JP4626950B2 - Eco-friendly gasoline and method for producing the same - Google Patents
Eco-friendly gasoline and method for producing the same Download PDFInfo
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- JP4626950B2 JP4626950B2 JP2004224340A JP2004224340A JP4626950B2 JP 4626950 B2 JP4626950 B2 JP 4626950B2 JP 2004224340 A JP2004224340 A JP 2004224340A JP 2004224340 A JP2004224340 A JP 2004224340A JP 4626950 B2 JP4626950 B2 JP 4626950B2
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- 239000003502 gasoline Substances 0.000 title claims description 90
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 150000003573 thiols Chemical class 0.000 claims description 67
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 54
- 229910052717 sulfur Inorganic materials 0.000 claims description 54
- 239000011593 sulfur Substances 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 50
- 125000004432 carbon atom Chemical group C* 0.000 claims description 44
- 150000001336 alkenes Chemical class 0.000 claims description 39
- 238000006477 desulfuration reaction Methods 0.000 claims description 34
- 230000023556 desulfurization Effects 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 23
- 239000003963 antioxidant agent Substances 0.000 claims description 19
- -1 aliphatic thiols Chemical class 0.000 claims description 17
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 12
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000011160 research Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 238000011156 evaluation Methods 0.000 claims description 3
- 239000002585 base Substances 0.000 description 41
- 239000003921 oil Substances 0.000 description 38
- 239000000463 material Substances 0.000 description 31
- 238000004523 catalytic cracking Methods 0.000 description 30
- 239000000203 mixture Substances 0.000 description 23
- 230000008569 process Effects 0.000 description 17
- 238000004821 distillation Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- 150000003464 sulfur compounds Chemical class 0.000 description 13
- 238000001833 catalytic reforming Methods 0.000 description 12
- 239000003086 colorant Substances 0.000 description 12
- 239000002270 dispersing agent Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 230000003009 desulfurizing effect Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 210000000540 fraction c Anatomy 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000003599 detergent Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- 238000009835 boiling Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 238000004508 fractional distillation Methods 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 210000002196 fr. b Anatomy 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000002898 organic sulfur compounds Chemical class 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000003747 fuel oil additive Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 102100039339 Atrial natriuretic peptide receptor 1 Human genes 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 101000961044 Homo sapiens Atrial natriuretic peptide receptor 1 Proteins 0.000 description 1
- 241001372564 Piona Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- ZQRGREQWCRSUCI-UHFFFAOYSA-N [S].C=1C=CSC=1 Chemical class [S].C=1C=CSC=1 ZQRGREQWCRSUCI-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 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
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 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
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 150000001993 dienes Chemical class 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
- 150000002019 disulfides Chemical class 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 210000003918 fraction a Anatomy 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000006078 metal deactivator Substances 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 230000000717 retained effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Liquid Carbonaceous Fuels (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
本発明は、環境への影響を低減するために硫黄分を１０質量ｐｐｍ以下に低減した環境対応ガソリンとその製造方法に関する。 The present invention relates to an environmentally friendly gasoline having a sulfur content reduced to 10 mass ppm or less and a method for producing the same in order to reduce the influence on the environment.
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、レギュラーガソリンは、接触改質ガソリン基材、アルキレートガソリン基材、ライトナフサ基材、接触分解ガソリン基材（接触分解ナフサ留分）のような基材を中心に、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 high-performance premium gasoline and the latter is regular. Commercially available as gasoline. Conventionally, regular gasoline has various base materials such as catalytic reforming gasoline base, alkylate gasoline base, light naphtha base, catalytic cracking gasoline base (catalytic cracking naphtha fraction). It is manufactured by blending.
重質な石油留分を接触分解することによって製造される接触分解ガソリン基材は、他のレギュラー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レギュラーガソリン中の硫黄分の大部分は、接触分解ガソリン基材に由来していた。 The catalytic cracking gasoline base produced by catalytic cracking of a heavy petroleum fraction has the advantage that it can be produced economically compared to other regular gasoline bases, but contains a high sulfur content. As a result, most of the sulfur content in the regular gasoline produced as described above was derived from the catalytic cracked gasoline base material.
接触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。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。そこで、硫黄分の多い重質な接触分解ガソリン基材のみを水素化精製することで全体としてのオレフィン分の低下を防ぐことが行われる。 The sulfur content of the catalytic cracking gasoline base can be easily reduced by a known technique of hydrotreating in the presence of high-pressure hydrogen and a catalyst. In that case, a large amount of the olefin component having a high RON contained in the catalytic cracking gasoline base material is hydrogenated and the RON of the base material is lowered. Accordingly, it is possible to prevent a decrease in the olefin content as a whole by hydrorefining only a heavy catalytic cracked gasoline base material having a high sulfur content.
本発明者は、このような重質な接触分解ガソリン基材の水素化精製を検討したところ、原料油中に含まれていない有機硫黄化合物が精製後の基材に含まれ、この成分が臭気や腐食性に大きな影響を与えていることを見出した。本発明はこのような水素化精製後に発生する有機硫黄化合物による問題を解決して、環境への影響を低減した超低硫黄分の環境対応ガソリンとその製造方法を提供することを目的とするものである。 The present inventor examined the hydrorefining of such a heavy catalytic cracking gasoline base material. As a result, an organic sulfur compound not contained in the raw material oil was contained in the refined base material, and this component was an odor. And found to have a significant effect on corrosivity. An object of the present invention is to solve the problem caused by the organic sulfur compound generated after hydrorefining, and to provide an environment-friendly gasoline having an ultra-low sulfur content with reduced environmental impact and a method for producing the same. It is.
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、水素化精製で発生する硫化水素と原料油中のオレフィンが反応することで、新たに有機硫黄化合物が発生しているとの着想を持ち、水素化精製の原料油中に含まれるオレフィン分を限定することで、水素化精製した接触分解ガソリン基材による問題を防止できることを見出した。これらの知見からこの発明に至った。 As a result of earnest research to solve the above problems, the present inventors have found that organic sulfur compounds are newly generated by the reaction of hydrogen sulfide generated by hydrorefining with olefins in the feedstock. It was found that by limiting the olefin content contained in the hydrorefining feedstock, problems due to hydrocracked catalytic cracked gasoline base materials can be prevented. These findings led to this invention.
すなわち、本発明による環境対応ガソリンの製造方法は、流動接触分解ナフサから炭素数７以上のオレフィンを１０容量％以下含む軽質ナフサ留分と、炭素数５以下のオレフィンを１.４容量％以下含む重質ナフサ留分を分取する第一工程、第一工程から得られた重質ナフサ留分を水素化脱硫して脱硫重質ナフサ留分を得る第二工程、及び２５容量％以上の脱硫重質ナフサ留分と２０容量％以上の軽質ナフサ留分を配合する第三工程を含む。
好ましくは、流動接触分解ナフサまたは第一工程で得られた軽質ナフサ留分から、さらには、第二工程で得られた脱硫重質ナフサ留分からチオール類を減じる処理を行う。チオール類を減じる処理は、例えば、銅、亜鉛、ニッケルおよび鉄から選ばれる少なくとも１種を含む多孔質脱硫剤またはアルカリ性物質と接触させることによって行うことが好ましい。
That is, the method for producing an environmentally friendly gasoline according to the present invention includes a light naphtha fraction containing 10% by volume or less of olefins having 7 or more carbon atoms from fluid catalytic cracking naphtha and 1.4% by volume or less of olefins having 5 or less carbon atoms. The first step of fractionating the heavy naphtha fraction, the second step of obtaining the desulfurized heavy naphtha fraction by hydrodesulfurizing the heavy naphtha fraction obtained from the first step, and desulfurization of 25% by volume or more A third step of blending the heavy naphtha fraction and the light naphtha fraction of 20% by volume or more is included.
