JP2011116861A - Gasoline composition - Google Patents
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- JP2011116861A JP2011116861A JP2009275806A JP2009275806A JP2011116861A JP 2011116861 A JP2011116861 A JP 2011116861A JP 2009275806 A JP2009275806 A JP 2009275806A JP 2009275806 A JP2009275806 A JP 2009275806A JP 2011116861 A JP2011116861 A JP 2011116861A
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- 239000003502 gasoline Substances 0.000 title claims abstract description 68
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 30
- 230000003647 oxidation Effects 0.000 claims abstract description 29
- -1 diene compounds Chemical class 0.000 claims abstract description 19
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- ATQUFXWBVZUTKO-UHFFFAOYSA-N 1-methylcyclopentene Chemical compound CC1=CCCC1 ATQUFXWBVZUTKO-UHFFFAOYSA-N 0.000 claims abstract description 17
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims abstract description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 17
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims abstract description 14
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001336 alkenes Chemical class 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001993 dienes Chemical class 0.000 claims abstract description 7
- 238000011160 research Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 abstract description 10
- 239000000446 fuel Substances 0.000 description 17
- 125000003118 aryl group Chemical group 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 239000010779 crude oil Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000010998 test method Methods 0.000 description 8
- 230000006698 induction Effects 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000010525 oxidative degradation reaction Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000002828 fuel tank Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- QTYUSOHYEPOHLV-FNORWQNLSA-N 1,3-Octadiene Chemical compound CCCC\C=C\C=C QTYUSOHYEPOHLV-FNORWQNLSA-N 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- OWWIWYDDISJUMY-UHFFFAOYSA-N 2,3-dimethylbut-1-ene Chemical compound CC(C)C(C)=C OWWIWYDDISJUMY-UHFFFAOYSA-N 0.000 description 1
- BWEKDYGHDCHWEN-UHFFFAOYSA-N 2-methylhex-2-ene Chemical compound CCCC=C(C)C BWEKDYGHDCHWEN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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- Liquid Carbonaceous Fuels (AREA)
Abstract
Description
本発明は、高いオクタン価を維持しつつ、酸化安定性が良好なガソリン組成物に関するものである。 The present invention relates to a gasoline composition having good oxidation stability while maintaining a high octane number.
ガソリン成分の酸化劣化により生じる生成物の中には、有機酸などの蒸気圧の低い化合物が含まれ、エンジン吸気系及び燃焼室内でのデポジット生成の原因物質と考えられている。デポジットの生成は、燃料供給や燃焼に不具合をきたし、燃費の悪化やエンジントラブルを引き起こす要因となる。また、有機酸は燃料タンクなどにおける腐食を引き起こす原因ともなる。 Products generated by oxidative degradation of gasoline components include compounds with low vapor pressure, such as organic acids, and are considered to be the cause of deposit formation in the engine intake system and the combustion chamber. The generation of deposits causes problems in fuel supply and combustion, causing fuel consumption deterioration and engine trouble. Organic acids also cause corrosion in fuel tanks and the like.
ガソリン成分の酸化劣化を防止するためには、ラジカル捕捉、金属イオン捕捉、過酸化物分解などの作用を有する酸化防止剤を添加する必要がある。 In order to prevent oxidative degradation of gasoline components, it is necessary to add an antioxidant having actions such as radical scavenging, metal ion scavenging, and peroxide decomposition.
ガソリン成分の酸化劣化は、ガソリンの主要構成成分であるオレフィン化合物が主な原因物質とされており、オレフィン化合物を多量に含む場合、酸化安定性が悪化することが知られている（下記特許文献１参照）。一方、オレフィン化合物はその他の炭化水素に比べて高オクタン価であることから、ガソリンの重要な構成基材として多く使用されている。 Oxidative degradation of gasoline components is mainly caused by olefin compounds, which are major components of gasoline, and it is known that oxidation stability deteriorates when olefin compounds are contained in large quantities (the following patent documents) 1). On the other hand, olefin compounds have a high octane number compared to other hydrocarbons, and are therefore frequently used as an important component base material for gasoline.
