本発明において、使用する水素化処理触媒の種類数は特に限定されない。例えば、一種類の触媒を単独で使用してもよく、活性金属種や担体構成成分の異なる触媒を複数使用してもよい。異なる触媒を複数使用する場合の好適な組み合せとしては、例えば、ニッケル−モリブデンを含有する触媒の後段にコバルト−モリブデンを含有する触媒、ニッケル−モリブデンを含有する触媒の後段にニッケル−コバルト−モリブデンを含有する触媒、ニッケル−タングステンを含有する触媒の後段にニッケル−コバルト−モリブデンを含有する触媒、ニッケル−コバルト−モリブデンを含有する触媒の後段にコバルト−モリブデンを含有する触媒を用いることが挙げられる。これらの組み合せの前段及び／又は後段にニッケル−モリブデン触媒を更に組み合せてもよい。 In the present invention, the number of types of hydrotreating catalyst used is not particularly limited. For example, one type of catalyst may be used alone, or a plurality of catalysts having different active metal species and carrier components may be used. As a suitable combination in the case where a plurality of different catalysts are used, for example, a catalyst containing cobalt-molybdenum after a catalyst containing nickel-molybdenum, and nickel-cobalt-molybdenum after a catalyst containing nickel-molybdenum are used. Examples thereof include a catalyst containing nickel, a catalyst containing nickel-cobalt-molybdenum after the catalyst containing nickel-tungsten, and a catalyst containing cobalt-molybdenum after the catalyst containing nickel-cobalt-molybdenum. A nickel-molybdenum catalyst may be further combined before and / or after these combinations.
担体成分が異なる複数の触媒を組み合せる場合には、例えば、担体の総質量を基準として酸化アルミニウムの含有量が３０質量％以上であり且つ８０質量％未満の触媒の後段に、酸化アルミニウムの含有量が８０〜９９質量％の範囲にある触媒を用いればよい。 In the case of combining a plurality of catalysts having different support components, for example, the content of aluminum oxide is included in the subsequent stage of the catalyst having an aluminum oxide content of 30% by mass or more and less than 80% by mass based on the total mass of the support. A catalyst having an amount in the range of 80 to 99% by mass may be used.
本発明において用いられる各触媒は一般的な水素化脱硫触媒と同様の方法で予備硫化した後に用いることができる。例えば、本発明の工程で得られた炭化水素油や石油系炭化水素油に含硫黄炭化水素化合物を添加したものを用いて、水素加圧条件下、２００℃以上の熱を所定の手順に従って与える。これにより、触媒上の活性金属が硫化された状態となり活性を発揮する。含硫黄炭化水素化合物としては、特に制限されないが、具体的には、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及びこれらの誘導体などが挙げられる。これらの含硫黄炭化水素化合物は単一の化合物であってもよく、あるいは２種以上の混合物であってもよい。さらに、硫黄分を含有する石油系炭化水素留分を直接用いてもよい。 Each catalyst used in the present invention can be used after preliminary sulfidation in the same manner as a general hydrodesulfurization catalyst. For example, using a hydrocarbon oil or petroleum hydrocarbon oil obtained by the process of the present invention to which a sulfur-containing hydrocarbon compound is added, heat at 200 ° C. or higher is given in accordance with a predetermined procedure under hydrogen pressure conditions. . As a result, the active metal on the catalyst becomes sulfided and exhibits activity. Although it does not restrict | limit especially as a sulfur-containing hydrocarbon compound, Specifically, sulfide, disulfide, polysulfide, thiol, thiophene, benzothiophene, dibenzothiophene, these derivatives, etc. are mentioned. These sulfur-containing hydrocarbon compounds may be a single compound or a mixture of two or more. Further, a petroleum hydrocarbon fraction containing a sulfur content may be used directly.
予備硫化は水素化脱酸素反応と同一の反応器で行ってもかまわないし、また予め硫化処理を施された触媒や、含硫黄、含酸素あるいは含窒素有機溶剤による活性化処理を施された触媒を使用することもできる。 The preliminary sulfidation may be performed in the same reactor as the hydrodeoxygenation reaction, or a catalyst that has been subjected to a sulfurization treatment in advance, or a catalyst that has been activated by a sulfur-containing, oxygen-containing, or nitrogen-containing organic solvent. Can also be used.
さらに、水素化処理触媒以外に、必要に応じて原料油に随伴して流入するスケール分をトラップしたり触媒床の区切り部分で水素化処理触媒を支持したりする目的でガード触媒、脱金属触媒、不活性充填物を用いてもよい。なお、これらは単独又は組み合せて用いることができる。 In addition to the hydrotreating catalyst, a guard catalyst and a demetallizing catalyst are provided for the purpose of trapping the scale that flows along with the feedstock as needed and supporting the hydrotreating catalyst at the separation part of the catalyst bed. Inert packing may be used. In addition, these can be used individually or in combination.
本発明で用いられる上記触媒の窒素吸着ＢＥＴ法による細孔容積は、０．３０〜０．８５ｍｌ／ｇであることが好ましく、０．４５〜０．８０ｍｌ／ｇであることがより好ましい。当該細孔容積が０．３０ｍｌ／ｇに満たない場合は担持される金属の分散性が不十分となり、活性点が検証する懸念がある。また、当該細孔容積が０．８５ｍｌ／ｇを超えると、触媒強度が不十分となり、使用中に触媒が粉化、破砕するおそれがある。 The pore volume by the nitrogen adsorption BET method of the catalyst used in the present invention is preferably 0.30 to 0.85 ml / g, and more preferably 0.45 to 0.80 ml / g. When the pore volume is less than 0.30 ml / g, the dispersibility of the supported metal becomes insufficient, and there is a concern that the active site is verified. Moreover, when the pore volume exceeds 0.85 ml / g, the catalyst strength becomes insufficient, and the catalyst may be pulverized or crushed during use.
また、上記測定方法によって求められる触媒の平均細孔直径は、５〜１１ｎｍであることが好ましく、６〜９ｎｍであることがより好ましい。平均細孔直径が５ｎｍ未満であると、反応基質が細孔内に十分に拡散せず、反応性が低下するおそれがある。また、平均細孔直径が１１ｎｍを超えると、細孔表面積が低下し、活性が不十分となるおそれがある。 Moreover, it is preferable that the average pore diameter of the catalyst calculated | required by the said measuring method is 5-11 nm, and it is more preferable that it is 6-9 nm. If the average pore diameter is less than 5 nm, the reaction substrate may not sufficiently diffuse into the pores, and the reactivity may be reduced. On the other hand, if the average pore diameter exceeds 11 nm, the pore surface area decreases, and the activity may be insufficient.
さらに、上記触媒においては、有効な触媒細孔を維持し、十分な活性を発揮させるために、全細孔容積に占める細孔直径３ｎｍ以下の細孔に由来する細孔容積の割合が３５容量％以下であることが好ましい。 Furthermore, in the above catalyst, the ratio of the pore volume derived from pores having a pore diameter of 3 nm or less to the total pore volume is 35 volumes in order to maintain effective catalyst pores and exhibit sufficient activity. % Or less is preferable.
