JP2008138185A - Gasoline composition - Google Patents
Gasoline composition Download PDFInfo
- Publication number
- JP2008138185A JP2008138185A JP2007288328A JP2007288328A JP2008138185A JP 2008138185 A JP2008138185 A JP 2008138185A JP 2007288328 A JP2007288328 A JP 2007288328A JP 2007288328 A JP2007288328 A JP 2007288328A JP 2008138185 A JP2008138185 A JP 2008138185A
- Authority
- JP
- Japan
- Prior art keywords
- content
- gasoline
- volume
- aromatic
- less
- 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.)
- Granted
Links
- 239000003502 gasoline Substances 0.000 title claims abstract description 124
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 35
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000001336 alkenes Chemical class 0.000 claims abstract description 26
- 125000003118 aryl group Chemical group 0.000 claims abstract description 25
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 19
- 239000011593 sulfur Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 238000011160 research Methods 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 41
- 238000003860 storage Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000004821 distillation Methods 0.000 description 40
- 239000002585 base Substances 0.000 description 38
- 239000003921 oil Substances 0.000 description 37
- 238000004517 catalytic hydrocracking Methods 0.000 description 29
- 239000003054 catalyst Substances 0.000 description 25
- 150000002430 hydrocarbons Chemical class 0.000 description 23
- 239000000463 material Substances 0.000 description 23
- 229930195733 hydrocarbon Natural products 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000004215 Carbon black (E152) Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000011148 porous material Substances 0.000 description 14
- -1 sludge Chemical class 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 13
- 238000009835 boiling Methods 0.000 description 12
- 239000000446 fuel Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 238000004523 catalytic cracking Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000006317 isomerization reaction Methods 0.000 description 8
- 238000002407 reforming Methods 0.000 description 8
- 238000010998 test method Methods 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000001833 catalytic reforming Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 6
- 230000001133 acceleration Effects 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 235000014676 Phragmites communis Nutrition 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000001491 aromatic compounds Chemical class 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
- 239000010779 crude oil Substances 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000005504 petroleum refining Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- VDMXPMYSWFDBJB-UHFFFAOYSA-N 1-ethoxypentane Chemical group CCCCCOCC VDMXPMYSWFDBJB-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- VSCUCHUDCLERMY-UHFFFAOYSA-N 2-ethoxybutane Chemical compound CCOC(C)CC VSCUCHUDCLERMY-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- QJMYXHKGEGNLED-UHFFFAOYSA-N 5-(2-hydroxyethylamino)-1h-pyrimidine-2,4-dione Chemical compound OCCNC1=CNC(=O)NC1=O QJMYXHKGEGNLED-UHFFFAOYSA-N 0.000 description 1
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241001372564 Piona Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000019568 aromas Nutrition 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
本発明は、環境保全に配慮しつつ優れた運転特性を有するガソリン組成物に関する。 The present invention relates to a gasoline composition having excellent driving characteristics while considering environmental conservation.
地球温暖化ガスの一つと考えられている二酸化炭素の排出量を削減するために、ガソリンのリサーチ法オクタン価（ＲＯＮ）を高めることが有効である。ＪＩＳ Ｋ ２２０２には、ＲＯＮが９６．０以上の１号自動車ガソリンと８９．０以上の２号自動車ガソリンが規定されており、前者は高性能なプレミアムガソリンとして、後者はレギュラーガソリンとして市販されている。従来、プレミアムガソリンは、接触改質ガソリン基材、メチル−ｔ−ブチルエーテル（ＭＴＢＥ）のような１００以上のＲＯＮをもつ基材、アルキレートガソリン基材、接触分解ガソリン軽質分のような９３以上のＲＯＮをもつ基材を中心に、各種のガソリン基材を配合して製造されている。また、レギュラーガソリンは、接触分解ガソリン基材を中心に、芳香族炭化水素やＲＯＮの低い脱硫直留ナフサ等を添加し製造されている（非特許文献１参照）。 In order to reduce the emission of carbon dioxide, which is considered to be one of the global warming gases, it is effective to increase the gasoline research octane number (RON). JIS K 2202 stipulates No. 1 automobile gasoline with RON of 96.0 or more and No. 2 automobile gasoline with 89.0 or more. The former is marketed as high-performance premium gasoline and the latter as regular gasoline. Yes. Conventionally, premium gasoline has a catalytic reforming gasoline base, a base with more than 100 RON such as methyl-t-butyl ether (MTBE), an alkylate gasoline base, a catalytic cracking gasoline lighter than 93 Manufactured by blending various gasoline base materials, centering on base materials with RON. Further, regular gasoline is produced by adding aromatic hydrocarbons, desulfurized straight naphtha having a low RON, etc. mainly on catalytic cracking gasoline bases (see Non-Patent Document 1).
一方、石油化学製品の海外需要増加等の事情により石油化学製品の増産の必要性が高まっており、石油化学原料である芳香族炭化水素を製造するため接触改質ガソリン製造装置の稼動が上がっているが、これに伴い副産物である重質芳香族炭化水素も大量に製造されている。この重質芳香族炭化水素は硫黄分をほとんど含まずＲＯＮが高いことからガソリン基材として有効である。しかし、このような沸点が高い重質基材を使用する場合、軽質炭化水素基材を一定比率以上混合してガソリン調製後の揮発性を一定範囲にすることが必要との混合バランス上の制約や、ガソリン中の重質芳香族炭化水素の配合量が多すぎるとガソリンエンジンの加速性や排ガス特性の悪化を招く等の問題があり、あまり多く使用することはできなかった。 On the other hand, the need for increased production of petrochemical products has increased due to the increase in overseas demand for petrochemical products, and the operation of catalytic reforming gasoline production equipment has increased to produce aromatic hydrocarbons as petrochemical raw materials. Along with this, heavy aromatic hydrocarbons, which are by-products, are also produced in large quantities. This heavy aromatic hydrocarbon is effective as a gasoline base material because it contains almost no sulfur and has a high RON. However, when using a heavy base material with such a high boiling point, there is a restriction on the mixing balance that it is necessary to mix a light hydrocarbon base material with a certain ratio or more to keep the volatility after gasoline preparation within a certain range. In addition, if the amount of heavy aromatic hydrocarbons in the gasoline is too large, there are problems such as the acceleration of the gasoline engine and the deterioration of the exhaust gas characteristics, and it cannot be used much.
炭素数９の特定の芳香族炭化水素含有量を規定して、耐摩耗性や潤滑性を向上させる方法が開示されている（特許文献１参照）。また、芳香族炭化水素を削減することで排ガス特性を改善する方法についても開示されている（特許文献２参照）。しかしながら、ＲＯＮの高い重質芳香族炭化水素留分をも削減させているため、ＲＯＮ、蒸気圧、蒸留性状（１０、５０、９０容量％留出温度など）等を適切な範囲に維持できておらず、また、具体的な製造方法に関する開示も無い。
さらに、炭素数９以上の芳香族炭化水素の含有量を削減することで排ガス特性を改善したガソリン組成物についても開示されている（特許文献３参照）が、同様にＲＯＮの高い重質芳香族炭化水素留分を削減させているため、ＲＯＮ、蒸気圧等を適切な範囲に維持できておらず、しかも、具体的な製造方法に関する開示も無い。
A method for improving the wear resistance and lubricity by specifying a specific aromatic hydrocarbon content of 9 carbon atoms is disclosed (see Patent Document 1). A method for improving exhaust gas characteristics by reducing aromatic hydrocarbons is also disclosed (see Patent Document 2). However, since the heavy aromatic hydrocarbon fraction with high RON is reduced, RON, vapor pressure, distillation properties (10, 50, 90 vol% distillation temperature, etc.) can be maintained in an appropriate range. Further, there is no disclosure regarding a specific manufacturing method.
Furthermore, a gasoline composition having improved exhaust gas characteristics by reducing the content of aromatic hydrocarbons having 9 or more carbon atoms is also disclosed (see Patent Document 3), but it is also a heavy aromatic having a high RON. Since the hydrocarbon fraction is reduced, RON, vapor pressure, etc. cannot be maintained in an appropriate range, and there is no disclosure regarding a specific production method.
芳香族炭化水素と共にＲＯＮの向上に大きく寄与し、広く使用されているオレフィン類は、一般的に接触分解ガソリンやその他の各種分解ガソリンなどには多く含まれている（非特許文献２参照）。しかしながら、オレフィン化合物は光化学的に不安定であること、スラッジ分などの固体状化合物を析出させてしまうことなどの欠点があり貯蔵安定性に問題がある。また、オレフィン化合物のうち比較的低分子量のものについては、ＲＯＮは高いものの蒸気圧も高い傾向があり、夏季用ガソリンの基材としてはその高い蒸気圧を相殺するために、蒸気圧の低い基材が必要とされることから、あまり多くを使用できない。また、芳香族炭化水素の多くが１００以上のＲＯＮを有しているのに対して、オレフィン化合物は７０程度から１１０程度まで幅があり、適切な留分を選定して使用する必要がある。 Olefins that contribute greatly to the improvement of RON together with aromatic hydrocarbons and are widely used are generally contained in catalytic cracked gasoline and other various cracked gasolines (see Non-Patent Document 2). However, olefinic compounds have disadvantages such as photochemical instability and precipitation of solid compounds such as sludge, which causes problems in storage stability. Further, among olefin compounds having relatively low molecular weight, although RON is high, the vapor pressure tends to be high, and as a base material for summer gasoline, a base having a low vapor pressure is used to offset the high vapor pressure. Not much can be used because the material is required. Further, most of the aromatic hydrocarbons have 100 or more RON, whereas olefin compounds have a range from about 70 to about 110, and it is necessary to select and use an appropriate fraction.
オレフィンの他、ＲＯＮの高い化合物として、イソパラフィンが挙げられる。イソパラフィンを選択的に製造してＲＯＮを向上させる方法として、炭化水素の骨格異性化が知られている（非特許文献３参照）。しかしながら、このような骨格異性化反応も、ＲＯＮとしては９０を超えるガソリン基材を製造するまでには至っておらず、芳香族化合物系のガソリン基材に置き換えることは困難である。 In addition to olefins, isoparaffins may be mentioned as compounds with high RON. As a method for selectively producing isoparaffin to improve RON, skeletal isomerization of hydrocarbons is known (see Non-Patent Document 3). However, such a skeletal isomerization reaction has not yet reached the production of a gasoline base of more than 90 as RON, and it is difficult to replace it with an aromatic compound-based gasoline base.