そこで、本発明の目的は、上記従来技術の問題を解決し、高いオクタン価を維持しつつ、酸化安定性が良好なガソリン組成物を提供することにある。 Therefore, an object of the present invention is to provide a gasoline composition that solves the above-described problems of the prior art and has good oxidation stability while maintaining a high octane number.
本発明者は、上記目的を達成するために鋭意研究を重ねた結果、ガソリン組成物において、ある特定の性状を満足するように調整した場合に、オレフィンの含有量（以下、オレフィン分ともいう）を減ずることなく酸化安定性を向上できることを見出し、本発明を完成するに至ったものである。 As a result of intensive studies to achieve the above object, the present inventor has an olefin content (hereinafter also referred to as an olefin content) when the gasoline composition is adjusted to satisfy a specific property. The present inventors have found that the oxidation stability can be improved without reducing the amount of hydrogen and have completed the present invention.
すなわち、本発明のガソリン組成物は、硫黄分が１０質量ｐｐｍ以下、ジエン価が０．３ｍｇ／１００ｇ以下、ジエン化合物の含有量が０．０１容量％未満、１−メチルシクロペンテンの含有量が０．４０容量％未満、オレフィン分が１０〜３０容量％、リサーチ法オクタン価が８８〜９２であることを特徴とする。 That is, the gasoline composition of the present invention has a sulfur content of 10 ppm by mass or less, a diene value of 0.3 mg / 100 g or less, a diene compound content of less than 0.01% by volume, and a 1-methylcyclopentene content of 0. Less than 40% by volume, olefin content is 10 to 30% by volume, and research octane number is 88 to 92.
また、本発明のガソリン組成物は、次式：
酸化安定性指標Ｘ＝ＯＬ１×１．７＋ＯＬ２×０．３＋ＯＬ３
［式中、ＯＬ１は１−メチルシクロペンテンの含有量（容量％）で、ＯＬ２は２−メチル−２−ブテンの含有量（容量％）で、ＯＬ３はシクロペンテンの含有量（容量％）である］で表される酸化安定性指標Ｘが１．９未満であることが好ましい。
The gasoline composition of the present invention has the following formula:
Oxidation stability index X = OL1 × 1.7 + OL2 × 0.3 + OL3
[Wherein OL1 is the content (volume%) of 1-methylcyclopentene, OL2 is the content (volume%) of 2-methyl-2-butene, and OL3 is the content (volume%) of cyclopentene] Is preferably less than 1.9.
本発明によれば、オレフィン化合物を一定量含有し、高いオクタン価を維持することができ、かつ酸化安定性に優れるガソリン組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the gasoline composition which contains a fixed quantity of an olefin compound, can maintain a high octane number, and is excellent in oxidation stability can be provided.
〔硫黄分〕
本発明のガソリン組成物は、硫黄分が１０質量ｐｐｍ以下であり、好ましくは５質量ｐｐｍ以下、更に好ましくは２質量ｐｐｍ以下である。ガソリン組成物中の硫黄分は、排気ガス中で硫黄酸化物となって、窒素酸化物除去触媒を被毒する。そのため、硫黄分が多いほど、窒素酸化物除去触媒の活性を回復すべく還元雰囲気を形成するために燃料がより多く消費され、燃費悪化の原因となっている。従って、ガソリン組成物中の硫黄分が少ないほど燃費が向上する。
[Sulfur content]
The gasoline composition of the present invention has a sulfur content of 10 ppm by mass or less, preferably 5 ppm by mass or less, more preferably 2 ppm by mass or less. The sulfur content in the gasoline composition becomes sulfur oxides in the exhaust gas and poisons the nitrogen oxide removal catalyst. Therefore, as the sulfur content increases, more fuel is consumed to form a reducing atmosphere in order to restore the activity of the nitrogen oxide removal catalyst, causing deterioration in fuel consumption. Therefore, the fuel efficiency improves as the sulfur content in the gasoline composition decreases.
