JPWO2005044959A1 - Unleaded gasoline composition and method for producing the same - Google Patents
Unleaded gasoline composition and method for producing the same Download PDFInfo
- Publication number
- JPWO2005044959A1 JPWO2005044959A1 JP2005515277A JP2005515277A JPWO2005044959A1 JP WO2005044959 A1 JPWO2005044959 A1 JP WO2005044959A1 JP 2005515277 A JP2005515277 A JP 2005515277A JP 2005515277 A JP2005515277 A JP 2005515277A JP WO2005044959 A1 JPWO2005044959 A1 JP WO2005044959A1
- Authority
- JP
- Japan
- Prior art keywords
- gasoline
- naphtha fraction
- less
- volume
- diene
- 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 292
- 239000000203 mixture Substances 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 107
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000011593 sulfur Substances 0.000 claims abstract description 104
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 89
- 230000023556 desulfurization Effects 0.000 claims abstract description 89
- 150000001993 dienes Chemical class 0.000 claims abstract description 83
- 238000000034 method Methods 0.000 claims abstract description 59
- 150000001336 alkenes Chemical class 0.000 claims abstract description 40
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000004821 distillation Methods 0.000 claims abstract description 33
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 28
- ZQRGREQWCRSUCI-UHFFFAOYSA-N [S].C=1C=CSC=1 Chemical class [S].C=1C=CSC=1 ZQRGREQWCRSUCI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005336 cracking Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 51
- 239000003795 chemical substances by application Substances 0.000 claims description 46
- 230000009467 reduction Effects 0.000 claims description 37
- 150000003464 sulfur compounds Chemical class 0.000 claims description 29
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 28
- 230000003009 desulfurizing effect Effects 0.000 claims description 26
- 238000005194 fractionation Methods 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 18
- 238000001179 sorption measurement Methods 0.000 claims description 18
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 claims description 17
- 229930192474 thiophene Natural products 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 150000003573 thiols Chemical class 0.000 claims description 13
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229910021472 group 8 element Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 description 80
- 238000004523 catalytic cracking Methods 0.000 description 59
- 238000002360 preparation method Methods 0.000 description 34
- 239000003921 oil Substances 0.000 description 32
- 230000003197 catalytic effect Effects 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000001833 catalytic reforming Methods 0.000 description 15
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000004508 fractional distillation Methods 0.000 description 9
- 239000000295 fuel oil Substances 0.000 description 9
- -1 diene compound Chemical class 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000005504 petroleum refining Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000004231 fluid catalytic cracking Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 125000004434 sulfur atom Chemical group 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000003463 adsorbent Substances 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
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002898 organic sulfur compounds Chemical class 0.000 description 4
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000002019 disulfides Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 150000003577 thiophenes Chemical class 0.000 description 3
- BQMLWEKOSHSOFT-UHFFFAOYSA-N 1-ethoxy-2,2-dimethylpropane Chemical compound CCOCC(C)(C)C BQMLWEKOSHSOFT-UHFFFAOYSA-N 0.000 description 2
- GWQOOADXMVQEFT-UHFFFAOYSA-N 2,5-Dimethylthiophene Chemical compound CC1=CC=C(C)S1 GWQOOADXMVQEFT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003747 fuel oil additive Substances 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 102100039339 Atrial natriuretic peptide receptor 1 Human genes 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101000961044 Homo sapiens Atrial natriuretic peptide receptor 1 Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241001372564 Piona Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JSOQIZDOEIKRLY-UHFFFAOYSA-N n-propylnitrous amide Chemical compound CCCNN=O JSOQIZDOEIKRLY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/04—Metals, or metals deposited on a carrier
-
- 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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Abstract
硫黄分が１質量ｐｐｍ以下で、十分な運転特性を保持した無鉛ガソリン組成物及びその製造方法を提供する。５容量％留出温度が２５℃以上、かつ９５容量％留出温度が２１０℃以下、オレフィン分が５質量％以上、ジエン価が０.３ｇ／１００ｇ以下である分解ナフサ留分を脱硫処理する工程、及び得られた脱硫分解ナフサ留分を、他のガソリン基材と混合するブレンド工程を含む、硫黄分が１質量ｐｐｍ以下、かつリサーチ法オクタン価が８９.０以上である無鉛ガソリン組成物の製造方法。また、リサーチ法オクタン価が８９.０以上、５０容量％留出温度が１０５℃以下、オレフィン分が１０容量％以上、全硫黄分が１質量ｐｐｍ以下、全硫黄分に占めるチオフェン類硫黄化合物の割合が硫黄分として５０質量％以上である無鉛ガソリン組成物。An unleaded gasoline composition having a sulfur content of 1 mass ppm or less and having sufficient operating characteristics and a method for producing the same. Desulfurization treatment is performed on a cracked naphtha fraction having a 5% by volume distillation temperature of 25 ° C. or more, a 95% by volume distillation temperature of 210 ° C. or less, an olefin content of 5% by mass or more, and a diene value of 0.3 g / 100 g or less. An unleaded gasoline composition having a sulfur content of 1 mass ppm or less and a research octane number of 89.0 or more, comprising a blending step of mixing the obtained desulfurization cracking naphtha fraction with another gasoline base Production method. In addition, the octane number of the research method is 89.0 or more, the 50% by volume distillation temperature is 105 ° C. or less, the olefin content is 10% by volume or more, the total sulfur content is 1 mass ppm or less, and the ratio of thiophene sulfur compounds in the total sulfur content An unleaded gasoline composition having a sulfur content of 50% by mass or more.
Description
本発明は、環境への影響を低減した無鉛ガソリン組成物とその製造方法に関する。特に、硫黄分を１質量ｐｐｍ以下に低減して、環境への影響に配慮しつつ十分な運転特性を確保した無鉛ガソリン組成物及びその製造方法に関する。 The present invention relates to an unleaded gasoline composition with reduced environmental impact and a method for producing the same. In particular, the present invention relates to an unleaded gasoline composition in which sulfur content is reduced to 1 mass ppm or less and sufficient operating characteristics are ensured while taking into consideration the influence on the environment, and a method for producing the same.
近年、自動車の高性能化に伴って、高い運転性能をもつ高性能ガソリンの需要が増加している。一方、自動車燃料やその燃焼排ガスによる環境汚染が社会問題になってきている。したがって、高い運転性能を維持するとともに、環境負荷の少ない自動車燃料が望まれている。特に、排ガス浄化と燃費改善の観点から、硫黄分の一層の低減が切望されている。 In recent years, the demand for high-performance gasoline having high driving performance has increased with the improvement in performance of automobiles. On the other hand, environmental pollution due to automobile fuel and its combustion exhaust gas has become a social problem. Therefore, an automobile fuel that maintains high driving performance and has a low environmental impact is desired. In particular, further reduction of sulfur content is desired from the viewpoint of exhaust gas purification and fuel efficiency improvement.
ＪＩＳ Ｋ ２２０２には、リサーチ法オクタン価（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、接触分解ガソリン基材のような９３以上のＲＯＮをもつ基材を中心に、各種の基材を配合して製造されている。 JIS K 2202 stipulates No. 1 automobile gasoline with a research octane number (RON) of 96.0 or more and No. 2 automobile gasoline with 89.0 or more. The former is a high-performance premium gasoline and the latter is regular. Commercially available as gasoline. Conventionally, premium gasoline has a catalytic reforming gasoline base, a base with more than 100 RON such as methyl t-butyl ether (MTBE), 93 or more RON such as alkylate gasoline base, catalytic cracking gasoline base It is manufactured by blending various types of base materials, mainly on base materials with
重質な石油留分を分解することによって製造される分解ガソリン基材は、他のガソリン基材に比べ、経済的に製造できるという利点がある一方、高い硫黄分を含んでいた。その結果、上述のようにして製造されるガソリン中の硫黄分の大部分は、分解ガソリン基材に由来していた。 The cracked gasoline base produced by cracking heavy petroleum fractions has the advantage that it can be produced economically compared to other gasoline bases, while containing a high sulfur content. As a result, most of the sulfur content in the gasoline produced as described above was derived from the cracked gasoline base material.
分解ガソリン基材の硫黄分の低減は、高圧水素と触媒の共存下で水素化精製するという公知技術で容易に可能である。しかし、その場合は、接触分解ガソリン基材中に多く含まれ、高いＲＯＮをもつオレフィン分が水素化されて基材のＲＯＮが低下してしまうため、それを配合したガソリンでは十分な運転性能が得られないという問題点があった。 The sulfur content of the cracked gasoline base material can be easily reduced by a known technique of hydrorefining in the presence of high-pressure hydrogen and a catalyst. However, in that case, a large amount of catalytic cracking gasoline base material is contained, and the olefin content having high RON is hydrogenated to lower the base material RON. There was a problem that it could not be obtained.
一方、炭化水素油を、特定の条件下、吸着剤と接触させて硫黄化合物を吸着させる工程と、吸着剤に水素を通気させることにより吸着剤から硫黄化合物を脱離する工程を繰り返すことにより、オレフィンの水素化反応など不要な反応を抑制し、ガソリンの基材となる炭化水素油に含まれる硫黄分を連続的に低減する方法が提案されている（特許文献１参照）。しかしながら、このような吸着剤を用いる方法も、原料油に含有される特定の炭化水素化合物によるせいか、硫黄の吸着能が阻害されて硫黄分を効率よく継続的に低減することができず、必ずしも満足できる方法ではなかった。
硫黄分が１質量ｐｐｍ以下と低く、かつ、十分な実用性能を確保した環境対応ガソリン、及びその製造方法は未だ確立されていない。本発明は、このような状況下で、硫黄分を低減し、かつ、十分な運転特性を確保した無鉛ガソリン組成物及びその製造方法を提供することを目的とするものである。 An environment-friendly gasoline having a sulfur content as low as 1 mass ppm or less and sufficient practical performance and a method for producing the same have not been established yet. An object of the present invention is to provide an unleaded gasoline composition that reduces sulfur content and secures sufficient operating characteristics under such circumstances, and a method for producing the same.
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、ジエン含有量が低い分解ナフサ留分を用いて水素化精製以外の脱硫処理を行うと、高いＲＯＮを維持したまま、硫黄分を効率よく低減できることを見出し、そして、このようにして得られた基材を用いることにより、十分な運転特性を確保した無鉛ガソリン組成物が得られることを見出し、本発明の無鉛ガソリン組成物及びその製造方法に想到した。 As a result of diligent research to solve the above problems, the present inventors have conducted a desulfurization treatment other than hydrorefining using a cracked naphtha fraction having a low diene content, while maintaining a high RON while maintaining a high RON. It is found that an unleaded gasoline composition having sufficient operating characteristics can be obtained by using the substrate thus obtained, and the unleaded gasoline composition of the present invention and I came up with the manufacturing method.
すなわち、本発明による硫黄分が１質量ｐｐｍ以下、かつリサーチ法オクタン価（ＲＯＮ）が８９.０以上である無鉛ガソリン組成物の製造方法は、
（１）５容量％留出温度が２５℃以上、かつ９５容量％留出温度が２１０℃以下、オレフィン分が５容量％以上、ジエン価が０.３ｇ／１００ｇ以下である分解ナフサ留分を脱硫処理する脱硫工程、及び
（２）前記（１）の脱硫工程で得られた脱硫分解ナフサ留分と他のガソリン基材とを混合するブレンド工程
を含む。That is, the method for producing an unleaded gasoline composition having a sulfur content of 1 mass ppm or less and a research octane number (RON) of 89.0 or more according to the present invention is as follows:
(1) A cracked naphtha fraction having a 5% by volume distillation temperature of 25 ° C. or more, a 95% by volume distillation temperature of 210 ° C. or less, an olefin content of 5% by volume or more, and a diene value of 0.3 g / 100 g or less. A desulfurization step of desulfurization treatment, and (2) a blending step of mixing the desulfurization cracked naphtha fraction obtained in the desulfurization step (1) and another gasoline base material.
好ましくは、（１）の工程において、予めジエン低減処理を経たジエン価が０.３ｇ／１００ｇ以下の分解ナフサ留分を用いる。すなわち、本発明の無鉛ガソリン組成物の製造方法は、分解ナフサ留分の原料油に対し、予めジエン低減処理を行う工程を含むことが好ましい。また、このとき、ジエン低減処理は、分解ナフサ留分の原料油と周期律表第８族の元素を含む触媒とを接触させることが好ましく、このとき、ジエン低減触媒が、コバルトまたはニッケルから選ばれる少なくとも１種を含むものであることが好ましい。 Preferably, a cracked naphtha fraction having a diene value of 0.3 g / 100 g or less previously subjected to a diene reduction treatment is used in the step (1). That is, it is preferable that the manufacturing method of the unleaded gasoline composition of this invention includes the process of performing the diene reduction process previously with respect to the raw material oil of a cracked naphtha fraction. In this case, the diene reduction treatment is preferably performed by bringing the cracked naphtha fraction feedstock into contact with the catalyst containing Group 8 element of the periodic table. At this time, the diene reduction catalyst is selected from cobalt or nickel. It is preferable that it contains at least one kind.