また、水素の存在下で上記の原料油と触媒とを接触させる際の水素圧力は１ＭＰａ以上６ＭＰａ未満が必要であり、好ましくは２〜４ＭＰａである。水素圧力が６ＭＰａ以上であると脱炭酸反応と脱水反応の比率が一定であるが、６ＭＰａ未満の場合は圧力の低下に応じて脱炭酸比率が増加し、反応による発熱量を抑制する効果が出現する。ただし、水素圧力１ＭＰａ未満では、反応性が低下したり活性が急速に低下したりする傾向がある。また脱炭酸反応の比率を過度に上げるこことは、副生した二酸化炭素の量に相当する分の炭化水素油の収率を損なうことになるので、上記下限を下回ってまで脱炭酸比率を増加させることは適切ではない。 Moreover, the hydrogen pressure at the time of making said raw material oil and a catalyst contact in presence of hydrogen needs 1 MPa or more and less than 6 MPa, Preferably it is 2-4 MPa. If the hydrogen pressure is 6 MPa or more, the ratio of decarboxylation reaction and dehydration reaction is constant, but if it is less than 6 MPa, the decarboxylation ratio increases as the pressure decreases, and the effect of suppressing the amount of heat generated by the reaction appears. To do. However, when the hydrogen pressure is less than 1 MPa, the reactivity tends to decrease or the activity tends to decrease rapidly. In addition, excessively increasing the ratio of decarboxylation reaction means that the yield of hydrocarbon oil corresponding to the amount of carbon dioxide produced as a by-product is impaired, so the decarboxylation ratio is increased until the lower limit is exceeded. It is not appropriate to do so.
水素化処理における、触媒に対する１時間当たりの動植物油に由来する物質の流通量は０．５〜５倍が好ましく、０．７〜３倍がさらに好ましい。触媒に対する１時間当たりの動植物油に由来する物質の流通量は高いほど脱炭酸反応の選択性は向上するが、反応性も低下する傾向にあることから５倍以上とすることは適切でない。他方、流通量を低くすることは触媒量の増加すなわち反応器の大型化を引き起こすものであることから０．５倍以上とするのが現実的である。 In the hydrotreatment, the flow rate of the substance derived from animal and vegetable oils per hour with respect to the catalyst is preferably 0.5 to 5 times, and more preferably 0.7 to 3 times. The selectivity of the decarboxylation reaction increases as the amount of the substance derived from the animal and vegetable oil per hour with respect to the catalyst increases. However, since the reactivity tends to decrease, it is not appropriate to set it to 5 times or more. On the other hand, reducing the flow rate causes an increase in the amount of catalyst, that is, an increase in the size of the reactor, so it is realistic to make it 0.5 times or more.
水素化処理における水素油比（水素／油比）１００〜１５００ＮＬ／Ｌの範囲であることが好ましく、２００〜１２００ＮＬ／Ｌの範囲であることがより好ましく、２５０〜１０００ＮＬ／Ｌの範囲であることが特に好ましい。水素油比が上記上限を超える場合には上記水素圧力における脱炭酸反応の比率の増加効果を阻害し、また上記下限を下回る場合には十分な水素化反応が進行しないおそれがある。 The hydrogen oil ratio (hydrogen / oil ratio) in the hydrotreatment is preferably in the range of 100 to 1500 NL / L, more preferably in the range of 200 to 1200 NL / L, and in the range of 250 to 1000 NL / L. Is particularly preferred. When the hydrogen oil ratio exceeds the above upper limit, the effect of increasing the ratio of decarboxylation reaction at the hydrogen pressure is inhibited. When the hydrogen oil ratio is below the lower limit, there is a possibility that sufficient hydrogenation reaction does not proceed.
水素化処理における反応温度は１８０〜３９０℃の範囲であることが好ましく、２００〜３８０℃の範囲であることがより好ましく、２５０〜３６５℃の範囲であることが特に好ましい。反応温度が１８０℃より低い場合には、十分な水素化反応が進行せず、３９０℃より高い場合には、過度の分解や原料油の重合、その他の副反応が進行するおそれがある。 The reaction temperature in the hydrotreatment is preferably in the range of 180 to 390 ° C, more preferably in the range of 200 to 380 ° C, and particularly preferably in the range of 250 to 365 ° C. When the reaction temperature is lower than 180 ° C., sufficient hydrogenation reaction does not proceed, and when it is higher than 390 ° C., excessive decomposition, polymerization of raw material oil, and other side reactions may proceed.
反応器の形式としては、固定床方式を採用することができる。すなわち、水素は原料油に対して向流又は並流のいずれの形式を採用することができる。また、複数の反応器を用いて、向流、並流を組み合せた形式としてもよい。一般的な形式としては、ダウンフローであり、気液双並流形式を採用することができる。また、反応器は単独又は複数を組み合せてもよく、一つの反応器内部を複数の触媒床に区分した構造を採用してもよい。 As the type of the reactor, a fixed bed system can be adopted. That is, hydrogen can adopt either a countercurrent or a cocurrent flow with respect to the feedstock. Moreover, it is good also as a form which combined the countercurrent and the parallel flow using several reactors. As a general format, it is a down flow, and a gas-liquid twin parallel flow format can be adopted. Moreover, the reactor may be used alone or in combination, and a structure in which one reactor is divided into a plurality of catalyst beds may be adopted.
反応器内で水素化処理された被処理油は気液分離工程や精留工程等を経て所定の留分を含有する水素化処理油に分画される。 The treated oil hydrotreated in the reactor is fractionated into hydrotreated oil containing a predetermined fraction through a gas-liquid separation process, a rectification process, and the like.
原料油に含まれている酸素分や硫黄分の反応に伴って、水、一酸化炭素、二酸化炭素、硫化水素など副生物が発生する可能性があるため、複数の反応器の間や生成物回収工程に気液分離設備やその他の副生ガス除去装置を設置して、これらの副生物を除去することが必要である。副生物を除去する装置としては、高圧セパレータ等を好ましく挙げることができる。 By-products such as water, carbon monoxide, carbon dioxide, and hydrogen sulfide may be generated with the reaction of oxygen and sulfur contained in the feedstock oil. It is necessary to install gas-liquid separation equipment and other by-product gas removal devices in the recovery process to remove these by-products. As a device for removing by-products, a high-pressure separator or the like can be preferably exemplified.
副生物を除去した後の流出油は、必要に応じて精留塔で複数留分に分留してもよい。例えば、ガス、ナフサ留分等の軽質留分、灯油、軽油留分等の中間留分、残さ留分等の重質留分に分留してもよい。この場合、軽質留分と中間留分とのカット温度は１００〜２００℃が好ましく、１２０〜１８０℃がより好ましく、１４０〜１６０℃がさらに好ましい。また、中間留分と重質留分とのカット温度は３００〜４００℃が好ましく、３００〜３８０℃がより好ましく、３００〜３６０℃がさらに好ましい。また、生成するこのような軽質炭化水素留分の一部を水蒸気改質装置において改質することにより水素を製造することができる。このようにして製造された水素は、水蒸気改質に用いた原料がバイオマス由来炭化水素であることから、カーボンニュートラルという特徴を有しており、環境への負荷を低減することができる。 The spilled oil after removing the by-products may be fractionated into a plurality of fractions in a rectifying tower as necessary. For example, it may be fractionated into light fractions such as gas and naphtha fractions, middle fractions such as kerosene and light oil fractions, and heavy fractions such as residue fractions. In this case, the cut temperature of the light fraction and the middle fraction is preferably 100 to 200 ° C, more preferably 120 to 180 ° C, and further preferably 140 to 160 ° C. Moreover, 300-400 degreeC is preferable, as for the cut temperature of a middle fraction and a heavy fraction, 300-380 degreeC is more preferable, and 300-360 degreeC is further more preferable. Moreover, hydrogen can be manufactured by reforming a part of such a light hydrocarbon fraction to be produced in a steam reformer. The hydrogen produced in this way has a characteristic of carbon neutral because the raw material used for steam reforming is a biomass-derived hydrocarbon, and can reduce the burden on the environment.