〔ジエン価〕
本発明のガソリン組成物は、ジエン価が０．３ｍｇ／１００ｇ以下である。ガソリンの酸化安定性の向上効果や吸気系および燃焼室内へのデポジット堆積防止の観点から、ジエン価は０．３ｍｇ／１００ｇ以下であることを要し、好ましくは０．２ｍｇ／１００ｇ以下、更に好ましくは０．１ｍｇ／１００ｇ以下である。
[Diene value]
The gasoline composition of the present invention has a diene value of 0.3 mg / 100 g or less. From the viewpoint of improving the oxidation stability of gasoline and preventing deposit accumulation in the intake system and the combustion chamber, the diene value needs to be 0.3 mg / 100 g or less, preferably 0.2 mg / 100 g or less, more preferably Is 0.1 mg / 100 g or less.
〔ジエン化合物含有量〕
本発明のガソリン組成物は、ジエン化合物の含有量が０．０１容量％未満である。ジエン化合物の含有量が多いと、酸化安定性を悪化させることから、ガソリン組成物中のジエン化合物の含有量は０．０１容量％未満であり、該ジエン化合物を含有しないことが特に好ましい。とりわけ、ジエン化合物の中でも、共役ジエン化合物は酸化安定性を著しく悪化させる為、これを含有しないことが好ましい。ジエン化合物としては、イソプレン、１，３−ペンタジエン、シクロペンタジエン、１,３−オクタジエン等が挙げられる。
[Diene compound content]
The gasoline composition of the present invention has a diene compound content of less than 0.01% by volume. When the content of the diene compound is large, the oxidation stability is deteriorated. Therefore, the content of the diene compound in the gasoline composition is less than 0.01% by volume, and it is particularly preferable that the diene compound is not contained. In particular, among the diene compounds, the conjugated diene compound remarkably deteriorates the oxidation stability, so that it is preferable not to contain it. Examples of the diene compound include isoprene, 1,3-pentadiene, cyclopentadiene, and 1,3-octadiene.
〔１−メチルシクロペンテン含有量〕
本発明のガソリン組成物は、１−メチルシクロペンテンの含有量が０．４０容量％未満である。１−メチルシクロペンテンはオレフィン化合物の中でも酸化安定性を悪化させる化合物である為、ガソリン組成物中の１−メチルシクロペンテンの含有量は、０．４０容量％未満であり、好ましくは０．３５容量％未満、更に好ましくは０．３０容量％未満であり、特に好ましくは０．２０容量％未満である。
[1-methylcyclopentene content]
The gasoline composition of the present invention has a content of 1-methylcyclopentene of less than 0.40% by volume. Since 1-methylcyclopentene is a compound that deteriorates oxidation stability among olefin compounds, the content of 1-methylcyclopentene in the gasoline composition is less than 0.40% by volume, preferably 0.35% by volume. Less than, more preferably less than 0.30% by volume, and particularly preferably less than 0.20% by volume.