さらに、本発明の無鉛ガソリン組成物の製造方法は、（１）の脱硫工程において、硫黄収着機能をもった多孔質脱硫剤を水素分圧１ＭＰａ以下の水素共存下で分解ナフサ留分と接触させて脱硫処理することが好ましく、このとき、多孔質脱硫剤が、銅、亜鉛、ニッケル及び鉄から選ばれる少なくとも１種を含むものであることが好ましい。
（２）のブレンド工程において、１０〜９０容量％の脱硫分解ナフサ留分と９０〜１０容量％の他のガソリン基材とを混合することが好ましい。Furthermore, in the method for producing an unleaded gasoline composition of the present invention, in the desulfurization step (1), a porous desulfurization agent having a sulfur sorption function is brought into contact with a cracked naphtha fraction in the presence of hydrogen having a hydrogen partial pressure of 1 MPa or less. The desulfurization treatment is preferably performed, and at this time, the porous desulfurization agent preferably contains at least one selected from copper, zinc, nickel, and iron.
In the blending step (2), it is preferable to mix 10 to 90% by volume of the desulfurized cracked naphtha fraction and 90 to 10% by volume of another gasoline base.
また、本発明の無鉛ガソリン組成物の製造方法は、よりオクタン価の高い、例えばリサーチ法オクタン価が９３.０以上、特には９６.０以上といった無鉛ガソリン組成物を得るために、分解ナフサ留分は、５容量％留出温度が２５〜４３℃、かつ９５容量％留出温度が５５〜１００℃、オレフィン分が５容量％以上、ジエン価が０.３ｇ／１００ｇ以下である軽質な分解ナフサ留分を前記（１）の脱硫工程で用いることが好ましい。
このような軽質な分解ナフサ留分は、当該分解ナフサ留分の原料油をジエン低減処理した後に分留して得たものであっても、あるいは前記分解ナフサ留分の原料油を分留した後にジエン低減処理して得たものであっても、あるいは分留とジエン低減処理を同時に行って得たものでもよい。
さらに、軽質な分解ナフサ留分を得る分留を行う前に、あるいは分留と同時に分解ナフサ留分の原料油又はジエン低減処理した分解ナフサ留分の原料油に対し、含まれる硫黄化合物の分子量を大きくする前処理を施しておくことが好ましく、こうすることによって、軽質な分解ナフサ留分に含まれる硫黄分を容易に低減しておくことができる。Further, the method for producing an unleaded gasoline composition of the present invention has a higher octane number, for example, to obtain an unleaded gasoline composition having a research octane number of 93.0 or more, particularly 96.0 or more. A light cracked naphtha fraction having a 5% by volume distillation temperature of 25 to 43 ° C, a 95% by volume distillation temperature of 55 to 100 ° C, an olefin content of 5% by volume or more, and a diene value of 0.3g / 100g or less. It is preferable to use the minute in the desulfurization step (1).
Such a light cracked naphtha fraction may be obtained by fractionating the raw oil of the cracked naphtha fraction after diene reduction treatment, or the raw oil of the cracked naphtha fraction was fractionated. It may be obtained later by diene reduction treatment, or obtained by performing fractional distillation and diene reduction treatment simultaneously.
Furthermore, the molecular weight of the sulfur compounds contained in the raw material oil of the cracked naphtha fraction or the raw material oil of the cracked naphtha fraction subjected to the diene reduction treatment before the fractionation to obtain a light cracked naphtha fraction or simultaneously with the fractionation It is preferable to carry out a pretreatment for increasing the amount of sulfur. By doing so, the sulfur content contained in the light cracked naphtha fraction can be easily reduced.
本発明の無鉛ガソリン組成物の好ましい製造方法は、このような軽質な分解ナフサ留分を前記（１）の工程で脱硫処理した後、前記（２）のブレンド工程において、１０〜６０容量％の軽質な脱硫分解ナフサ留分と９０〜４０容量％の他のガソリン基材とを混合し、リサーチ法オクタン価が９３.０以上である無鉛ガソリン組成物の製造方法である。 In a preferred method for producing the unleaded gasoline composition of the present invention, such a light cracked naphtha fraction is desulfurized in the step (1), and then 10 to 60% by volume in the blending step (2). This is a method for producing an unleaded gasoline composition in which a light desulfurization cracked naphtha fraction and 90 to 40% by volume of another gasoline base are mixed, and the research octane number is 93.0 or more.
本発明による無鉛ガソリン組成物は、リサーチ法オクタン価が８９.０以上、５０容量％留出温度が１０５℃以下、オレフィン分が１０容量％以上、全硫黄分が１質量ｐｐｍ以下、及び全硫黄分に占めるチオフェン類硫黄化合物の割合が硫黄分として５０質量％以上である。
また、好ましくは本発明の無鉛ガソリン組成物は、リサーチ法オクタン価が９３.０以上である。さらに好ましくは、全オレフィン分に占める沸点範囲３５〜１００℃のオレフィン分が９０容量％以上、全硫黄分に占めるチオフェン及び２−メチルチオフェンの合計量の割合が硫黄分として５０質量％以上、及び／又は、チオール類の含有量が硫黄分として０.１質量ｐｐｍ以下である。The unleaded gasoline composition according to the present invention has a research octane number of 89.0 or more, a 50% by volume distillation temperature of 105 ° C. or less, an olefin content of 10% by volume or more, a total sulfur content of 1 mass ppm or less, and a total sulfur content. The proportion of the thiophene sulfur compound in the total is 50% by mass or more as the sulfur content.
Preferably, the unleaded gasoline composition of the present invention has a research octane number of 93.0 or more. More preferably, the olefin content in the boiling range of 35 to 100 ° C. in the total olefin content is 90% by volume or more, the ratio of the total amount of thiophene and 2-methylthiophene in the total sulfur content is 50% by mass or more as the sulfur content, and / Or Content of thiols is 0.1 mass ppm or less as a sulfur content.
特に接触分解ガソリンや各種の分解ガソリンなどの分解ナフサ留分には、ジエン類が不可避的に含有される。ジエン類が含まれると、多孔質脱硫剤による処理において、ジエン類が多孔質脱硫剤に優先的に吸着し、硫黄を吸着（収着）する機能が阻害される。一方、本発明によれば、予めジエンを低減する処理を行い、ジエン価を０.３ｇ／１００ｇ以下に制限しているので、高い硫黄収着機能を長時間持続することができる。すなわち、接触分解ガソリンをジエン除去した後、わずかな水素共存の下、硫黄収着機能をもつ多孔質脱硫剤によって処理して得た脱硫分解ナフサ留分と、硫黄分が１０質量ｐｐｍ以下の他のガソリン基材とを混合することによって、硫黄分１質量ｐｐｍ以下の無鉛ガソリン組成物を製造することが可能となる。接触分解ガソリンなどの分解ナフサ留分中のチオフェン類硫黄化合物も除去することが可能なので、チオフェン類硫黄化合物を多く含む分解ナフサ留分などの軽質な分解ナフサ留分も脱硫処理が可能である。また、接触分解軽質ガソリンなどの軽質な分解ナフサ留分に多く含まれるオレフィン分はほとんど水素化されないので、脱硫処理に伴うオクタン価ロスを回避できる。したがって、従来得られている無鉛ガソリン組成物から他の性状をほとんど変えることなく硫黄分だけを１質量ｐｐｍ以下まで減じることが可能である。 In particular, dienes are inevitably contained in cracked naphtha fractions such as catalytically cracked gasoline and various cracked gasolines. When the diene is contained, in the treatment with the porous desulfurizing agent, the diene is preferentially adsorbed on the porous desulfurizing agent and the function of adsorbing (sorbing) sulfur is inhibited. On the other hand, according to the present invention, since the diene is reduced in advance and the diene value is limited to 0.3 g / 100 g or less, a high sulfur sorption function can be maintained for a long time. That is, after removing the catalytically cracked gasoline by diene, a desulfurized cracked naphtha fraction obtained by treating with a porous desulfurizing agent having a sulfur sorption function in the presence of a slight amount of hydrogen, and a sulfur content of 10 ppm by mass or less It is possible to produce an unleaded gasoline composition having a sulfur content of 1 mass ppm or less by mixing with the gasoline base. Since thiophene sulfur compounds in cracked naphtha fractions such as catalytic cracked gasoline can also be removed, light cracked naphtha fractions such as cracked naphtha fractions containing a large amount of thiophene sulfur compounds can also be desulfurized. Further, since the olefin content contained in the light cracked naphtha fraction such as catalytic cracked light gasoline is hardly hydrogenated, the octane loss associated with the desulfurization treatment can be avoided. Therefore, it is possible to reduce only the sulfur content to 1 ppm by mass or less without changing other properties from the conventional unleaded gasoline composition.
本発明は、特定の性状を有する分解ナフサ留分を脱硫処理する脱硫工程、及び得られた脱硫分解ナフサ留分を、他のガソリン基材と混合するブレンド工程を含む硫黄分が１質量ｐｐｍ以下、かつリサーチ法オクタン価が８９.０以上である無鉛ガソリン組成物の製造方法である。なお、以下の説明において、分解ナフサ留分として、いわゆる流動接触分解ガソリン（ＦＣＣガソリン）を主体的に引用して説明するが、本発明はＦＣＣガソリンに限定されるものでなく、その他の石油精製及び石油化学などのプロセス、装置から得られる製品、中間製品などで、例えば熱分解装置から生成する熱分解ナフサ、脱ろう装置から生成する脱ろうナフサ、ナフサクラッカーから生成する分解ナフサなどを分解ナフサ留分として用いることができる。要は、５容量％留出温度が２５℃以上、かつ９５容量％留出温度が２１０℃以下、オレフィン分が５容量％以上、ジエン価が０.３ｇ／１００ｇ以下の分解ナフサ留分であればよい。したがって、いわゆるホール（whole）の分解ナフサ留分のほかに、それをさらに分留して得た軽質な分解ナフサ留分、あるいは重質な分解ナフサ留分であっても、前記条件を満足すればよい。なお、これらの分解ナフサ留分の５容量％留出温度は２５〜１３０℃、及び９５容量％留出温度は５５〜２１０℃が好ましい。また、ジエン価が０.３ｇ／１００ｇ以下のものを用いるために、分解ナフサ留分は、予め以下に詳述するジエンを低減する処理が施され、前記ジエン価を有するものを使用することが好ましい。 The present invention includes a desulfurization step of desulfurizing a cracked naphtha fraction having specific properties, and a sulfur content of 1 mass ppm or less including a blending step of mixing the obtained desulfurized cracked naphtha fraction with another gasoline base material. And a method for producing an unleaded gasoline composition having a research octane number of 89.0 or more. In the following description, a so-called fluid catalytic cracking gasoline (FCC gasoline) will be mainly cited and explained as the cracked naphtha fraction, but the present invention is not limited to FCC gasoline, and other petroleum refining For example, pyrolysis naphtha produced from pyrolysis equipment, dewaxed naphtha produced from dewaxing equipment, cracked naphtha produced from naphtha crackers, etc. It can be used as a fraction. In short, a cracked naphtha fraction having a 5% by volume distillation temperature of 25 ° C. or more, a 95% by volume distillation temperature of 210 ° C. or less, an olefin content of 5% by volume or more, and a diene value of 0.3 g / 100 g or less. That's fine. Therefore, in addition to the so-called whole cracked naphtha fraction, even the light cracked naphtha fraction obtained by further fractional distillation or the heavy cracked naphtha fraction should satisfy the above conditions. That's fine. The 5 vol% distillation temperature of these cracked naphtha fractions is preferably 25 to 130 ° C, and the 95 vol% distillation temperature is preferably 55 to 210 ° C. In addition, since a diene value of 0.3 g / 100 g or less is used, the cracked naphtha fraction is subjected to a treatment for reducing diene, which will be described in detail below, and the one having the diene value is used. preferable.
〔ジエン低減処理〕
本発明の無鉛ガソリン組成物の製造方法において、予めＦＣＣガソリンのような分解ナフサ留分に対しジエン低減処理を行い、ジエン価が０.３ｇ／１００ｇ以下である分解ナフサ留分を得る。ジエン価が０.１ｇ／１００ｇ以下であると、なお一層好ましい。ジエン価が０.３ｇ／１００ｇを超えると、その後の脱硫工程に用いる硫黄収着機能をもつ多孔質脱硫剤の脱硫性能が低下し、特にチオフェン類硫黄化合物の脱硫が困難になる。脱硫性能の低下は、単位処理量における脱硫率の低下、あるいは所定の脱硫率を保持するための多孔質脱硫剤の再生頻度の増加によって知ることができる。したがって、ジエン化合物を低減する前処理を行ってから次の脱硫工程に供することが好ましい。ただし、このジエン低減処理工程においては、オレフィンが水素化されパラフィンに転化するとオクタン価が大きく低下するから、オレフィンが水素化されないように選択的なジエン低減処理をすることが好ましい。[Diene reduction treatment]
In the method for producing an unleaded gasoline composition of the present invention, a cracked naphtha fraction such as FCC gasoline is previously subjected to a diene reduction treatment to obtain a cracked naphtha fraction having a diene value of 0.3 g / 100 g or less. It is even more preferable that the diene value is 0.1 g / 100 g or less. When the diene value exceeds 0.3 g / 100 g, the desulfurization performance of the porous desulfurization agent having a sulfur sorption function used in the subsequent desulfurization step is lowered, and in particular, desulfurization of the thiophene sulfur compound becomes difficult. The decrease in the desulfurization performance can be recognized by a decrease in the desulfurization rate in the unit treatment amount or an increase in the regeneration frequency of the porous desulfurization agent for maintaining a predetermined desulfurization rate. Accordingly, it is preferable to perform the pretreatment for reducing the diene compound and then use it for the next desulfurization step. However, in this diene reduction treatment step, when the olefin is hydrogenated and converted to paraffin, the octane number is greatly reduced. Therefore, selective diene reduction treatment is preferably performed so that the olefin is not hydrogenated.