Preferably, the thiols are reduced from the fluid catalytic cracking naphtha or the light naphtha fraction obtained in the first step, and further from the desulfurized heavy naphtha fraction obtained in the second step. The treatment for reducing thiols is preferably performed by, for example, contacting with a porous desulfurization agent or an alkaline substance containing at least one selected from copper, zinc, nickel and iron.
また、本発明による環境対応ガソリンは、全硫黄分が１０質量ｐｐｍ以下、チオール類による硫黄分が３質量ｐｐｍ以下、炭素数７以上の脂肪族チオールによる硫黄分がチオール類による硫黄分の５０質量％以上を占め、かつリサーチ法オクタン価が８９〜９６である。
本発明による環境対応ガソリンは、好ましくは、チオール類による硫黄分が１.５質量ｐｐｍ以下、かつドクター試験が陰性であり、および／または、酸化防止剤を３０質量ｐｐｍ以上含み銅板腐食試験による評価が１以下である。
In addition, the environmentally friendly gasoline according to the present invention has a total sulfur content of 10 mass ppm or less, a sulfur content of thiols of 3 mass ppm or less, and a sulfur content of aliphatic thiols having 7 or more carbon atoms is 50 mass of sulfur content of thiols. % And the research octane number is 89-96.
The environmentally friendly gasoline according to the present invention preferably has a sulfur content of 1.5 ppm by mass or less due to thiols, a doctor test is negative, and / or an antioxidant is contained by 30 ppm by mass or more and is evaluated by a copper plate corrosion test. Is 1 or less.
本発明によれば、流動接触分解ナフサから炭素数５以下のオレフィンのほとんどを含まず、炭素数７以上のオレフィン分のほとんどを含む重質ナフサ留分と、炭素数５以下のオレフィン分のほとんどを含み炭素数７以上のオレフィンをほとんど含まない軽質ナフサ留分に分け、重質ナフサ留分のみを水素化脱硫するので、精製された脱硫重質ナフサ留分には、炭素数５以下の脂肪族チオールはほとんど含まれることなく、このような硫黄化合物による臭気や腐食性の問題を回避できる。また、相対的にオクタン価が高い炭素数５以下のオレフィン分は、硫黄分の少ない軽質ナフサ留分に含まれ、水素化精製せずにそのままガソリン基材として用いるので、水素化精製によるオクタン価の低下を回避することができる。さらに本発明ではガソリンに含有されるチオールの炭素数が増加することにより相対的に臭気が小さくなる。一方でチオールの炭素数の増加により、腐食性は大きくなり、比較的低濃度でドクター試験が陽性になるが、酸化防止剤の添加量を増加することにより銅板腐食試験による評価を改善することができる。 According to the present invention, a heavy naphtha fraction containing most of the olefins having 7 or more carbon atoms and most of the olefins having 5 or less carbon atoms, and most of the olefins having 7 or more carbon atoms are contained from the fluid catalytic cracking naphtha. Is divided into light naphtha fractions containing almost no olefins containing 7 or more carbon atoms, and only the heavy naphtha fractions are hydrodesulfurized. Therefore, the refined desulfurized heavy naphtha fraction contains fat with 5 or less carbon atoms. Almost no group thiol is contained, and odor and corrosive problems due to such sulfur compounds can be avoided. In addition, olefins with a relatively high octane number of 5 or less carbon atoms are contained in light naphtha fractions with low sulfur content and are used as gasoline bases without hydrorefining, so the octane number is reduced by hydrorefining. Can be avoided. Furthermore, in this invention, an odor becomes relatively small by the carbon number of the thiol contained in gasoline increasing. On the other hand, the increase in the carbon number of thiol increases the corrosivity, and the doctor test becomes positive at a relatively low concentration, but the evaluation by the copper plate corrosion test can be improved by increasing the amount of antioxidant added. it can.
〔水素化精製によって生成するチオール類の形態〕
接触分解ナフサを水素化精製によって脱硫処理すると硫化水素が発生する。接触分解ナフサにはオレフィンが含まれているため、オレフィンと硫化水素が反応しチオールが生成する。接触分解ナフサには元々チオールが含まれるが、チオールは非常に反応性が高く水素化精製による脱硫処理によって容易に脱硫されるため、脱硫接触分解ナフサに含まれるチオールは、水素化精製中に硫化水素とオレフィンとが反応して生成したものがほとんどである。接触分解ナフサには通常炭素数４〜１２のオレフィンが含まれているため、接触分解ナフサを水素化精製処理すると炭素数４〜１２のチオールが生成する。チオール類は、ガソリン中の悪臭物質の１つであり、チオール類の沸点が低いほど悪臭が強い。チオール類は炭素数が小さいほど沸点が低いため、炭素数５以下のチオールは特に悪臭が強い。チオール類は、オレフィンと硫化水素が反応して容易に生成するため、接触分解ナフサを水素化脱硫処理する前に、炭素数５以下のオレフィンを軽質ナフサ留分として分留して除去することによって、脱硫接触分解ナフサ中の炭素数５以下のチオール生成を抑制することができる。
[Forms of thiols produced by hydrorefining]
Hydrogen sulfide is generated when catalytic cracking naphtha is desulfurized by hydrorefining. Since catalytic cracking naphtha contains olefin, olefin and hydrogen sulfide react to generate thiol. Although thiol is originally contained in catalytic cracking naphtha, thiol is very reactive and easily desulfurized by desulfurization by hydrorefining, so thiol contained in desulfurizing catalytic cracking naphtha is sulfided during hydrorefining. Most of them are produced by reaction of hydrogen and olefins. Since the catalytic cracking naphtha usually contains an olefin having 4 to 12 carbon atoms, when the catalytic cracking naphtha is hydrorefined, a thiol having 4 to 12 carbon atoms is generated. Thiols are one of the malodorous substances in gasoline. The lower the boiling point of thiols, the stronger the malodor. Since thiols have a lower boiling point as the carbon number is smaller, thiols having 5 or less carbon atoms have a particularly strong odor. Thiols are easily generated by the reaction of olefin and hydrogen sulfide. Therefore, before hydrocracking the catalytic cracked naphtha, olefins having 5 or less carbon atoms are fractionated and removed as a light naphtha fraction. The generation of thiol having 5 or less carbon atoms in the desulfurization catalytic cracking naphtha can be suppressed.
チオール類を大別すると、鎖状パラフィンにＳＨ基が結合した鎖状チオール類、環状パラフィンにＳＨ基が結合した脂環式チオール類、芳香環に直接ＳＨ基が結合した芳香族チオール類に分けられる。このうち、水素化精製処理によって生成するのは、鎖状チオール類と脂環式チオール類であり、ここではこれらを合わせて脂肪族チオール類と呼ぶ。 The thiols are roughly classified into chain thiols with SH groups bonded to chain paraffins, alicyclic thiols with SH groups bonded to cyclic paraffins, and aromatic thiols with SH groups bonded directly to aromatic rings. It is done. Of these, chain thiols and alicyclic thiols are generated by hydrorefining treatment, and these are collectively referred to as aliphatic thiols here.