異性化反応と同様にイソパラフィンを選択的に製造する方法として、アルキレーション反応を用いるプロセスがある。アルキレーション反応は、硫酸などの酸触媒を使用し、主に炭素数４のオレフィンとイソパラフィンとを反応させて炭素数８のイソパラフィンを製造する反応であり、既に多くのプロセスが世界中で稼動している（非特許文献４参照）。しかし、アルキレートガソリンは異性化ガソリンよりもＲＯＮはやや高いものの９５程度であり、芳香族系の基材に置き換えられるレベルではない。また、原料として比較的高価な炭素数４の炭化水素化合物を使用しなければならないため、供給量やコストの制約からあまり大量に製造することができない。 Similar to the isomerization reaction, there is a process using an alkylation reaction as a method for selectively producing isoparaffin. The alkylation reaction is a reaction in which an acid catalyst such as sulfuric acid is used to react mainly with an olefin having 4 carbon atoms and isoparaffin to produce an isoparaffin having 8 carbon atoms. Many processes have already been operated all over the world. (See Non-Patent Document 4). However, alkylate gasoline has a RON slightly higher than that of isomerized gasoline, but is about 95, and is not at a level that can be replaced with an aromatic base material. In addition, since a relatively expensive hydrocarbon compound having 4 carbon atoms must be used as a raw material, it cannot be produced in large quantities due to supply and cost constraints.
以上の状況を考慮しつつガソリン製造の実態に目を向けると、高いＲＯＮを有する芳香族炭化水素の製造方法としては、原油の常圧蒸留装置、水素化脱硫装置を経て得られた脱硫直留重質ナフサ留分を接触改質するプロセスが従来から広く用いられてきた。しかし、前述の通り、石油化学原料として芳香族炭化水素の需要が増えているため、新たな芳香族系のガソリン基材を製造するルートが望まれており、特に、安価でかつ今後の需要減少が予想されている重質炭化水素から芳香族炭化水素を選択的に製造することが望まれている。
その一方で、硫黄含有量が１０質量ｐｐｍ以下と低く、かつ、重質な芳香族炭化水素やオレフィンの含有量を上げることなく、ＲＯＮが高く十分な実用性能を有するガソリン組成物、及びその製造方法が望まれている。
On the other hand, a gasoline composition having a high RON and sufficient practical performance without increasing the content of heavy aromatic hydrocarbons and olefins, and a low sulfur content of 10 ppm by mass or less, and its production A method is desired.
本発明は、オレフィン含有量が１５容量％以下、硫黄含有量が１０質量ｐｐｍ以下と低く、優れた貯蔵安定性、環境保全性に加え、芳香族炭化水素を特別に増量することなく、ＲＯＮが高く十分な実用性能を有するガソリン組成物を提供することを課題とするものである。 In the present invention, the olefin content is as low as 15% by volume or less and the sulfur content is as low as 10 ppm by mass or less. In addition to excellent storage stability and environmental conservation, RON An object of the present invention is to provide a gasoline composition having high and sufficient practical performance.
本発明者らは、上記課題を解決するために鋭意研究した結果、重質油の水素化分解において、重質油に含まれる多環芳香族炭化水素を水素化分解して選択的に１環芳香族炭化水素を生成する選択的水素化分解で得られた生成油を配合したガソリンは運転性、加速性及び排ガス特性が良好であり、加えてＲＯＮが高いため燃費が改善されて環境負荷が低減されることを見出した。さらに、このガソリンの特性の改善は、選択的水素化分解生成油に含まれる１，３，５−トリメチルベンゼンや１，２，４−トリメチルベンゼンなどの炭素数９の芳香族炭化水素によることを見出した。
一般的に炭素数９の芳香族炭化水素は排ガス性状を悪化させると言われている（特許文献１〜３）。しかし、炭素数９の芳香族炭化水素の中でも１，３，５−トリメチルベンゼンや１，２，４−トリメチルベンゼンはそれぞれＲＯＮが１２０、１１１と極めて高く、かつ、低いリード蒸気圧（ＲＶＰ）を有する。すなわち、これら特定の芳香族炭化水素の含有比率を高めたガソリン組成物は、蒸留性状とリード蒸気圧（ＲＶＰ）の良好なバランスを保持しながら、オレフィンや芳香族炭化水素、さらには炭素数９の芳香族炭化水素の総量も上げずに、高いＲＯＮ、低硫黄の環境対応型のガソリン組成物を調製することができる。
このように、本発明者らは、高いＲＯＮを有し、かつＲＶＰが低く、蒸留性状も好ましい特定の炭化水素化合物を見出し、その含有量を制御することで、高いＲＯＮを維持したまま硫黄分やオレフィン分、芳香族分を低減し、優れた貯蔵安定性、環境保全性に加え、十分な実用性能を備えたガソリン組成物が得られることを見出し、かかる知見に基づいて本発明を完成した。
As a result of diligent research to solve the above-mentioned problems, the present inventors have conducted hydrocracking of polycyclic aromatic hydrocarbons contained in heavy oil and selectively selectively produce one ring. Gasoline blended with product oil obtained by selective hydrocracking to produce aromatic hydrocarbons has good operability, acceleration and exhaust gas characteristics. In addition, high RON improves fuel efficiency and impacts on the environment. It was found to be reduced. Furthermore, the improvement in the characteristics of this gasoline is due to the aromatic hydrocarbons having 9 carbon atoms such as 1,3,5-trimethylbenzene and 1,2,4-trimethylbenzene contained in the selective hydrocracking product oil. I found it.
Generally, aromatic hydrocarbons having 9 carbon atoms are said to deteriorate exhaust gas properties (Patent Documents 1 to 3). However, among aromatic hydrocarbons having 9 carbon atoms, 1,3,5-trimethylbenzene and 1,2,4-trimethylbenzene have extremely high RON values of 120 and 111, respectively, and low Reed vapor pressure (RVP). Have. That is, these gasoline compositions having a higher content of specific aromatic hydrocarbons maintain an excellent balance between distillation properties and Reed vapor pressure (RVP), while maintaining olefins and aromatic hydrocarbons, and further having 9 carbon atoms. A high RON, low sulfur environment-friendly gasoline composition can be prepared without increasing the total amount of aromatic hydrocarbons.
Thus, the present inventors have found a specific hydrocarbon compound having a high RON, a low RVP, and a preferable distillation property, and controlling the content thereof, thereby maintaining a high RON and a sulfur content. It has been found that a gasoline composition with sufficient practical performance can be obtained in addition to excellent storage stability and environmental conservation, and the present invention has been completed based on such knowledge. .
すなわち、本発明は以下のとおりのガソリン組成物である。
（１）リサーチ法オクタン価が９６以上、硫黄含有量が１０質量ｐｐｍ以下、芳香族含有量が２０〜４０容量％、オレフィン含有量が１５容量％以下、炭素数９の芳香族炭化水素の含有量が１５容量％以下、炭素数９の芳香族炭化水素の含有量に対する１，２，４−トリメチルベンゼンと１，３，５−トリメチルベンゼンの合計含有量の比（容量）が０．５３以上、及び含酸素化合物の含有量が０〜１５容量％であるガソリン組成物。
（２）炭素数９の芳香族炭化水素の含有量に対する１，３，５−トリメチルベンゼンの含有量の比（容量）が０．１４以上である上記（１）に記載のガソリン組成物。
（３）硫黄分が１質量ｐｐｍ以下、リード蒸気圧が４４〜６５ｋＰａである上記（１）又は（２）に記載のガソリン組成物。
（４）オレフィン含有量が５．０容量％以下である上記（１）〜（３）のいずれかに記載のガソリン組成物。
That is, the present invention is a gasoline composition as follows.
(1) Research method Octane number of 96 or more, sulfur content of 10 mass ppm or less, aromatic content of 20 to 40% by volume, olefin content of 15% by volume or less, content of aromatic hydrocarbon having 9 carbon atoms Is 15% by volume or less, and the ratio (capacity) of the total content of 1,2,4-trimethylbenzene and 1,3,5-trimethylbenzene to the content of aromatic hydrocarbon having 9 carbon atoms is 0.53 or more, And a gasoline composition having an oxygen-containing compound content of 0 to 15% by volume.
(2) The gasoline composition according to (1), wherein the ratio (capacity) of the content of 1,3,5-trimethylbenzene to the content of aromatic hydrocarbon having 9 carbon atoms is 0.14 or more.
(3) The gasoline composition according to (1) or (2) above, wherein the sulfur content is 1 mass ppm or less and the lead vapor pressure is 44 to 65 kPa.
(4) The gasoline composition according to any one of (1) to (3), wherein the olefin content is 5.0% by volume or less.
本発明は、固体酸触媒存在下における多環芳香族炭化水素の選択的水素化分解反応により得られた１環芳香族炭化水素、特には、高いＲＯＮの１，２，４−トリメチルベンゼンと１，３，５−トリメチルベンゼンを特定量含有するガソリン組成物であるから、芳香族炭化水素やオレフィンの含有量を低減しながら高いＲＯＮを保持することができる。したがって、高いＲＯＮを維持したまま硫黄分やオレフィン分などを低減することが可能になり、優れた貯蔵安定性、環境保全性に加え、十分な実用性能を備えたガソリン組成物を提供することができる。 The present invention relates to a monocyclic aromatic hydrocarbon obtained by a selective hydrocracking reaction of a polycyclic aromatic hydrocarbon in the presence of a solid acid catalyst, in particular, 1,2,4-trimethylbenzene having a high RON and 1 Since it is a gasoline composition containing a specific amount of 1,3,5-trimethylbenzene, high RON can be maintained while reducing the content of aromatic hydrocarbons and olefins. Therefore, it is possible to reduce sulfur content and olefin content while maintaining high RON, and to provide a gasoline composition having sufficient practical performance in addition to excellent storage stability and environmental conservation. it can.
ガソリン組成物に含まれる炭化水素化合物のうち、芳香環を有するものを芳香族炭化水素（アロマともいう）、芳香族以外の形で不飽和結合を有するものをオレフィン、ナフテン環を有するものをナフテン、及びそれら以外の炭化水素化合物をパラフィンとする。また、パラフィンの内、直鎖状のものをノルマルパラフィン、分岐を有するものをイソパラフィンと分類する。
本発明のガソリン組成物を、以下に詳しく説明する。
Of the hydrocarbon compounds contained in the gasoline composition, those having an aromatic ring are aromatic hydrocarbons (also called aromas), those having an unsaturated bond in a form other than aromatic are olefins, and those having a naphthene ring are naphthenes. , And other hydrocarbon compounds are paraffin. Moreover, among paraffins, linear paraffins are classified as normal paraffins, and those having branches are classified as isoparaffins.
The gasoline composition of the present invention will be described in detail below.
〔オクタン価〕
本発明によるガソリン組成物のリサーチ法オクタン価（ＲＯＮ）は９６以上であり、好ましくは９８以上、さらには１００以上が好ましい。ＲＯＮが９６未満の場合は、とりわけ登坂加速時のノッキングや加速不良を起こす恐れがある他、燃費悪化の懸念から好ましくない。
[Octane number]
The research method octane number (RON) of the gasoline composition according to the present invention is 96 or more, preferably 98 or more, more preferably 100 or more. When RON is less than 96, there is a risk that knocking or acceleration failure may occur, particularly during uphill acceleration, and there is a concern about deterioration of fuel consumption.