なお、ここでいうジエン価とはＵＯＰ３２６−８２にて測定した値である。
また、ジエン低減処理において、用いる触媒と条件を選択することによって、硫黄分も同時に低減できる。そうすれば、収着機能をもった多孔質脱硫剤の寿命を延長させることが可能である。Here, the diene value is a value measured by UOP326-82.
In the diene reduction treatment, the sulfur content can be reduced simultaneously by selecting the catalyst and conditions to be used. By doing so, it is possible to extend the lifetime of the porous desulfurization agent having a sorption function.
ジエン低減処理の方法は、ジエン低減触媒と接触分解ナフサ留分を水素の共存下で接触させ、ジエンをモノオレフィンに転化するか、あるいは、ジエンと共存する硫黄化合物とを反応させスルフィドに転化させる方法が好ましい。ジエン低減触媒としてはアルミナなどの無機多孔質担体に周期律表第８属の金属を少なくとも１種を担持した触媒が好ましく用いられる。さらには、硫黄を含む原料油に対して耐性があるニッケルまたはコバルトを含む触媒がなおいっそう好ましい。反応条件としては、接触分解ナフサ留分中のジエン価が０.３ｇ／１００ｇ以下でありかつ、オレフィン水素化率が２０％以下となるように設定する必要がある。ここで、オレフィン水素化率とは、処理前のオレフィン含有量を１００％とした場合の、処理後のオレフィン含有量の低減率をいう。
なお、ジエン低減触媒と接触分解ナフサ留分を水素の共存下で接触させる好ましい反応条件は、反応温度４０〜３００℃、反応圧力０.０〜４.０ＭＰａ(ゲージ圧)、ＬＨＳＶ１.０〜１０.０ｈｒ−１、Ｈ２／ＯＩＬ比１〜１００ＮＬ／Ｌである。The diene reduction treatment method involves contacting the diene reduction catalyst and the catalytic cracking naphtha fraction in the presence of hydrogen to convert the diene to a monoolefin, or reacting the sulfur compound coexisting with the diene to convert to a sulfide. The method is preferred. As the diene-reducing catalyst, a catalyst in which at least one metal of Group 8 of the periodic table is supported on an inorganic porous carrier such as alumina is preferably used. Furthermore, a catalyst containing nickel or cobalt that is resistant to sulfur-containing feedstock is even more preferred. The reaction conditions must be set so that the diene value in the catalytic cracking naphtha fraction is 0.3 g / 100 g or less and the olefin hydrogenation rate is 20% or less. Here, the olefin hydrogenation rate means a reduction rate of the olefin content after the treatment when the olefin content before the treatment is 100%.
The preferable reaction conditions for contacting the diene-reducing catalyst and the catalytic cracking naphtha fraction in the presence of hydrogen are as follows: reaction temperature 40 to 300 ° C., reaction pressure 0.0 to 4.0 MPa (gauge pressure), LHSV 1.0 to 10 0.0 hr −1 , H 2 / OIL ratio is 1 to 100 NL / L.
従来から石油精製においては、オレフィン中のジエンを選択的に水素化精製することが行われており、本発明においてジエンを低減する方法として適用できる。具体的には、IFP Selective Hydrogenationプロセス、Hules Selective Hydrogenationプロセスなどが好ましく用いられる（石油学会編石油精製プロセス、p.62、講談社サイエンティフィク、1998、参照）。
また、本発明においてジエンを低減する方法として、SHUプロセス（21st JPI Petroleum Refining Conference “Recent Progress in Petroleum Process Technology”, 37(2002)）やCD Hydroプロセス（NPRA 2001 Annual Meeting, AM-01-39）も用いることができる。Conventionally, in petroleum refining, diene in olefins has been selectively hydrorefined, and can be applied as a method for reducing diene in the present invention. Specifically, the IFP Selective Hydrogenation process, the Hules Selective Hydrogenation process, etc. are preferably used (refer to Petroleum Institute Petroleum Refining Process, p.62, Kodansha Scientific, 1998).
In addition, as a method for reducing diene in the present invention, the SHU process (21st JPI Petroleum Refining Conference “Recent Progress in Petroleum Process Technology”, 37 (2002)) and the CD Hydro process (NPRA 2001 Annual Meeting, AM-01-39) Can also be used.
〔接触分解ガソリン〕
本発明の無鉛ガソリン組成物の製造方法において、分解ナフサ留分として前述のように接触分解ガソリンが代表的に用いられる。この接触分解ガソリンを製造するプロセスは、接触分解装置、原料油、運転条件を特に限定するものでなく、公知の任意の製造工程を採用できる。接触分解装置は、無定形シリカアルミナ、ゼオライトなどの触媒を使用して、軽油から減圧軽油までの石油留分の他、重油間接脱硫装置から得られる間脱軽油、重油直接脱硫装置から得られる直脱重油、常圧残さ油などを接触分解して高オクタン価ガソリン基材を得る装置である。例えば石油学会編「新石油精製プロセス」に記載のあるＵＯＰ接触分解法、フレキシクラッキング法、ウルトラ・オルソフロー法、テキサコ流動接触分解法などの流動接触分解法、ＲＣＣ法、ＨＯＣ法などの残油流動接触分解法などがある。[Catalytic cracking gasoline]
In the method for producing an unleaded gasoline composition of the present invention, catalytic cracked gasoline is typically used as the cracked naphtha fraction as described above. The process for producing the catalytic cracking gasoline does not particularly limit the catalytic cracking apparatus, the raw material oil, and the operating conditions, and any known production process can be employed. The catalytic cracker uses a catalyst such as amorphous silica alumina, zeolite, etc., in addition to the petroleum fraction from light oil to vacuum gas oil, while it is obtained from the heavy oil indirect desulfurization unit, the direct desulfurization unit obtained from the degasification oil and heavy oil direct desulfurization unit. This is a device that obtains a high octane gasoline base material by catalytically cracking degassed oil, atmospheric residue oil, etc. For example, UOP catalytic cracking method, flexi cracking method, ultra-orthoflow method, fluid catalytic cracking method such as Texaco fluid catalytic cracking method, RCC method, HOC method, etc. Examples include fluid catalytic cracking.
分解ナフサ留分中の硫黄化合物を低減するためには、接触分解装置の原料油として軽油から減圧軽油までの石油留分、特にその硫黄分を４０００質量ｐｐｍ以下、より好ましくは２０００質量ｐｐｍ以下、さらには１０００質量ｐｐｍ以下、特には５００質量ｐｐｍ以下に水素化精製などにより低減した留分を用いることが好ましい。 In order to reduce the sulfur compound in the cracked naphtha fraction, the petroleum fraction from light oil to vacuum gas oil as the feedstock for the catalytic cracking device, particularly the sulfur content is 4000 mass ppm or less, more preferably 2000 mass ppm or less, Furthermore, it is preferable to use a fraction reduced to 1000 mass ppm or less, particularly 500 mass ppm or less by hydrorefining or the like.
〔脱硫工程〕
本発明の無鉛ガソリン組成物の製造方法における脱硫工程では、ジエン価が０.３ｇ／１００ｇ以下である分解ナフサ留分を脱硫処理して、次のブレンド工程に供する脱硫分解ナフサ留分を得る。脱硫工程で得られる脱硫分解ナフサ留分の硫黄分を、２質量ｐｐｍ以下に脱硫することが好ましく、１質量ｐｐｍ以下、さらには０.５質量ｐｐｍ以下にすることができるとなお一層好ましい。脱硫工程においては、硫黄化合物のうちチオフェン類硫黄化合物が最も残留しやすい硫黄化合物であるため、脱硫分解ナフサ留分中の全硫黄分に占めるチオフェン類硫黄化合物の割合は硫黄分として５０質量％以上、さらには７０質量％以上であるのが好ましい。なお、ここでいうチオフェン類硫黄化合物とは、チオフェン、２−メチルチオフェン、２，５−ジメチルチオフェン等の分子内にチオフェン骨格を含む硫黄化合物のことである。また、脱硫接触分解ガソリンのオレフィン分は５〜６０容量％、特には２０〜４０容量％であることが好ましい。[Desulfurization process]
In the desulfurization step in the method for producing an unleaded gasoline composition of the present invention, a desulfurized naphtha fraction having a diene value of 0.3 g / 100 g or less is desulfurized to obtain a desulfurized cracked naphtha fraction for use in the next blending step. The sulfur content of the desulfurized cracked naphtha fraction obtained in the desulfurization step is preferably desulfurized to 2 ppm by mass or less, more preferably 1 ppm by mass or less, and even more preferably 0.5 ppm by mass or less. In the desulfurization process, among the sulfur compounds, the thiophene sulfur compound is the sulfur compound most likely to remain, so the proportion of the thiophene sulfur compound in the total sulfur content in the desulfurization cracked naphtha fraction is 50% by mass or more as the sulfur content. Furthermore, it is preferable that it is 70 mass% or more. The thiophene sulfur compound referred to herein is a sulfur compound containing a thiophene skeleton in the molecule, such as thiophene, 2-methylthiophene, 2,5-dimethylthiophene. The olefin content of the desulfurized catalytic cracking gasoline is preferably 5 to 60% by volume, particularly 20 to 40% by volume.
脱硫工程における脱硫処理の方法は、水素の共存下で収着機能をもった脱硫剤と分解ナフサ留分を接触させる方法が好ましい。水素化脱硫触媒と水素の存在下で、分解ナフサ留分を水素化精製処理する方法では、オレフィンが水素化されて得られるガソリン基材のＲＯＮが低下しやすく、また水素化脱硫によって生成する硫化水素がオレフィンと反応してチオール類を再生成しやすいため、十分に脱硫処理できないので不適切である。収着機能をもった脱硫剤を用いると有機硫黄化合物から除去される硫黄が脱硫剤上に固定化されオレフィンと反応してチオール類を再生成することがないので好ましい。 The desulfurization treatment method in the desulfurization step is preferably a method in which a desulfurization agent having a sorption function and a cracked naphtha fraction are contacted in the presence of hydrogen. In the method of hydrotreating a cracked naphtha fraction in the presence of a hydrodesulfurization catalyst and hydrogen, the RON of the gasoline base material obtained by hydrogenating the olefin is likely to decrease, and the sulfur produced by hydrodesulfurization Since hydrogen easily reacts with olefins to regenerate thiols, it cannot be adequately desulfurized and is inappropriate. Use of a desulfurizing agent having a sorption function is preferable because sulfur removed from the organic sulfur compound is immobilized on the desulfurizing agent and does not react with the olefin to regenerate thiols.
硫黄の収着機能をもった脱硫剤と分解ナフサ留分を接触させる方法を用いる場合の脱硫剤としては、硫黄化合物に対する収着機能を有するものであれば特に限定はない。銅、亜鉛、ニッケル及び鉄から選ばれる少なくとも１種を含む多孔質脱硫剤が好ましく用いられる。好ましい脱硫剤は、銅などの金属成分を０.５〜８５質量％、特には１〜８０質量％含有する。脱硫剤の製造方法は特に限定されないが、アルミナのような多孔質担体に銅などの金属成分を含浸、担持して焼成する製造方法や、共沈法によって銅などの金属成分とアルミニウムなどの成分とを沈殿させて成形、焼成等の工程を経る製造方法が、好ましい方法として挙げられる。また、成形、焼成された脱硫剤にさらに金属成分を含浸、担持して、焼成してもよい。脱硫剤は、焼成されたものをそのまま用いてもよいし、水素雰囲気下で処理して用いてもよい。脱硫剤の比表面積は、好ましくは３０ｍ２／ｇ以上、特には５０〜６００ｍ２／ｇである。脱硫剤の組成や製造方法は特に限定されないが、特許第３３２４７４６号公報、特許第３２３０８６４号公報および特開平１１-６１１５４号公報に開示されているような脱硫剤が好ましいものとして挙げられる。The desulfurization agent in the case of using a method of bringing a desulfurization agent having a sulfur sorption function into contact with a cracked naphtha fraction is not particularly limited as long as it has a sorption function for a sulfur compound. A porous desulfurization agent containing at least one selected from copper, zinc, nickel and iron is preferably used. A preferred desulfurizing agent contains 0.5 to 85% by mass, particularly 1 to 80% by mass of a metal component such as copper. The production method of the desulfurization agent is not particularly limited, but a production method in which a porous carrier such as alumina is impregnated with metal components such as copper, supported, and fired, or a metal component such as copper and a component such as aluminum by a coprecipitation method A preferable method is a production method in which the above is precipitated and subjected to steps such as molding and baking. Alternatively, the molded and fired desulfurizing agent may be further impregnated and supported with a metal component and fired. The desulfurization agent may be used as it is, or may be used after being treated in a hydrogen atmosphere. The specific surface area of the desulfurizing agent is preferably 30 m 2 / g or more, particularly 50 to 600 m 2 / g. The composition and production method of the desulfurizing agent are not particularly limited, and preferred desulfurizing agents are those disclosed in Japanese Patent No. 3324746, Japanese Patent No. 3230864 and Japanese Patent Laid-Open No. 11-61154.