〔接触分解プロセス〕
接触分解油を製造するプロセスは、接触分解装置、運転条件および用いる触媒を特に限定するものでなく、公知の任意の製造プロセスを採用できる。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。また、21st JPI Petroleum Refining Conference “Recent Progress in Petroleum Process Technology”, p.113-158 (2002)、Sulphur, 268, 35, (2000)、“Production of Low Sulfur Gasoline and Diesel Fuels: Tier 2 and Beyond”, Petroleum Refining Technology Seminar, p.4-24 (August 2001)、特開平６−２７７５１９に開示されているような、脱硫効果の高い接触分解触媒や脱硫効果をもった添加剤を接触分解触媒に添加して用いることもできる。
[Catalytic decomposition process]
The process for producing the catalytic cracking oil is not particularly limited to the catalytic cracking apparatus, the operating conditions and the catalyst to be used, and any known production process can be adopted. The catalytic cracking unit uses a catalyst such as amorphous silica alumina, zeolite, etc., in addition to petroleum fractions from light oil to vacuum gas oil, while being obtained from heavy oil indirect desulfurization unit, it can be obtained directly from degassing oil or heavy oil direct desulfurization unit. This is a device that obtains a high octane gasoline base material by catalytic cracking of degassed oil, atmospheric residue oil and the like. 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. Also, 21st JPI Petroleum Refining Conference “Recent Progress in Petroleum Process Technology”, p.113-158 (2002), Sulfur, 268, 35, (2000), “Production of Low Sulfur Gasoline and Diesel Fuels: Tier 2 and Beyond” , Petroleum Refining Technology Seminar, p.4-24 (August 2001), JP-A-6-277519, catalytic cracking catalyst having high desulfurization effect and additive having desulfurization effect are added to catalytic cracking catalyst It can also be used.
〔接触分解原料油〕
原油を常圧蒸留して得られる常圧蒸留残油、常圧蒸留残油を減圧蒸留して得られる留出油留分である減圧軽油、原油を常圧蒸留して得られる留出油留分のうちの直留軽油留分、常圧蒸留残渣油を減圧蒸留して得られる減圧蒸留残渣油を熱分解して得られる熱分解重質軽油留分等を硫黄分４０００質量ｐｐｍ以下、特には２０００質量ｐｐｍ以下、窒素分
１０００質量ｐｐｍ以下、特には５００質量ｐｐｍ以下となるように水素化精製処理したものが好ましく用いられる。また、接触分解プロセスで得られるガソリン留分より沸点の高いライトサイクルオイルや水素化分解プロセスで得られる減圧蒸留残油留分、またはそれら水素化精製処理したものも好ましく用いられる。硫黄分、窒素分、バナジウム分、ニッケル分の含有量が比較的低い原油の場合は、直留軽油、減圧軽油、常圧蒸留残油、減圧残油を水素化精製せずに、接触分解原料油としてまたはその一部として用いることもできる。
[Catalytic cracking feedstock]
An atmospheric distillation residue obtained by atmospheric distillation of crude oil, a vacuum gas oil that is a distillate fraction obtained by vacuum distillation of atmospheric distillation residue, a distillate distillation obtained by atmospheric distillation of crude oil Among the fractions, a pyrolysis heavy gas oil fraction obtained by pyrolyzing a vacuum distillation residue oil obtained by distilling an atmospheric distillation residue oil under reduced pressure, a sulfur content of 4000 mass ppm or less, particularly Is preferably subjected to a hydrorefining treatment so as to have 2000 ppm by mass or less and a nitrogen content of 1000 ppm by mass or less, particularly 500 ppm by mass or less. In addition, light cycle oil having a boiling point higher than that of the gasoline fraction obtained by the catalytic cracking process, reduced-pressure distillation residue obtained by the hydrocracking process, or those hydrorefined, are preferably used. For crude oils with relatively low sulfur, nitrogen, vanadium, and nickel content, the raw material for catalytic cracking can be obtained without hydrorefining straight-run gas oil, vacuum gas oil, atmospheric distillation residue, or vacuum residue. It can also be used as oil or as part of it.
〔第一工程〕
接触分解装置で処理した後に得られる生成物は、軽質ガス、流動接触分解ナフサ、ライトサイクルオイル、ヘビーサイクルオイル、コークである。これら生成物のうち、コーク以外は蒸留塔で蒸留し、各留分が得られる。本発明の第一工程では、流動接触分解油から炭素数５以下のオレフィンのほとんどを含む軽質ナフサ留分と、炭素数５以下のオレフィンを実質的に含まない重質ナフサ留分を分取する。接触分解装置の生成物から軽質ナフサ留分と重質ナフサ留分を直接に分留してもよいし、一旦、これらを含む留分を分留した後、さらに分留して軽質ナフサ留分と重質ナフサ留分に分けてもよい。
[First step]
The products obtained after processing in the catalytic cracker are light gas, fluid catalytic cracking naphtha, light cycle oil, heavy cycle oil, coke. Of these products, those other than coke are distilled in a distillation column to obtain each fraction. In the first step of the present invention, a light naphtha fraction containing most of an olefin having 5 or less carbon atoms and a heavy naphtha fraction substantially not containing an olefin having 5 or less carbon atoms are separated from a fluid catalytic cracking oil. . A light naphtha fraction and a heavy naphtha fraction may be directly fractionated from the product of the catalytic cracker, or after fractionating a fraction containing these fractions, the fraction is further fractionated to obtain a light naphtha fraction. And heavy naphtha fraction.
重質ナフサ留分には、接触分解装置の生成物に含まれる炭素数５以下のオレフィンの０〜１０質量％、特には０〜５質量％が含まれることが好ましく、また、炭素数７以上のオレフィンは５０〜１００質量％、特には７５〜１００質量％含まれることが好ましい。軽質ナフサ留分には、接触分解装置の生成物に含まれる炭素数５以下のオレフィンの９０〜１００質量％以上、特には９５〜１００質量％が含まれることが好ましく、炭素数７以上のオレフィンは０〜５０質量％、特には０〜２５質量％含まれることが好ましい。通常、軽質ナフサ留分は、５％留出温度が２５〜５０℃、９５％留出温度が６０〜１２０℃特には７５〜１００℃であり、重質ナフサ留分は、５％留出温度が６０〜１２０℃特には８０〜１００℃、９５％留出温度が１７０〜２２０℃であることが好ましい。重質ナフサ留分に炭素数５以下のオレフィンが多く含まれると、第二工程で得られる重質ナフサ留分中に炭素数５以下のチオール類が多く含まれてしまう。炭素数５以下のチオール類は沸点が比較的低く、揮発性が高い上、悪臭が強いため、炭素数５以下のチオール類がガソリン中に含まれないよう、炭素数５以下のオレフィンが重質ナフサ留分に入らないよう分留するのが好ましく、重質ナフサ留分中の炭素数５以下のオレフィンは１.４容量％以下、特には１.０容量％以下、さらには０.５容量％以下であるのが好ましい。 It is preferable that the heavy naphtha fraction contains 0 to 10% by mass, particularly 0 to 5% by mass, of the olefin having 5 or less carbon atoms contained in the product of the catalytic cracker, and 7 or more carbon atoms. The olefin is preferably contained in an amount of 50 to 100% by mass, particularly 75 to 100% by mass. It is preferable that the light naphtha fraction contains 90 to 100% by mass, particularly 95 to 100% by mass of the olefin having 5 or less carbon atoms contained in the product of the catalytic cracker, and the olefin having 7 or more carbon atoms. Is preferably contained in an amount of 0 to 50% by mass, particularly 0 to 25% by mass. Usually, the light naphtha fraction has a 5% distillation temperature of 25 to 50 ° C., a 95% distillation temperature of 60 to 120 ° C., particularly 75 to 100 ° C., and a heavy naphtha fraction has a 5% distillation temperature. Is preferably 60 to 120 ° C, particularly 80 to 100 ° C, and the 95% distillation temperature is preferably 170 to 220 ° C. If the heavy naphtha fraction contains a large amount of olefins having 5 or less carbon atoms, the heavy naphtha fraction obtained in the second step will contain many thiols having 5 or less carbon atoms. Thiols with 5 or less carbon atoms have a relatively low boiling point, high volatility, and strong odor, so olefins with 5 or less carbon atoms are heavy so that gasoline with 5 or less carbon atoms is not included in gasoline. It is preferable to carry out fractional distillation so that it does not enter the naphtha fraction. The olefin having 5 or less carbon atoms in the heavy naphtha fraction is 1.4% by volume or less, particularly 1.0% by volume or less, and further 0.5 volume. % Or less is preferable.