〔硫黄含有量〕
本発明によるガソリン組成物の硫黄含有量は、硫黄元素として１０質量ｐｐｍ以下、好ましくは５質量ｐｐｍ以下、より好ましくは１質量ｐｐｍ以下である。ガソリン中の硫黄分は、排ガス中で硫黄酸化物となり、エンジン排ガスを浄化する窒素酸化物除去触媒を被毒して触媒活性を低下させる。被毒した窒素酸化物除去触媒は、還元雰囲気下で再生されて活性を回復するが、このとき還元雰囲気を形成するために燃料が使用され、その分燃費が悪化する。したがって、ガソリン中の硫黄分が少ないほど燃費は向上する。さらに、ガソリン車両の燃料タンク液面計に銀合金が一部使用されていることから、硫黄化合物等による腐食を防止するためにも銀板腐食が1以下であることが望ましい。
[Sulfur content]
The sulfur content of the gasoline composition according to the present invention is 10 mass ppm or less, preferably 5 mass ppm or less, more preferably 1 mass ppm or less as elemental sulfur. The sulfur content in gasoline becomes sulfur oxides in the exhaust gas, poisoning the nitrogen oxide removal catalyst that purifies the engine exhaust gas, and reducing the catalytic activity. The poisoned nitrogen oxide removing catalyst is regenerated in a reducing atmosphere to recover its activity. At this time, fuel is used to form a reducing atmosphere, and fuel consumption is deteriorated accordingly. Therefore, the fuel efficiency improves as the sulfur content in gasoline decreases. Furthermore, since a silver alloy is partially used in a fuel tank level gauge of a gasoline vehicle, it is desirable that the corrosion of the silver plate is 1 or less in order to prevent corrosion due to sulfur compounds and the like.
〔オレフィン含有量〕
本発明によるガソリン組成物中のオレフィン含有量は、光安定性及び貯蔵安定性の観点から少ない方が好ましく、１５容量％以下であり、好ましくは１２容量％以下、より好ましくは５容量％以下である。
[Olefin content]
The olefin content in the gasoline composition according to the present invention is preferably smaller from the viewpoint of light stability and storage stability, and is 15% by volume or less, preferably 12% by volume or less, more preferably 5% by volume or less. is there.
〔芳香族含有量〕
本発明によるガソリン組成物において、芳香族炭化水素の含有量は２０容量％以上４０容量％以下であり、好ましくは２５容量％以上３９容量％以下、より好ましくは３０容量％以上３９容量％以下である。排ガス性状や低温運転性維持の観点から芳香族分は少ない方が好ましいが、ＲＯＮを維持するため及び燃費悪化防止の点から２０容量％以上が好ましい。また、芳香族分が４０容量％を超えると燃焼室デポジットが増加し、点火プラグのくすぶり発生や排ガス中のベンゼン濃度が高くなる恐れがある。また、ベンゼンの大気への拡散を抑制させるためには、ベンゼン含有量自体も１．０容量％以下が好ましく、さらに好ましくは０．１容量％以下である。
[Aromatic content]
In the gasoline composition according to the present invention, the content of the aromatic hydrocarbon is 20 volume% or more and 40 volume% or less, preferably 25 volume% or more and 39 volume% or less, more preferably 30 volume% or more and 39 volume% or less. is there. From the viewpoint of maintaining exhaust gas properties and low-temperature drivability, it is preferable that the aromatic content is small. However, 20% by volume or more is preferable for maintaining RON and preventing deterioration of fuel consumption. Further, when the aromatic content exceeds 40% by volume, the combustion chamber deposit increases, which may cause smoldering of the spark plug and increase the concentration of benzene in the exhaust gas. In order to suppress the diffusion of benzene into the atmosphere, the benzene content itself is preferably 1.0% by volume or less, more preferably 0.1% by volume or less.
〔炭素数９の芳香族炭化水素含有量〕
本発明によるガソリン組成物は、炭素数９の芳香族炭化水素（Ｃ９Ａ）の含有量が１５容量％以下であり、好ましくは１０容量％以下、より好ましくは８容量％以下、特に好ましくは６容量％以下である。また、１，３，５−トリメチルベンゼン（１３５ＴＭＢ）と１，２，４−トリメチルベンゼン（１２４ＴＭＢ）の合計含有量とＣ９Ａ含有量との容量比（（１３５ＴＭＢ＋１２４ＴＭＢ）／Ｃ９Ａ）は０．５３以上であり、好ましくは０．５８以上、より好ましくは０．６０以上である。また同様に、１，３，５−トリメチルベンゼン（１３５ＴＭＢ）の含有量とＣ９Ａ含有量との容量比（１３５ＴＭＢ／Ｃ９Ａ）は０．１４以上が好ましく、さらに好ましくは０．１６以上であり、特に好ましくは０．１８以上である。排ガス性状にとってあまり好ましくないＣ９Ａの総含有量を１０容量％以下に削減しようとした場合、（１３５ＴＭＢ＋１２４ＴＭＢ）／Ｃ９Ａ比が０．５３以上、好ましくは１３５ＴＭＢ／Ｃ９Ａ比（容量）が０．１４以上と高くなければ、オクタン価、蒸留性状、蒸気圧等のガソリン性状を満足できなくなる。
[Aromatic hydrocarbon content of 9 carbon atoms]
In the gasoline composition according to the present invention, the content of aromatic hydrocarbon having 9 carbon atoms (C9A) is 15% by volume or less, preferably 10% by volume or less, more preferably 8% by volume or less, particularly preferably 6% by volume. % Or less. In addition, the capacity ratio ((135TMB + 124TMB) / C9A) of the total content of 1,3,5-trimethylbenzene (135TMB) and 1,2,4-trimethylbenzene (124TMB) to the C9A content is 0.53 or more. Yes, preferably 0.58 or more, more preferably 0.60 or more. Similarly, the volume ratio (135TMB / C9A) between the content of 1,3,5-trimethylbenzene (135TMB) and the content of C9A is preferably 0.14 or more, more preferably 0.16 or more, Preferably it is 0.18 or more. When trying to reduce the total content of C9A, which is not very favorable for the exhaust gas properties, to 10% by volume or less, the (135TMB + 124TMB) / C9A ratio is 0.53 or more, preferably the 135TMB / C9A ratio (capacity) is 0.14 or more. If it is not high, the gasoline properties such as octane number, distillation properties and vapor pressure cannot be satisfied.
〔密度〕
本発明によるガソリン組成物において、密度は０．７０〜０．７８ｇ／ｃｍ３が好ましいが、より好ましくは０．７１〜０．７７ｇ／ｃｍ３、さらに好ましくは０．７２〜０．７６ｇ／ｃｍ３である。密度が０．７０ｇ／ｃｍ３未満では、出力が低下するとともにガソリン消費量が多大となる。一方、０．７８ｇ／ｃｍ３を越えると加速性の悪化やプラグのくすぶりを生じる可能性がある。
〔density〕
In gasoline composition according to the present invention, the density is preferably 0.70~0.78g / cm 3, more preferably 0.71~0.77g / cm 3, more preferably 0.72~0.76g / cm 3 . When the density is less than 0.70 g / cm 3 , the output is reduced and the gasoline consumption is increased. On the other hand, if it exceeds 0.78 g / cm 3 , acceleration may be deteriorated and plug smoldering may occur.
〔蒸留性状〕
本発明によるガソリン組成物において、５０％留出温度は７５〜１００℃であることが好ましく、より好ましくは７５〜９８℃、さらに好ましくは７５〜９６℃である。５０％留出温度が７５℃に満たない場合は、燃費の観点から好ましくなく、１００℃を超える場合は、常温運転性が悪化する場合があるため好ましくない。１０％留出温度は２５〜６０℃であることが好ましく、より好ましくは２５〜５０℃、さらに好ましくは２６〜４５℃である。１０％留出温度が低すぎると軽質炭化水素類の大気への拡散の可能性があり、高すぎると低温始動性が悪化するため好ましくない。９０％留出温度は１３５〜１８０℃であることが好ましく、より好ましくは１４０〜１７０℃、さらに好ましくは１４５〜１６５℃である。９０％留出温度が低すぎると燃費の悪化が懸念され、高すぎると吸気バルブや燃焼室のデポジット増加や中低温運転性が悪化するため好ましくない。
[Distillation properties]
In the gasoline composition according to the present invention, the 50% distillation temperature is preferably 75 to 100 ° C, more preferably 75 to 98 ° C, and further preferably 75 to 96 ° C. When the 50% distillation temperature is less than 75 ° C., it is not preferable from the viewpoint of fuel consumption, and when it exceeds 100 ° C., the normal temperature drivability may be deteriorated. The 10% distillation temperature is preferably 25 to 60 ° C, more preferably 25 to 50 ° C, and further preferably 26 to 45 ° C. If the 10% distillation temperature is too low, there is a possibility of diffusion of light hydrocarbons into the atmosphere, and if it is too high, the low-temperature startability deteriorates, which is not preferable. The 90% distillation temperature is preferably 135 to 180 ° C, more preferably 140 to 170 ° C, and still more preferably 145 to 165 ° C. If the 90% distillation temperature is too low, fuel consumption may be deteriorated, and if it is too high, the deposit in the intake valve and the combustion chamber will increase and the low-temperature operability will deteriorate.
〔リード蒸気圧〕
本発明によるガソリン組成物において、３７．８℃におけるリード蒸気圧（ＲＶＰ）は４４〜６４ｋＰａが好ましく、より好ましくは４４〜６３ｋＰａである。ＲＶＰが高いと蒸発損失の増加、ベーパーロックの懸念、危険性の増加などの問題が起こりやすい。また、ＲＶＰが低いと低温始動性が悪化する。
[Lead vapor pressure]
In the gasoline composition according to the present invention, the lead vapor pressure (RVP) at 37.8 ° C is preferably 44 to 64 kPa, more preferably 44 to 63 kPa. When the RVP is high, problems such as an increase in evaporation loss, a concern about vapor lock, and an increase in danger are likely to occur. Moreover, when RVP is low, low temperature startability deteriorates.