〔オレフィン分〕
本発明のガソリン組成物は、リサーチ法オクタン価（ＲＯＮ）の向上効果の観点から、オレフィン分が１０容量％以上であり、好ましくは１５容量％以上、更に好ましくは１７容量％以上、特に好ましくは１９容量％以上である。また、オレフィン分が多すぎると、ガソリン組成物の酸化安定性を悪化させ、吸気バルブでのデポジットを増加させる可能性があるため、本発明のガソリン組成物は、オレフィン分が３０容量％以下であり、好ましくは２５容量％以下、更に好ましくは２３容量％以下、特に好ましくは２１容量％以下である。オレフィン化合物としては、上記の１−メチルシクロペンテンの他、２−メチル−２−ブテン、２−メチル−２−ペンテン、２−メチル−２−ヘキセン、４−メチル−１−ペンテン、３−メチル−１−ペンテン、２，３−ジメチル−１−ブテン、シクロペンテン、シクロヘキセン、ｎ−ヘキセン、ｎ−ヘプテン、ｎ−オクテン等が挙げられる。
[Olefin content]
The gasoline composition of the present invention has an olefin content of 10% by volume or more, preferably 15% by volume or more, more preferably 17% by volume or more, and particularly preferably 19% from the viewpoint of the effect of improving the research octane number (RON). More than volume%. Further, if the olefin content is too much, the oxidation stability of the gasoline composition may be deteriorated and the deposit at the intake valve may be increased. Therefore, the gasoline composition of the present invention has an olefin content of 30% by volume or less. Yes, preferably 25% by volume or less, more preferably 23% by volume or less, and particularly preferably 21% by volume or less. Examples of the olefin compound include 1-methylcyclopentene, 2-methyl-2-butene, 2-methyl-2-pentene, 2-methyl-2-hexene, 4-methyl-1-pentene, 3-methyl- Examples include 1-pentene, 2,3-dimethyl-1-butene, cyclopentene, cyclohexene, n-hexene, n-heptene, and n-octene.
〔オクタン価〕
本発明のガソリン組成物は、リサーチ法オクタン価（ＲＯＮ）が８８〜９２である。燃費向上効果の観点から、本発明のガソリン組成物のＲＯＮは８８以上であり、好ましくは８９以上、さらに好ましくは９０以上である。また、ＲＯＮが高すぎると芳香族分の増加により排気ガス品質が悪化したり、蒸留性状が重質化したりすることにより冷機時の加速性に悪影響が及ぶことから、本発明のガソリン組成物のＲＯＮは９２以下であり、好ましくは９１．５以下、さらに好ましくは９１以下である。
[Octane number]
The gasoline composition of the present invention has a research octane number (RON) of 88 to 92. From the viewpoint of fuel efficiency improvement effect, the RON of the gasoline composition of the present invention is 88 or more, preferably 89 or more, more preferably 90 or more. Further, if the RON is too high, the exhaust gas quality deteriorates due to an increase in the aromatic content, or the distillation properties become heavy, which adversely affects the accelerating performance during cold operation. RON is 92 or less, preferably 91.5 or less, more preferably 91 or less.
〔酸化安定性指標〕
上述のように、１−メチルシクロペンテンは酸化安定性を悪化させる化合物であるが、２−メチル−２−ブテン、シクロペンテンといったオレフィン化合物も、ガソリン組成物の酸化安定性を低下させる原因となり得る。そこで、本発明のガソリン組成物は、次式：
酸化安定性指標Ｘ＝ＯＬ１×１．７＋ＯＬ２×０．３＋ＯＬ３
［式中、ＯＬ１は１−メチルシクロペンテンの含有量（容量％）で、ＯＬ２は２−メチル−２−ブテンの含有量（容量％）で、ＯＬ３はシクロペンテンの含有量（容量％）である］で表される酸化安定性指標Ｘが１．９未満であることが好ましい。
[Oxidation stability index]
As described above, 1-methylcyclopentene is a compound that deteriorates the oxidation stability, but olefin compounds such as 2-methyl-2-butene and cyclopentene can also cause a decrease in the oxidation stability of the gasoline composition. Therefore, the gasoline composition of the present invention has the following formula:
Oxidation stability index X = OL1 × 1.7 + OL2 × 0.3 + OL3
[Wherein OL1 is the content (volume%) of 1-methylcyclopentene, OL2 is the content (volume%) of 2-methyl-2-butene, and OL3 is the content (volume%) of cyclopentene] Is preferably less than 1.9.