本発明の硫黄収着機能を持った多孔質脱硫剤とは、有機硫黄化合物中の硫黄原子を脱硫剤に固定化するとともに、有機硫黄化合物中の硫黄原子以外の炭化水素残基については、有機硫黄化合物中の炭素−硫黄結合が開裂することによって脱硫剤から脱離させる機能をもった多孔質脱硫剤をいう。この炭化水素残基が脱離する際には、硫黄との結合が開裂した炭素に、系内に存在する水素が付加する。したがって、有機硫黄化合物から硫黄原子が除かれた炭化水素化合物が生成物として得られることになる。ただし、硫黄原子が除かれた炭化水素化合物が、さらに水素化、異性化、分解等の反応を受けた生成物を与えることがあっても構わない。一方、硫黄は脱硫剤に固定化されるため、水素化精製とは異なり、生成物として硫化水素などの硫黄化合物を発生しない。 The porous desulfurization agent having a sulfur sorption function of the present invention is to fix the sulfur atom in the organic sulfur compound to the desulfurization agent, and for the hydrocarbon residue other than the sulfur atom in the organic sulfur compound, A porous desulfurization agent having a function of desorbing from a desulfurization agent by cleavage of a carbon-sulfur bond in a sulfur compound. When this hydrocarbon residue is eliminated, hydrogen present in the system is added to the carbon whose bond with sulfur has been cleaved. Accordingly, a hydrocarbon compound obtained by removing sulfur atoms from the organic sulfur compound is obtained as a product. However, the hydrocarbon compound from which the sulfur atom is removed may give a product that has undergone a reaction such as hydrogenation, isomerization, or decomposition. On the other hand, since sulfur is fixed to the desulfurizing agent, unlike hydrorefining, sulfur compounds such as hydrogen sulfide are not generated as products.
脱硫処理は、バッチ式で行っても、流通式で行っても構わないが、脱硫剤を充填した固定床脱硫塔に分解ナフサ留分を流通させて行うことが、脱硫剤と得られる脱硫分解ナフサ留分の分離が簡便にできるので好ましい。脱硫処理する温度は、０〜４００℃の範囲から選ぶことができ、好ましくは２０〜３８０℃の範囲から選ぶとよい。脱硫剤と接触させただけでは脱硫されにくいチオフェン類の脱硫を促進するために、水素を共存させて脱硫処理を行ってもよい。ただし、オレフィンが水素化され、得られるガソリン基材のＲＯＮが低下することを避けるため、水素分圧は１ＭＰａ未満とすることが好ましく、さらには０.６ＭＰａ未満とすることが好ましい。固定床流通式で脱硫剤と分解ナフサ留分を接触させて脱硫処理を行う場合、ＬＨＳＶは、０.０１〜１００００ｈｒ−１の範囲から選ぶことが好ましい。The desulfurization treatment may be performed batchwise or flow-through, but the desulfurization cracking obtained with the desulfurization agent can be performed by circulating the cracked naphtha fraction through a fixed-bed desulfurization tower filled with a desulfurization agent. This is preferable because the naphtha fraction can be easily separated. The temperature for the desulfurization treatment can be selected from the range of 0 to 400 ° C, and preferably from the range of 20 to 380 ° C. In order to promote desulfurization of thiophenes that are not easily desulfurized only by contacting with a desulfurizing agent, desulfurization treatment may be performed in the presence of hydrogen. However, the hydrogen partial pressure is preferably less than 1 MPa, and more preferably less than 0.6 MPa in order to avoid hydrogenation of the olefin and a decrease in RON of the resulting gasoline base material. When the desulfurization treatment is performed by bringing the desulfurizing agent and cracked naphtha fraction into contact with each other in a fixed bed flow type, the LHSV is preferably selected from the range of 0.01 to 10,000 hr −1 .
プレミアムガソリンを製造する場合、用いるガソリン基材は高いオクタン価を有することが望ましい。また、高いオクタン価を有するガソリン基材は、レギュラーガソリンを製造するブレンドの際にも、ブレンドのフレキシビリティを広げる上で好ましい。分解ナフサ留分をさらに分留して、比較的高オクタン価の軽質な分解ナフサ留分を、上記のジエン低減処理、脱硫した物を、他のガソリン基材と混合して本発明の無鉛ガソリン組成物を製造することができる。 When producing premium gasoline, it is desirable that the gasoline base used has a high octane number. In addition, a gasoline base material having a high octane number is preferable in the case of blending for producing regular gasoline in order to expand the flexibility of the blend. The undiluted gasoline composition of the present invention is obtained by further fractionating the cracked naphtha fraction and mixing the light cracked naphtha fraction having a relatively high octane number with the above-mentioned diene reduction treatment and desulfurization with other gasoline base materials. Can be manufactured.
分留及びジエン低減処理後の軽質な分解ナフサ留分は、５容量％留出温度が２５〜４３℃、かつ９５容量％留出温度が５５〜１００℃、オレフィン分が５容量％以上、ジエン価が０.３ｇ／１００ｇ以下であるであることが好ましく、この軽質な分解ナフサ留分は、ジエン低減処理した後に分留して得たものであっても、分留した後にジエン低減処理して得たものであっても、あるいはジエン低減処理と分留を同時に行って得たものであってもよい。また、分留に先立ってあるいは分留中に、硫黄化合物の分子量を大きくする前処理を施しておくと、大きな分子量になった硫黄分は高沸点の重質な分解ナフサ留分中に移動して、軽質な分解ナフサ留分中の硫黄分を簡単な操作で少なくすることができる。以下、前記分留の工程、及び硫黄化合物の分子量を大きくする前処理の工程についてより詳しく説明する。 The light cracked naphtha fraction after fractionation and diene reduction treatment has a 5% by volume distillation temperature of 25 to 43 ° C, a 95% by volume distillation temperature of 55 to 100 ° C, an olefin content of 5% by volume or more, The light cracked naphtha fraction is preferably obtained by fractional distillation after diene reduction treatment, and diene reduction treatment after fractionation is preferable. Or obtained by performing diene reduction treatment and fractional distillation at the same time. In addition, if a pretreatment for increasing the molecular weight of the sulfur compound is performed prior to or during fractional distillation, the sulfur component having a large molecular weight moves into the high-boiling heavy cracked naphtha fraction. Thus, the sulfur content in the light cracked naphtha fraction can be reduced by a simple operation. Hereinafter, the fractionation step and the pretreatment step for increasing the molecular weight of the sulfur compound will be described in more detail.
〔分留工程〕
本発明の無鉛ガソリン組成物の製造方法における分留工程では、接触分解ガソリンを分留して５容量％留出温度が２５.０〜４３.０℃であって、かつ９５容量％留出温度が５５.０〜１００.０℃である接触分解軽質ガソリンなどの軽質な分解ナフサ留分を得る。５容量％留出温度が２５.０℃未満であると、無鉛ガソリン組成物の蒸気圧が高くなる。９５容量％留出温度が８０.０℃、特に１００.０℃を超えると、脱硫接触分解軽質ガソリンの硫黄分が高くなる。５容量％留出温度が４３.０℃を超えたり、９５容量％留出温度が５５.０℃未満であったりすると、無鉛ガソリン組成物の蒸留性状の調整が困難になったり、分留工程で得られる接触分解軽質ガソリンの得率が低下し無鉛ガソリン組成物のコストが高くなったりする。[Fractionation process]
In the fractionation step in the method for producing an unleaded gasoline composition of the present invention, the catalytically cracked gasoline is fractionated to give a 5% by volume distillation temperature of 25.0 to 43.0 ° C and a 95% by volume distillation temperature. A light cracked naphtha fraction, such as catalytically cracked light gasoline, having a 55.0 to 100.0 ° C. When the 5% by volume distillation temperature is less than 25.0 ° C, the vapor pressure of the unleaded gasoline composition increases. If the 95% by volume distillation temperature exceeds 80.0 ° C, particularly 100.0 ° C, the sulfur content of the desulfurized catalytically cracked light gasoline increases. If the 5% by volume distillation temperature exceeds 43.0 ° C. or the 95% by volume distillation temperature is less than 55.0 ° C., it is difficult to adjust the distillation properties of the unleaded gasoline composition, or the fractionation process. The yield of catalytically cracked light gasoline obtained at 1 is reduced and the cost of unleaded gasoline composition is increased.
分留工程で得られる接触分解軽質ガソリンは、チオフェン類硫黄化合物を硫黄分として０.１〜５０質量ｐｐｍ含むことが好ましい。２０質量ｐｐｍ以下、さらには１０質量ｐｐｍ以下であるとなお一層好ましい。チオフェン類硫黄化合物は、後の工程での脱硫処理で得られる脱硫接触分解軽質ガソリン中に残留しやすい硫黄化合物であるため、分留工程で得られる接触分解軽質ガソリンが、硫黄分として５０質量ｐｐｍを超えるチオフェン類硫黄化合物を含んでいると、脱硫工程において、脱硫剤の運転サイクルが短くなり好ましくない。分留工程で得られる接触分解軽質ガソリンが、硫黄分として０.１質量ｐｐｍ未満のチオフェンしか含まないようにすることは、該接触分解軽質ガソリンの得率を低下させるので、好ましくない。 The catalytically cracked light gasoline obtained in the fractionation step preferably contains 0.1 to 50 mass ppm of the thiophene sulfur compound as the sulfur content. It is still more preferable that it is 20 mass ppm or less, Furthermore, it is 10 mass ppm or less. Since the thiophene sulfur compound is a sulfur compound that tends to remain in the desulfurization catalytic cracking light gasoline obtained by the desulfurization treatment in the subsequent step, the catalytic cracking light gasoline obtained in the fractionation step has a sulfur content of 50 mass ppm. If it contains more than thiophene sulfur compounds, the operation cycle of the desulfurizing agent is shortened in the desulfurization step, which is not preferable. It is not preferable that the catalytically cracked light gasoline obtained in the fractionation step contains only thiophene having a sulfur content of less than 0.1 mass ppm because the yield of the catalytically cracked light gasoline is reduced.
また、分留工程で、接触分解ガソリンを分留して軽質な分解ナフサ留分を得ると、当然、比較的重質な分解ナフサ留分も製造することになる。このとき、本発明は重質な分解ナフサ留分を排除するものではなく、５容量％留出温度が２５℃以上、好ましくは２５〜１３０℃、かつ９５容量％留出温度が２１０℃以下、好ましくは５５〜２１０℃、オレフィン分が５質量％以上、ジエン価が０.３ｇ／１００ｇ以下を満足すれば、本発明の無鉛ガソリン組成物、特に比較的低オクタン価のガソリン組成物の製造に低コストで、好適に用いることができる。
通常、接触分解重質ガソリンは接触分解軽質ガソリンよりも硫黄分が多く、特に接触分解重質ガソリン中の硫黄分が５０質量ｐｐｍ以上の場合は、ジエンだけを除去して、水素の共存下で収着機能をもった脱硫剤による処理を行うと、脱硫剤の寿命が著しく短くなる。また、接触分解重質ガソリンは比較的オレフィン量が少ないため、高圧の水素存在下における水素化脱硫でも硫黄分５質量ｐｐｍ程度までならば、比較的オクタン価ロスを損なうことなく脱硫が可能である。したがって、高圧の水素共存下における水素化脱硫によって、オレフィン水素化率を２０％以下、好ましくは１０％以下に抑えながら接触分解重質ガソリン中の硫黄分を２０質量ｐｐｍ以下、好ましくは１０質量ｐｐｍ以下、さらには５質量ｐｐｍ以下に低減した後、水素の共存下で収着機能をもった脱硫剤による処理を行い脱硫することが好ましい。なお、ジエン量の低減については、水素化脱硫の際、脱硫と同時に行うことができる。好ましくはジエン重合等による水素化脱硫触媒や水素化脱硫装置への悪影響を抑制するため、予めジエン低減処理を行うのがよい。In the fractionation step, when catalytic cracked gasoline is fractionated to obtain a light cracked naphtha fraction, naturally a relatively heavy cracked naphtha fraction is also produced. At this time, the present invention does not exclude the heavy cracked naphtha fraction, 5 vol% distillation temperature is 25 ℃ or more, preferably 25 to 130 ℃, 95 vol% distillation temperature is 210 ℃ or less, Preferably, when the olefin content is 55 to 210 ° C., the olefin content is 5% by mass or more, and the diene value is 0.3 g / 100 g or less, the production of the unleaded gasoline composition of the present invention, particularly a gasoline composition having a relatively low octane number, is low. It can be suitably used at a low cost.
Normally, catalytically cracked heavy gasoline has a higher sulfur content than catalytically cracked light gasoline. Especially when the sulfur content in catalytically cracked heavy gasoline is 50 mass ppm or more, only diene is removed and hydrogen is present in the presence of hydrogen. When a treatment with a desulfurizing agent having a sorption function is performed, the life of the desulfurizing agent is remarkably shortened. In addition, since catalytically cracked heavy gasoline has a relatively small amount of olefin, hydrosulfurization in the presence of high-pressure hydrogen can be desulfurized with relatively low octane loss as long as the sulfur content is about 5 ppm by mass. Therefore, the sulfur content in catalytic cracked heavy gasoline is 20 mass ppm or less, preferably 10 mass ppm, while suppressing the olefin hydrogenation rate to 20% or less, preferably 10% or less by hydrodesulfurization in the presence of high-pressure hydrogen. In the following, it is preferable to further desulfurize by reducing to 5 ppm by mass or less and then treating with a desulfurizing agent having a sorption function in the presence of hydrogen. In addition, about the reduction | decrease of the amount of dienes, it can carry out simultaneously with desulfurization in the case of hydrodesulfurization. Preferably, diene reduction treatment is preferably performed in advance in order to suppress adverse effects on the hydrodesulfurization catalyst or hydrodesulfurization apparatus due to diene polymerization or the like.