〔ガソリン組成物の製造方法〕
本発明のガソリン組成物の製造方法は特に限定されないが、上記の性状を満たすように複数のガソリン基材を適切な割合でブレンドすることによって製造することができる。
本発明のガソリン組成物を調製するに際して、従来のガソリン製造に用いられているガソリン基材を使用することができる。具体的には、直留ナフサ留分を水素化脱硫後、その軽質分を蒸留分離することにより得た脱硫直留軽質ナフサ留分（ＤＳＬＧ）、これを骨格異性化させた異性化ガソリン（ＩＳＯ）、ブチレン留分とイソブタン留分をアルキル化して得たアルキレートガソリン（ＡＬＫＧ）、接触分解ナフサ留分（ＦＣＣＧ）あるいはそれを脱硫処理した脱硫接触分解ナフサ留分（ＤＳ−ＦＣＣＧ）、さらにその軽質留分を蒸留分離して得た接触分解軽質ナフサ留分（ＦＬ）、脱硫重質ナフサを固体改質触媒により改質して得た接触改質ガソリン、及び接触改質ガソリンを蒸留して得たベンゼン分を殆ど含有しない炭素数７を主成分とする留分（ＡＣ７）、同じく炭素数８を主成分とする留分（ＡＣ８）、あるいは炭素数９を主成分とする留分（ＡＣ９）、各種の石油精製工程や石油化学の工程から副生されるガソリン留分、さらに、単離されたブタン、ペンタン（特にイソペンタン（ｉＣ５））や、いわゆるＢＴＸなどのアロマ化合物などが挙げられる。
さらに、接触分解軽質サイクル油（ＬＣＯ）などのような多環芳香族炭化水素リッチな炭化水素を水素化分解して得られた選択的水素化分解生成油（ＳＨＣ）を蒸留し、ベンゼン以下の軽質留分と炭素数１０以上の芳香族炭化水素を含む高沸点留分を留去して得た選択的に１環芳香族炭化水素を高濃度で含有する選択的水素化分解ガソリン基材（ＳＨＣＧ）を用いることもできる。
なお、上記の各種の炭化水素留分について略号で示していないもの（例えば、ブタン、脱硫重質ナフサ、接触改質ガソリンなど）も本発明のガソリン組成物の基材として適宜用いることができることは断るまでもない。
[Method for producing gasoline composition]
Although the manufacturing method of the gasoline composition of this invention is not specifically limited, It can manufacture by blending a some gasoline base material in a suitable ratio so that said property may be satisfy | filled.
In preparing the gasoline composition of the present invention, a gasoline base material used in conventional gasoline production can be used. Specifically, after hydrodesulfurizing a straight-run naphtha fraction, a desulfurized straight-run light naphtha fraction (DSLG) obtained by distilling and separating the light fraction thereof, an isomerized gasoline (ISO) obtained by skeletal isomerization (ISO). ), Alkylate gasoline (ALKG) obtained by alkylating butylene fraction and isobutane fraction, catalytic cracked naphtha fraction (FCCG), or desulfurized catalytic cracked naphtha fraction (DS-FCCG) obtained by desulfurizing it, and further Distilling catalytically cracked light naphtha fraction (FL) obtained by distilling and separating light fraction, catalytic reformed gasoline obtained by reforming desulfurized heavy naphtha with solid reforming catalyst, and catalytic reformed gasoline The obtained fraction containing 7 carbon atoms as the main component (AC7), containing almost no benzene content (AC8), the same fraction containing 8 carbon atoms (AC8), or the fraction containing 9 carbon atoms as the main component (AC9) ),each Petroleum refining process and gasoline fraction by-produced from petrochemical processes, and further, an isolated butane, pentane (especially isopentane (iC5)) and, like aroma compounds, such as so-called BTX and the like.
Furthermore, the selective hydrocracked product oil (SHC) obtained by hydrocracking a hydrocarbon rich in polycyclic aromatic hydrocarbons such as catalytic cracking light cycle oil (LCO) is distilled, A selective hydrocracked gasoline base material containing a high concentration of a monocyclic aromatic hydrocarbon obtained by distilling off a high-boiling fraction containing a light fraction and an aromatic hydrocarbon having 10 or more carbon atoms ( SHCG) can also be used.
It should be noted that the above-mentioned various hydrocarbon fractions that are not indicated by abbreviations (for example, butane, desulfurized heavy naphtha, catalytic reformed gasoline, etc.) can be appropriately used as the base material of the gasoline composition of the present invention. Needless to say.
また、炭素数９の芳香族炭化水素の所定比率を調整する基材として、ＡＣ９を精密蒸留することにより実質的に１２４ＴＭＢ（沸点１６９．４℃）からなるガソリン基材（１２４ＴＭＢ−Ｇ）と１３５ＴＭＢ（沸点１６４．９℃）からなるガソリン基材（１３５ＴＭＢ−Ｇ）を分画して使用することもできる。 In addition, as a base material for adjusting the predetermined ratio of the aromatic hydrocarbon having 9 carbon atoms, gasoline base material (124TMB-G) and 135TMB substantially consisting of 124 TMB (boiling point 169.4 ° C.) are obtained by precision distillation of AC9. A gasoline base material (135TMB-G) composed of (boiling point 164.9 ° C.) can also be used after fractionation.
さらに本発明で使用するガソリン基材として、エタノールなどのアルコールや、アルコールからの誘導体であるエーテル類やエステル類等の、いわゆる「含酸素化合物」が挙げられ、０〜１５容量％含まれるように配合する。 Furthermore, as a gasoline base material used in the present invention, so-called “oxygen-containing compounds” such as alcohols such as ethanol, ethers and esters which are derivatives from alcohols, and 0 to 15% by volume are included. Blend.
上記のガソリン基材の配合量は特に限定されるものではなく、製品ガソリン特性の観点から、適切な配合量を適宜選ぶことができる。
ＦＣＣＧやＤＳ−ＦＣＣＧに関しては、比較的ＲＯＮが高く安価に製造できるガソリン基材であるため、多い場合では８０容量％程度まで使用されることもあるが、オレフィンの含有量がやや多いため、製品中のオレフィン含有量を低減させるためにはこれら基材の配合量を低減した方が好ましいこともある。その場合好ましい配合量としては１０容量％以下、特には５容量％以下である。
The blending amount of the above gasoline base material is not particularly limited, and an appropriate blending amount can be appropriately selected from the viewpoint of product gasoline characteristics.
FCCG and DS-FCCG are gasoline bases that are relatively high in RON and can be manufactured at low cost. In many cases, they are used up to about 80% by volume. In order to reduce the olefin content therein, it may be preferable to reduce the blending amount of these base materials. In such a case, the preferred blending amount is 10% by volume or less, particularly 5% by volume or less.
接触改質ガソリン、およびそれから誘導されるＡＣ７、ＡＣ８、ＡＣ９については、本発明のガソリン組成物のように炭素数９の特定の芳香族炭化水素構成比率が制御されていないので少ない方が好ましく、好ましくは１４容量％以下、特に好ましくは１０容量％以下である。 For catalytically reformed gasoline and AC7, AC8, AC9 derived therefrom, it is preferable that the specific aromatic hydrocarbon constituent ratio of 9 carbon atoms is not controlled as in the gasoline composition of the present invention. Preferably it is 14 volume% or less, Most preferably, it is 10 volume% or less.
ＳＨＣＧを使用する場合には、ガソリン組成物に対し、５容量％以上、好ましくは１０容量％以上で、かつ、５０容量％以下、より好ましくは４５容量％以下使用する。５容量％未満では、炭素数９以下の芳香族炭化水素を前記特定組成比率に維持することが難しく、５０容量％以上使用すると、芳香族分の増加により、点火プラグのくすぶり発生や排ガス性状が悪化する。 When SHCG is used, it is used in an amount of 5% by volume or more, preferably 10% by volume or more, and 50% by volume or less, more preferably 45% by volume or less based on the gasoline composition. If it is less than 5% by volume, it is difficult to maintain aromatic hydrocarbons having 9 or less carbon atoms at the specific composition ratio. If 50% by volume or more is used, smoldering and exhaust gas properties of the spark plug are caused by an increase in aromatic content. Getting worse.
含酸素化合物としては、例えば、炭素数２〜５のアルコール類、炭素数４〜８のエーテル類が好適であり、具体的には、エタノール、プロピルアルコール類、ブチルアルコール類などのアルコールや、アルコールからの誘導体であるエーテル類やエステル類、例えば、エチルイソプロピルエーテル、エチルターシャリーブチルエーテル（ＥＴＢＥ）、エチルセカンダリーブチルエーテル（ＥＳＢＥ）、ジイソプロピルエーテル、ターシャリーアミルエチルエーテル（ＴＡＥＥ）や、酢酸エチル、プロピオン酸エチル等が挙げられる。 As the oxygen-containing compound, for example, alcohols having 2 to 5 carbon atoms and ethers having 4 to 8 carbon atoms are suitable. Specifically, alcohols such as ethanol, propyl alcohols and butyl alcohols, alcohols Ethers and esters, such as ethyl isopropyl ether, ethyl tertiary butyl ether (ETBE), ethyl secondary butyl ether (ESBE), diisopropyl ether, tertiary amyl ethyl ether (TAEE), ethyl acetate, propionic acid And ethyl.
これらの含酸素化合物は、全ガソリン組成物基準で、０〜１５容量％、好ましくは３〜１２容量％、より好ましくは、５〜１０容量％配合する。少なすぎると添加効果が少なく、また、多すぎると水分等の不純物を取り込みやすくなり、配管やシール材の腐食等のトラブルを引き起こすことがある。燃料中に含酸素化合物が多い場合、例えば１５容量％を超える量が含まれると、既存エンジンの空気／燃料比の最適値から外れて酸素過剰気味となることから、排ガス中の窒素酸化物（ＮＯｘ）の量が増加する傾向がある。 These oxygen-containing compounds are blended in an amount of 0 to 15% by volume, preferably 3 to 12% by volume, more preferably 5 to 10% by volume based on the total gasoline composition. If the amount is too small, the effect of addition is small, and if the amount is too large, impurities such as moisture are easily taken in, which may cause troubles such as corrosion of piping and sealing materials. If the fuel contains a large amount of oxygen-containing compounds, for example, if the amount exceeds 15% by volume, it will deviate from the optimum value of the air / fuel ratio of the existing engine, resulting in an excess of oxygen. The amount of NOx) tends to increase.
（選択的水素化分解）
本発明のガソリン組成物の調製に用いることができる選択的水素化分解ガソリン基材（ＳＨＣＧ）について以下に説明する。
通常の水素化分解において芳香族炭化水素は多環芳香族炭化水素を含めて、ナフテン、オレフィン又はパラフィンに変換されるが、選択的に、すなわち１環芳香族炭化水素をできるだけ残すように水素化分解することを選択的水素化分解という。
選択的水素化分解の原料油として使用する炭化水素留分は、蒸留性状として１０％留出温度が１８０℃以上、９０％留出温度が３５０℃以下、好ましくは１０％留出温度が１９０〜２４０℃、９０％留出温度が２６０〜３２０℃である。このような基準で、２環芳香族炭化水素が多く、かつ３環芳香族炭化水素のアントラセンやフェナントレン（沸点３３９℃、３４０℃）が多く含まれないような原料を選択することができる。
(Selective hydrocracking)
The selective hydrocracked gasoline base (SHCG) that can be used to prepare the gasoline composition of the present invention is described below.