前記式の値は、ガソリン組成物中の各組成の量と酸化安定性との関係について実験を行い、各化合物の含有量と酸化安定性の関係から、本発明者が見出した指標である。前記式の値（即ち、酸化安定性指標Ｘ）が１．９未満であると、酸化安定性が大幅に向上するため、本発明のガソリン組成物は、好ましくは酸化安定性指標Ｘが１．９未満であり、更に好ましくは１．５以下、一層好ましくは１．０以下、特に好ましくは０．６以下である。 The value of the above formula is an index found by the present inventor from the relationship between the content of each compound and the oxidation stability by conducting an experiment on the relationship between the amount of each composition in the gasoline composition and the oxidation stability. When the value of the above formula (that is, the oxidation stability index X) is less than 1.9, the oxidation stability is greatly improved. Therefore, the gasoline composition of the present invention preferably has an oxidation stability index X of 1. It is less than 9, more preferably 1.5 or less, still more preferably 1.0 or less, and particularly preferably 0.6 or less.
〔ベンゼン分〕
また、本発明のガソリン組成物は、排ガス性状の悪化防止の観点から、ベンゼン分が１容量％以下であることが好ましく、更に好ましくは０．５容量％以下、特に好ましくは０．４容量％以下が好ましい。
[Benzene content]
The gasoline composition of the present invention preferably has a benzene content of 1% by volume or less, more preferably 0.5% by volume or less, and particularly preferably 0.4% by volume from the viewpoint of preventing deterioration of exhaust gas properties. The following is preferred.
〔芳香族分〕
本発明のガソリン組成物は、芳香族分が１５〜４０容量％であることが好ましい。芳香族分は、オクタン価を増大させる効果を有するが、芳香族分が４０容量％を超えるとプラグの燻りや揮発性の悪化を引き起こし、冷機時の加速性が悪化する。また、芳香族分が多すぎると排出ガス性状が悪化するため、本発明のガソリン組成物中の芳香族分は、４０容量％以下が好ましく、更に好ましくは３８容量％以下、特に好ましくは３５容量％以下である。また、芳香族分が１５容量％より少ないと発熱量低下により燃費悪化を引き起こすことがあるため好ましくなく、燃費向上の観点から、本発明のガソリン組成物中の芳香族分は１５容量％以上が好ましく、更に好ましくは１８容量％以上、一層好ましくは２０容量％以上、特に好ましくは２２容量％以上である。
[Aromatic content]
The gasoline composition of the present invention preferably has an aromatic content of 15 to 40% by volume. The aromatic component has an effect of increasing the octane number. However, when the aromatic component exceeds 40% by volume, the plug is turned and the volatility is deteriorated, and the acceleration performance at the time of cooling is deteriorated. Further, since the exhaust gas properties deteriorate when the aromatic content is too much, the aromatic content in the gasoline composition of the present invention is preferably 40% by volume or less, more preferably 38% by volume or less, and particularly preferably 35% by volume. % Or less. Further, if the aromatic content is less than 15% by volume, it is not preferable because the fuel consumption may be deteriorated due to a decrease in the calorific value. From the viewpoint of improving the fuel consumption, the aromatic content in the gasoline composition of the present invention is 15% by volume or more. It is preferably 18% by volume or more, more preferably 20% by volume or more, and particularly preferably 22% by volume or more.
〔蒸気圧〕
本発明のガソリン組成物のリード蒸気圧は、蒸発ガス低減のため７０ｋＰａ以下が好ましく、より好ましくは６８ｋＰａ以下、特に好ましくは６５ｋＰａ以下である。ここで、リード蒸気圧はＪＩＳ Ｋ ２２５８「原油及び燃料油−蒸気圧試験方法−リード法」により測定される３７．５℃での蒸気圧である。なお、特に限定されるものではないが、本発明のガソリン組成物のリード蒸気圧は、４５ｋＰａ以上であることが好ましく、５０ｋＰａ以上であることが更に好ましい。
[Vapor pressure]
The lead vapor pressure of the gasoline composition of the present invention is preferably 70 kPa or less, more preferably 68 kPa or less, and particularly preferably 65 kPa or less for reducing the evaporation gas. Here, the lead vapor pressure is a vapor pressure at 37.5 ° C. measured by JIS K 2258 “Crude oil and fuel oil—Vapor pressure test method—Reed method”. Although not particularly limited, the lead vapor pressure of the gasoline composition of the present invention is preferably 45 kPa or more, and more preferably 50 kPa or more.