チオフェン類硫黄化合物の中でもとりわけ、２位にアルキル基をもつチオフェン類硫黄化合物は、脱硫工程で得られる脱硫接触分解軽質ガソリン中に最も残留しやすい硫黄化合物である。接触分解軽質ガソリン中においては、チオフェン類硫黄化合物として主にチオフェン、２−メチルチオフェン、３−メチルチオフェンが含まれるが、２位にアルキル基をもつチオフェン類硫黄化合物としては２−メチルチオフェンが該当する。したがって、分留工程において、２−メチルチオフェンを低減しておくことが好ましい。このためには、分留時の９５容量％留出温度を１００.０℃、特には８５.０℃、さらには７５℃以下とすることが好ましい。分留時の９５容量％留出温度を７５℃以下まで下げると２−メチルチオフェンだけでなく３−メチルチオフェンも接触分解軽質ガソリン中にほとんど含まれなくなるため、このとき含まれるチオフェン類硫黄化合物は主にチオフェンとなる。したがって、分留時の９５容量％留出温度が７５℃以下の場合には、脱硫工程で得られる脱硫接触分解軽質ガソリン中に最も残留しやすい硫黄化合物はチオフェンとなる。 Among the thiophene sulfur compounds, the thiophene sulfur compound having an alkyl group at the 2-position is the sulfur compound most likely to remain in the desulfurized catalytically cracked light gasoline obtained in the desulfurization step. In catalytically cracked light gasoline, thiophene sulfur compounds mainly include thiophene, 2-methylthiophene, and 3-methylthiophene, but 2-thiophene is a thiophene sulfur compound having an alkyl group at the 2-position. To do. Therefore, it is preferable to reduce 2-methylthiophene in the fractionation step. For this purpose, the 95% by volume distillation temperature during fractional distillation is preferably 100.0 ° C., more preferably 85.0 ° C., and even more preferably 75 ° C. or less. When the 95% by volume distillation temperature during fractional distillation is lowered to 75 ° C. or lower, not only 2-methylthiophene but also 3-methylthiophene is hardly contained in the catalytically cracked light gasoline. Mainly thiophene. Therefore, when the 95% by volume distillation temperature during fractional distillation is 75 ° C. or lower, the sulfur compound most likely to remain in the desulfurized catalytically cracked light gasoline obtained in the desulfurization step is thiophene.
〔硫黄化合物の分子量を大きくする前処理〕
分留工程に供する接触分解ガソリンについて、含まれる硫黄化合物の分子量を大きくする前処理を行って分留工程に供するか、あるいは分留と同時に硫黄化合物の分子量を大きくする前処理を行うことが好ましい。チオール類などの硫黄化合物の分子量を選択的に大きくすることにより、その含硫黄化合物の沸点が高くなるため、分留工程において、含硫黄化合物を接触分解重質ガソリン中に移行することができ、分留工程で得られる接触分解軽質ガソリンの硫黄分を低減することができる。具体的には、接触分解軽質ガソリンのチオール類の含有量を硫黄分として合計０.１質量ｐｐｍ以下にすると一層好ましい。[Pretreatment to increase the molecular weight of sulfur compounds]
About catalytically cracked gasoline to be subjected to the fractionation step, it is preferable to perform a pretreatment for increasing the molecular weight of the contained sulfur compound to be used for the fractionation step, or to perform a pretreatment for increasing the molecular weight of the sulfur compound simultaneously with the fractionation. . By selectively increasing the molecular weight of the sulfur compound such as thiols, the boiling point of the sulfur-containing compound is increased, so that the sulfur-containing compound can be transferred into catalytically cracked heavy gasoline in the fractionation step, The sulfur content of the catalytically cracked light gasoline obtained in the fractionation process can be reduced. Specifically, it is more preferable that the content of thiols in the catalytically cracked light gasoline is 0.1 mass ppm or less in terms of the sulfur content.
従来から石油精製においては、チオール類を処理して製品を無臭化するためのスイートニングが行われるが、酸化法や酸化抽出法によって、チオール類をジスルフィド類に転化する公知の方法は、本発明において硫黄化合物の分子量を大きくする方法として適用できる。具体的には、マーロックス法、ドクター法などが好ましく用いられる（産業図書株式会社、石油精製技術便覧第３版、1981、参照）。 Conventionally, in petroleum refining, sweetening for treating thiols to make the product non-brominated is performed, but a known method for converting thiols to disulfides by an oxidation method or an oxidation extraction method is the present invention. Can be applied as a method of increasing the molecular weight of the sulfur compound. Specifically, the Marlox method, the doctor method and the like are preferably used (see Sangyo Tosho Co., Ltd., Petroleum Refining Technology Handbook 3rd Edition, 1981).
また、本発明において硫黄化合物の分子量を大きくする方法として、分解ナフサ留分に含まれる硫黄化合物とオレフィン類とを反応させる方法も好適に用いられる。具体的には、チオール類とオレフィン類とを反応させる方法（特開２００１-５５５８４号公報参照）やチオール類やチオフェン類をオレフィン類と反応させる方法（“Production of Low Sulfur Gasoline and Diesel Fuels: Tier 2 and Beyond”, Petroleum Refining Technology Seminar August 2001, 11-18、参照）が挙げられる。また、特に好ましくは硫黄化合物の分子量を大きくする処理とジエン低減処理を同時にできるプロセスを用いるのがよい。具体的には、前記のSHUプロセスが好適に用いられる。さらには、分留を行いながら、硫黄化合物の分子量を大きくする処理とジエン低減処理を同時にできるプロセスを用いるのがいっそう好ましい。具体的には、前記のCD Hydroプロセスが好適に用いられる。 In the present invention, as a method for increasing the molecular weight of the sulfur compound, a method of reacting the sulfur compound contained in the cracked naphtha fraction with olefins is also preferably used. Specifically, a method of reacting thiols with olefins (see JP 2001-55584 A) or a method of reacting thiols or thiophenes with olefins (“Production of Low Sulfur Gasoline and Diesel Fuels: Tier 2 and Beyond ”, Petroleum Refining Technology Seminar August 2001, 11-18). Further, it is particularly preferable to use a process capable of simultaneously performing a treatment for increasing the molecular weight of the sulfur compound and a diene reduction treatment. Specifically, the above SHU process is preferably used. Furthermore, it is more preferable to use a process capable of simultaneously performing a treatment for increasing the molecular weight of the sulfur compound and a diene reduction treatment while performing fractional distillation. Specifically, the CD Hydro process is preferably used.
〔ブレンド工程に用いられる他のガソリン基材〕
ブレンド工程で混合される他のガソリン基材としては、接触改質ガソリン基材、アルキレートガソリン基材、直留ナフサを脱硫処理した基材、異性化ガソリン基材、ナフサクラッカーから生成したナフサ基材、トルエン、キシレン及びＭＴＢＥ、エチルｔ−ブチルエーテル（ＥＴＢＥ）、ｔ−アミルエチルエーテル（ＴＡＥＥ）、エタノール、メタノール等の含酸素ガソリン基材等、公知のガソリン基材を用いることができる。ブレンド工程で混合される他のガソリン基材は、硫黄分が１０質量ｐｐｍ以下であり、好ましくは３質量ｐｐｍ以下、さらには１質量ｐｐｍ以下、特には０.５質量ｐｐｍ以下であることが好ましい。他のガソリン基材の硫黄分が１０質量ｐｐｍを超えると、そのガソリン基材のブレンド工程での配合量が制約され、好ましくない。[Other gasoline base materials used in the blending process]
Other gasoline base materials mixed in the blending process include catalytic reformed gasoline base materials, alkylate gasoline base materials, base materials obtained by desulfurizing straight-run naphtha, isomerized gasoline base materials, and naphtha bases generated from naphtha crackers. Known gasoline base materials such as oxygen-containing gasoline base materials such as wood, toluene, xylene and MTBE, ethyl t-butyl ether (ETBE), t-amyl ethyl ether (TAEE), ethanol and methanol can be used. The other gasoline base material mixed in the blending process has a sulfur content of 10 mass ppm or less, preferably 3 mass ppm or less, more preferably 1 mass ppm or less, and particularly preferably 0.5 mass ppm or less. . When the sulfur content of other gasoline base materials exceeds 10 mass ppm, the blending amount in the blending process of the gasoline base materials is restricted, which is not preferable.
好ましい配合量について各リサーチ法オクタン価別に説明する。例えば、リサーチ法オクタン価が９６〜１０２の場合の好ましい配合量は、脱硫分解ナフサ留分を２５〜８０容量％、特には３０〜５０容量％、接触改質ガソリン基材を２５〜５０容量％、特には３０〜４５容量％、アルキレートガソリン基材を１０〜４０容量％、特には１５〜３０容量％である。
リサーチ法オクタン価が９３〜９６の場合の好ましい配合量は、脱硫分解ナフサ留分を５０〜９０容量％特には６０〜８０容量％、接触改質ガソリン基材を５〜３５容量％、特には１０〜２５容量％、アルキレートガソリン基材を１０〜２５容量％、特には５〜１５容量％である。
リサーチ法オクタン価が８９〜９３の場合の好ましい配合量は、脱硫分解ナフサ留分を５５〜９０容量％、特には６５〜８５容量％、接触改質ガソリン基材を０〜２０容量％、特には５〜１５容量％、アルキレートガソリン基材を０〜１５容量％、特には０〜１０容量％である。A preferable blending amount will be described for each research method octane number. For example, when the research octane number is 96 to 102, the preferable blending amount is 25 to 80% by volume of the desulfurization cracked naphtha fraction, particularly 30 to 50% by volume, 25 to 50% by volume of the catalytic reformed gasoline base, In particular, it is 30 to 45% by volume, 10 to 40% by volume, especially 15 to 30% by volume of the alkylate gasoline base.
A preferable blending amount when the research octane number is 93 to 96 is 50 to 90% by volume of desulfurization cracking naphtha fraction, particularly 60 to 80% by volume, and 5 to 35% by volume of catalytic reformed gasoline base material, particularly 10 -25% by volume, 10-25% by volume of alkylate gasoline base, in particular 5-15% by volume.
A preferable blending amount when the research octane number is 89 to 93 is 55 to 90% by volume of desulfurization cracking naphtha fraction, particularly 65 to 85% by volume, and 0 to 20% by volume of catalytic reformed gasoline base, particularly 5 to 15% by volume, 0 to 15% by volume, especially 0 to 10% by volume of alkylate gasoline base.
〔添加剤〕
さらに、本発明のガソリン組成物には、当業界で公知の燃料油添加剤の１種又は２種以上を必要に応じて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配合量を０.１質量％以下に維持することが好ましい。本発明のガソリンで使用可能な燃料油添加剤を例示すれば、フェノール系、アミン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、多価アルコール又は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又は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、アゾ染料などの着色剤を挙げることができる。〔Additive〕
Furthermore, the gasoline composition of the present invention may contain one or more fuel oil additives known in the art as needed. Although these compounding quantities can be selected suitably, it is preferable to maintain the total compounding quantity of an additive to 0.1 mass% or less normally. Examples of fuel oil additives that can be used in the gasoline of the present invention include phenolic, amine-based antioxidants, Schiff-type compounds, metal deactivators such as thioamide-type compounds, and organic phosphorus-based surfaces. Anti-ignition agent, detergent / dispersant such as succinimide, polyalkylamine, polyetheramine, anti-icing agent such as polyhydric alcohol or its ether, alkali metal salt or alkaline earth metal salt of organic acid, sulfuric acid of higher alcohol Examples include an auxiliary combustor such as an ester, an anionic surfactant, a cationic surfactant, an antistatic agent such as an amphoteric surfactant, and a colorant such as an azo dye.
〔無鉛ガソリン組成物〕
本発明の無鉛ガソリン組成物は、リサーチ法オクタン価が８９.０以上、５０容量％留出温度が１０５℃以下で、オレフィン分が１０容量％以上、全硫黄分が１質量ｐｐｍ以下、全硫黄分に占めるチオフェン類硫黄化合物の割合が硫黄分として５０〜１００質量％である。好ましくは、リサーチ法オクタン価の下限が、９３.０以上、特には９６.０以上、上限が通常１０２.０以下、全オレフィン分に占める沸点範囲３５〜１００℃のオレフィン分が９０容量％以上、全硫黄分に占めるチオフェン及び２−メチルチオフェンの合計量の割合が硫黄分として５０質量％以上、さらには７０質量％以上、チオール類の含有量が硫黄分として０.１質量ｐｐｍ以下である。[Unleaded gasoline composition]
The unleaded gasoline composition of the present invention has a research octane number of 89.0 or more, a 50% by volume distillation temperature of 105 ° C. or less, an olefin content of 10% by volume or more, a total sulfur content of 1 mass ppm or less, and a total sulfur content. The ratio of the thiophene sulfur compound in the total is 50 to 100% by mass as the sulfur content. Preferably, the lower limit of the research octane number is 93.0 or more, particularly 96.0 or more, the upper limit is usually 102.0 or less, and the olefin content in the boiling range 35 to 100 ° C. in the total olefin content is 90% by volume or more. The ratio of the total amount of thiophene and 2-methylthiophene in the total sulfur content is 50 mass% or more, further 70 mass% or more as the sulfur content, and the content of thiols is 0.1 mass ppm or less as the sulfur content.