In normal hydrocracking, aromatic hydrocarbons, including polycyclic aromatic hydrocarbons, are converted to naphthenes, olefins or paraffins, but hydrogenated selectively, that is, to leave as much as possible of one-ring aromatic hydrocarbons. Decomposing is called selective hydrocracking.
The hydrocarbon fraction used as the feedstock for selective hydrocracking has a distillation property of 10% distillation temperature of 180 ° C. or higher, 90% distillation temperature of 350 ° C. or lower, preferably 10% distillation temperature of 190 to 90 ° C. 240 degreeC and 90% distillation temperature are 260-320 degreeC. On the basis of such criteria, a raw material that is rich in two-ring aromatic hydrocarbons and does not contain a large amount of anthracene or phenanthrene (boiling points 339 ° C., 340 ° C.) of the three-ring aromatic hydrocarbons can be selected.
このようなものとしては、原油の常圧蒸留から得られる留出分、常圧残渣の減圧蒸留から得られる減圧軽油、各種の重質油の軽質化プロセス（接触分解装置、熱分解装置等）から得られる留出分、例えば接触分解装置から得られる接触分解油、特に重質サイクル油（ＨＣＯ）や軽質サイクル油（ＬＣＯ）、熱分解装置（コーカーやビスブレーキング等）から得られる熱分解油、エチレンクラッカーから得られるエチレンクラッカー重質残渣、接触改質装置から得られる接触改質油、特に接触改質油を抽出、蒸留、あるいは膜分離して得られる芳香族リッチな接触改質油（ここで、芳香族リッチな接触改質油とは、接触改質装置から得られる炭素数１０以上でかつ芳香族化合物の含有量が５０容量％を超えるものを指す）、潤滑油ベースオイルを製造する芳香族抽出装置から得られる留分、溶媒脱ろう装置から得られる芳香族リッチな留分などが挙げられる。その他、常圧蒸留残渣、減圧蒸留残渣、脱ろうオイルなどを精製する脱硫法又は水素化転化法から生ずる蒸留物等も用いることができる。上記の炭化水素留分のなかでも、接触分解油、熱分解油、エチレンクラッカー重質残渣、接触改質油が好ましく、特にＬＣＯを好ましく用いることができる。 As such, distillate obtained from atmospheric distillation of crude oil, vacuum gas oil obtained from vacuum distillation of atmospheric residue, lightening process of various heavy oils (catalytic cracker, thermal cracker, etc.) For example, catalytic cracking oil obtained from catalytic cracking equipment, especially heavy cycle oil (HCO) or light cycle oil (LCO), thermal cracking obtained from thermal cracking equipment (coker, visbreaking, etc.) Oil, heavy cracking residue obtained from ethylene crackers, contact reforming oil obtained from catalytic reforming equipment, especially aromatic rich contact reforming oil obtained by extraction, distillation or membrane separation of contact reforming oil (Here, the aromatic-rich contact reforming oil refers to an oil having 10 or more carbon atoms and an aromatic compound content exceeding 50% by volume obtained from the contact reforming apparatus), lubricating oil base oil Fraction derived from an aromatic extraction unit for producing partial, and the like and aromatic-rich fractions obtained from the solvent dewaxing unit. In addition, a distillate produced from a desulfurization method or a hydroconversion method for purifying an atmospheric distillation residue, a vacuum distillation residue, a dewaxed oil, or the like can also be used. Among the above hydrocarbon fractions, catalytic cracking oil, pyrolysis oil, ethylene cracker heavy residue, and catalytic reforming oil are preferable, and LCO can be particularly preferably used.
選択的水素化分解反応に使用する触媒は、複合酸化物とそれを結合するバインダーとを含む担体に、周期律表の第６族および第８族から選ばれる少なくとも１種の金属成分を担持して調製することができる。選択的水素化分解触媒は、比表面積が１００〜６００ｍ２／ｇ、好ましくは１５０〜５５０ｍ２／ｇ、さらに好ましくは２００〜５００ｍ２／ｇであり、中央細孔直径が４〜１２ｎｍ、好ましくは４．５〜１１ｎｍ、さらには５．０〜１０ｎｍであり、細孔直径２〜６０ｎｍの範囲の細孔容積が０．１〜１．０ｍＬ／ｇ、好ましくは０．１５〜０．８ｍＬ／ｇ、さらには０．２〜０．７ｍＬ／ｇであることが好ましい。
比表面積はＡＳＴＭ規格Ｄ３６６３−７８に基づき窒素吸着によって求めたＢＥＴ比表面積の値であり、また、中央細孔直径は、窒素ガス吸着法において相対圧０．９６６７の条件で得られる細孔直径２〜６０ｎｍの細孔容積の累積をＶとするとき、各細孔直径の容積量を累積させた累積細孔容積曲線において、累積細孔容積がＶ／２となる細孔直径をいう。
The catalyst used for the selective hydrocracking reaction carries at least one metal component selected from Groups 6 and 8 of the periodic table on a support containing a composite oxide and a binder that binds the composite oxide. Can be prepared. The selective hydrocracking catalyst has a specific surface area of 100 to 600 m 2 / g, preferably 150 to 550 m 2 / g, more preferably 200 to 500 m 2 / g, and a central pore diameter of 4 to 12 nm, preferably The pore volume in the range of 4.5 to 11 nm, more preferably 5.0 to 10 nm, and a pore diameter of 2 to 60 nm is 0.1 to 1.0 mL / g, preferably 0.15 to 0.8 mL / g. Further, it is preferably 0.2 to 0.7 mL / g.
The specific surface area is a value of the BET specific surface area obtained by nitrogen adsorption based on ASTM standard D3663-78, and the central pore diameter is a pore diameter of 2 obtained under the condition of a relative pressure of 0.9667 in the nitrogen gas adsorption method. When the cumulative pore volume of ˜60 nm is V, the cumulative pore volume curve obtained by accumulating the volume of each pore diameter means the pore diameter at which the cumulative pore volume is V / 2.
複合酸化物としては、シリカ−アルミナ、シリカ−チタニア、シリカ−ジルコニア、シリカ−マグネシア、シリカ−アルミナ−チタニア、シリカ−アルミナ−ジルコニア、酸化タングステン−ジルコニア、硫酸化ジルコニア、ゼオライトから選ばれる１種以上を組み合わせて用いることもできる。特に、複合酸化物としてシリカ−アルミナを用いる場合、シリカ／アルミナのモル比で１〜２０になるように用いることが好ましい。 The composite oxide is at least one selected from silica-alumina, silica-titania, silica-zirconia, silica-magnesia, silica-alumina-titania, silica-alumina-zirconia, tungsten oxide-zirconia, sulfated zirconia, and zeolite. Can also be used in combination. In particular, when silica-alumina is used as the composite oxide, it is preferably used so that the silica / alumina molar ratio is 1-20.
前記ゼオライトとしてはＸ型やＹ型のゼオライトが好ましく、中でもＵＳＹゼオライトを好適に用いることができる。ＵＳＹ型ゼオライトは、格子定数が２．４３〜２．４６ｎｍの結晶性アルミノシリケートを用いることが好ましい。なお、格子定数とはＸ線回折法により得られた面間隔ｄの値より、次の式で算出される値である。
格子定数＝ｄ×(ｈ２＋ｋ２＋ｌ２)１/２
ここで、ｈ、ｋ、及びｌはミラー指数を示す。
As the zeolite, X-type and Y-type zeolites are preferable, and among them, USY zeolite can be suitably used. The USY-type zeolite is preferably a crystalline aluminosilicate having a lattice constant of 2.43 to 2.46 nm. The lattice constant is a value calculated from the value of the interplanar distance d obtained by the X-ray diffraction method by the following formula.
Lattice constant = d × (h 2 + k 2 + l 2 ) 1/2
Here, h, k, and l represent Miller indices.
結晶性アルミノシリケートに対して各種金属イオンを導入し、遷移金属含有結晶性アルミノシリケートや希土類含有結晶性アルミノシリケートとして、後述する選択的水素化分解反応に使用してもよい。 Various metal ions may be introduced into the crystalline aluminosilicate and used as a transition metal-containing crystalline aluminosilicate or a rare earth-containing crystalline aluminosilicate for the selective hydrocracking reaction described later.
バインダーとしては、アルミナ、シリカ−アルミナ、チタニア−アルミナ、ジルコニア−アルミナなど、多孔質でかつ非晶質のものを好適に用いることができる。バインダーの比表面積は３０ｍ２／ｇ以上であることが望ましい。 As the binder, porous and amorphous ones such as alumina, silica-alumina, titania-alumina, zirconia-alumina can be suitably used. The specific surface area of the binder is desirably 30 m 2 / g or more.
バインダーの配合割合は、触媒を構成する複合酸化物とバインダーの合計質量に対して５〜７０質量％、特には１０〜６０質量％とすることが好ましい。複合酸化物としてＵＳＹゼオライトを用いる場合、触媒を構成する複合酸化物部分及びバインダー部分の合計質量に対するＵＳＹゼオライトの質量は１〜８０質量％、特には１０〜７０質量％とすることが好ましい。 The blending ratio of the binder is preferably 5 to 70% by mass, particularly 10 to 60% by mass with respect to the total mass of the composite oxide and the binder constituting the catalyst. When USY zeolite is used as the composite oxide, the mass of USY zeolite relative to the total mass of the composite oxide part and the binder part constituting the catalyst is preferably 1 to 80% by mass, particularly preferably 10 to 70% by mass.
選択的水素化分解反応に使用する触媒は、周期律表の第６族および第８族から選ばれる金属を活性成分として含むが、第６族のモリブデン、タングステン、および第８族の鉄、ルテニウム、オスミウム、コバルト、ロジウム、イリジウム、ニッケル、パラジウム、白金が特に好適に用いられる。これら金属の添加量は、水素化分解触媒中に占める第６族と第８族の金属元素の合計量が０．０５〜３５質量％、特には０．１〜３０質量％となるように含有することが好ましい。金属としてモリブデンを用いる場合、その含有量は水素化分解触媒中５〜２０質量％、特には７〜１５質量％とすることが好ましい。また、タングステンを用いる場合、その含有量は水素化分解触媒中５〜３０質量％、特には７〜２５質量％とすることが好ましい。 The catalyst used for the selective hydrocracking reaction contains, as an active component, a metal selected from Groups 6 and 8 of the periodic table, but Group 6 molybdenum, tungsten, and Group 8 iron, ruthenium. , Osmium, cobalt, rhodium, iridium, nickel, palladium and platinum are particularly preferably used. These metals are added so that the total amount of Group 6 and Group 8 metal elements in the hydrocracking catalyst is 0.05 to 35% by mass, particularly 0.1 to 30% by mass. It is preferable to do. When molybdenum is used as the metal, the content thereof is preferably 5 to 20% by mass, particularly 7 to 15% by mass in the hydrocracking catalyst. Moreover, when using tungsten, the content is 5-30 mass% in a hydrocracking catalyst, It is preferable to set it as 7-25 mass% especially.