炭素数７以上のオレフィンは軽質ナフサ留分にあまり含まれない方が好ましい。炭素数７以上のオレフィンが軽質ナフサ留分に多く含まれるよう分留すると、軽質ナフサ留分の硫黄濃度が高くなり、軽質ナフサ留分の脱硫が必要となるが、このとき軽質ナフサ留分に含まれる硫黄化合物は多くが脱硫されにくいチオフェン類硫黄化合物であるため、オクタン価ロスを伴わずに脱硫するのが困難になる。軽質ナフサ留分中の炭素数７以上のオレフィンは１０容量％以下、特には５容量％以下、さらには３容量％以下であるのが好ましい。 It is preferable that olefins having 7 or more carbon atoms are not included in the light naphtha fraction. When fractionating so that olefins with 7 or more carbon atoms are contained in the light naphtha fraction, the sulfur concentration of the light naphtha fraction increases, and desulfurization of the light naphtha fraction is required. Since most of the sulfur compounds contained are thiophene sulfur compounds that are not easily desulfurized, it is difficult to desulfurize without involving octane loss. The olefin having 7 or more carbon atoms in the light naphtha fraction is preferably 10% by volume or less, particularly 5% by volume or less, and more preferably 3% by volume or less.
〔軽質ナフサ留分からチオール類を減じる処理〕
軽質ナフサ留分については、硫黄分が１０質量ｐｐｍ未満かつチオールによる硫黄分が１.５質量ｐｐｍ未満であれば特に何らかの処理を行う必要はない。チオールによる硫黄分が１.５質量ｐｐｍ以上の場合は、チオールによる硫黄分が１.５質量ｐｐｍ未満となるよう、チオールを減ずる処理をするのが好ましい。チオールを減ずる処理については、チオールによる硫黄分を除去する方法と、チオールをチオールではない別の硫黄化合物に重質化する方法がある。チオールによる硫黄分を除去する方法としてはペトロテック17(11),974(1994)や講談社サイエンティフィク社「石油精製プロセス」(1998)記載の抽出型のスイートニングプロセス、抽出酸化型のスイートニングプロセス、あるいは、硫黄化合物の吸着または収着機能をもった脱硫剤と接触分解軽質ナフサ留分を接触させる方法があげられる。チオールをチオールではない別の硫黄化合物に重質化する方法としては、ペトロテック17 (11), 974 (1994)や講談社サイエンティフィク社「石油精製プロセス」(1998)記載の酸化型のスイートニングプロセスや、チオール類を接触分解ナフサ中のジオレフィンやオレフィンと反応させて重質化させる方法が好ましい方法としてあげられる。チオール類を減ずる処理は分留する前でも後でもどちらでもよいが、重質化によってチオール類を減じる場合には分留する前の方が、軽質ナフサ留分中の硫黄分を減じることができるためなお一層好ましい。軽質ナフサ留分の硫黄分が１０質量ｐｐｍ以上の場合は、脱硫重質ナフサ留分と混合した後の脱硫接触分解ナフサの硫黄分が２０質量ｐｐｍ以下、好ましくは１０質量ｐｐｍ以下となるよう任意の方法で脱硫処理をするのが好ましい。脱硫処理としては、特に限定はしないが、硫黄化合物の吸着または収着機能をもった脱硫剤と軽質ナフサ留分を接触させる方法や抽出によって軽質ナフサ留分から硫黄化合物を選択的に除去する方法が好ましい方法として挙げられる。触媒と水素の存在下で、軽質ナフサ留分を水素化精製処理する方法も挙げられるが、高圧の水素の存在下では、オレフィンが水素化されやすく、得られるガソリン基材のＲＯＮが低下しやすい。そのため、脱硫処理は、水素が実質的に存在しない状態、または水素分圧１ＭＰａ未満で行うことが好ましい。
[Treatment to reduce thiols from light naphtha fraction]
As for the light naphtha fraction, if the sulfur content is less than 10 ppm by mass and the sulfur content by thiol is less than 1.5 ppm by mass, no particular treatment is required. When the sulfur content by thiol is 1.5 mass ppm or more, it is preferable to reduce the thiol so that the sulfur content by thiol is less than 1.5 mass ppm. Regarding the treatment for reducing thiol, there are a method of removing sulfur content by thiol and a method of making thiol heavy to another sulfur compound that is not thiol. Extraction-type sweetening process and extraction-oxidation-type sweetening described in Petrotech 17 (11), 974 (1994) and Kodansha Scientific Co., Ltd. "Oil Refining Process" (1998) Examples thereof include a process or a method in which a desulfurization agent having an adsorption or sorption function for sulfur compounds and a catalytically cracked light naphtha fraction are brought into contact with each other. As a method of making thiol into another sulfur compound that is not thiol, sweetening of oxidized type described in Petrotech 17 (11), 974 (1994) and Kodansha Scientific “Oil Refining Process” (1998) A preferable method is a process or a method in which a thiol is reacted with a diolefin or an olefin in a catalytic cracking naphtha to make it heavier. The treatment for reducing thiols can be performed either before or after fractional distillation. However, when the thiols are reduced by heavyization, the sulfur content in the light naphtha fraction can be reduced before fractional distillation. Therefore, it is still more preferable. When the sulfur content of the light naphtha fraction is 10 ppm by mass or more, the sulfur content of the desulfurized catalytic cracked naphtha after mixing with the desulfurized heavy naphtha fraction is 20 ppm by mass or less, preferably 10 ppm by mass or less. It is preferable to carry out the desulfurization treatment by this method. The desulfurization treatment is not particularly limited, but there are a method of contacting a light naphtha fraction with a desulfurization agent having a sulfur compound adsorption or sorption function, and a method of selectively removing the sulfur compound from the light naphtha fraction by extraction. It is mentioned as a preferable method. A method of hydrotreating a light naphtha fraction in the presence of a catalyst and hydrogen can also be mentioned, but in the presence of high-pressure hydrogen, olefins are easily hydrogenated, and the RON of the resulting gasoline base material is likely to decrease. . Therefore, the desulfurization treatment is preferably performed in a state where hydrogen is not substantially present, or at a hydrogen partial pressure of less than 1 MPa.
〔第二工程〕
本発明の第二工程では第一工程で得られた重質ナフサ留分を水素化脱硫処理して、第三工程に供する脱硫重質ナフサ留分を得る。水素化脱硫処理は、重質ナフサ留分と水素化脱硫触媒を高圧水素の存在下で接触させるものである。水素化脱硫触媒は、アルミナなどの無機多孔質担体にモリブデン、ニッケル、コバルト、リンのうち少なくとも１種を担持した触媒が好ましく用いられる。好ましい反応条件は、反応温度１５０〜３５０℃、反応圧力０.１〜４.０ＭＰａ、ＬＨＳＶ１.０〜１０ｈ−１、Ｈ２／ＯＩＬ＝５０〜１０００ＮＬ／Ｌである。特に好ましい反応条件は、反応温度２００〜３００℃、反応圧力１.０〜２.５ＭＰａ、ＬＨＳＶ２.０〜６.０ｈ−１、Ｈ２／ＯＩＬ＝１００〜５００ＮＬ／Ｌである。
[Second step]
In the second step of the present invention, the heavy naphtha fraction obtained in the first step is hydrodesulfurized to obtain a desulfurized heavy naphtha fraction used in the third step. In the hydrodesulfurization treatment, a heavy naphtha fraction and a hydrodesulfurization catalyst are contacted in the presence of high-pressure hydrogen. As the hydrodesulfurization catalyst, a catalyst in which at least one of molybdenum, nickel, cobalt, and phosphorus is supported on an inorganic porous carrier such as alumina is preferably used. Preferred reaction conditions are a reaction temperature of 150 to 350 ° C., a reaction pressure of 0.1 to 4.0 MPa, LHSV 1.0 to 10 h −1 , H 2 / OIL = 50 to 1000 NL / L. Particularly preferable reaction conditions are a reaction temperature of 200 to 300 ° C., a reaction pressure of 1.0 to 2.5 MPa, LHSV of 2.0 to 6.0 h −1 , and H 2 / OIL = 100 to 500 NL / L.