以下に、実施例に基づいて本発明をより詳しく説明するが、本発明は下記の実施例に限定されるものではない。
ガソリン基材の調製１
アルミナにニッケルを２０質量％担持した触媒５ｃｍ３をｎ−ヘプタンにジメチルジスルフィドを２質量％溶かした溶液を用い３００℃にて硫化した後、反応温度２５０℃、反応圧力常圧、液空間速度（ＬＨＳＶ）４ｈｒ-１、Ｈ２／Ｏｉｌ比３４０ＮＬ／Ｌの条件のもと、中東系原油の減圧軽油留分を水素化精製処理したものを主たる原料油とする流動接触分解で得られた接触分解ガソリンＡを通油してジエン低減処理を行い、接触分解ガソリンＢを得た。共沈法にて調製した銅亜鉛アルミニウム複合酸化物（銅含有量３５質量％、亜鉛含有量３５質量％、アルミニウム含有量５質量％）５ｃｍ３を反応管に充填し、これに水素ガスを５ｃｍ３／ｍｉｎ、温度２００℃の条件にて１６ｈｒ流通させ、還元処理を行った。その後、この反応管に接触分解ガソリンＢを、反応温度１００℃、反応圧力常圧、ＬＨＳＶ２.０ｈｒ-１、Ｈ２／Ｏｉｌ比０.０６ＮＬ／Ｌの条件のもと２０時間通油して収着機能をもった脱硫剤によって脱硫した脱硫接触分解ガソリンＣを得た。接触分解ガソリンＡ、接触分解ガソリンＢ及び脱硫接触分解ガソリンＣの性状は、表１のとおりであった。Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the following examples.
Preparation of gasoline base material 1
After 5 cm 3 of a catalyst having 20% by mass of nickel supported on alumina was sulfurized at 300 ° C. using a solution of 2% by mass of dimethyl disulfide in n-heptane, the reaction temperature was 250 ° C., the reaction pressure was normal pressure, the liquid space velocity ( LHSV) 4hr -1, H 2 / oil ratio under the conditions of 340NL / L, catalytic cracking obtained by fluid catalytic cracking of a main raw material oil that treated hydrotreated vacuum gas oil fraction Middle Eastern crude Gasoline A was passed through to reduce the diene, and catalytic cracking gasoline B was obtained. A reaction tube was filled with 5 cm 3 of copper-zinc-aluminum composite oxide (copper content 35 mass%, zinc content 35 mass%, aluminum content 5 mass%) prepared by coprecipitation method, and hydrogen gas was added 5 cm to this. The reduction treatment was performed by circulating for 16 hours under the conditions of 3 / min and a temperature of 200 ° C. Thereafter, catalytic cracked gasoline B was passed through the reaction tube for 20 hours under the conditions of a reaction temperature of 100 ° C., a reaction pressure of normal pressure, LHSV of 2.0 hr −1 , and an H 2 / Oil ratio of 0.06 NL / L. Desulfurized catalytic cracking gasoline C desulfurized with a desulfurizing agent having an adhesion function was obtained. Properties of catalytic cracking gasoline A, catalytic cracking gasoline B and desulfurized catalytic cracking gasoline C are shown in Table 1.
なお、密度はＪＩＳ Ｋ ２２４９、蒸気圧はＪＩＳ Ｋ ２２５８、蒸留性状はＪＩＳ Ｋ ２２５４、ジエン価はＵＯＰ３２６−８２に準拠して測定した。硫黄分は、ＡＳＴＭ Ｄ ５４５３（紫外蛍光法）に準拠して測定した。硫黄化合物の含有量（硫黄換算）は、化学発光によって硫黄化合物を選択的に検出、定量するＡＮＴＥＫ製硫黄化学発光検出器を備えた島津製作所製ガスクロマトグラフ装置を用いて、ガスクロマトグラフ法で測定した。炭化水素成分組成及びＲＯＮは、ヒューレットパッカード社製ＰＩＯＮＡ装置を用いて、ガスクロマトグラフ法で測定した。 The density was measured according to JIS K 2249, the vapor pressure was measured according to JIS K 2258, the distillation property was measured according to JIS K 2254, and the diene value was measured according to UOP 326-82. The sulfur content was measured according to ASTM D 5453 (ultraviolet fluorescence method). The sulfur compound content (sulfur equivalent) was measured by gas chromatography using a Shimadzu gas chromatograph equipped with an ANTEK sulfur chemiluminescence detector that selectively detects and quantifies sulfur compounds by chemiluminescence. . The hydrocarbon component composition and RON were measured by a gas chromatograph method using a PIONA device manufactured by Hewlett-Packard Company.
接触分解ガソリンＡはジエン価０.６ｇ／１００ｇであったが、接触分解ガソリンＢはジエン価が０.１ｇ／１００ｇとなりジエンがほぼ除去されていた。接触分解ガソリンＢは５.０質量ｐｐｍの硫黄分を含んでいたが、脱硫剤による処理によって硫黄分０.２質量ｐｐｍの脱硫接触分解ガソリンＣが得られた。得られた脱硫接触分解ガソリンＣは、チオフェン類を０.２質量ｐｐｍ含んでいたが、その他の硫黄化合物は含んでいなかった。 The catalytically cracked gasoline A had a diene value of 0.6 g / 100 g, but the catalytically cracked gasoline B had a diene value of 0.1 g / 100 g, and the diene was almost removed. Although catalytic cracking gasoline B contained 5.0 mass ppm of sulfur, desulfurization catalytic cracking gasoline C having a sulfur content of 0.2 mass ppm was obtained by treatment with a desulfurizing agent. The obtained desulfurized catalytic cracking gasoline C contained 0.2 mass ppm of thiophenes but did not contain other sulfur compounds.
ガソリン基材の調製２
前記ガソリン基材の調製１と同様にして中東系原油から得られた別のロットの接触分解ガソリンＤを軽質分と重質分に分留し、接触分解軽質ガソリンＥを得た。この接触分解軽質ガソリンＥを用い、反応温度を２００℃、ＬＨＳＶを２ｈｒ-１とした以外、前記ガソリン基材の調製１と同様にジエン低減処理を行い、接触分解軽質ガソリンＦを得た。次いで、ガソリン基材の調製１と全く同じ方法、条件で、接触分解軽質ガソリンＦを脱硫して脱硫接触分解軽質ガソリンＧを得た。接触分解ガソリンＤ、接触分解軽質ガソリンＥ、接触分解軽質ガソリンＦ及び脱硫接触分解軽質ガソリンＧの性状は、表２のとおりであった。 Preparation of gasoline base material 2
In the same manner as in the preparation of the gasoline base material, another batch of catalytic cracked gasoline D obtained from Middle Eastern crude oil was fractionated into a light fraction and a heavy fraction to obtain catalytic cracked light gasoline E. Using this catalytically cracked light gasoline E, except that the reaction temperature was 200 ° C. and LHSV was 2 hr −1 , the diene reduction treatment was performed in the same manner as in preparation of the gasoline base material to obtain catalytically cracked light gasoline F. Subsequently, catalytic cracking light gasoline F was desulfurized under exactly the same method and conditions as in preparation of gasoline base material 1 to obtain desulfurized catalytic cracking light gasoline G. Properties of catalytic cracking gasoline D, catalytic cracking light gasoline E, catalytic cracking light gasoline F and desulfurized catalytic cracking light gasoline G were as shown in Table 2.
接触分解軽質ガソリンＥはジエン価１.６ｇ／１００ｇであったが、接触分解軽質ガソリンＦはジエン価が０.１ｇ／１００ｇとなりジエンがほぼ除去されていた。接触分解軽質ガソリンＦは１４質量ｐｐｍの硫黄分を含んでいたが、脱硫剤による処理によって硫黄分０.２質量ｐｐｍの脱硫接触分解軽質ガソリンＧが得られた。得られた脱硫接触分解軽質ガソリンＧは、２−メチルチオフェンを０.２質量ｐｐｍ含んでいたが、チオフェン及び３-メチルチオフェンは含んでいなかった。 The catalytically cracked light gasoline E had a diene value of 1.6 g / 100 g, whereas the catalytically cracked light gasoline F had a diene value of 0.1 g / 100 g, and the diene was almost removed. Catalytic cracked light gasoline F contained 14 mass ppm of sulfur, but desulfurized catalytic cracked light gasoline G having a sulfur content of 0.2 mass ppm was obtained by treatment with a desulfurizing agent. The obtained desulfurized catalytically cracked light gasoline G contained 0.2 mass ppm of 2-methylthiophene, but did not contain thiophene and 3-methylthiophene.
ガソリン基材の調製３
接触分解ガソリンＤをスイートニング処理し接触分解ガソリンＨを得た。接触分解ガソリンＨを軽質分と重質分に分留し、接触分解軽質ガソリンＩを得た。ガソリン基材の調製２と同じ方法によって、接触分解軽質ガソリンＩに対してジエン低減処理を行い、接触分解軽質ガソリンＪを得た。この接触分解軽質ガソリンＪを、ガソリン基材の調製１にて調製した銅亜鉛複合酸化物を用い、ガソリン基材の調製１と同じ条件にて脱硫処理を行い、脱硫接触分解軽質ガソリンＫを得た。接触分解ガソリンＨ、接触分解軽質ガソリンＩ、ジエンを除去した接触分解軽質ガソリンＪ及び脱硫接触分解軽質ガソリンＫの性状は、表３のとおりであった。 Preparation of gasoline base 3
The catalytic cracking gasoline D was sweetened and the catalytic cracking gasoline H was obtained. Catalytic cracking gasoline H was fractionated into light and heavy fractions to obtain catalytic cracking light gasoline I. Diene reduction treatment was performed on catalytically cracked light gasoline I by the same method as Preparation 2 of the gasoline base material to obtain catalytically cracked light gasoline J. This catalytic cracking light gasoline J is desulfurized under the same conditions as in gasoline base material preparation 1 using the copper zinc composite oxide prepared in gasoline base material preparation 1 to obtain desulfurized catalytic cracking light gasoline K. It was. Properties of catalytic cracking gasoline H, catalytic cracking light gasoline I, catalytic cracking light gasoline J from which diene was removed, and desulfurized catalytic cracking light gasoline K were as shown in Table 3.
接触分解ガソリンＤに含まれていた軽質チオール類は、スイートニング処理によって、より高分子量のジスルフィド類に転化していた。接触分解軽質ガソリンＩはジエン価１.６ｇ／１００ｇであったが、接触分解軽質ガソリンＪはジエン価が０.１ｇ／１００ｇとなりジエンがほぼ除去されていた。接触分解軽質ガソリンＪは、１１質量ｐｐｍの硫黄分を含んでいたが、脱硫剤で処理することにより、硫黄分０.２質量ｐｐｍの脱硫接触分解軽質ガソリンＫが得られた。得られた脱硫接触分解軽質ガソリンＫは、２−メチルチオフェンを０.２質量ｐｐｍ含んでいたが、チオフェン及び３-メチルチオフェンを含んでいなかった。分留する前にスイートニングすることによってチオール類はジスルフィドとなり重質分に移行するため、接触分解軽質ガソリン中の硫黄分はスイートニングしない場合の２１質量ｐｐｍと比べて１１質量ｐｐｍに低減できる。これにより、収着剤の負荷が低減できるため、収着剤を長寿命化できると考えられる。 Light thiols contained in the catalytic cracking gasoline D were converted to higher molecular weight disulfides by sweetening treatment. The catalytically cracked light gasoline I had a diene value of 1.6 g / 100 g, whereas the catalytically cracked light gasoline J had a diene value of 0.1 g / 100 g, and the diene was almost removed. Catalytic cracking light gasoline J contained 11 mass ppm of sulfur, but desulfurization catalytic cracking light gasoline K having a sulfur content of 0.2 mass ppm was obtained by treatment with a desulfurizing agent. The obtained desulfurized catalytically cracked light gasoline K contained 0.2 mass ppm of 2-methylthiophene, but did not contain thiophene and 3-methylthiophene. By sweetening before fractionation, the thiols become disulfides and shift to heavy components, so the sulfur content in the catalytically cracked light gasoline can be reduced to 11 ppm by mass compared to 21 ppm by mass when not sweetened. Thereby, since the load of a sorbent can be reduced, it is thought that a lifetime of a sorbent can be extended.
ガソリン基材の調製４
接触分解ガソリンＡ及び接触分解軽質ガソリンＥをそれぞれガソリン基材の調製１にて調製した銅亜鉛複合酸化物を用い、ガソリン基材の調製１と同じ条件にて脱硫処理を行い、脱硫接触分解ガソリンＬ及び脱硫接触分解軽質ガソリンＭを得た。脱硫接触分解ガソリンＬ及び脱硫接触分解軽質ガソリンＭの性状は、表４のとおりであった。 Preparation of gasoline base 4
Catalytic cracking gasoline A and catalytic cracking light gasoline E were each subjected to desulfurization treatment using the copper-zinc composite oxide prepared in gasoline base preparation 1 under the same conditions as in gasoline base preparation 1, and desulfurized catalytic cracking gasoline L and desulfurized catalytic cracking light gasoline M was obtained. Table 4 shows the properties of the desulfurized catalytic cracked gasoline L and the desulfurized catalytic cracked light gasoline M.