〔５０％留出温度〕
本発明のガソリン組成物の蒸留性状における５０％留出温度は、冷機時の加速性や排ガスの性状の観点から、９９．０℃以下であることが好ましく、更に好ましくは９８．０℃以下、一層好ましくは９７．０℃以下である。また、５０％留出温度が低すぎると燃費が悪化するため、本発明のガソリン組成物は、５０％留出温度が８５．０℃以上であることが好ましく、更に好ましくは８７．０℃以上、一層好ましくは９０．０℃以上である。
[50% distillation temperature]
The 50% distillation temperature in the distillation properties of the gasoline composition of the present invention is preferably 99.0 ° C. or less, more preferably 98.0 ° C. or less, from the viewpoint of acceleration during cooling and properties of exhaust gas. More preferably, it is 97.0 ° C. or lower. Further, if the 50% distillation temperature is too low, the fuel efficiency is deteriorated. Therefore, the gasoline composition of the present invention preferably has a 50% distillation temperature of 85.0 ° C or higher, more preferably 87.0 ° C or higher. More preferably, it is 90.0 ° C. or higher.
上述した本発明のガソリン組成物の調製方法は、特に限定されず、上述した各成分含有量、物性を満たすように、脱硫直留軽質ナフサ、アルキレートガソリン、接触分解ガソリン等の公知のガソリン基材を適宜配合することで調製できる。例えば、本発明のガソリン組成物に含有される１−メチルシクロペンテンの量を低くするには、１−メチルシクロペンテンを比較的多く含有する接触分解ガソリンのガソリン混合比率を低下させるか、１−メチルシクロペンテンの含有量が少ない接触分解ガソリンの混合比率を増加させることが有効である。 The method for preparing the gasoline composition of the present invention described above is not particularly limited, and a known gasoline group such as desulfurized straight-run light naphtha, alkylate gasoline, catalytic cracked gasoline or the like so as to satisfy the above-described component contents and physical properties. It can be prepared by appropriately blending materials. For example, in order to reduce the amount of 1-methylcyclopentene contained in the gasoline composition of the present invention, the gasoline mixture ratio of catalytically cracked gasoline containing a relatively large amount of 1-methylcyclopentene is reduced, or 1-methylcyclopentene is reduced. It is effective to increase the mixing ratio of catalytic cracking gasoline with a low content of.
以下に、本発明を実施例により具体的に説明するが、本発明は下記の実施例に何ら限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
実施例及び比較例のガソリン組成物を調製するに際して用いたガソリン基材は、次のものである。なお、ガソリン基材（ＧＴＮ、ＦＧＳ、ＰＦＭ）の性状を表１に示す。 The gasoline base materials used in preparing the gasoline compositions of Examples and Comparative Examples are as follows. Table 1 shows properties of gasoline base materials (GTN, FGS, PFM).
・ＧＴＮ：脱硫直留軽質ナフサであり、中東系原油のナフサ留分を水素化脱硫後、その軽質分を蒸留分離することにより得た。 GTN: desulfurized straight-run light naphtha, obtained by hydrodesulfurizing a naphtha fraction of Middle Eastern crude oil, and distilling the light fraction.
・ＦＧＳ：中東系原油の減圧軽油留分を水素化精製処理して得られた間接脱硫軽油を固体触媒により流動床式反応装置を用いて接触分解して得られるガソリン留分を水素化精製処理して得た。 -FGS: Hydrorefining of gasoline fraction obtained by catalytic cracking of indirect desulfurized gas oil obtained by hydrorefining middle-class crude oil using a fluidized bed reactor with a solid catalyst. I got it.