重質ナフサ留分の硫黄分は５００質量ｐｐｍ以下、特には５０〜５００質量ｐｐｍ、さらには４０〜２００質量ｐｐｍが好ましい。重質ナフサ留分の硫黄分が５００質量ｐｐｍを超えると、水素化精製におけるオクタン価ロスが大きくなり好ましくない。 The sulfur content of the heavy naphtha fraction is preferably 500 ppm by mass or less, particularly 50 to 500 ppm by mass, and more preferably 40 to 200 ppm by mass. If the sulfur content of the heavy naphtha fraction exceeds 500 ppm by mass, the octane loss in hydrorefining increases, which is not preferable.
水素化脱硫処理に用いる原料油として、接触分解ナフサ以外に硫黄分を高濃度に含む他のガソリン相当留分の油も選択することができる。具体的には、常圧蒸留装置から留出する直留ナフサ、熱分解装置から留出する熱分解ナフサ、脱ろう装置から留出する脱ろうナフサ、直接脱硫装置から留出する直脱ナフサ、間接脱硫装置から留出する間脱ナフサなどがあげられる。これらは分留する前の接触分解ナフサに混合してもよいし、分留後の重質ナフサ留分に混合してもよいが、重質ナフサ留分の硫黄分が５００質量ｐｐｍ以下になるよう混合するのが好ましい。分留する前にチオール類を減じる処理を行う場合は、その前に混合するのが好ましい。 As the feed oil used for the hydrodesulfurization treatment, other gasoline equivalent fraction oil containing a high concentration of sulfur can be selected in addition to catalytic cracking naphtha. Specifically, straight naphtha distilled from an atmospheric distillation unit, thermal naphtha distilled from a pyrolysis unit, dewaxed naphtha distilled from a dewaxing device, direct desulfurization naphtha distilled from a direct desulfurization unit, For example, denaphtha is used while distilling from the indirect desulfurization unit. These may be mixed with the catalytic cracking naphtha before fractionation, or may be mixed with the heavy naphtha fraction after fractionation, but the sulfur content of the heavy naphtha fraction becomes 500 mass ppm or less. It is preferable to mix them. When performing the process which reduces thiols before fractional distillation, it is preferable to mix before that.
脱硫重質ナフサ留分の硫黄分は４０質量ｐｐｍ以下、特には２０質量ｐｐｍ以下、さらには１０質量ｐｐｍ以下が好ましい。硫黄化合物別には、チオール類は１５質量ｐｐｍ以下、特には８質量ｐｐｍ以下、さらには３質量ｐｐｍ以下であることが好ましい。炭素数７以上の脂肪族チオールは１５質量ｐｐｍ以下、特には２.５質量ｐｐｍ以下が好ましく、０．１〜１５質量ｐｐｍ、特には０．１〜２.５質量ｐｐｍとすることもできる。炭素数６以下の脂肪族チオールは１０質量ｐｐｍ以下、特には２質量ｐｐｍ以下が好ましく、０．１〜１０質量ｐｐｍ以下、特には０．１〜２質量ｐｐｍとすることもできる。 The sulfur content of the desulfurized heavy naphtha fraction is preferably 40 ppm by mass or less, particularly preferably 20 ppm by mass or less, more preferably 10 ppm by mass or less. For each sulfur compound, the thiols are preferably 15 ppm by mass or less, particularly 8 ppm by mass or less, more preferably 3 ppm by mass or less. The aliphatic thiol having 7 or more carbon atoms is preferably 15 ppm by mass or less, particularly preferably 2.5 ppm by mass or less, and may be 0.1 to 15 ppm by mass, particularly 0.1 to 2.5 ppm by mass. The aliphatic thiol having 6 or less carbon atoms is preferably 10 ppm by mass or less, particularly preferably 2 ppm by mass or less, and may be 0.1 to 10 ppm by mass, particularly 0.1 to 2 ppm by mass.
〔脱硫重質ナフサ留分からチオール類を減じる処理〕
脱硫重質ナフサ留分からチオール類を減じる方法は、特に限定はしないが、水素化脱硫以外の方法であり、チオール類を選択的に減じることが好ましい。具体的には、アルカリ性物質と接触させて脱硫重質ナフサ留分中のチオール類をスイートニングする方法や硫黄化合物の吸着または収着機能をもった脱硫剤と脱硫重質ナフサ留分を接触させる方法によってチオール類を選択的に除去する方法が好ましい方法として挙げられる。
[Treatment to reduce thiols from desulfurized heavy naphtha fraction]
The method for reducing thiols from the desulfurized heavy naphtha fraction is not particularly limited, but is a method other than hydrodesulfurization, and it is preferable to selectively reduce thiols. Specifically, a method of sweetening thiols in a desulfurized heavy naphtha fraction by contacting with an alkaline substance, or a desulfurizing agent having a sulfur compound adsorption or sorption function and a desulfurized heavy naphtha fraction are contacted. A preferable method is a method of selectively removing thiols by a method.
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ており、ペトロテック17 (11), 974 (1994)や講談社サイエンティフィク社「石油精製プロセス」(1998)記載のマーロックス法などが好ましく用いられる。スイートニングにおいては、オレフィン類はそのまま保持されるのでＲＯＮは減少しない。ただし、脱硫重質ナフサ留分には炭素数が７以上の重質なチオールが多く含まれているが、このようなチオールは従来のマーロックス法などでは反応性が低く、十分に転化できない可能性がある。その場合には、重質なチオールが除去できるスイートニングプロセスを選択する必要がある。具体的には、NPRA 2000 Annual Meeting AM-00-54記載のＭＥＲＩＣＡＴ−IIプロセスなどが挙げられる。 Conventionally, in oil refining, sweetening has been performed to treat thiols to make the product non-brominated, such as Petrotech 17 (11), 974 (1994) and Kodansha Scientific “Oil Refining Process”. The Marlox method described in (1998) is preferably used. In sweetening, since olefins are retained as they are, RON does not decrease. However, the desulfurized heavy naphtha fraction contains a lot of heavy thiols with 7 or more carbon atoms, but such thiols have low reactivity by the conventional Marlox method and may not be converted sufficiently. There is. In that case, it is necessary to select a sweetening process capable of removing heavy thiols. Specific examples include the MERICAT-II process described in NPRA 2000 Annual Meeting AM-00-54.
チオール類は苛性ソーダやアンモニア等のアルカリ性物質の存在によってジスルフィド類に転化する。このとき、添加剤や触媒を用いることによって転化効率を向上させることができる。また、抽出型のスイートニングプロセスはチオール類をアルカリ性物質と反応させ、油分から分離できるため、油中の硫黄分を減ずることができる。 Thiols are converted to disulfides by the presence of alkaline substances such as caustic soda and ammonia. At this time, conversion efficiency can be improved by using an additive and a catalyst. In addition, since the extraction type sweetening process allows thiols to react with an alkaline substance and be separated from the oil, the sulfur content in the oil can be reduced.
〔多孔質脱硫剤による処理〕
吸着または収着機能をもった脱硫剤と脱硫重質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吸着または収着機能を有するものであれば特に限定はない。銅、亜鉛、ニッケルおよ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重量％、特には１〜８０重量％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、３０ｍ２／ｇ以上、特には５０ｍ２／ｇ以上、さらには５０〜６００ｍ２／ｇが好ましい。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。
[Treatment with porous desulfurization agent]
The desulfurization agent in the case of using a method of contacting a desulfurization agent having an adsorption or sorption function with a desulfurized heavy naphtha fraction is not particularly limited as long as it has an adsorption or 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 weight, particularly 1 to 80% by weight, of a metal component such as copper. The method for producing the desulfurizing agent is not particularly limited, but a metal component such as copper and a component such as aluminum by a production method or a coprecipitation method in which a porous carrier such as alumina is impregnated with a metal component such as copper and supported. 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, 30 m 2 / g or more, particularly 50 m 2 / g or more, further 50 to 600 m 2 / g are preferred. 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.