水素ガスは加熱炉を通過前もしくは通過後の原料油に随伴させて最初の反応器の入口から導入することが一般的であるが、これとは別に、反応器内の温度を制御するとともに、反応器内全体にわたって水素圧力を維持する目的で触媒床の間や複数の反応器の間から水素ガスを導入してもよい。このようにして導入される水素を一般にクエンチ水素と呼ぶ。原料油に随伴して導入する水素ガスに対するクエンチ水素の割合は、１０〜６０容量％であることが好ましく、１５〜５０容量％であることがより好ましい。クエンチ水素の割合が１０容量未満であると後段の反応部位での反応が十分に進行しない傾向があり、クエンチ水素の割合が６０容積％を超えると反応器入口付近での反応が十分に進行しない傾向がある。 In general, hydrogen gas is introduced from the inlet of the first reactor in association with the feed oil before or after passing through the heating furnace, but separately from this, the temperature in the reactor is controlled, Hydrogen gas may be introduced from between the catalyst beds or between a plurality of reactors for the purpose of maintaining the hydrogen pressure throughout the reactor. The hydrogen thus introduced is generally called quench hydrogen. The ratio of quench hydrogen to hydrogen gas introduced along with the feedstock oil is preferably 10 to 60% by volume, and more preferably 15 to 50% by volume. If the rate of quench hydrogen is less than 10 volumes, the reaction at the subsequent reaction site tends not to proceed sufficiently. If the rate of quench hydrogen exceeds 60% by volume, the reaction near the reactor inlet does not proceed sufficiently. Tend.
本発明によって製造される炭化水素油を軽油留分基材として用いる場合は、少なくとも２６０〜３００℃の沸点を有する留分を含有し、硫黄分の含有量が１５質量ｐｐｍ以下であり且つ酸素分の含有量０．５質量％以下であることが好ましく、硫黄分の含有量が１２質量ｐｐｍ以下であり且つ酸素分の含有量０．３質量％以下であることがより好ましい。硫黄分及び酸素分が上記の上限値を超える場合、ディーゼルエンジンの排出ガス処理装置で使用されるフィルターや触媒、さらにエンジンその他の材質に影響を及ぼす恐れがある。 When the hydrocarbon oil produced by the present invention is used as a light oil fraction base, it contains a fraction having a boiling point of at least 260 to 300 ° C., the sulfur content is 15 mass ppm or less, and the oxygen content The content of is preferably 0.5 mass% or less, more preferably the sulfur content is 12 mass ppm or less, and the oxygen content is 0.3 mass% or less. When the sulfur content and the oxygen content exceed the above upper limit values, there is a risk of affecting the filter and catalyst used in the exhaust gas treatment device of the diesel engine, and further the engine and other materials.
（異性化処理方法）
本発明によって製造される炭化水素油を軽油留分基材として用いる場合に、被処理油又は該被処理油から水素、硫化水素、二酸化炭素及び水を分離した後の炭化水素油を、異性化触媒と接触させて分岐炭化水素化合物の含有量を増加させることで、軽油留分基材としての低温流動性を向上させることができる。(Isomerization method)
When the hydrocarbon oil produced according to the present invention is used as a gas oil fraction base, the oil to be treated or the hydrocarbon oil after separating hydrogen, hydrogen sulfide, carbon dioxide and water from the oil to be treated is isomerized. By making it contact with a catalyst and increasing content of a branched hydrocarbon compound, the low temperature fluidity | liquidity as a light oil fraction base material can be improved.
異性化の反応帯域は単一の触媒床から構成されていてもよいし、また複数の触媒床から構成されていてもよい。また、反応帯域が複数の触媒床から構成される場合、それらの触媒床は単一の反応器内に離隔して設置してもよいし、あるいは複数の反応器を直列または並列に配置し、各反応器内に触媒床を設置してもよい。 The reaction zone for isomerization may be composed of a single catalyst bed or may be composed of a plurality of catalyst beds. When the reaction zone is composed of a plurality of catalyst beds, the catalyst beds may be installed separately in a single reactor, or a plurality of reactors are arranged in series or in parallel, A catalyst bed may be installed in each reactor.
異性化の反応帯域における反応器の形式としては、固定床方式を採用することができる。すなわち、水素は被処理油に対して向流又は並流のいずれの形式を採用することができる。また、複数の反応器を用いて、向流、並流を組み合せた形式としてもよい。一般的な形式としては、ダウンフローであり、気液双並流形式を採用することができる。また、反応器は単独又は複数を組み合せてもよく、一つの反応器内部を複数の触媒床に区分した構造を採用してもよい。 A fixed bed system can be adopted as a reactor type in the reaction zone of isomerization. That is, hydrogen can adopt either a countercurrent or a parallel flow type with respect to the oil to be treated. Moreover, it is good also as a form which combined the countercurrent and the parallel flow using several reactors. As a general format, it is a down flow, and a gas-liquid twin parallel flow format can be adopted. Moreover, the reactor may be used alone or in combination, and a structure in which one reactor is divided into a plurality of catalyst beds may be adopted.
（触媒）
異性化触媒は、水素化異性化活性を有するものであれば特に制限されないが、アルミニウム、ケイ素、ジルコニウム、ホウ素、チタン及びマグネシウムから選ばれる２種以上の元素を含んで構成される多孔性無機酸化物、並びに該多孔性無機酸化物に担持された周期律表第ＶＩＩＩ族の元素から選ばれる１種以上の金属元素を含有する触媒が好ましく用いられる。(catalyst)
The isomerization catalyst is not particularly limited as long as it has hydroisomerization activity, but is a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium. And a catalyst containing at least one metal element selected from Group VIII elements of the Periodic Table supported on the porous inorganic oxide are preferably used.
異性化触媒の担体としては、水素化異性化活性を一層向上できる点から、アルミニウム、ケイ素、ジルコニウム、ホウ素、チタン及びマグネシウムから選ばれる２種以上であることが好ましく、アルミニウムと他の元素とを含む無機酸化物（酸化アルミニウムと他の酸化物との複合酸化物）が更に好ましい。 The support for the isomerization catalyst is preferably at least two selected from aluminum, silicon, zirconium, boron, titanium and magnesium from the viewpoint of further improving the hydroisomerization activity. An inorganic oxide (a composite oxide of aluminum oxide and another oxide) is more preferable.