金属としてモリブデン又はタングステンを用いる場合には、さらに、コバルト又はニッケルを添加すると、活性金属の水素化機能が向上し一層好ましい。その場合のコバルト又はニッケルの合計含有量は、水素化分解触媒中０．５〜１０質量％、特には１〜７質量％とすることが好ましい。 When molybdenum or tungsten is used as the metal, it is more preferable to add cobalt or nickel to improve the hydrogenation function of the active metal. In this case, the total content of cobalt or nickel is preferably 0.5 to 10% by mass, particularly 1 to 7% by mass in the hydrocracking catalyst.
選択的水素化分解反応用原料と水素化分解触媒とを、水素の存在下で、温度３００〜４８０℃、好ましくは３３０〜４５０℃、より好ましくは３４０〜４３０℃で、圧力１〜１０ＭＰａ、好ましくは２〜８ＭＰａ、液空間速度（ＬＨＳＶ）０．１〜１０．０ｈ−１、好ましくは０．１〜８．０ｈ−１、より好ましくは０．２〜５．０ｈ−１、水素／炭化水素（容積比）１００〜５，０００ＮＬ／Ｌ、好ましくは１５０〜３，０００ＮＬ／Ｌで接触させる。以上の操作により、選択的水素化分解反応用原料中の多環芳香族炭化水素は分解され、所望の１環芳香族炭化水素に転化する。 The raw material for selective hydrocracking reaction and the hydrocracking catalyst are heated in the presence of hydrogen at a temperature of 300 to 480 ° C, preferably 330 to 450 ° C, more preferably 340 to 430 ° C, and a pressure of 1 to 10 MPa, preferably Is 2 to 8 MPa, liquid hourly space velocity (LHSV) is 0.1 to 10.0 h −1 , preferably 0.1 to 8.0 h −1 , more preferably 0.2 to 5.0 h −1 , hydrogen / hydrocarbon. (Volume ratio) 100 to 5,000 NL / L, preferably 150 to 3,000 NL / L. By the above operation, the polycyclic aromatic hydrocarbon in the raw material for selective hydrocracking reaction is decomposed and converted to a desired monocyclic aromatic hydrocarbon.
前述の操作により、原料油中に含まれる沸点２１５℃以上の留分の５０容量％以上が２１５℃未満の留分へ転化され、原料油中に占める芳香族環を構成する炭素比率に対する生成油中に占める芳香族環を構成する炭素比率の比（芳香族環炭素残存比）が０．５以上、好ましくは０．６以上、特に好ましくは０．７以上である選択的水素化分解生成油が得られる。
選択的水素化分解生成油は、沸点２１５℃以下の炭化水素、すなわちナフタレン（沸点２１８℃）よりも軽質な炭化水素の含有量が５０容量％以上であることが好ましく、より好ましくは６０容量％以上、さらに好ましくは７０容量％以上、もっとも好ましくは１００％である。また、水素化分解処理によって得られる水素化分解油中の多環芳香族炭化水素の含有量は少ないほど好ましく、１０容量％以下、さらに好ましくは７容量％以下である。
By the above-described operation, 50% by volume or more of the fraction having a boiling point of 215 ° C. or higher contained in the raw material oil is converted into a fraction having a boiling point of less than 215 ° C., and the produced oil with respect to the carbon ratio constituting the aromatic ring in the raw material oil Selective hydrocracking product oil in which the ratio of the proportion of carbon constituting the aromatic ring (aromatic ring carbon residual ratio) is 0.5 or more, preferably 0.6 or more, particularly preferably 0.7 or more Is obtained.
The selective hydrocracked product oil preferably has a hydrocarbon content of 50% by volume or more, more preferably 60% by volume, with a hydrocarbon having a boiling point of 215 ° C. or lower, that is, a lighter hydrocarbon than naphthalene (boiling point 218 ° C.). Above, more preferably 70% by volume or more, and most preferably 100%. Further, the content of the polycyclic aromatic hydrocarbon in the hydrocracked oil obtained by hydrocracking treatment is preferably as small as possible, and is 10% by volume or less, more preferably 7% by volume or less.
水素化分解生成油は、その後、蒸留分離等により所望のガソリン基材にする。選択的水素化分解から得られる選択的水素化分解ガソリン基材（ＳＨＣＧ）としては、１０％留出温度は９０〜１５０℃、より好ましくは１００〜１３０℃、９０％留出温度は１４０〜１８０℃、より好ましくは１５０〜１７０℃であり、このような沸点範囲が得られるように蒸留条件を設定することにより、適切なＲＯＮ、蒸気圧、蒸留性状を有する製品ガソリンを得ることができる。 Thereafter, the hydrocracked product oil is made into a desired gasoline base material by distillation separation or the like. As a selective hydrocracked gasoline base (SHCG) obtained from selective hydrocracking, the 10% distillation temperature is 90 to 150 ° C, more preferably 100 to 130 ° C, and the 90% distillation temperature is 140 to 180. It is 150 degreeC, More preferably, it is 150-170 degreeC, By setting distillation conditions so that such a boiling point range may be obtained, the product gasoline which has suitable RON, vapor pressure, and distillation property can be obtained.
〔添加剤〕
本発明のガソリン組成物は、必要に応じて公知の燃料添加剤を配合することができる。これらの配合量は適宜選べるが、通常は添加剤の合計量として０．１質量％以下とすることが好ましい。本発明のガソリン組成物で使用可能な添加剤を例示すれば、アミン系、フェノール系、アミノフェノール系などの酸化防止剤、シッフ型化合物、チオアミド型化合物などの金属不活性化剤、有機リン系化合物などの表面着火防止剤、コハク酸イミド、ポリアルキルアミン、ポリエーテルアミンなどの清浄分散剤、多価アルコールやそのエーテルなどの氷結防止剤、有機酸のアルカリ金属塩やアルカリ土類金属塩、高級アルコールの硫酸エステルなどの助燃剤、アニオン系界面活性剤、カチオン系界面活性剤、両性界面活性剤などの帯電防止剤、アルケニルコハク酸エステルなどのさび止め剤、キニザリン、クマリンなどの識別剤、アゾ染料などの着色剤を挙げることができる。
〔Additive〕
The gasoline composition of this invention can mix | blend a well-known fuel additive as needed. Although these compounding quantities can be selected suitably, it is usually preferable to set it as 0.1 mass% or less as a total amount of an additive. Examples of additives that can be used in the gasoline composition of the present invention include amine-based, phenol-based, aminophenol-based antioxidants, Schiff-type compounds, thioamide-type compound metal deactivators, organophosphorus-based compounds, etc. Surface ignition inhibitors such as compounds, detergent dispersants such as succinimide, polyalkylamine and polyetheramine, anti-icing agents such as polyhydric alcohols and ethers thereof, alkali metal salts and alkaline earth metal salts of organic acids, Combustors such as sulfates of higher alcohols, anionic surfactants, cationic surfactants, antistatic agents such as amphoteric surfactants, rust inhibitors such as alkenyl succinates, discriminating agents such as quinizarin and coumarin, Colorants such as azo dyes can be mentioned.
以下に、実施例により本発明をより具体的に説明するが、本発明はこれらの例により何ら制限されるものではない。 Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples.
実施例及び比較例のガソリン組成物の調製に、以下のようにして得たガソリン基材を用いた。それらの性状を表１に示す。 The gasoline base material obtained as follows was used for preparation of the gasoline composition of an Example and a comparative example. Their properties are shown in Table 1.
イソペンタン留分（ｉＣ５）
イソペンタンを多く含む炭素数５が主体の留分である。脱硫重質ナフサの接触改質で副生する軽質留分、脱硫軽質ナフサ留分などを蒸留分離することにより、純度９５％以上の炭素数５のイソパラフィン留分を得た。
Isopentane fraction (iC5)
This fraction is mainly composed of 5 carbon atoms rich in isopentane. By distilling off a light fraction by-produced by catalytic reforming of desulfurized heavy naphtha, a desulfurized light naphtha fraction, etc., an isoparaffin fraction having a carbon number of 5 with a purity of 95% or more was obtained.
脱硫直留軽質ガソリン（ＤＳＬＧ）
中東系原油のナフサ留分を水素化脱硫後、蒸留処理することにより、脱硫直留軽質ガソリンと脱硫直留重質ガソリンに分離して得た。
Desulfurized straight run light gasoline (DSLG)
The naphtha fraction of Middle Eastern crude oil was hydrodesulfurized and then subjected to distillation treatment to separate it into desulfurized straight-run light gasoline and desulfurized straight-run heavy gasoline.
異性化ガソリン（ＩＳＯ）
脱硫直留軽質ガソリン（ＤＳＬＧ）を固体酸触媒存在下、骨格異性化反応によりイソパラフィン分の高い異性化ガソリンを得た。
Isomerized gasoline (ISO)
An isomerized gasoline having a high isoparaffin content was obtained by skeletal isomerization reaction of desulfurized straight-run light gasoline (DSLG) in the presence of a solid acid catalyst.
接触分解軽質ナフサ留分（ＦＬ）
脱硫軽油あるいは脱硫重油を原料に用い、固体触媒存在下、流動床式反応装置での接触分解反応によりオレフィン分の高い接触分解ナフサ留分（ＦＣＣＧ）を得、このＦＣＣＧを軽質留分と重質留分に蒸留分離して得た軽質留分（ＦＬ）である。
Catalytic cracking light naphtha fraction (FL)
Desulfurized light oil or desulfurized heavy oil is used as a raw material, and in the presence of a solid catalyst, a catalytic cracking reaction in a fluidized bed reactor is used to obtain a catalytically cracked naphtha fraction (FCCG) having a high olefin content. This FCCG is divided into a light fraction and a heavy fraction. It is a light fraction (FL) obtained by distillation separation into a fraction.
アルキレートガソリン（ＡＬＫＧ）
ブチレンを主成分とする留分とイソブタンを主成分とする留分を硫酸触媒により反応させて、炭素数８のイソパラフィン分の高い炭化水素を得た。
Alkylate gasoline (ALKG)
A fraction containing butylene as a main component and a fraction containing isobutane as a main component were reacted with a sulfuric acid catalyst to obtain a hydrocarbon having a high C8 isoparaffin content.