多孔質脱硫剤による脱硫処理は、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脱硫重質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重質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、１５〜４００℃の範囲から選ぶことができ、好ましくは８０〜３８０℃の範囲から選ぶとよい。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軽質ナフサ留分を接触させて脱硫処理を行う場合、ＬＨＳＶは、０.０１〜１００００ｈ−１の範囲から選ぶことが好ましい。 The desulfurization treatment with the porous desulfurization agent may be performed in a batch type or a flow type, but it is performed by circulating a desulfurized heavy naphtha fraction in a fixed bed desulfurization tower filled with a desulfurization agent. The desulfurization agent and the resulting desulfurized heavy naphtha fraction can be easily separated, which is preferable. The temperature for the desulfurization treatment can be selected from the range of 15 to 400 ° C, and preferably from the range of 80 to 380 ° C. The 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 contacting the desulfurizing agent and the light naphtha fraction in a fixed bed flow type, the LHSV is preferably selected from the range of 0.01 to 10,000 h −1 .
〔第三工程に用いる他のガソリン基材〕
本発明で、軽質ナフサ留分、脱硫重質ナフサ留分に第三工程にて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、およびメチルｔ−ブチルエーテル（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。混合される他のガソリン基材は、硫黄分が１０質量ｐｐｍ以下であることが好ましく、さらには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、軽質ナフサ留分、脱硫重質ナフサ留分への配合量が制約され好ましくない。
[Other gasoline base materials used in the third step]
In the present invention, as other gasoline base materials mixed in the third step with light naphtha fraction and desulfurized heavy naphtha fraction, catalytic reforming gasoline base material, alkylate gasoline base material, straight-run naphtha is desulfurized. Treated base materials and known gasoline base materials such as methyl t-butyl ether (MTBE), ethyl t-butyl ether (ETBE), t-amyl ethyl ether (TAEE), and oxygen-containing gasoline base materials such as ethanol and methanol are used. be able to. The other gasoline base material to be mixed preferably has a sulfur content of 10 mass ppm or less, and more preferably 5 mass ppm or less. When the sulfur content of other gasoline bases exceeds 10 ppm by mass, the blending amount into the light naphtha fraction and the desulfurized heavy naphtha fraction is restricted, which is not preferable.
好ましい配合量は、軽質ナフサ留分を２０〜６０容量％特には３０〜５０容量％、脱硫重質ナフサ留分を２５〜６５容量％特には３５〜５５容量％、接触改質ガソリン基材を５〜５０容量％特には１０〜４０容量％、脱硫処理した直留ナフサなどの他の基材５０容量％以下、特には５〜３５容量％である。 Preferred blending amounts are 20 to 60% by volume of light naphtha fraction, particularly 30 to 50% by volume, 25 to 65% by volume of desulfurized heavy naphtha fraction, particularly 35 to 55% by volume, and a catalytically modified gasoline base. 5 to 50% by volume, particularly 10 to 40% by volume, and 50% by volume or less of other base materials such as desulfurized straight run naphtha, particularly 5 to 35% by volume.
〔他の成分〕
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重量％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。
[Other ingredients]
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 weight% 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.
〔環境対応ガソリン〕
本発明による環境対応ガソリンは、全硫黄分が１０質量ｐｐｍ以下、チオール類による硫黄分が３質量ｐｐｍ以下、炭素数７以上の脂肪族チオールによる硫黄分がチオール類による硫黄分の５０質量％以上を占め、かつリサーチ法オクタン価が８９〜９６である。また、チオール類による硫黄分が０．５〜３質量ｐｐｍ、特には０．５〜１．５質量ｐｐｍ、かつリサーチ法オクタン価が８９〜９２とすることもできる。好ましくは、チオール類による硫黄分が１.５質量ｐｐｍ以下、ドクター試験が陰性であり、および／または、酸化防止剤を３０質量ｐｐｍ以上含み銅板腐食試験による評価が１以下である。
[Environmentally friendly gasoline]
The environmentally friendly gasoline according to the present invention has a total sulfur content of 10 mass ppm or less, a sulfur content of thiols of 3 mass ppm or less, and a sulfur content of aliphatic thiols having 7 or more carbon atoms of 50 mass% or more of sulfur content of thiols. And the research octane number is 89-96. Moreover, the sulfur content by thiols can also be 0.5-3 mass ppm, especially 0.5-1.5 mass ppm, and the research method octane number can also be 89-92. Preferably, the sulfur content by thiols is 1.5 ppm by mass or less, the doctor test is negative, and / or the antioxidant is contained by 30 ppm by mass or more and the evaluation by the copper plate corrosion test is 1 or less.
好ましくは、５０容量％留出温度が１０５℃以下、さらに好ましくは８０〜１００℃であり、オレフィン分が１０容量％以上、好ましくは１０〜３０容量％である。硫黄分は０.１〜１０質量ｐｐｍが好ましい。硫黄化合物別には、チオール類は３.０質量ｐｐｍ以下、特には１.５質量ｐｐｍ以下であることが好ましい。炭素数７以上の脂肪族チオールは全チオール類のうち５０質量％以上であるのが好ましい。炭素数７以上の脂肪族チオールを全チオール類中の５０質量％未満とすることはＲＯＮを大幅に損ない好ましくない。炭素数６以下の脂肪族チオールは、１.５質量ｐｐｍ以下、特には１.０質量ｐｐｍ以下が好ましい。 Preferably, the 50 volume% distillation temperature is 105 ° C. or less, more preferably 80 to 100 ° C., and the olefin content is 10 volume% or more, preferably 10 to 30 volume%. The sulfur content is preferably 0.1 to 10 mass ppm. For each sulfur compound, the thiols are preferably 3.0 ppm by mass or less, particularly 1.5 ppm by mass or less. The aliphatic thiol having 7 or more carbon atoms is preferably 50% by mass or more of all thiols. Setting the aliphatic thiol having 7 or more carbon atoms to less than 50% by mass in the total thiols is not preferable because RON is significantly impaired. The aliphatic thiol having 6 or less carbon atoms is preferably 1.5 mass ppm or less, particularly preferably 1.0 mass ppm or less.
以下に、本発明を実施例に基づいてより詳細に説明するが、本発明は、これらに限定されるものではない。
なお、本実施例では、密度はＪＩＳ Ｋ ２２４９に、蒸留性状はＪＩＳ Ｋ ２２５４に、また、蒸気圧はＪＩＳ Ｋ ２２５８に準拠して測定した。硫黄分はＪＩＳ Ｋ ２５４１の微量電量滴定式酸化法によって測定した。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。炭化水素成分組成および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。ドクター試験はＪＩＳ Ｋ ２２７６に、銅板腐食はＪＩＳ Ｋ ２５１３に準拠して測定した。
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
In this example, the density was measured according to JIS K 2249, the distillation property was measured according to JIS K 2254, and the vapor pressure was measured according to JIS K 2258. The sulfur content was measured by the microcoulometric titration method of JIS K2541. 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. The doctor test was measured according to JIS K 2276, and the copper plate corrosion was measured according to JIS K 2513.
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ナフサ留分Ａを、酸化型のスイートニング装置によって処理してナフサ留分Ｂを得た。これらの留分の性状を表１、２に示す。ナフサ留分Ｂを分留し、軽質ナフサ留分Ｃと重質ナフサ留分Ｄを得た。これらの留分の性状を表３、４に示す。ここで、スイートニング処理は、ＵＯＰ社のマーロックスプロセスによって行った。 Naphtha fraction A obtained by fluid catalytic cracking using a hydrorefined gas oil fraction of Middle Eastern crude oil as the main feed oil is treated with an oxidation-type sweetening device to obtain naphtha fraction B It was. The properties of these fractions are shown in Tables 1 and 2. Naphtha fraction B was fractionated to obtain light naphtha fraction C and heavy naphtha fraction D. The properties of these fractions are shown in Tables 3 and 4. Here, the sweetening process was performed by the Marlocks process of UOP.
