JP5048329B2 - Gasoline composition - Google Patents

Gasoline composition Download PDF

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JP5048329B2
JP5048329B2 JP2006519923A JP2006519923A JP5048329B2 JP 5048329 B2 JP5048329 B2 JP 5048329B2 JP 2006519923 A JP2006519923 A JP 2006519923A JP 2006519923 A JP2006519923 A JP 2006519923A JP 5048329 B2 JP5048329 B2 JP 5048329B2
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gasoline
volume
gasoline composition
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composition according
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JP2009513750A (en
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エードリアン・フィリップ・グローヴズ
クリストファー・モーレイ
ヨハン・スミス
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Shell Internationale Research Maatschappij BV
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Detergent Compositions (AREA)

Description

本発明はガソリン組成物に関し、更に詳しくはレブリン酸エステル含有ガソリン組成物及びその製造法及び用法に関する。   The present invention relates to a gasoline composition, and more particularly to a levulinate ester-containing gasoline composition and a method for producing and using the same.

Ｚｈ．Ｐｒｉｋｌ．ｈｉｍ．（レニングラード）（１９６９）４２（４），９５８−９には、レブリン酸エステル（レブリン酸のエステル）、特にメチル、エチル、プロピル、ブチル、ペンチル及びヘキシルエステル、及び適当なアルコールとフルフリルアセテートとの反応によるレブリン酸エステルの製造法が記載されている。   Zh. Prikl. him. (Leningrad) (1969) 42 (4), 958-9 includes levulinic acid esters (esters of levulinic acid), in particular methyl, ethyl, propyl, butyl, pentyl and hexyl esters, and the appropriate alcohols and furfuryl acetates. A process for producing a levulinic acid ester by the reaction is described.

ＷＯ ９４２１７５３（ＶＥＢＡ ＯＥＬ）は、Ｃ４〜Ｃ６ケトカルボン酸、好ましくはレブリン酸のＣ１〜Ｃ２２アルコールによるエステルを或る割合（例えば１〜９０容量％、１〜５０容量％、好ましくは１〜２０容量％）含有する内燃機関用ガソリン及びディーゼルの両燃料を開示している。ガソリンに含有させるにはＣ１〜Ｃ８アルコールによるエステルが特に好適で、またディーゼル燃料に含有させるにはＣ９〜Ｃ２２アルコールによるエステルが特に好適である旨、記載されている。 WO 9421753 (VEBA OEL) describes a certain proportion of esters of C 4 to C 6 ketocarboxylic acids, preferably levulinic acid with C 1 to C 22 alcohols (eg 1 to 90% by volume, 1 to 50% by volume, preferably 1 Both gasoline and diesel fuels for internal combustion engines are disclosed. It is described that esters with C 1 to C 8 alcohols are particularly suitable for inclusion in gasoline, and esters with C 9 to C 22 alcohols are particularly suitable for inclusion in diesel fuel.

ＷＯ ９４２１７５３の実施例は全て、オクタン価（ＲＯＮ及びＭＯＮ）向上のため、ガソリンに或る量のレブリン酸エステルを含有させている。実施例１、７、１０では、異種のベースガソリンにレブリン酸メチルを１０容量％取り込んでいる。実施例２〜６は、それぞれレブリン酸エチル、レブリン酸ｎ−プロピル、レブリン酸イソプロピル、レブリン酸イソブチル、レブリン酸ｓｅｃ−ブチルを使用している。実施例８、９は、レブリン酸メチルと蟻酸メチルとのそれぞれ１：１及び２：１比の混合物１０容量％を使用している。実施例１１は、無鉛ユーロスーパーガソリンにレブリン酸メチルを５〜９０容量％の範囲の割合を使用している。   All of the examples of WO 9421753 contain a certain amount of levulinic acid ester in the gasoline to improve the octane number (RON and MON). In Examples 1, 7, and 10, 10% by volume of methyl levulinate is incorporated into different types of base gasoline. Examples 2 to 6 use ethyl levulinate, n-propyl levulinate, isopropyl levulinate, isobutyl levulinate, and sec-butyl levulinate, respectively. Examples 8 and 9 use 10% by volume of a 1: 1 and 2: 1 ratio mixture of methyl levulinate and methyl formate, respectively. Example 11 uses unleaded euro super gasoline in a proportion ranging from 5 to 90% by volume of methyl levulinate.