多孔性無機酸化物としては、アルミニウム、ケイ素、ジルコニウム、チタンのうち少なくとも二種類以上の元素を含んで構成されていることがより好ましい。多孔性無機酸化物は、非結晶性、結晶性のいずれの形態でもよく、ゼオライトを用いることもできる。ゼオライトを用いる場合には、国際ゼオライト学会が定める構造コードのうち、ＦＡＵ、ＢＥＡ、ＭＯＲ、ＭＦＩ、ＭＥＬ、ＭＷＷ、ＴＯＮ、ＡＥＬ、ＭＴＴなどの結晶構造を有するゼオライトを用いることが好ましい。 The porous inorganic oxide is more preferably configured to include at least two elements of aluminum, silicon, zirconium, and titanium. The porous inorganic oxide may be either amorphous or crystalline, and zeolite can also be used. In the case of using zeolite, it is preferable to use zeolite having a crystal structure such as FAU, BEA, MOR, MFI, MEL, MWW, TON, AEL, MTT among the structure codes defined by the International Zeolite Society.
異性化触媒に担持する金属としては、周期律表第ＶＩＩＩ族の元素から選ばれる１種以上の金属であることが好ましく、このうち、Ｐｔ、Ｐｄ、Ｒｕ、Ｒｈ、Ａｕ、Ｉｒ、Ｎｉ、Ｃｏから選ばれる１種以上の金属であることがより好ましく、Ｐｔ、Ｒｄ、Ｒｕ、Ｎｉであることが特に好ましい。なお、これらの活性金属は、２種類以上の金属を組み合わせてもよく、たとえば、Ｐｔ−Ｐｄ、Ｐｔ−Ｒｕ、Ｐｔ−Ｒｈ、Ｐｔ−Ａｕ、Ｐｔ−Ｉｒなどの例が挙げられる。 The metal supported on the isomerization catalyst is preferably one or more metals selected from Group VIII elements of the periodic table, and among these, Pt, Pd, Ru, Rh, Au, Ir, Ni, Co It is more preferably one or more metals selected from the group consisting of Pt, Rd, Ru, and Ni. These active metals may be a combination of two or more kinds of metals, and examples thereof include Pt—Pd, Pt—Ru, Pt—Rh, Pt—Au, and Pt—Ir.
これらの活性金属を触媒に含有させる方法は特に限定されず、通常の水素化触媒を製造する際に適用される公知の方法を用いることができる。通常、活性金属の塩を含む溶液を触媒担体に含浸する方法が好ましく採用される。また、平衡吸着法、Ｐｏｒｅ−ｆｉｌｌｉｎｇ法、Ｉｎｃｉｐｉｅｎｔ−ｗｅｔｎｅｓｓ法なども好ましく採用される。例えば、Ｐｏｒｅ−ｆｉｌｌｉｎｇ法は、担体の細孔容積を予め測定しておき、これと同じ容積の金属塩溶液を含浸する方法である。なお、含浸方法は特に限定されるものではなく、金属担持量や触媒担体の物性に応じて適当な方法で含浸することができる。これらの金属は、硝酸塩、硫酸塩、あるいは錯塩の形態の金属源を水溶液あるいは適当な有機溶剤に溶解し、含浸溶液として使用することができる。 The method for incorporating these active metals into the catalyst is not particularly limited, and a known method applied when producing an ordinary hydrogenation catalyst can be used. Usually, a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed. In addition, an equilibrium adsorption method, a pore-filling method, an incident-wetness method, and the like are also preferably employed. For example, the pore-filling method is a method in which the pore volume of the carrier is measured in advance and impregnated with a metal salt solution having the same volume. The impregnation method is not particularly limited, and it can be impregnated by an appropriate method according to the amount of metal supported and the physical properties of the catalyst carrier. These metals can be used as an impregnation solution by dissolving a metal source in the form of nitrate, sulfate or complex in an aqueous solution or an appropriate organic solvent.
（反応条件）
また、異性化の反応帯域入口においては、異性化の原料油に含まれる硫黄分含有量が１質量ｐｐｍ以下であることが好ましく、０．５質量ｐｐｍであることがより好ましい。硫黄分含有量が１質量ｐｐｍを超えると第１の工程における水素化異性化の進行が妨げられる恐れがある。加えて、同様の理由で、異性化の原料油と共に導入される水素を含む反応ガスについても硫黄分濃度が十分に低いことが必要であり、１容量ｐｐｍ以下であることが好ましく、０．５容量ｐｐｍ以下であることがより好ましい。(Reaction conditions)
In addition, at the isomerization reaction zone inlet, the sulfur content contained in the isomerization feedstock is preferably 1 ppm by mass or less, more preferably 0.5 ppm by mass. If the sulfur content exceeds 1 mass ppm, the progress of hydroisomerization in the first step may be hindered. In addition, for the same reason, it is necessary for the reaction gas containing hydrogen introduced together with the isomerization raw material oil to have a sufficiently low sulfur content concentration, preferably 1 ppm by volume or less, More preferably, the volume is not more than ppm.
異性化工程における反応条件としては、好ましくは、水素圧力１〜１０ＭＰａ、液空間速度（ＬＨＳＶ）０．１〜３．０ｈ−１、水素油比（水素／油比）１００〜１５００ＮＬ／Ｌであり；より好ましくは、水素圧力２〜８ＭＰａ、液空間速度０．２〜２．５ｈ−１、水素油比２００〜１２００ＮＬ／Ｌであり；さらに好ましくは、水素圧力２．５〜８ＭＰａ、空間速度０．２〜２．０ｈ−１、水素油比２５０〜１０００ＮＬ／Ｌである。これらの条件はいずれも触媒の反応活性を左右する因子であり、例えば水素圧力及び水素油比が上記の下限値に満たない場合には、反応性が低下したり触媒活性が急速に低下したりする傾向がある。他方、水素圧力及び水素油比が上記の上限値を超える場合には、圧縮機等の過大な設備投資が必要となる傾向がある。また、液空間速度は低いほど反応に有利な傾向にあるが、上記の下限値未満の場合は、極めて大きな内容積の反応器が必要となり過大な設備投資が必要となる傾向があり、他方、液空間速度が上記の上限値を超える場合は、反応が十分に進行しなくなる傾向にある。 The reaction conditions in the isomerization step are preferably a hydrogen pressure of 1 to 10 MPa, a liquid space velocity (LHSV) of 0.1 to 3.0 h-1, and a hydrogen oil ratio (hydrogen / oil ratio) of 100 to 1500 NL / L. More preferably hydrogen pressure 2-8 MPa, liquid space velocity 0.2-2.5 h-1, hydrogen oil ratio 200-1200 NL / L; still more preferably hydrogen pressure 2.5-8 MPa, space velocity 0. .2 to 2.0 h-1 and hydrogen oil ratio of 250 to 1000 NL / L. These conditions are factors that influence the reaction activity of the catalyst. For example, when the hydrogen pressure and the hydrogen oil ratio do not satisfy the above lower limit values, the reactivity decreases or the catalyst activity decreases rapidly. Tend to. On the other hand, when the hydrogen pressure and the hydrogen oil ratio exceed the above upper limit values, there is a tendency that excessive equipment investment such as a compressor is required. Further, the lower the liquid space velocity tends to be advantageous for the reaction, but if the liquid space velocity is less than the above lower limit value, there is a tendency that an extremely large internal volume reactor is required and excessive equipment investment is required, When the liquid space velocity exceeds the above upper limit, the reaction tends not to proceed sufficiently.