改質ガソリン（ＡＣ７）
脱硫重質ナフサを貴金属系固体改質触媒により移動床式反応装置を用いて反応させることにより、アロマ含量の多い炭化水素に改質して改質ガソリンを得る。改質ガソリンはそのまま使用することもできるが、ここでは蒸留分離することにより炭素数７の芳香族炭化水素を主成分として含有するＡＣ７(炭素数６の芳香族炭化水素約１容量％、炭素数７の芳香族炭化水素約７７容量％、炭素数８の芳香族炭化水素約９容量％、及びオレフィンを約０．３容量％含有)を用いた。
Reformed gasoline (AC7)
Desulfurized heavy naphtha is reacted with a noble metal-based solid reforming catalyst using a moving bed reactor to reform the hydrocarbon into a high aroma content to obtain a reformed gasoline. The reformed gasoline can be used as it is, but here AC7 containing approximately 7% C7 aromatic hydrocarbons as a main component by distillation separation (about 6% C6 aromatic hydrocarbons, carbon number) 7 aromatic hydrocarbons (about 7% by volume), aromatic hydrocarbons having 8 carbon atoms (about 9% by volume), and olefins (about 0.3% by volume).
改質ガソリン（ＡＣ９）
ＡＣ７と同様に改質ガソリンを蒸留分離することにより炭素数９の芳香族炭化水素を主成分として含有するＡＣ９(炭素数８の芳香族炭化水素約１８容量％、炭素数９の芳香族炭化水素約８０容量％、炭素数１０の芳香族炭化水素約２容量％、及びオレフィンを約０．１容量％含有)を用いた。
Reformed gasoline (AC9)
As with AC7, the reformed gasoline is separated by distillation to provide AC9 containing approximately 9% of C9 aromatic hydrocarbons (approximately 8% by volume of C8 aromatic hydrocarbons and 9 hydrocarbons). About 80% by volume, about 2% by volume of C10 aromatic hydrocarbon, and about 0.1% by volume of olefin).
１，２，４−トリメチルベンゼンリッチガソリン基材（１２４ＴＭＢ−Ｇ）及び１，３，５−トリメチルベンゼンリッチガソリン基材（１３５ＴＭＢ−Ｇ）
ＡＣ９を精密蒸留することにより、１，２，４−トリメチルベンゼンを純度９９％以上含有する１２４ＴＭＢ−Ｇ及び１，３，５−トリメチルベンゼンを純度９９％以上含有する１３５ＴＭＢ−Ｇそれぞれ得た。
1,2,4-trimethylbenzene rich gasoline base (124TMB-G) and 1,3,5-trimethylbenzene rich gasoline base (135TMB-G)
By precision distillation of AC9, 124TMB-G containing 99% or more of 1,2,4-trimethylbenzene and 135TMB-G containing 99% or more of 1,3,5-trimethylbenzene were obtained.
エタノール（ＥｔＯＨ）
市販の発酵エタノール（９９度１級、日本アルコール販売（株）製）を使用した。
Ethanol (EtOH)
Commercially available fermented ethanol (99 degrees first grade, manufactured by Nippon Alcohol Sales Co., Ltd.) was used.
エチルターシャリーブチルエーテル（ＥＴＢＥ）
イオン交換樹脂触媒（Ａｍｂｅｒｌｙｓｔ−１５）を用いてエタノールとイソブチレンとを反応させ、次いで蒸留法により精製し、純度９５％以上のＥＴＢＥを得た。
Ethyl tertiary butyl ether (ETBE)
Ethanol and isobutylene were reacted using an ion exchange resin catalyst (Amberlyst-15) and then purified by distillation to obtain ETBE having a purity of 95% or more.
選択的水素化分解ガソリン基材（ＳＨＣＧ）
選択的水素化分解ガソリン基材（ＳＨＣＧ）は以下のようにして調製した。
（選択的水素化分解触媒）
ナトリウム型Ｙ型結晶性アルミノシリケート（ＳｉＯ２／Ａｌ２Ｏ３比２．９、Ｎａ２Ｏ含有量１２．３質量％、格子定数２．４６０ｎｍ）２００ｇを、１Ｍの硝酸アンモニウム水溶液２Ｌを用いて５０℃でプロトン型にイオン交換した後、ろ過、洗浄した。さらに１３０℃で３時間乾燥したのち、４５０℃で３時間焼成した。この一連の操作を９回繰り返した結果、Ｎａ２Ｏ含有量が０．５質量％に減少し、ＳｉＯ２／Ａｌ２Ｏ３比が５．８、格子定数が２．４５５ｎｍであるＹ型結晶性アルミノシリケートを得た（以下これを「ＳＹ」と称する）。ＳＹを７００℃の水蒸気と３時間接触させ、ｐＨ１．５に調整した５０℃の硝酸水溶液２Ｌに２時間浸し、ろ過、洗浄した。次いで１３０℃で３時間乾燥した後、４５０℃で３時間焼成した（以下これを「ＵＳＹ」と称する）。このようにして得られたＵＳＹは、ＳｉＯ２／Ａｌ２Ｏ３比が１０．５、格子定数が２．４３８ｎｍ、比表面積が４００ｍ２／ｇであった。
Selective hydrocracking gasoline base (SHCG)
A selective hydrocracked gasoline base (SHCG) was prepared as follows.
(Selective hydrocracking catalyst)
200 g of sodium-type Y-type crystalline aluminosilicate (SiO 2 / Al 2 O 3 ratio 2.9, Na 2 O content 12.3% by mass, lattice constant 2.460 nm) was added to 50 g with 2 L of 1M aqueous ammonium nitrate solution. After ion exchange to proton type at ° C., filtration and washing were performed. Furthermore, after drying at 130 degreeC for 3 hours, it baked at 450 degreeC for 3 hours. As a result of repeating this series of operations 9 times, the Na 2 O content is reduced to 0.5% by mass, the SiO 2 / Al 2 O 3 ratio is 5.8, and the lattice constant is 2.455 nm. An aluminosilicate was obtained (hereinafter referred to as “SY”). SY was brought into contact with water vapor at 700 ° C. for 3 hours, immersed in 2 L of nitric acid solution at 50 ° C. adjusted to pH 1.5 for 2 hours, filtered and washed. Next, after drying at 130 ° C. for 3 hours, baking was performed at 450 ° C. for 3 hours (hereinafter referred to as “USY”). The USY thus obtained had a SiO 2 / Al 2 O 3 ratio of 10.5, a lattice constant of 2.438 nm, and a specific surface area of 400 m 2 / g.
このＵＳＹ７５０ｇをアルミナ粉末（ＳＡＳＯＬ社製アルミナＰｕｒａｌ ＳＢ）１，０００ｇと混合し、４．０質量％の希硝酸溶液５００ｍｌ、イオン交換水８７５ｇを添加して混練し、断面三つ葉形の柱状（ペレット）に押し出し成形した。ペレットを１３０℃で６時間乾燥した後、６００℃で２時間焼成して担体とした。
この担体に、モリブデン酸アンモニウム水溶液をスプレー含浸した後、１３０℃で６時間乾燥した。その後、さらに硝酸ニッケル水溶液をスプレー含浸した後、１３０℃で６時間乾燥した。次いで、空気の気流下で、５００℃で３０分間焼成して触媒Ａを得た。触媒Ａの組成はＭｏ：８．０質量％、Ｎｉ：３．０質量％、ゼオライト：４４．５質量％、アルミナ：４４．５質量％であった。
750 g of this USY is mixed with 1,000 g of alumina powder (Alumina Pural SB manufactured by SASOL), 500 ml of 4.0% by weight dilute nitric acid solution and 875 g of ion-exchanged water are added and kneaded, and a columnar shape (pellet) having a cross-section of a three-leaf shape Extruded. The pellet was dried at 130 ° C. for 6 hours and then calcined at 600 ° C. for 2 hours to obtain a carrier.
This carrier was spray impregnated with an aqueous ammonium molybdate solution and then dried at 130 ° C. for 6 hours. Thereafter, the nickel nitrate aqueous solution was further spray impregnated and then dried at 130 ° C. for 6 hours. Next, catalyst A was obtained by calcination at 500 ° C. for 30 minutes under an air stream. The composition of catalyst A was Mo: 8.0% by mass, Ni: 3.0% by mass, zeolite: 44.5% by mass, and alumina: 44.5% by mass.
この触媒Ａの細孔特性を窒素ガス吸着法で測定したところ、比表面積が３８７ｍ２／ｇ、細孔直径２〜６０ｎｍの範囲にある細孔の容積が０．５４３ｍＬ／ｇ、中央細孔直径は９．６ｎｍであった。また、この触媒Ａは安定径１．２ｍｍ、平均長さ４．０ｍｍであり、平均側面圧壊強度は１２．０ｋｇ、バルク密度は０．６６８ｇ/ｃｍ３であった。ここで、安定径とは、ペレットを平板に固定した際の高さを意味する。 When the pore characteristics of this catalyst A were measured by a nitrogen gas adsorption method, the specific surface area was 387 m 2 / g, the pore volume in the pore diameter range of 2 to 60 nm was 0.543 mL / g, the center pore diameter Was 9.6 nm. Further, this catalyst A had a stable diameter of 1.2 mm, an average length of 4.0 mm, an average side surface crushing strength of 12.0 kg, and a bulk density of 0.668 g / cm 3 . Here, the stable diameter means the height when the pellet is fixed to a flat plate.
（選択的水素化分解工程）
水素化分解触媒として触媒Ａを使用し、反応圧力：７．０ＭＰａ、ＬＨＳＶ：１．０ｈｒ−１、水素／原料油比：１，４００ＮＬ／Ｌ、反応温度：４００℃の条件下で、原料油として接触分解軽質サイクル油（ＬＣＯ）を用いて水素化分解反応を行った。さらに得られた選択的水素化分解生成油（ＳＨＣ）を、低沸点側にベンゼンが含有されないように、また高沸点側に炭素数１０の芳香族炭化水素が含有されないように精密蒸留により分留して、１０%留出温度が１１１．０℃、９０%留出温度が１６３．０℃の蒸留性状を有する選択的水素化分解ガソリン基材（ＳＨＣＧ）を得た。
原料油ＬＣＯの性状および反応の結果得られた選択的水素化分解生成油（ＳＨＣ）と選択的水素化分解ガソリン基材（ＳＨＣＧ）の性状を表２に示す。表２において、２１５℃以上留分の転化率は、次式で得られた値である。
２１５℃以上留分の転化率（％）＝１００−生成油中の２１５℃以上留分（容量％）／原料油中の２１５℃以上留分（容量％）×１００
また、水素化分解前の炭化水素留分（ここではＬＣＯ）中に占める芳香族環を構成する炭素比率に対する水素化分解生成油中に占める芳香族環を構成する炭素比率の比（芳香族環炭素残存率）も表２に記載した。
(Selective hydrocracking process)
Under the conditions of using catalyst A as the hydrocracking catalyst, reaction pressure: 7.0 MPa, LHSV: 1.0 hr −1 , hydrogen / feed oil ratio: 1,400 NL / L, reaction temperature: 400 ° C., feed oil The hydrocracking reaction was carried out using catalytic cracking light cycle oil (LCO). Further, the obtained hydrocracked product oil (SHC) is fractionated by precision distillation so that benzene is not contained on the low boiling point side and aromatic hydrocarbons having 10 carbon atoms are not contained on the high boiling point side. Thus, a selective hydrocracked gasoline base material (SHCG) having a distillation property with a 10% distillation temperature of 111.0 ° C. and a 90% distillation temperature of 163.0 ° C. was obtained.