この重質ナフサ留分Ｄ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２５０℃、反応圧力１.０ＭＰａ、ＬＨＳＶ＝５.０ｈ−１、Ｈ２／ＯＩＬ＝３０７ＮＬ／Ｌの条件下にて水素化脱硫を行い、脱硫重質ナフサ留分Ｇを得た。この留分の性状を表７、８に示す。 Using this heavy naphtha fraction D with a catalyst in which cobalt, molybdenum and phosphorus are supported on alumina (cobalt content 2.4 mass%, molybdenum content 9.4 mass%, phosphorus content 2.0 mass%), Hydrodesulfurization was performed under the conditions of a reaction temperature of 250 ° C., a reaction pressure of 1.0 MPa, LHSV = 5.0 h −1 , H 2 / OIL = 307 NL / L, and a desulfurized heavy naphtha fraction G was obtained. Properties of this fraction are shown in Tables 7 and 8.
この脱硫重質ナフサ留分Ｇ、軽質ナフサ留分Ｃと、さらに表９に性状を示す他のガソリン基材（脱硫ナフサＬ、接触改質中質油Ｍ、接触改質重質油Ｎ、アルキレートガソリンＯ）及び酸化防止剤を表１０に示す割合で配合し、着色剤、清浄分散剤を加え環境対応ガソリンＰを調製した。酸化防止剤としては、ＡＣＴＥＬ社製ＡＯ−５５０を用いた。環境対応ガソリン組成物Ｐの性状、含まれる硫黄成分の種類と含有量などを表１１および１２に示す。なお、以下の実施例及び比較例の無鉛ガソリン組成物Ｑ〜Ｙの調製において、酸化防止剤はＡＣＴＥＬ社製ＡＯ−５５０を表１０に示す割合で添加し、着色剤と清浄分散剤は、本例と同じものを、同じ量添加、配合した。 This desulfurized heavy naphtha fraction G, light naphtha fraction C, and other gasoline base materials having properties shown in Table 9 (desulfurized naphtha L, catalytic reforming medium oil M, catalytic reforming heavy oil N, al Chelating gasoline O) and an antioxidant were blended in the proportions shown in Table 10, and an environmentally friendly gasoline P was prepared by adding a colorant and a cleaning dispersant. As the antioxidant, AO-550 manufactured by ACTEL was used. Tables 11 and 12 show the properties of the environment-friendly gasoline composition P, the types and contents of sulfur components contained therein, and the like. In the preparation of the unleaded gasoline compositions Q to Y of the following examples and comparative examples, an antioxidant is added in a ratio shown in Table 10 as an antioxidant, and the coloring agent and the cleaning dispersant are the same. The same amount as the example was added and blended.
実施例１と同じ重質ナフサ留分Ｄを反応温度２４０℃とする以外は実施例１と同様に水素化脱硫を行い、脱硫重質ナフサ留分Ｈを得た。この脱硫重質ナフサ留分Ｈの性状等を表７〜８に示す。この脱硫重質ナフサ留分Ｈと、軽質ナフサ留分Ｃと、さらに実施例１と同じ他のガソリン基材及び酸化防止剤を表１０の配合量で配合し、着色剤、清浄分散剤を加えて、環境対応ガソリン組成物Ｑを調製した。環境対応ガソリン組成物Ｑの性状等を表１１〜１２に示す。 Hydrodesulfurization was performed in the same manner as in Example 1 except that the same heavy naphtha fraction D as in Example 1 was set at a reaction temperature of 240 ° C., and a desulfurized heavy naphtha fraction H was obtained. Properties and the like of this desulfurized heavy naphtha fraction H are shown in Tables 7-8. This desulfurized heavy naphtha fraction H, light naphtha fraction C, and other gasoline base materials and antioxidants same as those in Example 1 are blended in the blending amounts shown in Table 10, and a colorant and a cleaning dispersant are added. Then, an environmentally friendly gasoline composition Q was prepared. Tables 11 to 12 show the properties and the like of the environment-friendly gasoline composition Q.
実施例２と同様の方法によって得られた脱硫重質ナフサ留分Ｈ１００ｃｃを１２規定の水酸化ナトリウム溶液１００ｃｃに加え、室温で３０分撹拌しながら接触させた後、油分を抽出処理して脱硫重質ナフサ留分Ｉを得た。この脱硫重質ナフサ留分Ｉの性状等を表７〜８に示す。この脱硫重質ナフサ留分Ｉと、軽質ナフサ留分Ｃと、さらに実施例１と同じ他のガソリン基材を表１０に示す割合で配合し、さらに実施例１と同様に酸化防止剤１０質量ｐｐｍ、着色剤、清浄分散剤を加えて、環境対応ガソリン組成物Ｒを調製した。環境対応ガソリン組成物Ｒの性状を表１１〜１２に示す。 Desulfurized heavy naphtha fraction H100 cc obtained by the same method as in Example 2 was added to 100 cc of 12N sodium hydroxide solution and brought into contact with stirring at room temperature for 30 minutes, and then the oil was extracted and desulfurized heavy. A quality naphtha fraction I was obtained. Properties and the like of this desulfurized heavy naphtha fraction I are shown in Tables 7-8. The desulfurized heavy naphtha fraction I, the light naphtha fraction C, and another gasoline base material similar to that in Example 1 were blended in the proportions shown in Table 10 and further 10 masses of antioxidant as in Example 1. An environmentally friendly gasoline composition R was prepared with the addition of ppm, colorant and detergent dispersant. Tables 11 to 12 show the properties of the environment-friendly gasoline composition R.
無鉛ガソリン基材として脱硫ナフサＬを用いなかった以外は、実施例２と全く同じ基材（軽質ナフサ留分Ｃ、脱硫重質ナフサ留分Ｈ、接触改質中質油Ｍ、接触改質重質油Ｎ、及びアルキレートガソリンＯ）及び酸化防止剤を表１０に示す割合で配合し、着色剤、清浄分散剤を加えて、ＲＯＮ９３の環境対応ガソリン組成物Ｓを調製した。該環境対応ガソリン組成物Ｓの性状等を表１１〜１２に示す。 Except that desulfurized naphtha L was not used as a lead-free gasoline base material, the same base materials as in Example 2 (light naphtha fraction C, desulfurized heavy naphtha fraction H, catalytic reforming medium oil M, catalytic reforming heavy weight) Quality oil N, alkylate gasoline O) and antioxidants were blended in the proportions shown in Table 10, and coloring agents and detergent dispersants were added to prepare RON93 environmentally friendly gasoline composition S. Tables 11 to 12 show the properties and the like of the environment-friendly gasoline composition S.
実施例４と全く同じ基材（軽質ナフサ留分Ｃ、脱硫重質ナフサ留分Ｈ、接触改質中質油Ｍ、接触改質重質油Ｎ、及びアルキレートガソリンＯ）及び酸化防止剤を表１０に示す割合で配合し、着色剤、清浄分散剤を加えて、ＲＯＮ９４強の環境対応ガソリン組成物Ｔを調製した。該環境対応ガソリン組成物Ｔの性状等を表１１〜１２に示す。 Exactly the same base material as in Example 4 (light naphtha fraction C, desulfurized heavy naphtha fraction H, catalytic reforming medium oil M, catalytic reforming heavy oil N, and alkylate gasoline O) and an antioxidant Blended in the proportions shown in Table 10, a coloring agent and a detergent / dispersant were added to prepare an environmentally-friendly gasoline composition T having a strength of RON 94. Tables 11 to 12 show the properties and the like of the environment-friendly gasoline composition T.
実施例４と全く同じ基材（軽質ナフサ留分Ｃ、脱硫重質ナフサ留分Ｈ、接触改質中質油Ｍ、接触改質重質油Ｎ、及びアルキレートガソリンＯ）及び酸化防止剤を表１０に示す割合で配合し、着色剤、清浄分散剤を加えて、ＲＯＮ９５の環境対応ガソリン組成物Ｕを調製した。該環境対応ガソリン組成物Ｕの性状等を表１１〜１２に示す。 Exactly the same base material as in Example 4 (light naphtha fraction C, desulfurized heavy naphtha fraction H, catalytic reforming medium oil M, catalytic reforming heavy oil N, and alkylate gasoline O) and an antioxidant RON 95 environmentally friendly gasoline composition U was prepared by blending in the proportions shown in Table 10 and adding a colorant and a cleaning dispersant. Tables 11 to 12 show properties of the environmentally friendly gasoline composition U.
実施例４と全く同じ基材（軽質ナフサ留分Ｃ、脱硫重質ナフサ留分Ｈ、接触改質中質油Ｍ、接触改質重質油Ｎ、及びアルキレートガソリンＯ）に加えてＥＴＢＥを表１０に示す割合で配合し、酸化防止剤１０質量ｐｐｍ、着色剤、清浄分散剤を加えて、ＲＯＮ９４強の環境対応ガソリン組成物Ｖを調製した。該環境対応ガソリン組成物Ｖの性状等を表１１〜１２に示す。 In addition to the same base material as in Example 4 (light naphtha fraction C, desulfurized heavy naphtha fraction H, catalytic reforming medium oil M, catalytic reforming heavy oil N, and alkylate gasoline O), ETBE was added. Blended in the proportions shown in Table 10 and added 10 mass ppm of antioxidant, colorant, and detergent / dispersant, an environmentally-friendly gasoline composition V of RON 94 was prepared. Tables 11 to 12 show properties of the environmentally friendly gasoline composition V.
実施例２と同様の方法によって得られた脱硫重質ナフサ留分Ｈ１００ｃｃを酸化銅−アルミナ系脱硫剤（銅を金属原子として７.６質量％含有）２０ｇと、室温で、２時間、フラスコ中で攪拌混合処理した後、脱硫剤を濾別して脱硫重質ナフサ留分Ｊを得た。この脱硫重質ナフサ留分Ｊの性状等を表７〜８に示す。この脱硫重質ナフサ留分Ｊ、軽質ナフサ留分Ｃと、さらに実施例１と同じ他のガソリン基材を表１０に示す割合で配合し、実施例１と同様に酸化防止剤１０質量ｐｐｍ、着色剤、清浄分散剤を加えて、環境対応ガソリン組成物Ｗを調製した。環境対応ガソリン組成物Ｗの性状などを表１１〜１２に示す。 Desulfurized heavy naphtha fraction H100cc obtained by the same method as in Example 2 and 20 g of a copper oxide-alumina desulfurizing agent (containing 7.6% by mass of copper as a metal atom) at room temperature for 2 hours in a flask Then, the desulfurization agent was filtered off to obtain a desulfurized heavy naphtha fraction J. Properties and the like of this desulfurized heavy naphtha fraction J are shown in Tables 7-8. This desulfurized heavy naphtha fraction J, light naphtha fraction C, and another gasoline base material similar to that in Example 1 were blended in the proportions shown in Table 10, and in the same manner as in Example 1, 10 mass ppm of antioxidant, An environmentally friendly gasoline composition W was prepared by adding a colorant and a cleaning dispersant. Tables 11 to 12 show properties of the environment-friendly gasoline composition W and the like.
実施例１と同じナフサ留分Ｂを分留し、軽質ナフサ留分Ｅと重質ナフサ留分Ｆを得た。軽質ナフサ留分Ｅと重質ナフサ留分Ｆの性状等を表５〜６に示す。この重質ナフサ留分Ｆを実施例２と同様に水素化脱硫を行い、脱硫重質ナフサ留分Ｋを得た。脱硫重質ナフサ留分Ｋの性状等を表７〜８に示す。この脱硫重質ナフサ留分Ｋ、軽質ナフサ留分Ｅと、さらに実施例１と同じ他のガソリン基材を表１０に示す割合で配合し、酸化防止剤１００質量ｐｐｍ、着色剤、清浄分散剤を加えて、比較例の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１１〜１２に示す。 The same naphtha fraction B as in Example 1 was fractionated to obtain a light naphtha fraction E and a heavy naphtha fraction F. Properties of light naphtha fraction E and heavy naphtha fraction F are shown in Tables 5-6. This heavy naphtha fraction F was hydrodesulfurized in the same manner as in Example 2 to obtain a desulfurized heavy naphtha fraction K. Properties and the like of the desulfurized heavy naphtha fraction K are shown in Tables 7-8. This desulfurized heavy naphtha fraction K, light naphtha fraction E, and another gasoline base material similar to Example 1 were blended in the proportions shown in Table 10, antioxidant 100 mass ppm, colorant, detergent dispersant And an unleaded gasoline composition X of Comparative Example was prepared. Properties of the unleaded gasoline composition X are shown in Tables 11-12.
重質ナフサ留分Ｄを水素化脱硫して得た脱硫重質ナフサ留分Ｈと、軽質ナフサ留分Ｃと、さらに実施例１と同じ他のガソリン基材を表１０に示す割合で配合し、実施例１と同様に酸化防止剤１０質量ｐｐｍ、着色剤、清浄分散剤を加えて、環境対応ガソリン組成物Ｙを得た。環境対応ガソリン組成物Ｙの性状を表１１〜１２に示す。 Desulfurized heavy naphtha fraction H obtained by hydrodesulfurizing heavy naphtha fraction D, light naphtha fraction C, and another gasoline base material similar to that in Example 1 were blended in the proportions shown in Table 10. In the same manner as in Example 1, 10 mass ppm of antioxidant, a colorant, and a detergent / dispersant were added to obtain an environment-friendly gasoline composition Y. Tables 11 to 12 show the properties of the environment-friendly gasoline composition Y.
実施例と比較例を比べるとわかるように、接触分解ナフサをスイートニングした後、重質ナフサ留分中のＣ５オレフィンが１．４容量％以下となるよう接触分解ナフサを分留し、重質ナフサ留分のみを脱硫することによって、脱硫接触分解ナフサに含まれるチオール類は臭気が比較的弱い炭素数７以上の脂肪族チオール類が５０％以上となる。したがって、これを混ぜたガソリンは、炭素数６以下の脂肪族チオール類を多く含むガソリンに比べて臭気が弱くなる。またドクター試験も陰性となることがわかる。たとえ実施例９のように陽性であっても、実施例２に示すように酸化防止剤の添加量を調節することによって容易に陰性にすることができ、本発明の環境への影響を低減した超低硫黄分の環境対応ガソリンの商品価値を向上することができる。 As can be seen from a comparison between Examples and Comparative Examples, after sweetening the catalytic cracking naphtha, the catalytic cracking naphtha was fractionated so that the C5 olefin in the heavy naphtha fraction was 1.4 vol% or less. By desulfurizing only the naphtha fraction, the thiols contained in the desulfurization catalytic cracking naphtha are 50% or more of aliphatic thiols having 7 or more carbon atoms that have a relatively weak odor. Therefore, gasoline mixed with this has a weaker odor than gasoline containing a large amount of aliphatic thiols having 6 or less carbon atoms. The doctor test is also negative. Even if it is positive as in Example 9, it can be easily made negative by adjusting the amount of antioxidant added as shown in Example 2, and the environmental impact of the present invention is reduced. The product value of environmentally friendly gasoline with ultra-low sulfur content can be improved.
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