異性化工程における反応温度は２２０〜３９０℃の範囲であることが好ましく、２４０〜３８０℃の範囲であることがより好ましく、２５０〜３６５℃の範囲であることが特に好ましい。反応温度が２２０℃より低い場合には、十分な水素化異性化反応が進行せず、３９０℃より高い場合には、過度の分解あるいは他の副反応が進行するおそれがある。 The reaction temperature in the isomerization step is preferably in the range of 220 to 390 ° C, more preferably in the range of 240 to 380 ° C, and particularly preferably in the range of 250 to 365 ° C. When the reaction temperature is lower than 220 ° C., sufficient hydroisomerization reaction does not proceed, and when it is higher than 390 ° C., excessive decomposition or other side reaction may proceed.
異性化工程において、異性化の原料油と共に反応帯域に導入される水素ガスは、所定の反応温度まで昇温するための加熱炉の上流もしくは下流において原料油に随伴させて反応帯域入口から導入することが一般的であるが、これとは別に、反応帯域内の温度を制御するとともに、反応帯域全体にわたって水素圧力を維持する目的で、触媒床の間や複数の反応器の間から水素ガスを導入してもよい（クエンチ水素）。または、生成油、未反応油、反応中間油などのいずれかまたは複数組み合わせて、一部を反応帯域入口や触媒床の間、複数の反応器の間などから導入してもよい。これにより反応温度を制御し、反応温度上昇による過度の分解反応や反応暴走を回避することができる。 In the isomerization step, the hydrogen gas introduced into the reaction zone together with the isomerization feedstock is introduced from the reaction zone inlet along with the feedstock upstream or downstream of the heating furnace for raising the temperature to a predetermined reaction temperature. In general, however, hydrogen gas is introduced between the catalyst beds and between the reactors in order to control the temperature in the reaction zone and maintain the hydrogen pressure throughout the reaction zone. (Quenched hydrogen). Alternatively, any or a combination of product oil, unreacted oil, intermediate reaction oil and the like may be combined and introduced partially from the reaction zone inlet, the catalyst bed, between the plurality of reactors, or the like. Thereby, the reaction temperature can be controlled, and an excessive decomposition reaction or reaction runaway due to an increase in the reaction temperature can be avoided.
（分留）
異性化処理後の生成油は、必要に応じて精留塔で複数留分に分留してもよい。
例えば、ガス、ナフサ留分等の軽質留分、灯油、軽油留分等の中間留分、残さ留分等の重質留分に分留してもよい。この場合、軽質留分と中間留分とのカット温度は１００〜２００℃が好ましく、１２０〜１８０℃がより好ましく、１４０〜１６０℃がさらに好ましい。また、中間留分と重質留分とのカット温度は３００〜４００℃が好ましく、３００〜３８０℃がより好ましく、３００〜３６０℃がさらに好ましい。また、生成するこのような軽質炭化水素留分の一部を水蒸気改質装置において改質することにより水素を製造することができる。このようにして製造された水素は、水蒸気改質に用いた原料がバイオマス由来炭化水素であることから、カーボンニュートラルという特徴を有しており、環境への負荷を低減することができる。(Fractionation)
The product oil after the isomerization treatment may be fractionated into a plurality of fractions in a rectifying column as necessary.
For example, it may be fractionated into light fractions such as gas and naphtha fractions, middle fractions such as kerosene and light oil fractions, and heavy fractions such as residue fractions. In this case, the cut temperature of the light fraction and the middle fraction is preferably 100 to 200 ° C, more preferably 120 to 180 ° C, and further preferably 140 to 160 ° C. Moreover, 300-400 degreeC is preferable, as for the cut temperature of a middle fraction and a heavy fraction, 300-380 degreeC is more preferable, and 300-360 degreeC is further more preferable. Moreover, hydrogen can be manufactured by reforming a part of such a light hydrocarbon fraction to be produced in a steam reformer. The hydrogen produced in this way has a characteristic of carbon neutral because the raw material used for steam reforming is a biomass-derived hydrocarbon, and can reduce the burden on the environment.
（異性化処理後の生成油性状）
水素化精製油の異性化処理を実施する場合、異性化工程で得られる生成油は、分岐炭化水素化合物を含有する。この場合、分岐炭化水素化合物の含有量は、全生成油に対して重量比で５〜９０％であることが好ましく、１０〜８０％であることがより好ましく、２０〜６０％であることが特に好ましい。分岐炭化水素化合物の含有量が上記下限より低い場合は低温流動性向上の効果が低く、上記上限より高い場合は、副反応である分解反応が過度に進行し、目的とする軽油留分収率が低下する。(Product oil properties after isomerization)
When carrying out the isomerization treatment of the hydrorefined oil, the product oil obtained in the isomerization step contains a branched hydrocarbon compound. In this case, the content of the branched hydrocarbon compound is preferably 5 to 90%, more preferably 10 to 80%, and more preferably 20 to 60% by weight ratio with respect to the total product oil. Particularly preferred. When the content of the branched hydrocarbon compound is lower than the lower limit, the effect of improving low-temperature fluidity is low, and when it is higher than the upper limit, the cracking reaction as a side reaction proceeds excessively, and the intended light oil fraction yield Decreases.
本発明によって製造される炭化水素油及びその異性化油は、特にディーゼル軽油や重油基材として好適に用いることができる。本発明にかかる炭化水素油は単独でディーゼル軽油や重油基材として用いてもよいが、他の基材などの成分を混合したディーゼル軽油又は重質基材として用いることができる。他の基材としては、一般的な石油精製工程で得られる軽油留分及び／又は灯油留分、本発明の製造方法で得られる残さ留分を混合することもできる。さらに、水素と一酸化炭素から構成される、いわゆる合成ガスを原料とし、フィッシャートロプシュ反応などを経由して得られる合成軽油もしくは合成灯油を混合することができる。これらの合成軽油や合成灯油は芳香族分をほとんど含有せず、飽和炭化水素を主成分とし、セタン価が高いことが特徴である。なお、合成ガスの製造方法としては公知の方法を用いることができ、特に限定されるものではない。 The hydrocarbon oil and its isomerized oil produced by the present invention can be suitably used particularly as a diesel light oil or heavy oil base material. The hydrocarbon oil according to the present invention may be used alone as a diesel light oil or heavy oil base material, but can be used as a diesel light oil or a heavy base material mixed with components such as other base materials. As other base materials, a light oil fraction and / or kerosene fraction obtained in a general petroleum refining process and a residual fraction obtained by the production method of the present invention can be mixed. Furthermore, a synthetic light oil or a kerosene obtained through a Fischer-Tropsch reaction or the like using so-called synthesis gas composed of hydrogen and carbon monoxide as a raw material can be mixed. These synthetic light oils and kerosene are characterized by containing almost no aromatic content, having a saturated hydrocarbon as a main component, and a high cetane number. In addition, a well-known method can be used as a manufacturing method of synthesis gas, and it is not specifically limited.