脱硫接触分解ガソリンＬには３.６質量ｐｐｍの硫黄分が含まれており、また、脱硫接触分解軽質ガソリンＭは１１質量ｐｐｍの硫黄分が含まれており、ともに、ジエンを除去しないで収着処理を行うと特にチオフェン類硫黄化合物の除去が困難であることが明らかである。 Desulfurized catalytic cracking gasoline L contains 3.6 mass ppm of sulfur, and desulfurized catalytic cracking light gasoline M contains 11 mass ppm of sulfur, both of which are collected without removing diene. It is clear that the removal of the thiophene sulfur compound is particularly difficult when the deposition treatment is performed.
ガソリン基材の調製５
接触分解以外の公知技術で得られるガソリン基材として、脱硫直留ナフサＮ、接触改質中質油Ｏ、接触改質重質油Ｐ、アルキレートガソリンＱ、ＥＴＢＥ基材Ｒがあり、その性状は表５に示すとおりである。接触改質中質油Ｏは、接触改質ガソリンから、トルエンを多く含む留分を蒸留分離したものである。接触改質重質油Ｐは、接触改質ガソリンから、炭素数９以上であって１１未満の芳香族を蒸留分離したものである。 Preparation of gasoline base material 5
Gasoline base materials obtained by known techniques other than catalytic cracking include desulfurization straight-run naphtha N, catalytic reforming medium oil O, catalytic reforming heavy oil P, alkylate gasoline Q, ETBE base material R, and their properties. Is as shown in Table 5. The catalytic reforming medium oil O is obtained by distilling and separating a fraction rich in toluene from catalytic reforming gasoline. The catalytically modified heavy oil P is obtained by distilling and separating aromatics having 9 or more carbon atoms and less than 11 from catalytically modified gasoline.
脱硫直留ナフサＮを１０.０容量％、接触改質中質油Ｏを５.０容量％、接触改質重質油Ｐを５.０容量％、アルキレートガソリンＱを５.０容量％と、ガソリン基材の調製１記載の脱硫接触分解ガソリンＣを７５.０容量％配合し、無鉛ガソリン組成物Ｓを調製した。また、添加剤として、着色剤（シラド化学製ＣＬ−５３）２ｍｇ/Ｌ、酸化防止剤（住友化学工業製スミライザー４ＭＬ）２０ｍｇ/Ｌ、清浄分散剤（ビーエーエスエフ製Ｋｅｒｏｐｕｒ ＡＰ−９５）１００ｍｇ/Ｌをそれぞれ添加した。なお、この添加剤の添加は、下記の実施例及び比較例の無鉛ガソリン組成物の調製においても全く同じ方法で行った。調製した無鉛ガソリン組成物Ｓの性状を表６に示す。 Desulfurization straight-run naphtha N is 10.0% by volume, catalytic reforming medium oil O is 5.0% by volume, catalytic reforming heavy oil P is 5.0% by volume, alkylate gasoline Q is 5.0% by volume. And 75.0% by volume of desulfurized catalytic cracking gasoline C described in Preparation 1 of gasoline base material to prepare an unleaded gasoline composition S. Moreover, as an additive, a coloring agent (CL-53 manufactured by Shirad Chemical Co., Ltd.) 2 mg / L, an antioxidant (Sumilyzer 4ML manufactured by Sumitomo Chemical Co., Ltd.) 20 mg / L, a cleaning dispersant (Keropur AP-95 manufactured by BASF) 100 mg / L Was added respectively. The addition of this additive was performed in exactly the same manner in the preparation of the unleaded gasoline compositions of the following Examples and Comparative Examples. Table 6 shows the properties of the prepared unleaded gasoline composition S.
また、脱硫直留ナフサＮを３.５容量％、接触改質中質油Ｏを１９.０容量％、接触改質重質油Ｐを１５.０容量％、アルキレートガソリンＱを２３.０容量％と、ガソリン基材の調製３記載の脱硫接触分解軽質ガソリンＫを３９.５容量％配合し、無鉛ガソリン組成物Ｔを調製した。無鉛ガソリン組成物Ｔの性状を表６に示す。 Also, desulfurized straight-run naphtha N is 3.5% by volume, catalytic reforming medium oil O is 19.0% by volume, catalytic reforming heavy oil P is 15.0% by volume, and alkylate gasoline Q is 23.0%. The unleaded gasoline composition T was prepared by blending 39.5% by volume of the desulfurization catalytic cracking light gasoline K described in Preparation 3 of the gasoline base. Table 6 shows the properties of the unleaded gasoline composition T.
脱硫直留ナフサＮを６.０容量％、接触改質中質油Ｏを８.０容量％、接触改質重質油Ｐを５.０容量％、アルキレートガソリンＱを８.０容量％、ＥＴＢＥ基材Ｒを６.０容量％と、ガソリン基材の調製１記載の脱硫接触分解ガソリンＣを６７.０容量％配合し、無鉛ガソリン組成物Ｕを調製した。無鉛ガソリン組成物Ｕの性状を表６に示す。 Desulfurization straight-run naphtha N is 6.0% by volume, catalytic reforming medium oil O is 8.0% by volume, catalytic reforming heavy oil P is 5.0% by volume, alkylate gasoline Q is 8.0% by volume. An unleaded gasoline composition U was prepared by blending 6.0% by volume of ETBE base material R and 67.0% by volume of desulfurization catalytic cracking gasoline C described in Preparation 1 for gasoline base material. Table 6 shows the properties of the unleaded gasoline composition U.
脱硫直留ナフサＮを６.０容量％、接触改質中質油Ｏを９.０容量％、接触改質重質油Ｐを８.０容量％、アルキレートガソリンＱを１０.０容量％と、ガソリン基材の調製１記載の脱硫接触分解ガソリンＣを５７.０容量％、ガソリン基材の調製３記載の脱硫接触分解軽質ガソリンＫを１０.０容量％配合し、無鉛ガソリン組成物Ｖを調製した。無鉛ガソリン組成物Ｖの性状を表６に示す。 Desulfurization straight-run naphtha N is 6.0% by volume, catalytic reforming medium oil O is 9.0% by volume, catalytic reforming heavy oil P is 8.0% by volume, alkylate gasoline Q is 10.0% by volume. And 57.0% by volume of desulfurized catalytic cracking gasoline C described in Preparation 1 of the gasoline base material and 10.0% by volume of desulfurized catalytic cracking light gasoline K described in Preparation 3 of the gasoline base material, and lead-free gasoline composition V Was prepared. Table 6 shows the properties of the unleaded gasoline composition V.
脱硫接触分解ガソリンＣを用いる代わりに、接触分解ガソリンＡを用いた以外は、実施例１の無鉛ガソリン組成物Ｓの場合と全く同じ処方で、無鉛ガソリン組成物Ｗを調製した。無鉛ガソリン組成物Ｗの性状を表６に示す。 Instead of using desulfurized catalytic cracking gasoline C, an unleaded gasoline composition W was prepared with exactly the same formulation as the unleaded gasoline composition S of Example 1 except that catalytic cracking gasoline A was used. Table 6 shows the properties of the unleaded gasoline composition W.
ガソリン基材の調製３記載の脱硫接触分解軽質ガソリンＫを用いる代わりに、ガソリン基材の調製３記載の接触分解軽質ガソリンＩを用いた以外は、実施例２の無鉛ガソリン組成物Ｔの場合と全く同じ処方で、無鉛ガソリン組成物Ｘを調製した。無鉛ガソリン組成物Ｘの性状を表６に示す。 In the case of the unleaded gasoline composition T of Example 2, except that the catalytically cracked light gasoline I described in Preparation 3 of the gasoline base was used instead of using the desulfurized catalytically cracked light gasoline K described in Preparation 3 of the gasoline base An unleaded gasoline composition X was prepared with exactly the same formulation. Table 6 shows the properties of the unleaded gasoline composition X.
表６によれば、本発明によって提供される無鉛ガソリン組成物Ｓは、従来技術によって提供される無鉛ガソリン組成物Ｗと比較して、他の性状をほとんど変えることなく、硫黄分を１質量ｐｐｍ以下に低減できることが明らかである。また、本発明によって提供される無鉛ガソリン組成物Ｔも対応する無鉛ガソリン組成物Ｘと比較して、他の性状をほとんど変えることなく、硫黄分を１質量ｐｐｍ以下に低減できる。本発明によって提供される無鉛ガソリン組成物Ｕ、Ｖも硫黄分を１質量ｐｐｍ以下に低減できる。 According to Table 6, the unleaded gasoline composition S provided by the present invention has a sulfur content of 1 ppm by mass with almost no other change compared to the unleaded gasoline composition W provided by the prior art. It is clear that the following can be reduced. Moreover, compared with the corresponding unleaded gasoline composition X, the unleaded gasoline composition T provided by the present invention can reduce the sulfur content to 1 ppm by mass or less without changing other properties. The unleaded gasoline compositions U and V provided by the present invention can also reduce the sulfur content to 1 ppm by mass or less.
ガソリン基材の調製６
上記のガソリン基材の調製１とは異なるロットの中東系原油をガソリン基材の調製１と同様に処理して得られた接触分解ガソリンＡＡをスイートニング処理した後、軽質分と重質分に分留し、重質分を接触分解重質ガソリンＢＢとして得た。この接触分解重質ガソリンＢＢをコバルト、モリブデンおよびリンをアルミナに担持した触媒（コバルト含有量２.４質量％、モリブデン含有量９.４質量％、リン含有量２.０質量％）を用い、反応温度２２０℃、反応圧力１.０ＭＰａ、ＬＨＳＶ４.０ｈｒ−１、Ｈ２／Ｏｉｌ比３０７ＮＬ／Ｌの条件下にてジエン低減処理を行い、ジエンを除去してジエン価が０.６ｇ／１００ｇから０.１ｇ／１００ｇ未満の接触分解重質ガソリンＣＣを得た。この、ジエン除去接触分解重質ガソリンＣＣを、Ｈ２／Ｏｉｌ比を０.１８ＮＬ／Ｌとした以外はガソリン基材の調製１と全く同じ方法、条件で脱硫し、硫黄分０.９質量ｐｐｍの脱硫接触分解重質ガソリンＤＤを得た。各ガソリン（接触分解ガソリンＡＡ〜脱硫接触分解重質ガソリンＤＤ）の性状を表７に示す。 Preparation of gasoline base 6
After sweetening the catalytically cracked gasoline AA obtained by treating Middle Eastern crude oil different from the above gasoline base preparation 1 in the same manner as gasoline base preparation 1, it is converted into light and heavy components. Fractionation was carried out to obtain a heavy component as catalytic cracked heavy gasoline BB. A catalyst (cobalt content 2.4 mass%, molybdenum content 9.4 mass%, phosphorus content 2.0 mass%) in which catalytic cracked heavy gasoline BB is supported on cobalt, molybdenum and phosphorus on alumina is used. Diene reduction treatment is carried out under conditions of a reaction temperature of 220 ° C., a reaction pressure of 1.0 MPa, LHSV of 4.0 hr −1 , and an H 2 / Oil ratio of 307 NL / L, and the diene is removed to reduce the diene number from 0.6 g / 100 g. A catalytically cracked heavy gasoline CC of less than 0.1 g / 100 g was obtained. This diene-removed catalytic cracked heavy gasoline CC was desulfurized in exactly the same manner and under the same conditions as in the gasoline base preparation 1 except that the H 2 / Oil ratio was 0.18 NL / L, and the sulfur content was 0.9 mass ppm. The desulfurization catalytic cracking heavy gasoline DD was obtained. Table 7 shows the properties of each gasoline (catalytic cracked gasoline AA to desulfurized catalytic cracked heavy gasoline DD).
ガソリン基材の調製７
前記のガソリン基材の調製６で用いた接触分解重質ガソリンＢＢを、ジエン低減処理を行うことなく、Ｈ２／Ｏｉｌ比を０.１８ＮＬ／Ｌとした以外はガソリン基材の調製１と全く同じ方法、条件で脱硫し、脱硫接触分解重質ガソリンＥＥを得た。脱硫接触分解重質ガソリンＥＥの性状を表７に示す。 Preparation of gasoline base material 7
The catalytically cracked heavy gasoline BB used in Preparation 6 of the gasoline base was completely the same as Preparation 1 of the gasoline base except that the H 2 / Oil ratio was changed to 0.18 NL / L without performing diene reduction treatment. Desulfurization was performed in the same manner and conditions to obtain desulfurized catalytic cracked heavy gasoline EE. Table 7 shows the properties of desulfurized catalytic cracked heavy gasoline EE.
脱硫直留ナフサＮを１０.０容量％、接触改質中質油Ｏを７.０容量％、接触改質重質油Ｐを５.０容量％、アルキレートガソリンＱを６.０容量％と、ガソリン基材の調製３記載の脱硫接触分解軽質ガソリンＫを３７.０容量％、及びガソリン基材の調製６記載の脱硫接触分解重質ガソリンＤＤを３５．０容量％配合し、無鉛ガソリン組成物Ｙを調製した。無鉛ガソリン組成物Ｙの性状を表６に示す。 Desulfurization straight-run naphtha N is 10.0% by volume, catalytic reforming medium oil O is 7.0% by volume, catalytic reforming heavy oil P is 5.0% by volume, alkylate gasoline Q is 6.0% by volume. And 37.0% by volume of desulfurized catalytically cracked light gasoline K described in Preparation 3 of the gasoline base material and 35.0% by volume of desulfurized catalytically cracked heavy gasoline DD described in Preparation 6 of the gasoline base material. Composition Y was prepared. Table 6 shows the properties of the unleaded gasoline composition Y.