・ＰＦＭ：中東系原油由来の接触改質ガソリンである。 -PFM: Catalytic reforming gasoline derived from Middle Eastern crude oil.
・ｎ−ヘキセン：９５％純度の１−ヘキセンの試薬品［東京化成工業(株)製］を用いた。 N-hexene: A 95% pure 1-hexene reagent product [manufactured by Tokyo Chemical Industry Co., Ltd.] was used.
・シクロペンテン：９５％純度のシクロペンテンの試薬品［東京化成工業(株)製］を用いた。 Cyclopentene: A 95% pure cyclopentene reagent product [manufactured by Tokyo Chemical Industry Co., Ltd.] was used.
・ブタン：原油の蒸留分離によって得られる液化石油ガス（ＬＰＧ）を精製することにより得られたブタンである。 Butane: Butane obtained by refining liquefied petroleum gas (LPG) obtained by distillation separation of crude oil.
〔供試ガソリンの調製と酸化安定性の評価〕
上記ガソリン基材を、表２に示す混合割合（容量％）でブレンドし、実施例１〜３及び比較例１〜３のガソリン組成物（それぞれ、供試ガソリン１〜６とする）を調製し、酸化安定性を評価した。
[Preparation of test gasoline and evaluation of oxidation stability]
The said gasoline base material is blended by the mixing ratio (volume%) shown in Table 2, and the gasoline composition (it is set as test gasoline 1-6, respectively) of Examples 1-3 and Comparative Examples 1-3 is prepared. The oxidation stability was evaluated.
なお、酸化安定性を評価する試験方法には、誘導期間法を用いた。この方法により測定した値（誘導期間）は、ガソリン組成物の貯蔵中でのガム生成傾向の目安として用いることができる。貯蔵中のガム生成量は、貯蔵条件によって大きな影響を受けるが、一般に誘導期間の長い方が、酸化安定性に優れることを示す。また、これまでに行った実験データから、燃料噴射装置によりガソリン組成物が熱負荷を受けた後にその一部が燃料タンクに戻る車両では、誘導期間が長いほど、燃料中にガムが生成されるまでの期間が長くなることが分かっている。更に、一旦燃料中にガムが生成されると、燃料噴射装置、吸気ポート及び吸気弁の汚れが多くなり、エンジン始動の悪化や排出ガス性状の悪化に繋がる。
・「ＪＩＳハンドブック２００９ 石油」p.２１８２（２１）誘導期間 参照
The induction period method was used as a test method for evaluating oxidation stability. The value (induction period) measured by this method can be used as a measure of the tendency of gum formation during storage of the gasoline composition. The amount of gum produced during storage is greatly influenced by the storage conditions, but in general, the longer the induction period, the better the oxidation stability. Also, from experimental data conducted so far, in a vehicle in which a gasoline composition is subjected to a thermal load by a fuel injector and a part thereof returns to the fuel tank, the longer the induction period, the more gum is generated in the fuel. It is known that the period until is longer. Further, once the gum is generated in the fuel, the fuel injection device, the intake port and the intake valve become dirty, leading to deterioration of engine start and exhaust gas properties.
・ Refer to “JIS Handbook 2009 Petroleum” p. 2182 (21) induction period
また、表１及び表２に示すガソリン基材の性状、並びに実施例及び比較例のガソリン組成物の性状は、次の方法に準拠して測定した。 Moreover, the property of the gasoline base material shown in Table 1 and Table 2, and the property of the gasoline composition of an Example and a comparative example were measured based on the following method.