本発明の製造方法で得られる残さ留分は、硫黄分の含有量が０．１質量％以下であり、酸素分の含有量が１質量％以下であり、低硫黄重質基材として使用することができる。また、当該残さ留分は、接触分解用原料油として好適である。このように低硫黄レベルの残さ留分を接触分解装置に供することにより、硫黄分の少ないガソリン基材やその他燃料油基材を製造することができる。さらに、当該残さ留分は、水素化分解用原料油として用いることもできる。このような残さ留分を水素化分解装置に供することにより、分解活性の向上や生成油各留分性状の高品質化を達成することができる。 The residual fraction obtained by the production method of the present invention has a sulfur content of 0.1% by mass or less and an oxygen content of 1% by mass or less, and is used as a low sulfur heavy substrate. be able to. The residual fraction is suitable as a feedstock for catalytic cracking. Thus, a gasoline base material and other fuel oil base materials with little sulfur content can be manufactured by using the residue fraction of a low sulfur level for a catalytic cracking apparatus. Further, the residual fraction can be used as a feedstock for hydrocracking. By providing such a residual fraction to a hydrocracking apparatus, it is possible to improve the cracking activity and to improve the quality of each product oil fraction.
以下、実施例及び比較例に基づき本発明を更に具体的に説明するが、本発明は以下の実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.
（触媒の調製）
＜触媒Ａ＞
濃度５質量％のアルミン酸ナトリウム水溶液３０００ｇに水ガラス３号１８．０ｇを加え、６５℃に保温した容器に入れた。他方、６５℃に保温した別の容器において濃度２．５質量％の硫酸アルミニウム水溶液３０００ｇにリン酸（濃度８５％）６．０ｇを加えた溶液を調製し、これに前述のアルミン酸ナトリウムを含む水溶液を滴下した。混合溶液のｐＨが７．０になる時点を終点とし、得られたスラリー状の生成物をフィルターに通して濾取し、ケーキ状のスラリーを得た。(Preparation of catalyst)
<Catalyst A>
18.0 g of water glass No. 3 was added to 3000 g of an aqueous sodium aluminate solution having a concentration of 5% by mass, and the mixture was placed in a container kept at 65 ° C. On the other hand, in another container kept at 65 ° C., a solution in which 6.0 g of phosphoric acid (concentration 85%) is added to 3000 g of an aluminum sulfate aqueous solution having a concentration of 2.5% by mass is prepared, and this contains sodium aluminate as described above An aqueous solution was added dropwise. The time when the pH of the mixed solution reached 7.0 was set as the end point, and the resulting slurry product was filtered through a filter to obtain a cake slurry.
ケーキ状のスラリーを還流冷却器を取り付けた容器に移し、蒸留水１５０ｍｌと２７％アンモニア水溶液１０ｇを加え、７５℃で２０時間加熱攪拌した。該スラリーを混練装置に入れ、８０℃以上に加熱し水分を除去しながら混練し、粘土状の混練物を得た。得られた混練物を押出し成形機によって直径１．５ｍｍシリンダーの形状に押し出し、１１０℃で１時間乾燥した後、５５０℃で焼成し、成形担体を得た。 The cake-like slurry was transferred to a container equipped with a reflux condenser, 150 ml of distilled water and 10 g of 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 75 ° C. for 20 hours. The slurry was put in a kneading apparatus and heated to 80 ° C. or higher and kneaded while removing moisture to obtain a clay-like kneaded product. The obtained kneaded material was extruded into a shape of a cylinder having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 550 ° C. to obtain a molded carrier.
得られた成形担体５０ｇをナス型フラスコに入れ、ロータリーエバポレータ−で脱気しながら三酸化モリブデン１７．３ｇ、硝酸ニッケル（ＩＩ）６水和物１３．２ｇ、リン酸（濃度８５％）３．９ｇ及びリンゴ酸４．０ｇを含む含浸溶液をフラスコ内に注入した。含浸した試料は１２０℃で１時間乾燥した後、５５０℃で焼成し、触媒Ａを得た。調製した触媒Ａの物性を表１に示す。 2. 50 g of the obtained shaped carrier was put into an eggplant-shaped flask, and while degassing with a rotary evaporator, 17.3 g of molybdenum trioxide, 13.2 g of nickel (II) nitrate hexahydrate, phosphoric acid (concentration 85%) An impregnation solution containing 9 g and 4.0 g malic acid was poured into the flask. The impregnated sample was dried at 120 ° C. for 1 hour and then calcined at 550 ° C. to obtain Catalyst A. Table 1 shows the physical properties of the prepared catalyst A.
＜触媒Ｂ＞
市販のシリカアルミナ担体（日揮化学社製Ｎ６３２ＨＮ）５０ｇをナス型フラスコに入れ、ロータリーエバポレーターで脱気しながらテトラアンミン白金（II）クロライド水溶液をフラスコ内に注入した。含浸した試料は１１０℃で乾燥した後、３５０℃で焼成し、触媒Ｂを得た。触媒Ｂにおける白金の担持量は、触媒全量を基準として０．５質量％であった。<Catalyst B>
50 g of a commercially available silica alumina carrier (N632HN manufactured by JGC Chemical Co., Ltd.) was placed in an eggplant type flask, and an aqueous tetraammineplatinum (II) chloride solution was injected into the flask while degassing with a rotary evaporator. The impregnated sample was dried at 110 ° C. and then calcined at 350 ° C. to obtain Catalyst B. The amount of platinum supported on catalyst B was 0.5% by mass based on the total amount of catalyst.
（実施例１）
触媒Ａ（１００ｍｌ）を充填した反応管（内径２０ｍｍ）を固定床流通式反応装置に取り付けた。その後、ジメチルジサルファイドを加えた直留軽油（硫黄分３質量％）を用いて触媒層平均温度３００℃、水素分圧６ＭＰａ、液空間速度１ｈ−１、水素／油比２００ＮＬ／Ｌの条件下で、４時間触媒の予備硫化を行った。Example 1
A reaction tube (inner diameter 20 mm) filled with catalyst A (100 ml) was attached to a fixed bed flow type reactor. Then, using straight-run gas oil to which dimethyl disulfide was added (sulfur content: 3% by mass), catalyst layer average temperature of 300 ° C., hydrogen partial pressure of 6 MPa, liquid space velocity of 1 h −1 , hydrogen / oil ratio of 200 NL / L. The catalyst was presulfided for 4 hours.