脱硫接触分解重質ガソリンＤＤの代わりにガソリン基材の調製７記載の脱硫接触分解重質ガソリンＥＥを用いた以外は、実施例５と全く同様にして無鉛ガソリン組成物Ｚを調製した。無鉛ガソリン組成物Ｚの性状を表６に示す。 An unleaded gasoline composition Z was prepared in exactly the same manner as in Example 5 except that the desulfurized catalytically cracked heavy gasoline EE described in Preparation 7 of the gasoline base material was used instead of the desulfurized catalytically cracked heavy gasoline DD. Table 6 shows the properties of the unleaded gasoline composition Z.
表７で、ガソリン基材の調製６の脱硫接触分解重質ガソリンＤＤとガソリン基材の調製７の脱硫接触分解重質ガソリンＥＥとを比較すると、高いジエン価、高い硫黄分のままで収着機能をもった脱硫剤によって脱硫しても硫黄分を１質量ｐｐｍ以下とするのは非常に困難であることが分かる。したがって、ジエン低減処理を行った後に収着機能をもった脱硫剤によって脱硫した脱硫接触分解重質ガソリンＤＤを、その他の低硫黄のガソリン基材と共に用いて、硫黄分が１質量ｐｐｍ以下で、十分な運転特性を保持した無鉛ガソリン組成物を容易に調製できることは、表６に無鉛ガソリン組成物Ｙとして示すとおりである。 In Table 7, when desulfurization catalytic cracking heavy gasoline DD of gasoline base preparation 6 and desulfurization catalytic cracking heavy gasoline EE of gasoline base preparation 7 are compared, sorption remains with a high diene number and high sulfur content. It can be seen that it is very difficult to reduce the sulfur content to 1 mass ppm or less even when desulfurization is performed with a desulfurizing agent having a function. Therefore, desulfurization catalytic cracking heavy gasoline DD desulfurized by a desulfurizing agent having a sorption function after performing diene reduction treatment is used together with other low sulfur gasoline base materials, and the sulfur content is 1 mass ppm or less. As shown in Table 6 as unleaded gasoline composition Y, an unleaded gasoline composition having sufficient operating characteristics can be easily prepared.
［参考例］
ガソリン基材の調製１に記したものと同じ銅亜鉛アルミニウム複合酸化物（銅含有量３５質量％、亜鉛含有量３５質量％、アルミニウム含有量５質量％）５ｃｍ３を反応管に充填し、これに水素ガスを５ｃｍ３／ｍｉｎの条件にて１６ｈｒ流通させ、還元処理を行った。その後、この反応管にチオフェンを２６３質量ｐｐｍ（硫黄分として１００質量ｐｐｍ）含むトルエン溶液を、反応温度１００℃、反応圧力常圧、ＬＨＳＶ２.０ｈｒ−１、Ｈ２／Ｏｉｌ比０.１８ＮＬ／Ｌの条件のもと通油し、表８に示す生成物を得た。[Reference example]
The reaction tube was filled with 5 cm 3 of the same copper zinc aluminum composite oxide (copper content 35 mass%, zinc content 35 mass%, aluminum content 5 mass%) as described in Preparation 1 of the gasoline base material. Then, hydrogen gas was circulated for 16 hr under the condition of 5 cm 3 / min to perform a reduction treatment. Thereafter, a toluene solution containing 263 ppm by mass of thiophene (100 ppm by mass as the sulfur content) in this reaction tube was reacted at a reaction temperature of 100 ° C., a normal pressure of reaction, LHSV of 2.0 hr −1 , and an H 2 / Oil ratio of 0.18 NL / L. The product shown in Table 8 was obtained.
表から、水素共存下で銅亜鉛アルミニウム複合酸化物を用いた処理によって、原料油中のチオフェンから硫黄が除去され、チオフェン中の硫黄原子以外の炭化水素残基に由来する炭化水素が生成物として得られる一方、硫化水素を生成しておらず、銅亜鉛アルミニウム複合酸化物が本発明の硫黄収着機能をもった多孔質脱硫剤として作用したことが明らかである。 From the table, sulfur is removed from thiophene in the feedstock by treatment with copper zinc aluminum composite oxide in the presence of hydrogen, and hydrocarbons derived from hydrocarbon residues other than sulfur atoms in thiophene are the products. On the other hand, no hydrogen sulfide was produced, and it is clear that the copper zinc aluminum composite oxide acted as a porous desulfurization agent having the sulfur sorption function of the present invention.
本発明は、分解ガソリン留分をジエン除去した後、わずかな水素共存の下、硫黄収着機能をもつ多孔質脱硫剤によって処理して、硫黄分を低減し、オレフィン分を残し、脱硫処理に伴うオクタン価ロスを回避して得た脱硫分解ナフサ留分と、硫黄分が１０質量ｐｐｍ以下の他のガソリン基材とを混合する硫黄分１質量ｐｐｍ以下の無鉛ガソリン組成物である。よって、従来得られている無鉛ガソリン組成物から他の性状をほとんど変えることなく硫黄分だけを１質量ｐｐｍ以下まで減じることができた。したがって、本発明の無鉛ガソリン組成物は、高い運転性能を維持するとともに、環境負荷の少ない自動車燃料として有用である。
In the present invention, after removing the diene from the cracked gasoline fraction, it is treated with a porous desulfurization agent having a sulfur sorption function in the presence of a slight amount of hydrogen to reduce the sulfur content and leave the olefin content. It is an unleaded gasoline composition having a sulfur content of 1 mass ppm or less, in which a desulfurization cracked naphtha fraction obtained by avoiding the accompanying octane number loss and another gasoline base material having a sulfur content of 10 mass ppm or less. Therefore, it was possible to reduce only the sulfur content to 1 ppm by mass or less without changing other properties from the previously obtained unleaded gasoline composition. Therefore, the unleaded gasoline composition of the present invention is useful as an automobile fuel having a low environmental load while maintaining high driving performance.
Claims (16)
The unleaded gasoline composition according to any one of claims 12 to 15, wherein the thiol content is 0.1 mass ppm or less as a sulfur content.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005515277A JP4932257B2 (en) | 2003-11-07 | 2004-10-29 | Unleaded gasoline composition and method for producing the same |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003378503 | 2003-11-07 | ||
| JP2003378503 | 2003-11-07 | ||
| JP2004168365 | 2004-06-07 | ||
| JP2004168365 | 2004-06-07 | ||
| PCT/JP2004/016115 WO2005044959A1 (en) | 2003-11-07 | 2004-10-29 | Lead-free gasoline composition and method for production thereof |
| JP2005515277A JP4932257B2 (en) | 2003-11-07 | 2004-10-29 | Unleaded gasoline composition and method for producing the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008039867A Division JP5024884B2 (en) | 2003-11-07 | 2008-02-21 | Unleaded gasoline composition and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2005044959A1 true JPWO2005044959A1 (en) | 2007-05-17 |
| JP4932257B2 JP4932257B2 (en) | 2012-05-16 |
Family
ID=34575930
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005515277A Active JP4932257B2 (en) | 2003-11-07 | 2004-10-29 | Unleaded gasoline composition and method for producing the same |
| JP2008039867A Active JP5024884B2 (en) | 2003-11-07 | 2008-02-21 | Unleaded gasoline composition and method for producing the same |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008039867A Active JP5024884B2 (en) | 2003-11-07 | 2008-02-21 | Unleaded gasoline composition and method for producing the same |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20070068849A1 (en) |
| EP (1) | EP1686166A4 (en) |
| JP (2) | JP4932257B2 (en) |
| KR (1) | KR101114742B1 (en) |
| CA (1) | CA2543953C (en) |
| WO (1) | WO2005044959A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009067893A1 (en) * | 2007-11-09 | 2009-06-04 | Ranfeng Ding | A system and a process for recombining catalytic hydrocarbon to produce high quality gasoline |
| US8142646B2 (en) * | 2007-11-30 | 2012-03-27 | Saudi Arabian Oil Company | Process to produce low sulfur catalytically cracked gasoline without saturation of olefinic compounds |
| CN104511283B (en) * | 2013-09-30 | 2016-10-05 | 中国石油化工股份有限公司 | A kind of desulphurization catalyst and preparation method thereof and the method for desulfurization of hydrocarbon oil |
| SG10201604013RA (en) * | 2015-05-28 | 2016-12-29 | Evonik Degussa Gmbh | Hydrogen-assisted adsorption of sulphur compounds from olefin mixtures |
| WO2023049647A1 (en) * | 2021-09-27 | 2023-03-30 | ExxonMobil Technology and Engineering Company | Method of refinery processing of renewable naphtha |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5352354A (en) * | 1991-08-15 | 1994-10-04 | Mobil Oil Corporation | Gasoline upgrading process |
| US5851382A (en) | 1995-12-18 | 1998-12-22 | Texaco Inc. | Selective hydrodesulfurization of cracked naphtha using hydrotalcite-supported catalysts |
| FR2753717B1 (en) | 1996-09-24 | 1998-10-30 | PROCESS AND PLANT FOR THE PRODUCTION OF LOW SULFUR CATALYTIC CRACKING ESSENCES | |
| WO2001044412A1 (en) * | 1999-12-17 | 2001-06-21 | Idemitsu Kosan Co., Ltd. | Fuel oil for fuel cell, fuel oil composition and automobile driving system |
| JP2001303070A (en) * | 2000-04-24 | 2001-10-31 | Idemitsu Kosan Co Ltd | Fuel oil composition and driving system of automobile |
| JPWO2002031090A1 (en) * | 2000-10-11 | 2004-02-19 | 新日本石油株式会社 | Gasoline vehicle and fuel for fuel cell system, and storage and / or supply system thereof |
| US6444118B1 (en) | 2001-02-16 | 2002-09-03 | Catalytic Distillation Technologies | Process for sulfur reduction in naphtha streams |
| JP5027971B2 (en) * | 2001-09-06 | 2012-09-19 | 出光興産株式会社 | Fuel oil composition |
| US6913688B2 (en) | 2001-11-30 | 2005-07-05 | Exxonmobil Research And Engineering Company | Multi-stage hydrodesulfurization of cracked naphtha streams with interstage fractionation |
| JP2003277768A (en) | 2002-03-27 | 2003-10-02 | Cosmo Oil Co Ltd | Method for reducing content of sulfur compound in hydrocarbon oil |
| JP3958103B2 (en) * | 2002-04-12 | 2007-08-15 | 株式会社ジョモテクニカルリサーチセンター | Environmentally friendly gasoline |
-
2004
- 2004-10-29 EP EP04793223A patent/EP1686166A4/en not_active Withdrawn
- 2004-10-29 US US10/577,951 patent/US20070068849A1/en not_active Abandoned
- 2004-10-29 CA CA2543953A patent/CA2543953C/en not_active Expired - Fee Related
- 2004-10-29 KR KR1020067010974A patent/KR101114742B1/en not_active IP Right Cessation
- 2004-10-29 WO PCT/JP2004/016115 patent/WO2005044959A1/en active Application Filing
- 2004-10-29 JP JP2005515277A patent/JP4932257B2/en active Active
-
2008
- 2008-02-21 JP JP2008039867A patent/JP5024884B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005044959A1 (en) | 2005-05-19 |
| JP2008156663A (en) | 2008-07-10 |
| US20070068849A1 (en) | 2007-03-29 |
| KR20060113721A (en) | 2006-11-02 |
| JP4932257B2 (en) | 2012-05-16 |
| KR101114742B1 (en) | 2012-02-29 |
| CA2543953A1 (en) | 2005-05-19 |
| JP5024884B2 (en) | 2012-09-12 |
| EP1686166A4 (en) | 2010-04-21 |
| EP1686166A1 (en) | 2006-08-02 |
| CA2543953C (en) | 2012-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20080044768A (en) | Process for deep desulphurization of cracking gasolines with a small loss of octane number | |
| JP5219247B2 (en) | Method for producing low sulfur cracking gasoline base and unleaded gasoline composition | |
| JP5024884B2 (en) | Unleaded gasoline composition and method for producing the same | |
| JP4889095B2 (en) | Eco-friendly gasoline composition and method for producing the same | |
| JP4803785B2 (en) | Method for producing gasoline base material, environmentally friendly gasoline, and method for producing the same | |
| JP4632738B2 (en) | Unleaded gasoline composition and method for producing the same | |
| JP4371937B2 (en) | Method for producing catalytic cracking gasoline base and unleaded gasoline composition using the same | |
| JP4626950B2 (en) | Eco-friendly gasoline and method for producing the same | |
| JP2004269871A (en) | Unleaded gasoline composition and preparation process thereof | |
| JP5036074B2 (en) | Environmentally friendly gasoline | |
| JP5280624B2 (en) | Unleaded gasoline composition | |
| JP4850412B2 (en) | Method for producing environmentally friendly gasoline composition | |
| JP4633409B2 (en) | Gasoline composition | |
| JP2009263681A (en) | Process for producing catalytically cracked gasoline base and unleaded gasoline composition using the same | |
| JP4599545B2 (en) | Method for producing unleaded gasoline composition | |
| JP4371925B2 (en) | Unleaded gasoline composition and method for producing the same | |
| JP4633411B2 (en) | Gasoline composition | |
| JP5280623B2 (en) | Unleaded gasoline composition | |
| JP4931052B2 (en) | Method for producing gasoline base material | |
| JP5280625B2 (en) | Unleaded gasoline composition | |
| JP4553352B2 (en) | Gasoline composition | |
| JP4633410B2 (en) | Gasoline composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070920 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080221 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20100915 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110309 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110425 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120214 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120215 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 4932257 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150224 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |