JP4804971B2 - Unleaded gasoline and method for producing the same - Google Patents
Unleaded gasoline and method for producing the same Download PDFInfo
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- JP4804971B2 JP4804971B2 JP2006073672A JP2006073672A JP4804971B2 JP 4804971 B2 JP4804971 B2 JP 4804971B2 JP 2006073672 A JP2006073672 A JP 2006073672A JP 2006073672 A JP2006073672 A JP 2006073672A JP 4804971 B2 JP4804971 B2 JP 4804971B2
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- 239000003502 gasoline Substances 0.000 title claims description 110
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 76
- 238000000034 method Methods 0.000 claims description 34
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 238000004821 distillation Methods 0.000 claims description 20
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000001833 catalytic reforming Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 238000004523 catalytic cracking Methods 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 235000014676 Phragmites communis Nutrition 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000002585 base Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 230000001133 acceleration Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000001273 butane Substances 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- -1 alkaline earth metal salts Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000002816 fuel additive Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000003599 detergent 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
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003556 thioamides Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Liquid Carbonaceous Fuels (AREA)
Description
本発明は、エタノールおよびエチル・ターシャリー・ブチル・エーテルを配合したガソリンに関し、詳しくは特定された蒸留性状及び特定された成分組成を有し、自動車用燃料として環境に配慮し、かつ始動性、運転性に優れた無鉛ガソリンに関する。 The present invention relates to a gasoline blended with ethanol and ethyl tertiary butyl ether, and in particular has a specified distillation property and a specified component composition, is environmentally friendly as a fuel for automobiles, and has a startability, It relates to unleaded gasoline with excellent drivability.
近年、ガソリンエンジン用燃料油としては、高オクタン価で運転性能に優れると共に、環境性能にも優れるものが要望されるようになってきた。
一般に、高オクタン価ガソリンとして、重質で芳香族分含有量の多い高オクタン価基材を配合し、特定の蒸留性状及び成分組成を有するものが知られている（例えば、特許文献１参照）。
In recent years, fuel oils for gasoline engines have been demanded that have a high octane number and excellent driving performance as well as excellent environmental performance.
In general, as a high-octane gasoline, a high octane number base material having a heavy and high aromatic content and a specific distillation property and component composition are known (see, for example, Patent Document 1).
この高オクタン価ガソリンの場合、重質で芳香族分含有量が多い高オクタン価基材を配合するために、高沸点留分のオクタン価は向上するが、ガソリンの重質化、エンジン内のデポジットの生成、特に吸気バルブへのデポジットの付着、及び運転性への影響等が懸念される。
このような、ガソリンの重質化、吸気バルブへのデポジットの付着を改善するには、軽質・高オクタン価基材を配合することが重要であると考えられる。
In the case of this high-octane gasoline, the octane number of the high-boiling fraction is improved because a high-octane base material with a heavy aromatic content is added. However, the gasoline becomes heavier and produces deposits in the engine. In particular, there are concerns about deposits on the intake valves and influence on drivability.
In order to improve the heaviness of gasoline and the adhesion of deposits to the intake valve, it is considered important to add a light and high octane base material.
また、自動車排出ガス中の一酸化炭素（CO）、全炭化水素（THC）等の低減には、含酸素化合物であるメチルターシャリーブチルエーテル（MTBE）を配合したガソリンが知られている（例えば、特許文献２参照）。
しかしながら、ＭＴＢＥの環境面への影響が懸念され、現在は日本国内でのＭＴＢＥを配合したガソリンの生産・販売が自制されている。ＭＴＢＥはオクタン価が高い基材であるために、ＭＴＢＥの配合を中止する場合には、それに代わる高いオクタン価基材が必要とされている。その中で、ガソリンのオクタン価低下を補い、また環境負荷が低いと考えられる、ＭＴＢＥ以外の含酸素有機化合物が新しいガソリン基材として注目されている。中でも、エタノールは、オクタン価も高く、芳香族分やオレフィン分を含まず、バイオマスとして考える場合には再生可能燃料としてとらえることができるといった利点を有している（例えば、非特許文献１参照）。
In addition, gasoline that contains methyl tertiary butyl ether (MTBE), which is an oxygen-containing compound, is known for reducing carbon monoxide (CO), total hydrocarbons (THC), and the like in automobile exhaust gases (for example, Patent Document 2).
However, there is concern about the environmental impact of MTBE, and now production and sales of gasoline containing MTBE are restrained in Japan. Since MTBE is a base material having a high octane number, when the mixing of MTBE is stopped, a high octane number base material is required instead. Among them, oxygen-containing organic compounds other than MTBE, which compensate for the decrease in octane number of gasoline and are considered to have a low environmental load, are attracting attention as new gasoline base materials. Among these, ethanol has a high octane number, does not contain aromatics and olefins, and has an advantage that it can be regarded as a renewable fuel when considered as biomass (see, for example, Non-Patent Document 1).
一方、ＣＯ２削減の観点から、バイオマス由来のエタノールあるいはそれから派生するＥＴＢＥをガソリンへ混合する議論がされている。しかしながら、ＣＯ２削減量を多くするために、エタノールをよりガソリンに配合しようとすると、炭化水素とエタノールの共沸現象が顕著になり、蒸留曲線がいびつになることで運転性などが悪化する場合があることが知られている。これを回避するために、エタノールをイソブチレンと反応させて得られるＥＴＢＥをガソリンへ配合することが考えられるが、バイオマス混合によるＣＯ２削減の観点から見ると、多量のＥＴＢＥをガソリンへ配合する必要が生じ、ガソリン生産の経済性が劣ることになる。 On the other hand, from the viewpoint of CO 2 reduction, there is a discussion of mixing ethanol derived from biomass or ETBE derived therefrom with gasoline. However, if ethanol is added to gasoline in order to increase CO 2 reduction, the azeotropic phenomenon of hydrocarbon and ethanol becomes prominent, and the operability and the like deteriorate due to the distorted distillation curve. It is known that there is. In order to avoid this, it is conceivable to blend ETBE obtained by reacting ethanol with isobutylene into gasoline. From the viewpoint of CO 2 reduction by biomass mixing, it is necessary to blend a large amount of ETBE into gasoline. This will make the economy of gasoline production inferior.
エタノールとＥＴＢＥをガソリンに配合したものとしては、エタノールを１〜１０容量％、エチル・ターシャリー・ブチル・エーテルを１〜２０容量％、炭素数４の炭化水素を５．５容量％以上含有したものや、エタノールを１〜３容量％ 、エチル・ターシャリー・ブチル・エーテルを０〜２０容量％含有するガソリン組成物が挙げられる（例えば、特許文献３、特許文献４）。 As a blend of ethanol and ETBE in gasoline, it contained 1 to 10% by volume of ethanol, 1 to 20% by volume of ethyl tertiary butyl ether, and 5.5% by volume or more of hydrocarbons having 4 carbon atoms. And gasoline compositions containing 1 to 3% by volume of ethanol and 0 to 20% by volume of ethyl tertiary butyl ether (for example, Patent Document 3 and Patent Document 4).
特許文献３は、エタノールの蒸気圧が従来の石油のみから製造されるガソリンよりも高いことから、エタノールを添加した場合でも、軽質な炭化水素の含有量を減らすことのないことを課題としており、特許文献４は、エタノールの水分の影響について検討し、比較的低濃度のエタノールを添加した場合でも相分離が起こりにくいガソリンの提供を課題としている。しかし、いずれもエタノールとＥＴＢＥを配合したガソリンによる自動車の始動性や加速性については更なる改善が必要である。 Patent Document 3 has a problem that the content of light hydrocarbons is not reduced even when ethanol is added because the vapor pressure of ethanol is higher than that of gasoline produced only from conventional petroleum. Patent Document 4 examines the influence of the water content of ethanol, and has a problem of providing gasoline that hardly causes phase separation even when a relatively low concentration of ethanol is added. However, in any case, further improvement is required in terms of startability and acceleration of a vehicle using gasoline containing ethanol and ETBE.
本発明は、大気環境に配慮し、自動車の始動性や加速性にも優れたエタノールおよびエチル・ターシャリー・ブチル・エーテルを配合した無鉛ガソリンを提供することを目的とするものである。 An object of the present invention is to provide unleaded gasoline blended with ethanol and ethyl tertiary butyl ether that is excellent in startability and acceleration of an automobile in consideration of the atmospheric environment.
本発明者らは、上記目的を達成するために鋭意研究を重ねた結果、軽質な高オクタン価基材であるエタノール（ＥｔＯＨ）とエチル・ターシャリー・ブチル・エーテル（ＥＴＢＥ）を選定し、ＥｔＯＨとＥＴＢＥの特定量と特定の成分組成及び特定の蒸留性状を有するようにガソリンを構成することにより、優れた諸性能を有するガソリンが得られ、上記目的を達成し得ることを見出し、本発明を完成するに至った。
即ち、本発明は、下記無鉛ガソリン及びその製造方法を提供する。
［１］ エタノール（ＥｔＯＨ）を０．５〜１０．０容量％、エチルターシャリーブチルエーテル（ＥＴＢＥ）を１．０〜１０．０容量％含み、かつ、以下の性状を満足することを特徴とする無鉛ガソリン。
（１）リサーチ法オクタン価（ＲＯＮ）が８９以上９７未満
（２）モーター法オクタン価（ＭＯＮ）が７９以上８７未満
（３）リード蒸気圧（ＲＶＰ）が４５〜９３ｋＰａ
（４）５０％留出温度（Ｔ５０）が７５〜１１０℃
（５）７０℃留出量（Ｅ７０）が１８〜４０容量％
（６）芳香族分含有量が５〜１７．０容量％
（７）オレフィン分含有量が５〜１５．２容量％
（８）ベンゼン含有量が１容量％以下
（９）硫黄分含有量が１０質量ｐｐｍ以下
（１０）６０℃における気液比（Ｖ／Ｌ）が３０〜７０
［２］ 炭素数９以上の芳香族分／全芳香族分の容量比が０．８０以下である上記［１］に記載の無鉛ガソリン。
［３］ 脱ベンゼン接触改質ガソリン、脱ベンゼン軽質接触改質ガソリン、脱ベンゼン重質接触改質ガソリン、接触分解ガソリン、脱硫軽質ナフサ、アルキレート、Ｃ４留分、アイソメレート、イソペンタン、トルエン、キシレン、及び炭素数９以上の芳香族を主体とする成分からなる群より選ばれる１種以上をさらに含むことを特徴とする上記［１］又は［２］に記載の無鉛ガソリン。
［４］ ガソリン基材に、エタノール（ＥｔＯＨ）を０．５〜１０．０容量％、及びエチルターシャリーブチルエーテル（ＥＴＢＥ）を１．０〜１０．０容量％の割合で配合し、得られる無鉛ガソリンが以下の性状を満足するように調整することを特徴とする無鉛ガソリンの製造方法。
（１）リサーチ法オクタン価（ＲＯＮ）が８９以上９７未満
（２）モーター法オクタン価（ＭＯＮ）が７９以上８７未満
（３）リード蒸気圧（ＲＶＰ）が４５〜９３ｋＰａ
（４）５０％留出温度（Ｔ５０）が７５〜１１０℃
（５）７０℃留出量（Ｅ７０）が１８〜４０容量％
（６）芳香族分含有量が５〜１７．０容量％
（７）オレフィン分含有量が５〜１５．２容量％
（８）ベンゼン含有量が１容量％以下
（９）硫黄分含有量が１０質量ｐｐｍ以下
（１０）６０℃における気液比（Ｖ／Ｌ）が３０〜７０
［５］ 前記無鉛ガソリンがさらに炭素数９以上の芳香族分／全芳香族分の容量比が０．８０以下である性状を満足するように調整することを特徴とする上記［４］に記載の無鉛ガソリンの製造方法。
［６］ 前記ガソリン基材が、脱ベンゼン接触改質ガソリン、脱ベンゼン軽質接触改質ガソリン、脱ベンゼン重質接触改質ガソリン、接触分解ガソリン、脱硫軽質ナフサ、アルキレート、Ｃ４留分、アイソメレート、イソペンタン、トルエン、キシレン、及び炭素数９以上の芳香族を主体とする成分からなる群より選ばれる１種以上であることを特徴とする上記［４］又は［５］に記載の無鉛ガソリンの製造方法。
As a result of intensive studies to achieve the above object, the present inventors selected ethanol (EtOH) and ethyl tertiary butyl ether (ETBE), which are light high octane base materials, and EtOH and Completing the present invention, it was found that by configuring gasoline so that it has a specific amount of ETBE, a specific component composition, and a specific distillation property, a gasoline having excellent performances can be obtained and the above object can be achieved. It came to do.
That is, this invention provides the following unleaded gasoline and its manufacturing method.
[1] 0.5 to 10.0% by volume of ethanol (EtOH), 1.0 to 10.0 % by volume of ethyl tertiary butyl ether (ETBE), and satisfy the following properties: Unleaded gasoline .
(1) Research method octane number (RON) is 89 or more and less than 97 (2) Motor method octane number (MON) is 79 or more and less than 87 (3) Reed vapor pressure (RVP) is 45 to 93 kPa
(4) 50% distillation temperature (T50) is 75 to 110 ° C
(5) 70 ° C. distillate (E70) is 18 to 40% by volume
(6) Aromatic content is 5-17.0% by volume
(7) Olefin content is 5 to 15.2% by volume
(8) Benzene content is 1% by volume or less (9) Sulfur content is 10 mass ppm or less (10) Gas-liquid ratio (V / L) at 60 ° C. is 30 to 70
[2] The unleaded gasoline according to the above [1], wherein the volume ratio of aromatic content / total aromatic content having 9 or more carbon atoms is 0.80 or less.
[3] Debenzene catalytic reforming gasoline, debenzene light catalytic reforming gasoline, debenzene heavy catalytic reforming gasoline, catalytic cracking gasoline, desulfurized light naphtha, alkylate, C4 fraction, isomerate, isopentane, toluene, xylene And the lead-free gasoline as described in the above item [1] or [2], further comprising at least one selected from the group consisting of components mainly composed of aromatics having 9 or more carbon atoms.
[4] Lead-free obtained by blending ethanol (EtOH) in a proportion of 0.5 to 10.0% by volume and ethyl tertiary butyl ether (ETBE) in a proportion of 1.0 to 10.0% by volume in a gasoline base material A method for producing unleaded gasoline, wherein the gasoline is adjusted so as to satisfy the following properties.
(1) Research octane number (RON) is 89 or more and less than 97
(2) Motor method octane number (MON) is 79 or more and less than 87
(3) Reed vapor pressure (RVP) is 45 to 93 kPa
(4) 50% distillation temperature (T50) is 75 to 110 ° C
(5) 70 ° C. distillate (E70) is 18 to 40% by volume
(6) Aromatic content is 5-17.0% by volume
(7) Olefin content is 5 to 15.2% by volume
(8) Benzene content is 1% by volume or less
(9) Sulfur content is 10 mass ppm or less
(10) Gas-liquid ratio (V / L) at 60 ° C. is 30 to 70
[5] The above-mentioned [4], wherein the unleaded gasoline is further adjusted so as to satisfy a property that the volume ratio of aromatic content / total aromatic content having 9 or more carbon atoms is 0.80 or less. Manufacturing method of unleaded gasoline.
[6] The gasoline base material is debenzene catalytic reformed gasoline, debenzene light catalytic reformed gasoline, debenzene heavy catalytic reformed gasoline, catalytic cracked gasoline, desulfurized light naphtha, alkylate, C4 fraction, isomerate. The unleaded gasoline according to [4] or [5] above, which is at least one selected from the group consisting of isopentane, toluene, xylene, and an aromatic component mainly having 9 or more carbon atoms. Production method.
本発明の無鉛ガソリンは、エタノールとエチルターシャリーブチルエーテルを特定量配合し、自動車のガソリンエンジンに用いられ、大気環境の保全性に優れ、始動性や運転性にも優れたものであり、実用性能を維持しつつ大気環境の保全が図られるものである。 The unleaded gasoline of the present invention contains a specific amount of ethanol and ethyl tertiary butyl ether, is used in automobile gasoline engines, has excellent air environment conservation, excellent startability and drivability, and practical performance The air environment can be preserved while maintaining the above.
以下、本発明の内容を更に詳しく説明する。
本発明の無鉛ガソリンに用いられるエタノール（EtOH）は、純度が９２．０容量％以上であって、好ましくは９５．０容量％以上、更に好ましくは９９．５容量％以上である。
エタノールの製造方法は特に限定されるものではなく、一般的に製造される全てのエタノールが使用可能である。
エタノールの含有量は、エタノール配合ガソリン全量に対し０．５容量％以上１０．０容量％以下の範囲にあり、好ましくは１．０容量％以上７．０容量％以下である。０．５容量％以上であれば、エタノール配合によるオクタン価向上の利点が得られ、１０．０容量％以下とすることで他のガソリン基材との共沸現象により蒸発特性が著しく変化することがなく、ガソリン自動車の適正な運転性が確保できる。
Hereinafter, the contents of the present invention will be described in more detail.
Ethanol (EtOH) used in the unleaded gasoline of the present invention has a purity of 92.0% by volume or more, preferably 95.0% by volume or more, more preferably 99.5% by volume or more.
The method for producing ethanol is not particularly limited, and all generally produced ethanol can be used.
The ethanol content is in the range of 0.5% by volume or more and 10.0% by volume or less, preferably 1.0% by volume or more and 7.0% by volume or less, with respect to the total amount of ethanol-blended gasoline. If it is 0.5% by volume or more, the advantage of improving the octane number by blending with ethanol is obtained, and if it is 10.0% by volume or less, the evaporation characteristics may change significantly due to the azeotropic phenomenon with other gasoline base materials. Therefore, it is possible to ensure proper driving performance of gasoline cars.
本発明の無鉛ガソリンに用いられるエチルターシャリーブチルエーテル（ETBE）は、公知の製造法から得られるもの全て使用可能であり、その製造方法は特に限定されるものではない。本発明の無鉛ガソリンにおけるETBEの配合量は０．５〜１５．０容量％、好ましくは１．０〜１０．０容量％である。ETBEの配合量が上記範囲内であれば、発熱量の低下による燃費への悪影響の懸念なく、排出ガス中のCO、THC等の低減などを図ることができる。 Any ethyl tertiary butyl ether (ETBE) used in the unleaded gasoline of the present invention can be obtained from a known production method, and the production method is not particularly limited. The blending amount of ETBE in the unleaded gasoline of the present invention is 0.5 to 15.0% by volume, preferably 1.0 to 10.0% by volume. If the blending amount of ETBE is within the above range, it is possible to reduce CO, THC, etc. in the exhaust gas without fear of an adverse effect on fuel consumption due to a decrease in calorific value.
本発明の無鉛ガソリンの(a)リサーチ法オクタン価（RON）は、89以上97未満、好ましくは89〜95、（ｂ）モーター法オクタン価（MON）は、79以上87未満、好ましくは79〜85であり、RONが89以上ならば、高い運転性能を維持することが可能となり、MONが79以上であれば高速走行時のアンチノック性の低下を防止することができる。なお、このRON及びMONは、JIS K 2280に準拠して測定した値である。 (A) Research method octane number (RON) of the unleaded gasoline of the present invention is 89 or more and less than 97, preferably 89 to 95, and (b) Motor method octane number (MON) is 79 or more and less than 87, preferably 79 to 85. If RON is 89 or more, it is possible to maintain high driving performance, and if MON is 79 or more, it is possible to prevent a decrease in anti-knock property at high speed. Note that RON and MON are values measured in accordance with JIS K 2280.
また、本発明の無鉛ガソリンのリード蒸気圧（RVP）は、45〜93kPa、好ましくは50〜90kPaである。RVPを93kPa以下にすることによって蒸発ガスの量を少なくすることができ、45kPa以上とすることで低温始動性、暖気性の低下を防ぐことができる。なお、このリード蒸気圧（RVP）は、JIS K 2258に準拠して測定した値である。 The lead vapor pressure (RVP) of the unleaded gasoline of the present invention is 45 to 93 kPa, preferably 50 to 90 kPa. By setting the RVP to 93 kPa or less, the amount of evaporative gas can be reduced, and by setting it to 45 kPa or more, it is possible to prevent the low temperature startability and warming performance from being deteriorated. This Reid vapor pressure (RVP) is a value measured according to JIS K 2258.
本発明の無鉛ガソリンの蒸留性状は、(a)50％留出温度（T50）が、75〜110℃、好ましくは75〜105℃、(b)70℃留出量（E70）が、18〜40容量％、好ましくは20〜40容量％であり、T50、E70が上記範囲内であれば、始動性、運転性、加速性に不具合が生じる場合を防ぐことができる。なお、これらの蒸留性状はJIS K 2254に準拠して測定した値である。 The distillation properties of the unleaded gasoline of the present invention are as follows: (a) 50% distillation temperature (T50) is 75 to 110 ° C, preferably 75 to 105 ° C, (b) 70 ° C distillation amount (E70) is 18 to If it is 40 vol%, preferably 20-40 vol%, and T50 and E70 are within the above ranges, it is possible to prevent the occurrence of problems in startability, drivability and acceleration. These distillation properties are values measured in accordance with JIS K 2254.
本発明の無鉛ガソリンの芳香族分含有量は、40容量％以下、好ましくは5〜35容量％である。この芳香族分含有量が40容量％以内であれば、排出ガス中の有害成分の増加を防ぐことができる。なお、この芳香族分含有量は、石油学会法JPI-5S-33-90（ガスクロマトグラフ法）に準拠して測定した値である。 The aromatic content of the unleaded gasoline of the present invention is 40% by volume or less, preferably 5 to 35% by volume. If the aromatic content is within 40% by volume, an increase in harmful components in the exhaust gas can be prevented. The aromatic content is a value measured in accordance with the Petroleum Institute Method JPI-5S-33-90 (gas chromatographic method).
本発明の無鉛ガソリンのオレフィン分含有量は、30容量％以下、好ましくは5〜27容量
％である。このオレフィン分含有量が30容量％以内であれば、酸化安定性の低下を防ぐことができる。なお、このオレフィン分含有量は、石油学会法JPI-5S-33-90（ガスクロマトグラフ法）に準拠して測定した値である。
The olefin content of the unleaded gasoline of the present invention is 30% by volume or less, preferably 5 to 27% by volume. When the olefin content is within 30% by volume, it is possible to prevent a decrease in oxidation stability. The olefin content is a value measured in accordance with the Petroleum Institute method JPI-5S-33-90 (gas chromatographic method).
本発明の無鉛ガソリンのベンゼン含有量は、1容量％以下、好ましくは0.8容量％以下である。このベンゼン含有量が1容量％以内であれば、大気中のベンゼン濃度の増加を防止
し、環境汚染を低減できる可能性がある。なお、このベンゼン含有量は、石油学会法JPI-5S-33-90（ガスクロマトグラフ法）に準拠して測定した値である。
The benzene content of the unleaded gasoline of the present invention is 1% by volume or less, preferably 0.8% by volume or less. If the benzene content is within 1% by volume, there is a possibility that the increase in benzene concentration in the atmosphere can be prevented and environmental pollution can be reduced. The benzene content is a value measured according to the Petroleum Institute method JPI-5S-33-90 (gas chromatographic method).
本発明の無鉛ガソリンの硫黄分含有量は、10質量ppm以下、好ましくは8質量ppm以下である。この硫黄分含有量が10質量ppm以内であれば、排出ガス浄化触媒の能力低下を防止し、排出ガス中のNOｘ、CO、THCの濃度上昇を防止できる可能性がある。なお、この硫黄分含有量は、JIS K 2541に準拠して測定した値である。 The sulfur content of the unleaded gasoline of the present invention is 10 mass ppm or less, preferably 8 mass ppm or less. If the sulfur content is within 10 ppm by mass, there is a possibility that the exhaust gas purification catalyst capacity can be prevented from being lowered and the concentration of NOx, CO and THC in the exhaust gas can be prevented from increasing. The sulfur content is a value measured according to JIS K 2541.
本発明の無鉛ガソリンの60℃における気液比（V/L）は、30〜70、好ましくは30〜60である。このV/Lが30以上とすることで、良好な始動性を確保することができる。また、V/Lを70以下とすることで、加速性、運転性の不具合が低減できる可能性がある。なお、このV/Lは、ASTM D 2533-93aに準拠して測定した値である。 The gas-liquid ratio (V / L) at 60 ° C. of the unleaded gasoline of the present invention is 30 to 70, preferably 30 to 60. When this V / L is 30 or more, good startability can be ensured. In addition, by setting V / L to 70 or less, there is a possibility that defects in acceleration and drivability can be reduced. The V / L is a value measured according to ASTM D 2533-93a.
本発明の無鉛ガソリンにおいて、炭素数９以上の芳香族分と全芳香族分の比（以下、（Ｃ９＋Ａ）／ＴＡともいう。）は０．８０以下、好ましくは０．１０〜０．８０である。炭素数９以上の芳香族分と全芳香族分の比が０．８０以下ならば、プラグの対くすぶり性の低下を防止できる可能性があるので好ましい。なお、この芳香族分含有量は、石油学会法JPI-5S-33-90（ガスクロマトグラフ法）に準拠して測定した値である。 In the unleaded gasoline of the present invention, the ratio of aromatics having 9 or more carbon atoms to the total aromatics (hereinafter also referred to as (C9 + A) / TA) is 0.80 or less, preferably 0.10 to 0.80. is there. It is preferable that the ratio of the aromatic component having 9 or more carbon atoms and the total aromatic component is 0.80 or less because it is possible to prevent the smoldering property of the plug from being lowered. The aromatic content is a value measured in accordance with the Petroleum Institute Method JPI-5S-33-90 (gas chromatographic method).
上記のような性状を有する無鉛ガソリンを製造するためのEtOHおよびETBE以外の基材については、特に制限はないが、例えば、下記のような各種留分を基材として用いることができる。
（イ）重質の直留ナフサなどを接触改質法（プラットフォーミング法、マグナフォーミング法、アロマイジング法、レニフォーミング法、フードリフォーミング法、ウルトラフォーミング法、パワーフォーミング法等）により、水素気流中で高温・加圧下で触媒（例えば、アルミナ担体に白金やロジウムと塩素とを担持したもの等）と接触処理して得られた改質ガソリンからベンゼン留分を蒸留により取り除いた脱ベンゼン接触改質ガソリン。
（ロ）上記接触改質法により接触処理して得られた改質ガソリンを蒸留により、軽質留分、ベンゼン留分、重質留分に分けた内の軽質留分（脱ベンゼン軽質接触改質ガソリン）及び重質留分（脱ベンゼン重質接触改質ガソリン）。
（ハ）灯・軽油から常圧残油に至る石油留分、好ましくは重質軽油や減圧軽油を、従来から知られている接触分解法、特に流動接触分解法（UOP法、シェル二段式法、フレキシ
クラッキング法、ウルトラオルソフロー法、テキサコ法、ガルフ法、ウルトラキャットクラッキング法、RCC法、HOC法等）により、固体酸触媒（例えば、シリカ・アルミナにゼオライトを配合したもの等）で分解して得られる接触分解ガソリン。
（ニ）原油を常圧蒸留した直留ナフサを脱硫処理して得られた脱硫直留ナフサを蒸留により、軽質留分と重質留分に分けた内の軽質留分である脱硫軽質ナフサ。
（ホ）イソブタンと低級オレフィン（ブテン、プロピレン等）を原料として、酸触媒（硫酸、フッ化水素、塩化アルミニウム等）の存在下で反応させて得られるアルキレート。
（ヘ）原油や粗油等の常圧蒸留時、改質ガソリン製造時、あるいは分解ガソリン製造時等に蒸留して得られるブタン、ブテン類を主成分としたＣ４留分。
（ト）直鎖の低級パラフィン系炭化水素の異性化によって得られるアイソメレート、あるいはアイソメレートを精密蒸留して得られるイソペンタン、接触改質ガソリンから得られるトルエン、キシレン、あるいは炭素数９以上の芳香族を主体とする成分等。
The base material other than EtOH and ETBE for producing unleaded gasoline having the above-described properties is not particularly limited. For example, the following various fractions can be used as the base material.
(B) Hydrogen stream by contact reforming method (Platforming method, Magnaforming method, Aromaizing method, Reforming method, Food reforming method, Ultraforming method, Powerforming method, etc.) for heavy straight-run naphtha, etc. In which the benzene fraction is removed by distillation from a reformed gasoline obtained by contact treatment with a catalyst (for example, platinum, rhodium and chlorine supported on an alumina carrier) at high temperature and pressure. Quality gasoline.
(B) The reformed gasoline obtained by contact treatment by the above catalytic reforming method is separated into light fraction, benzene fraction, and heavy fraction by distillation. Gasoline) and heavy fractions (debenzene heavy catalytic reforming gasoline).
(C) Petroleum fraction ranging from kerosene / light oil to atmospheric residual oil, preferably heavy gas oil or vacuum gas oil, is conventionally known catalytic cracking method, especially fluid catalytic cracking method (UOP method, shell two-stage type) Decomposition with a solid acid catalyst (eg, silica / alumina blended with zeolite) by the method, flexi cracking method, ultra ortho flow method, texaco method, Gulf method, ultra cat cracking method, RCC method, HOC method, etc. Catalytic cracking gasoline.
(D) Desulfurized light naphtha, which is a light fraction obtained by distilling a straight-run naphtha obtained by desulfurizing straight-run naphtha obtained by atmospheric distillation of crude oil into a light fraction and a heavy fraction by distillation.
(E) An alkylate obtained by reacting isobutane with a lower olefin (butene, propylene, etc.) in the presence of an acid catalyst (sulfuric acid, hydrogen fluoride, aluminum chloride, etc.).
(F) C4 fraction mainly composed of butane and butenes obtained by distillation during the atmospheric distillation of crude oil or crude oil, during the production of reformed gasoline, or during the production of cracked gasoline.
(G) Isomerate obtained by isomerization of straight-chain lower paraffin hydrocarbons, isopentane obtained by precision distillation of isomerate, toluene, xylene obtained from catalytically reformed gasoline, or aroma having 9 or more carbon atoms Ingredients mainly composed of tribes.
上記のような各種留分を、前記各性状を満たすように、該各種留分の性状等に応じて配合量を適宜選択して、EtOH＋ETBEと共に適宜配合することにより本発明の無鉛ガソリンを製造することができる。例えば、（I）EtOHを0.5〜10.0容量％、(II)ETBEを0.5〜15.0容量％、（III）RONが93以上、MONが83以上、RVPが30kPa以上、沸点範囲が28〜200℃の脱ベンゼン接触改質ガソリンを2〜20容量％、又は（VI）RONが78以上、MONが70以上、RVPが85kPa以上、沸点範囲が26〜80℃の脱ベンゼン軽質接触改質ガソリンを2〜10容量％、RONが101以上、MONが89以上、RVPが3kPa以上、沸点範囲が90〜200℃の脱ベンゼン重質接触改質ガソリンを2〜15容量％、及び（V）RONが88以上、MONが77以上、RVPが40kPa以上、沸点範囲が30〜210℃の接触分解ガソリンを30〜70容量％、RONが65以上、MONが62以上、RVPが75kPa以上、沸点範囲が25〜100℃の脱硫軽質ナフサを5〜30容量％、前記各性状を満たすように配合して本発明の無鉛ガソリンを製造することができる。また、上記のような各基材の配合物に、更に（VI）RONが93以上、MONが90以上、RVPが40kPa以上、沸点範囲が30〜210℃、Ｃ８留分が65容量％以上のアルキレートを3〜20容量％、又はブタン、ブテン類を主成分としたＣ４留分を1〜10容量％、前記各性状を満たすように配合して本発明の無鉛ガソリンを製造することもできる。 The unleaded gasoline of the present invention is produced by appropriately selecting the blending amount of the above various fractions according to the properties of the various fractions so as to satisfy the above properties and appropriately blending with EtOH + ETBE. be able to. For example, (I) EtOH 0.5-10.0% by volume, (II) ETBE 0.5-15.0% by volume, (III) RON 93 or more, MON 83 or more, RVP 30kPa or more, and boiling point range 28-200 ° C 2 to 20% by volume of debenzene-catalyzed reformed gasoline, or (VI) 2 or more of debenzene light-catalyzed reformed gasoline with RON of 78 or more, MON of 70 or more, RVP of 85 kPa or more, and boiling point range of 26-80 ° C 10% by volume, RON 101 or more, MON 89 or more, RVP 3kPa or more, 2-15% by volume of debenzene heavy catalytic reforming gasoline with a boiling range of 90-200 ° C, and (V) RON 88 or more , MON is 77 or more, RVP is 40 kPa or more, 30 to 70% by volume of catalytic cracked gasoline with a boiling range of 30 to 210 ° C, RON is 65 or more, MON is 62 or more, RVP is 75 kPa or more, and boiling range is 25 to 100 The unleaded gasoline of the present invention can be produced by blending 5-30% by volume of desulfurized light naphtha at 0 ° C. so as to satisfy the above properties. In addition, the composition of each substrate as described above has (VI) RON of 93 or more, MON of 90 or more, RVP of 40 kPa or more, boiling range of 30 to 210 ° C., and C8 fraction of 65% by volume or more. The lead-free gasoline of the present invention can be produced by blending 3 to 20% by volume of an alkylate or 1 to 10% by volume of a C4 fraction mainly composed of butane and butenes so as to satisfy the above properties. .
さらに、本発明の無鉛ガソリンには、必要に応じて、各種の添加剤を適宜配合することが出来る。このような添加剤としては、フェノール系、アミン系等の酸化防止剤、チオアミド化合物等の金属不活性剤、有機リン系化合物等の表面着火防止剤、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、ポリイソブチレンアミン等の清浄分散剤、多価アルコール及びそのエーテル等の氷結防止剤、有機酸のアルカリ金属やアルカリ土類金属塩、高級アルコールの硫酸エステル等の助燃剤、アニオン系界面活性剤、カチオン系界面活性剤、両性界面活性剤等の帯電防止剤、アルケニル琥珀酸エステル等の錆止め剤、及びアゾ染料等の着色剤等、公知の燃料添加剤が挙げられる。これらを１種または数種組み合わせて添加することが出来る。これら燃料添加剤の添加量は任意であるが、通常、その合計添加量が０．１質量％以下とすることが好ましい。 Furthermore, various additives can be appropriately blended in the unleaded gasoline of the present invention as necessary. Such additives include phenolic and amine antioxidants, metal deactivators such as thioamide compounds, surface ignition inhibitors such as organophosphorus compounds, succinimides, polyalkylamines, polyetheramines. Detergents such as polyisobutylene amine, anti-freezing agents such as polyhydric alcohols and ethers thereof, organic metal alkali metal and alkaline earth metal salts, auxiliary alcohols such as higher alcohol sulfates, anionic surfactants, Known fuel additives include antistatic agents such as cationic surfactants and amphoteric surfactants, rust inhibitors such as alkenyl succinates, and colorants such as azo dyes. These can be added singly or in combination. The addition amount of these fuel additives is arbitrary, but usually the total addition amount is preferably 0.1% by mass or less.
以下に本発明の内容を実施例及び比較例により具体的に説明するが、本発明はこれらによって制限されるものではない。 The content of the present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
実施例１，２
接触分解装置、接触改質装置又は常圧蒸留装置から生成するＣ４留分（ブタン、ブテン類）、表2に示す性状の脱ベンゼン接触改質ガソリン、脱ベンゼン軽質接触改質ガソリン、脱ベンゼン重質接触改質ガソリン、接触分解ガソリン、アルキレート、脱硫軽質ナフサ、及びETBE、EtOHを表3に示す配合比で配合することにより、表3に記載する性状のガソリンを得た。
Examples 1 and 2
C4 fraction (butane, butenes) produced from catalytic cracking equipment, catalytic reforming equipment or atmospheric distillation equipment, debenzene catalyzed reformed gasoline, debenzene light catalytic reformed gasoline, debenzene heavy weight with properties shown in Table 2 Gasoline reforming gasoline, catalytic cracking gasoline, alkylate, desulfurized light naphtha, and ETBE and EtOH were blended at the blending ratios shown in Table 3 to obtain gasoline having the properties shown in Table 3.
比較例１〜３
実施例1、2に記載のC4留分（ブタン、ブテン類）、脱ベンゼン接触改質ガソリン、脱ベンゼン軽質接触改質ガソリン、脱ベンゼン重質接触改質ガソリン、接触分解ガソリン、アルキレート、及び脱硫軽質ナフサを表3に示す配合比で配合することにより、表3に記載する性状のガソリンを得た。
Comparative Examples 1-3
C4 fraction (butane, butenes) described in Examples 1 and 2, debenzene catalytic reformed gasoline, debenzene light catalytic reformed gasoline, debenzene heavy catalytic reformed gasoline, catalytic cracked gasoline, alkylate, and By blending desulfurized light naphtha with the blending ratio shown in Table 3, gasoline having the properties shown in Table 3 was obtained.
上記実施例と比較例で得られたガソリンを用いて、以下に述べる各種の性能評価試験を行った。 Various performance evaluation tests described below were performed using the gasoline obtained in the above Examples and Comparative Examples.
始動性、運転性、及びデメリット点数評価を、排気量2L、直接噴射方式（DI）、オートマチックトランスミッション（AT）の車両を用い、試験温度20℃、湿度50％の条件で行った。
これらの評価ないし試験方法を以下に記し、結果を表3に示す。
Startability, drivability, and demerit scores were evaluated using a 2L displacement, direct injection (DI), automatic transmission (AT) vehicle at a test temperature of 20 ° C and humidity of 50%.
These evaluations and test methods are described below, and the results are shown in Table 3.
（始動性）
クランキング開始から完爆までの時間（エンジンが自力で回転が続けられるようになるまでの時間）で評価した。
（加速性）
エンジン始動後、10秒間アイドリングを行い、アクセル開度50％で車速が40km/hに到達するまでの時間で評価した。
（デメリット点数）
CRC（Coordinating Research Council）Report No.483評価方法に準拠して評価した。
評価方法としては、発生した現象の程度によって与えられるデメリット点数（Σ＝デメリット評点×不具合の係数）により判断した。
なお、アイドル時及び走行中ストールは演算せず、それぞれの係数を加算した。点数が小さい方が性能が優れていることを示す。
(Startability)
It was evaluated by the time from the start of cranking to the complete explosion (time until the engine can continue to rotate on its own).
(Acceleration)
The engine was idled for 10 seconds after the engine was started, and the time until the vehicle speed reached 40 km / h with an accelerator opening of 50% was evaluated.
(Demerit points)
Evaluation was performed according to the CRC (Coordinating Research Council) Report No. 483 evaluation method.
The evaluation method was determined by the demerit score given by the degree of the phenomenon that occurred (Σ = demerit score × defect coefficient).
Note that stalls during idling and running were not calculated, and the respective coefficients were added. The smaller the score, the better the performance.
（プラグのくすぶり性試験）
総排気量２Ｌ、ＭＰＩ方式、オートマチックトランスミッション（ＡＴ）の車両を用い、−１０℃の試験温度条件で、１サイクル約３０分（エンジン始動⇒１０−２０ｋｍ／ｈの加減速を１０回繰り返し⇒２８分間冷却）の繰返し試験を行い、そのプラグの絶縁抵抗を測定することによりプラグの汚損度を測定した。なお、プラグのくすぶりは、プラグの絶縁抵抗値が１００ＭΩ以下で発生したと判定した。
(Plug smoldering test)
Using a vehicle with a total displacement of 2L, MPI method, automatic transmission (AT), and a test temperature condition of -10 ° C, about 30 minutes per cycle (engine start ⇒ 10-20 km / h acceleration / deceleration repeated 10 times ⇒ 28 The degree of fouling of the plug was measured by measuring the insulation resistance of the plug. It was determined that plug smoldering occurred when the plug insulation resistance value was 100 MΩ or less.
以上の結果から、本発明の無鉛ガソリンは、エタノールとエチルターシャリーブチルエーテルを特定量配合し、始動性や運転性能に優れ、実用性能を維持しつつ大気環境の保全が図れるものであることは明らかである。 From the above results, it is clear that the unleaded gasoline of the present invention contains a specific amount of ethanol and ethyl tertiary butyl ether, has excellent startability and operating performance, and can maintain the atmospheric environment while maintaining practical performance. It is.
Claims (6)
（１）リサーチ法オクタン価（ＲＯＮ）が８９以上９７未満
（２）モーター法オクタン価（ＭＯＮ）が７９以上８７未満
（３）リード蒸気圧（ＲＶＰ）が４５〜９３ｋＰａ
（４）５０％留出温度（Ｔ５０）が７５〜１１０℃
（５）７０℃留出量（Ｅ７０）が１８〜４０容量％
（６）芳香族分含有量が５〜１７．０容量％
（７）オレフィン分含有量が５〜１５．２容量％
（８）ベンゼン含有量が１容量％以下
（９）硫黄分含有量が１０質量ｐｐｍ以下
（１０）６０℃における気液比（Ｖ／Ｌ）が３０〜７０ A lead-free gasoline containing 0.5 to 10.0% by volume of ethanol (EtOH) and 1.0 to 10.0 % by volume of ethyl tertiary butyl ether (ETBE) and satisfying the following properties.
(1) Research method octane number (RON) is 89 or more and less than 97 (2) Motor method octane number (MON) is 79 or more and less than 87 (3) Reed vapor pressure (RVP) is 45 to 93 kPa
(4) 50% distillation temperature (T50) is 75 to 110 ° C
(5) 70 ° C. distillate (E70) is 18 to 40% by volume
(6) Aromatic content is 5-17.0% by volume
(7) Olefin content is 5 to 15.2% by volume
(8) Benzene content is 1% by volume or less (9) Sulfur content is 10 mass ppm or less (10) Gas-liquid ratio (V / L) at 60 ° C. is 30 to 70
（１）リサーチ法オクタン価（ＲＯＮ）が８９以上９７未満(1) Research octane number (RON) is 89 or more and less than 97
（２）モーター法オクタン価（ＭＯＮ）が７９以上８７未満(2) Motor method octane number (MON) is 79 or more and less than 87
（３）リード蒸気圧（ＲＶＰ）が４５〜９３ｋＰａ(3) Reed vapor pressure (RVP) is 45 to 93 kPa
（４）５０％留出温度（Ｔ５０）が７５〜１１０℃(4) 50% distillation temperature (T50) is 75 to 110 ° C
（５）７０℃留出量（Ｅ７０）が１８〜４０容量％(5) 70 ° C. distillate (E70) is 18 to 40% by volume
（６）芳香族分含有量が５〜１７．０容量％(6) Aromatic content is 5-17.0% by volume
（７）オレフィン分含有量が５〜１５．２容量％(7) Olefin content is 5 to 15.2% by volume
（８）ベンゼン含有量が１容量％以下(8) Benzene content is 1% by volume or less
（９）硫黄分含有量が１０質量ｐｐｍ以下(9) Sulfur content is 10 mass ppm or less
（１０）６０℃における気液比（Ｖ／Ｌ）が３０〜７０(10) Gas-liquid ratio (V / L) at 60 ° C. is 30 to 70
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