予備硫化後、表２に示す性状を有するパーム油（含酸素炭化水素化合物に占めるトリグリセリド構造を有する化合物の割合：９８モル％）に後述の精留塔にて分留した中間留分の一部をパーム油（原料油）に対して１質量倍となる量をリサイクルし、パーム油に対する硫黄分含有量（硫黄原子換算）が１０質量ｐｐｍになるようにジメチルサルファイドを添加して被処理油の調整を行った。その後、被処理油を用いて、水素化精製を行った。被処理油の１５℃密度は０．９１６ｇ／ｍｌ、酸素分含有量は１１．４質量％であった。また、水素化精製の条件は、反応管入り口温度を１８０℃、水素圧力を３ＭＰａ、液空間速度を０．５ｈ−１、水素／油比を５００ＮＬ／Ｌとした。水素化精製後の処理油を高圧セパレータに導入し、処理油から水素、硫化水素、二酸化炭素および水の除去を行った。高圧セパレータ導入後の流出油は精留塔に導かれ、沸点範囲１５０℃未満の軽質留分、１５０〜３５０℃の中間留分、３５０℃を超える重質留分に分留した。中間留分の一部は、冷却水で４０℃まで冷却して、前述の通り原料油であるパーム油にリサイクルし、残りは軽油基材として採取した。水素化精製条件を表３に、反応管出口と入り口の温度差（ΔＴ）、得られた結果を表４に示す。なお、表４中、「脱炭酸率」とは、水素化脱酸素反応に占める水素化脱炭酸反応の占める割合を意味する。また、ΔＴの値は大きいほど、水素化精製処理における発熱が大きいことを意味する。After preliminary sulfidation, a part of middle fraction fractionated in palm oil having the properties shown in Table 2 (ratio of compound having triglyceride structure in oxygen-containing hydrocarbon compound: 98 mol%) in a rectification column described later Of palm oil (raw material oil) is recycled in an amount of 1 mass times, and dimethyl sulfide is added so that the sulfur content relative to palm oil (in terms of sulfur atom) is 10 mass ppm. Adjustments were made. Thereafter, hydrotreating was performed using the oil to be treated. The 15 ° C. density of the oil to be treated was 0.916 g / ml, and the oxygen content was 11.4% by mass. The hydrorefining conditions were a reaction tube inlet temperature of 180 ° C., a hydrogen pressure of 3 MPa, a liquid space velocity of 0.5 h −1 , and a hydrogen / oil ratio of 500 NL / L. The treated oil after hydrorefining was introduced into a high-pressure separator, and hydrogen, hydrogen sulfide, carbon dioxide and water were removed from the treated oil. The spilled oil after introduction of the high-pressure separator was guided to a rectifying column, and fractionated into a light fraction having a boiling point range of less than 150 ° C, an intermediate fraction having a temperature of 150 to 350 ° C, and a heavy fraction having a temperature exceeding 350 ° C. A part of the middle distillate was cooled to 40 ° C. with cooling water and recycled to palm oil as a raw material oil as described above, and the rest was collected as a light oil base material. The hydrorefining conditions are shown in Table 3, the temperature difference (ΔT) between the outlet and inlet of the reaction tube, and the results obtained are shown in Table 4. In Table 4, “Decarboxylation rate” means the proportion of hydrodecarboxylation in the hydrodeoxygenation reaction. Moreover, it means that the larger the value of ΔT, the greater the heat generated in the hydrotreating process.
（参考例１）
水素圧力を５ＭＰａとした以外は実施例１と同様にして水素化精製を行った。水素化精製条件を表３に、得られた結果を表４に示す。
( Reference Example 1 )
Hydrorefining was performed in the same manner as in Example 1 except that the hydrogen pressure was 5 MPa. The hydrorefining conditions are shown in Table 3, and the obtained results are shown in Table 4.
（実施例２）
分留後の中間留分をリサイクルする代わりに、高圧セパレータで副生物を除去した処理油の一部を冷却水で４０℃まで冷却した後パーム油に対して１質量倍となる量をリサイクルする以外は、実施例１と同様にして水素化精製を行った。水素化精製条件を表３に、得られた結果を表４に示す。
(Example 2 )
Instead of recycling the middle distillate after fractional distillation, a portion of the treated oil from which by-products have been removed with a high-pressure separator is cooled to 40 ° C. with cooling water, and then recycled in an amount that is 1 times the mass of palm oil. Except for the above, hydrorefining was performed in the same manner as in Example 1. The hydrorefining conditions are shown in Table 3, and the obtained results are shown in Table 4.
（比較例１）
高圧セパレータで副生物を除去した処理油の一部をパーム油にリサイクルしない以外は、実施例１と同様にして水素化精製を行った。水素化精製条件を表３に得られた結果を、表４に示す。(Comparative Example 1)
Hydrorefining was performed in the same manner as in Example 1 except that part of the treated oil from which by-products were removed with a high-pressure separator was not recycled to palm oil. The results obtained in Table 3 for the hydrorefining conditions are shown in Table 4.
（比較例２）
圧力を６ＭＰａとし、パーム油に対する硫黄分含有量（硫黄原子換算）１００質量ｐｐｍとなるようにジメチルサルファイドをパーム油に添加した以外は実施例１と同様にして水素化精製を行った。水素化精製条件を表３に得られた結果を、表４に示す。(Comparative Example 2)
Hydrorefining was carried out in the same manner as in Example 1 except that dimethyl sulfide was added to palm oil so that the pressure was 6 MPa and the sulfur content relative to palm oil (sulfur atom conversion) was 100 mass ppm. The results obtained in Table 3 for the hydrorefining conditions are shown in Table 4.
（比較例３）
圧力を１０ＭＰａとした以外は実施例１と同様にして水素化精製を行った。水素化精製条件を表３に得られた結果を、表４に示す。(Comparative Example 3)
Hydrorefining was performed in the same manner as in Example 1 except that the pressure was 10 MPa. The results obtained in Table 3 for the hydrorefining conditions are shown in Table 4.
（比較例４）
中間留分のリサイクルをパーム油に対して７質量倍とした以外は実施例１と同様にして水素化精製を行った。生成油には未反応原料が含まれており、水素化脱酸素反応が十分に進行していなかった。水素化精製条件を表３に得られた結果を、表４に示す。(Comparative Example 4)
Hydrorefining was performed in the same manner as in Example 1 except that the middle distillate was recycled 7 times by mass with respect to palm oil. The product oil contained unreacted raw materials, and the hydrodeoxygenation reaction did not proceed sufficiently. The results obtained in Table 3 for the hydrorefining conditions are shown in Table 4.
（実施例３）
実施例1の固定床流通式反応装置に、触媒Ｂ（５０ｍＬ）を充填した第二の反応管（内径２０ｍｍ）を接続した。触媒Ｂに対して、触媒層平均温度３２０℃、水素圧力５ＭＰａ、水素ガス量８３ｍｌ／ｍｉｎの条件化で６時間、還元処理を行った。
中間留分を得るまでの工程は実施例１と同様にし、リサイクルした残りの中間留分を、触媒Ｂ（５０ｍｌ）を充填した反応管（内径２０ｍｍ）を固定床流通式反応装置（異性化装置）に導入し、異性化処理を行った。まず、触媒Ｂに対して、触媒層平均温度３２０℃、水素圧力５ＭＰａ、水素ガス量８３ｍｌ／ｍｉｎの条件化で６時間、還元処理を行い、次に、触媒層平均温度を３３０℃、水素圧力を３ＭＰａ、液空間速度を１ｈ−１、水素／油比を５００ＮＬ／Ｌの条件で異性化処理を行った。異性化処理後の油は、さらに第２の精留塔に導かれ、沸点範囲１５０℃未満の軽質留分、１５０〜３５０℃の中間留分、３５０℃を超える重質留分に分留した。この第２の中間留分は軽油基材に用いる。水素化精製条件を表３に、得られた結果を表４に示す。異性化処理によって、軽油基材のイソパラフィン比率が高まり、流動点が低く（低温性能を向上できる）なっていることが分かる。
(Example 3 )
A second reaction tube (inner diameter 20 mm) filled with catalyst B (50 mL) was connected to the fixed bed flow reactor of Example 1. The catalyst B was subjected to reduction treatment for 6 hours under conditions of an average catalyst layer temperature of 320 ° C., a hydrogen pressure of 5 MPa, and a hydrogen gas amount of 83 ml / min.