・密度：ＪＩＳ Ｋ ２２４９「原油及び石油製品−密度試験方法」
・蒸気圧（ＲＶＰ）：ＪＩＳ Ｋ ２２５８「原油及び燃料油−蒸気圧試験方法−リード法」
・オクタン価（ＲＯＮ）：ＪＩＳ Ｋ ２２８０「石油製品−燃料油−オクタン価及びセタン価試験方法並びにセタン指数算出方法」のリサーチ法オクタン価試験方法
・蒸留性状：ＪＩＳ Ｋ ２２５４「石油製品−蒸留試験法」
・組成成分（炭化水素化合物：オレフィン分、ジエン化合物含有量、芳香族分、ベンゼン分、１−メチルシクロペンテン含有量、２−メチル−２−ブテン含有量、シクロペンテン含有量）：ＪＩＳ Ｋ ２５３６「石油製品−成分試験方法」のガスクロマトグラフィー法
・硫黄分：ＪＩＳ Ｋ ２５４１「原油及び石油製品−硫黄分試験方法」の微量電量滴定式酸化法
・未洗実在ガム：ＪＩＳ Ｋ ２２６１「石油製品−自動車ガソリン及び航空燃料油−実在ガム試験方法−噴射蒸発法」
・ジエン価：ＵＯＰ３２６−８２
・誘導期間：ＪＩＳ Ｋ ２２８７「ガソリン−酸化安定度試験方法−誘導期間法」
・過酸化物価：ＪＰＩ―５Ｓ―４６―９６「灯油の過酸化物価試験方法」
Density: JIS K 2249 "Crude oil and petroleum products-Density test method"
・ Vapor pressure (RVP): JIS K 2258 "Crude oil and fuel oil-Vapor pressure test method-Reed method"
-Octane number (RON): Research method octane number test method of JIS K 2280 "Petroleum products-Fuel oil-Octane number and cetane number test method and cetane index calculation method"-Distillation property: JIS K 2254 "Petroleum product-Distillation test method"
Composition component (hydrocarbon compound: olefin content, diene compound content, aromatic content, benzene content, 1-methylcyclopentene content, 2-methyl-2-butene content, cyclopentene content): JIS K 2536 “Petroleum Product-component test method "gas chromatography method, sulfur content: JIS K 2541" crude oil and petroleum products-sulfur content test method "microcoulometric titration method, unwashed real gum: JIS K 2261" petroleum products-automobile Gasoline and Aviation Fuel Oil-Real Gum Test Method-Injection Evaporation Method "
・ Diene value: UOP326-82
・ Induction period: JIS K 2287 “Gasoline-oxidation stability test method-induction period method”
・ Peroxide value: JPI-5S-46-96 “Test method for peroxide value of kerosene”
表２から、実施例１〜３のガソリン組成物は、比較例１〜３のガソリン組成物とリサーチ法オクタン価（ＲＯＮ）が同等であるにもかかわらず、誘導期間が１０００分以上と長いため、比較例１〜３のガソリン組成物と比べて酸化安定性に優れることが分かる。 From Table 2, the gasoline compositions of Examples 1 to 3 have a long induction period of 1000 minutes or more despite the fact that the gasoline compositions of Comparative Examples 1 to 3 and the research octane number (RON) are equivalent. It turns out that it is excellent in oxidation stability compared with the gasoline composition of Comparative Examples 1-3.
Claims (2)
酸化安定性指標Ｘ＝ＯＬ１×１．７＋ＯＬ２×０．３＋ＯＬ３
［式中、ＯＬ１は１−メチルシクロペンテンの含有量（容量％）で、ＯＬ２は２−メチル−２−ブテンの含有量（容量％）で、ＯＬ３はシクロペンテンの含有量（容量％）である］で表される酸化安定性指標Ｘが１．９未満であることを特徴とする請求項１に記載のガソリン組成物。 The following formula:
Oxidation stability index X = OL1 × 1.7 + OL2 × 0.3 + OL3
[Wherein OL1 is the content (volume%) of 1-methylcyclopentene, OL2 is the content (volume%) of 2-methyl-2-butene, and OL3 is the content (volume%) of cyclopentene] The gasoline composition according to claim 1, wherein the oxidation stability index X represented by the formula is less than 1.9.
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