Table 2 shows the properties of the feedstock LCO and the properties of the selective hydrocracked product oil (SHC) and the selective hydrocracked gasoline base (SHCG) obtained as a result of the reaction. In Table 2, the conversion rate of 215 ° C. or higher fraction is a value obtained by the following formula.
215 ° C. or higher fraction conversion (%) = 100−215 ° C. or higher fraction in product oil (volume%) / 215 ° C. or higher fraction in feed oil (volume%) × 100
Further, the ratio of the carbon ratio constituting the aromatic ring in the hydrocracked product oil to the carbon ratio constituting the aromatic ring in the hydrocarbon fraction (LCO in this case) before hydrocracking (aromatic ring) The carbon residual ratio is also shown in Table 2.
これらのガソリン基材は、表３〜６の上部に示す配合割合でブレンドして実施例１〜１３及び比較例１〜１３のガソリン組成物を調製した。実施例及び比較例のガソリン組成物の性状を、実施例１〜４と比較例１〜４については表３に、実施例５〜７と比較例５〜７については表４に、実施例８〜９と比較例８〜９については表５に、そして実施例１０〜１３と比較例１０〜１３については表６にそれぞれ示す。 These gasoline base materials were blended at the blending ratios shown in the upper parts of Tables 3 to 6 to prepare gasoline compositions of Examples 1 to 13 and Comparative Examples 1 to 13. The properties of the gasoline compositions of Examples and Comparative Examples are shown in Table 3 for Examples 1 to 4 and Comparative Examples 1 to 4, Table 4 for Examples 5 to 7 and Comparative Examples 5 to 7, and Example 8 To 9 and Comparative Examples 8 to 9 are shown in Table 5, and Examples 10 to 13 and Comparative Examples 10 to 13 are shown in Table 6.
上記の実施例及び比較例において、使用した原料油、生成油、各種のガソリン基材及びガソリン組成物の性状は、以下の方法で分析した。
密度はＪＩＳ Ｋ ２２４９の振動式密度試験方法、リード法蒸気圧（ＲＶＰ）はＪＩＳ Ｋ ２２５８のリード法蒸気圧試験方法、蒸留性状はＪＩＳ Ｋ ２２５４の常圧法蒸留試験方法によってそれぞれ測定した。
In the above Examples and Comparative Examples, the properties of the raw material oils, product oils, various gasoline base materials and gasoline compositions used were analyzed by the following methods.
The density was measured by the vibration type density test method of JIS K 2249, the Reed method vapor pressure (RVP) was measured by the Reed method vapor pressure test method of JIS K 2258, and the distillation property was measured by the atmospheric pressure distillation test method of JIS K 2254.
硫黄分の測定は、ＪＩＳ Ｋ ２５４１の硫黄分試験方法に従い、高濃度領域では蛍光Ｘ線法を、および低濃度領域では微量電量滴定法を使用して行った。銀板腐食はＪＩＳ Ｋ２５１３（石油製品−銅板腐食試験方法：対応 ＡＳＴＭ Ｄ１３０）のボンベ法（ジェット燃料）で、銅板の代わりにＪＩＳ Ｋ２２７６（石油製品−航空燃料油試験方法）の「１４．銀板腐食試験方法」に用いる銀板を使用して評価した。窒素分の測定は、ＪＩＳ Ｋ ２６０９の窒素分試験方法に従い、化学発光法を使用して行った。 The sulfur content was measured using a fluorescent X-ray method in the high concentration region and a microcoulometric titration method in the low concentration region according to the sulfur content test method of JIS K2541. Silver plate corrosion is the cylinder method (jet fuel) of JIS K2513 (Petroleum products-Copper plate corrosion test method: corresponding ASTM D130). Instead of the copper plate, “14. The silver plate used in the “corrosion test method” was evaluated. The nitrogen content was measured using a chemiluminescence method according to the nitrogen content test method of JIS K 2609.
アロマ分、オレフィン分、パラフィン分等の各種炭化水素化合物の成分組成はＪＩＳ Ｋ ２５３６のガスクロマトグラフ法による全成分試験方法により測定した。リサーチ法オクタン価（ＲＯＮ）はヒューレッドパッカード社製ＰＩＯＮＡ装置を用いて、ガスクロマトグラフ法によって測定した。 The component composition of various hydrocarbon compounds such as aroma, olefin, and paraffin was measured by the all component test method based on the gas chromatograph method of JIS K2536. The research method octane number (RON) was measured by a gas chromatograph method using a PIONA manufactured by Hured Packard.
芳香族化合物のタイプ分析（環分析）の測定は、石油学会法ＪＰＩ−５Ｓ−４９−９７に従って、高速液体クロマトグラフ装置を使用し、固定相にはシリカゲル充填剤としてＰＡＲＴＩＳＩＬ ５ ＰＡＣ（カラムサイズ：２５ｃｍ×４．６ｍｍφ）及びＡｇＮＯ３−１０７１Ｙ（７ｃｍ×４．６ｍｍφ）、移動相にはノルマルヘキサン、検出にはＲＩ法を用いて実施した。 The type analysis (ring analysis) of aromatic compounds was measured using a high-performance liquid chromatograph apparatus according to the Petroleum Institute method JPI-5S-49-97, and PARTISIL 5 PAC (column size: 25 cm × 4.6 mmφ) and AgNO 3 -1071Y (7 cm × 4.6 mmφ), normal hexane for mobile phase, and RI method for detection.
芳香族構成炭素比率の測定には、溶媒に重クロロホルム、内部標準にテトラメチルシランを用い、日本電子製ＧＳＸ２７０型核磁気共鳴装置を用いて行った。炭素種分類ごとの芳香族環構成炭素と脂肪族構成炭素の定量は、１Ｈ−ゲーテッドデカップリング法（ＳＧＮＮＥモード）を用い、データポイント３２，７６８点、観測周波数領域幅２７，０２７Ｈｚ、パルス幅２μｓ、パルス待ち時間３０ｓ、積算回数２，０００回で測定し、フーリエ変換したスペクトルのシグナルの積分比から算出した。得られたスペクトルのシフト値において、１２０〜１５０ｐｐｍの領域のものを芳香族炭素に帰属するものとし、全炭素に対するモル％として表した。 The measurement of the aromatic constituent carbon ratio was carried out using deuterated chloroform as a solvent and tetramethylsilane as an internal standard, using a JSX GSX270 nuclear magnetic resonance apparatus. Quantification of aromatic ring carbon and aliphatic carbon for each carbon species classification uses 1 H-gated decoupling method (SGNNE mode), data points 32,768 points, observation frequency region width 27,027 Hz, pulse width The measurement was performed at 2 μs, a pulse waiting time of 30 s, and an integration number of 2,000 times, and was calculated from the integration ratio of the signal of the Fourier transformed spectrum. In the obtained spectrum shift value, those in the range of 120 to 150 ppm were attributed to aromatic carbon and expressed as mol% with respect to the total carbon.
表３〜６に示すとおり、実施例１〜１３の本発明のガソリンと比較例１〜１３の従来型ガソリンはオレフィン含有量が１５容量％以下に低減されたガソリン組成物であるが、実施例は比較例と比べて選択的水素化分解ガソリン（ＳＨＣＧ）を用いることにより、炭素数９の芳香族炭化水素含有量に対する１，２，４−トリメチルベンゼンと１，３，５−トリメチルベンゼンの合計含有量の比（（１２４ＴＭＢ＋１３５ＴＭＢ）／Ｃ９Ａ）が高く、さらに炭素数９の芳香族炭化水素含有量に対する１，３，５-トリメチルベンゼンの含有割合（１３５ＴＭＢ／Ｃ９Ａ）が高いため、オレフィン分を低減したにもかかわらずＲＯＮが高い。すなわち、実施例１〜１３のガソリンは、比較例１〜１３と硫黄分、オレフィン分やアロマ分が同程度であっても、良好な蒸留性状およびＲＶＰで、かつ高いＲＯＮであり、優れた実用性能を有することがわかる。 As shown in Tables 3-6, the gasoline of the present invention of Examples 1-13 and the conventional gasoline of Comparative Examples 1-13 are gasoline compositions with an olefin content reduced to 15% by volume or less. Is the sum of 1,2,4-trimethylbenzene and 1,3,5-trimethylbenzene with respect to the aromatic hydrocarbon content of 9 carbon atoms by using selective hydrocracked gasoline (SHCG) compared to the comparative example. The content ratio ((124TMB + 135TMB) / C9A) is high, and the content ratio of 1,3,5-trimethylbenzene (135TMB / C9A) to the content of aromatic hydrocarbons with 9 carbon atoms is high, reducing the olefin content. Despite this, RON is high. In other words, the gasolines of Examples 1 to 13 have good distillation properties and RVP and high RON even when the sulfur content, olefin content and aroma content are the same as those of Comparative Examples 1 to 13, and excellent practical use. It can be seen that it has performance.
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| JP2011032453A (en) * | 2009-07-10 | 2011-02-17 | Jx Nippon Oil & Energy Corp | Gasoline composition |
| JP2013001846A (en) * | 2011-06-17 | 2013-01-07 | Cosmo Oil Co Ltd | Gasoline composition and method of producing gasoline composition |
| JP2013001844A (en) * | 2011-06-17 | 2013-01-07 | Cosmo Oil Co Ltd | Gasoline composition and method for producing gasoline composition |
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| JP2006143833A (en) * | 2004-11-18 | 2006-06-08 | Japan Energy Corp | Gasoline composition |
| JP2006233033A (en) * | 2005-02-25 | 2006-09-07 | Japan Energy Corp | Gasoline composition exhausting small amount of carbon dioxide |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010116469A (en) * | 2008-11-12 | 2010-05-27 | Japan Energy Corp | Gasoline composition |
| JP2011032453A (en) * | 2009-07-10 | 2011-02-17 | Jx Nippon Oil & Energy Corp | Gasoline composition |
| JP2013001846A (en) * | 2011-06-17 | 2013-01-07 | Cosmo Oil Co Ltd | Gasoline composition and method of producing gasoline composition |
| JP2013001844A (en) * | 2011-06-17 | 2013-01-07 | Cosmo Oil Co Ltd | Gasoline composition and method for producing gasoline composition |
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