The steps up to obtaining the middle distillate were the same as in Example 1. The remaining middle distillate was recycled and the reaction tube (inner diameter 20 mm) filled with catalyst B (50 ml) was connected to a fixed bed flow reactor (isomerization unit). ) And subjected to isomerization treatment. First, the catalyst B is subjected to a reduction treatment for 6 hours under conditions of an average catalyst layer temperature of 320 ° C., a hydrogen pressure of 5 MPa, and a hydrogen gas amount of 83 ml / min, and then the catalyst layer average temperature of 330 ° C. and a hydrogen pressure of Was isomerized under the conditions of 3 MPa, liquid space velocity of 1 h-1, and hydrogen / oil ratio of 500 NL / L. The oil after the isomerization treatment was further guided to the second rectification column and fractionated into a light fraction having a boiling point range of less than 150 ° C, an intermediate fraction having a boiling point of 150 to 350 ° C, and a heavy fraction having a temperature exceeding 350 ° C. . This second middle distillate is used as a light oil base material. The hydrorefining conditions are shown in Table 3, and the obtained results are shown in Table 4. It can be seen that the isoparaffin ratio of the light oil base is increased and the pour point is lowered (low temperature performance can be improved) by the isomerization treatment.
（実施例４）
実施例1の固定床流通式反応装置に、触媒Ｂ（５０ｍＬ）を充填した第二の反応管（内径２０ｍｍ）を接続した。触媒Ｂに対して、触媒層平均温度３２０℃、水素圧力５ＭＰａ、水素ガス量８３ｍｌ／ｍｉｎの条件化で６時間、還元処理を行った。
高圧セパレータで処理油から水素、硫化水素、二酸化炭素および水の除去を行うまでの工程は実施例１と同様にし、高圧セパレータから得られた流出油を触媒Ｂ（５０ｍｌ）を充填した反応管（内径２０ｍｍ）を固定床流通式反応装置（異性化装置）に導入し、異性化処理を行った。まず、触媒Ｂに対して、触媒層平均温度３２０℃、水素圧力５ＭＰａ、水素ガス量８３ｍｌ／ｍｉｎの条件化で６時間、還元処理を行い、次に、触媒層平均温度を３３０℃、水素圧力を３ＭＰａ、液空間速度を１ｈ−１、水素／油比を５００ＮＬ／Ｌの条件で異性化処理を行った。異性化処理後の油は、さらに精留塔に導かれ、沸点範囲１５０℃未満の軽質留分、１５０〜３５０℃の中間留分、３５０℃を超える重質留分に分留した。この中間留分は軽油基材に用いる。水素化精製条件を表３に、得られた結果を表４に示す。異性化処理によって、軽油基材のイソパラフィン比率が高まり、流動点が低く（低温性能を向上できる）なっていることが分かる。
(Example 4 )
A second reaction tube (inner diameter 20 mm) filled with catalyst B (50 mL) was connected to the fixed bed flow reactor of Example 1. The catalyst B was subjected to reduction treatment for 6 hours under conditions of an average catalyst layer temperature of 320 ° C., a hydrogen pressure of 5 MPa, and a hydrogen gas amount of 83 ml / min.
The process until the removal of hydrogen, hydrogen sulfide, carbon dioxide and water from the treated oil with the high-pressure separator was the same as in Example 1, and the reaction tube (50 ml) filled with the spilled oil obtained from the high-pressure separator ( An inner diameter of 20 mm) was introduced into a fixed bed flow type reaction apparatus (isomerization apparatus) and subjected to isomerization treatment. First, the catalyst B is subjected to a reduction treatment for 6 hours under conditions of an average catalyst layer temperature of 320 ° C., a hydrogen pressure of 5 MPa, and a hydrogen gas amount of 83 ml / min, and then the catalyst layer average temperature of 330 ° C. and a hydrogen pressure of Was isomerized under the conditions of 3 MPa, liquid space velocity of 1 h-1, and hydrogen / oil ratio of 500 NL / L. The oil after the isomerization treatment was further guided to a rectification column, and fractionated into a light fraction having a boiling point range of less than 150 ° C., an intermediate fraction having a temperature of 150 to 350 ° C., and a heavy fraction having a temperature exceeding 350 ° C. This middle distillate is used as a light oil base material. The hydrorefining conditions are shown in Table 3, and the obtained results are shown in Table 4. It can be seen that the isoparaffin ratio of the light oil base is increased and the pour point is lowered (low temperature performance can be improved) by the isomerization treatment.
上記表４に示した通り、実施例１〜４及び参考例１では、水素圧力、リサイクル量を適正な範囲に制御することにより、原料油の処理効率の低下を招くことなく、水素化脱炭酸反応選択性の向上と反応熱の抑制を行うことができ、効率の良い原料油の水素化精製方法を実現することができた。
As shown in Table 4 above, in Examples 1 to 4 and Reference Example 1 , by controlling the hydrogen pressure and the recycle amount to an appropriate range, hydrodecarboxylation without causing a decrease in the processing efficiency of the raw material oil. The reaction selectivity could be improved and the heat of reaction could be suppressed, and an efficient feed hydrotreating method could be realized.
Claims (11)
前記原料油は、前記工程を経て得られた前記炭化水素油の一部を前記含酸素炭化水素化合物に対して０．５〜５質量倍となるようにリサイクル供給したリサイクル油と、前記含酸素炭化水素化合物に対して硫黄原子換算で１〜５０質量ｐｐｍの含硫黄炭化水素化合物と、を含有することを特徴とする、炭化水素油の製造方法。 A porous inorganic material comprising a raw material oil containing an oxygen-containing hydrocarbon compound derived from animal and vegetable oils in the presence of hydrogen, and two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium Hydrotreating an oxide and a catalyst containing one or more metals selected from Group 6A and Group 8 elements supported on the porous inorganic oxide at a hydrogen pressure of 2 MPa to 4 MPa And removing hydrogen, hydrogen sulfide, carbon dioxide, and water from the product to be treated to obtain a hydrocarbon oil,
The raw material oil is a recycled oil obtained by recycling a part of the hydrocarbon oil obtained through the step so as to be 0.5 to 5 times by mass with respect to the oxygen-containing hydrocarbon compound, and the oxygen-containing oil. A method for producing a hydrocarbon oil, comprising 1 to 50 ppm by mass of a sulfur-containing hydrocarbon compound in terms of sulfur atom with respect to the hydrocarbon compound.
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| JP2007308563A (en) * | 2006-05-17 | 2007-11-29 | Nippon Oil Corp | Hydrofining method |
| JP2007308573A (en) * | 2006-05-17 | 2007-11-29 | Nippon Oil Corp | Light oil composition |
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| JP2007308563A (en) * | 2006-05-17 | 2007-11-29 | Nippon Oil Corp | Hydrofining method |
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