ＷＯ ０３００２６９６（ＡＡＥ Ｔｅｃｈ． Ｉｎｔ．）は、エタノール又はＭＴＢＥやＥＴＢＥのような従来の酸素化物よりも多くの酸素容量を供給して、燃料のリード蒸気圧の増大を殆ど又は全くなくすと共に、ベース燃料の引火点への影響を殆ど又は全くなくす目的で、レブリン酸又はその官能性誘導体を取り込んだ燃料組成物を開示している。この官能性誘導体としては、アルキル誘導体、好ましくはＣ１〜Ｃ１０アルキル誘導体が好ましい。レブリン酸エチルが好ましく、代りはレブリン酸メチルが好ましいと言われる。レブリン酸又はその官能性誘導体は、燃料の０．１〜５％を形成するのに使用されている。 WO 03002696 (AAE Tech. Int.) Provides more oxygen capacity than conventional oxygenates such as ethanol or MTBE and ETBE, with little or no increase in fuel lead vapor pressure, and base fuel A fuel composition incorporating levulinic acid or a functional derivative thereof for the purpose of eliminating little or no effect on the flash point is disclosed. As the functional derivative, alkyl derivatives, preferably C 1 -C 10 alkyl derivatives preferred. Ethyl levulinate is preferred, and methyl levulinate is said to be preferred instead. Levulinic acid or a functional derivative thereof has been used to form 0.1-5% of the fuel.

ＷＯ ０３００２６９６が開示する一態様では、更に以下の群から選ばれた別の添加剤を０．１〜５％取り込んでいる。
ａ）エチレンオキシドをアルコール１モル当り０又は１〜２０モル及び／又はプロピレンオキシドを１〜５モル含有する、任意にアルコキシル化した炭素原子数８〜２４の直鎖又は分岐鎖飽和又は不飽和ものアルコール、又は
ｂ）任意に炭素原子数１〜２４の脂肪酸で部分エステル化した、炭素原子数２〜６のポリオール、又は
ｃ）脂肪酸１モル当りエチレンオキシド４〜２０モル含有する炭素原子数１２〜１４のアルコキシル化脂肪酸、又は
ｄ）エトキシル化二量体脂肪酸。
このような燃料はディーゼル燃料が好ましい（第７頁１１〜２２行） In one embodiment disclosed by WO 03002696, another additive selected from the following group is further incorporated in an amount of 0.1 to 5%.
a) An optionally alkoxylated linear or branched saturated or unsaturated alcohol having 8 to 24 carbon atoms containing 0 or 1 to 20 moles of ethylene oxide per mole of alcohol and / or 1 to 5 moles of propylene oxide Or b) a polyol having 2 to 6 carbon atoms, optionally partially esterified with a fatty acid having 1 to 24 carbon atoms, or c) 12 to 14 carbon atoms containing 4 to 20 moles of ethylene oxide per mole of fatty acid. Alkoxylated fatty acids, or d) ethoxylated dimer fatty acids.
Such fuel is preferably diesel fuel (page 7, lines 11-22).

別の一態様では、燃料は実質的にアルコキシル化化合物や長鎖アルキルアルコールを含まないが、式Ｒ−ＣＯ−ＮＲ１Ｒ２（但し、Ｒは炭素原子数６〜２１で飽和又は不飽和の直鎖又は分岐鎖アルキル基（数平均分子量が８５〜２９５に相当する）を表わし、Ｒ１及びＲ２は各々独立にＣ１〜Ｃ４ヒドロキシアルキル基を表わす）の添加剤を含有する。代りの添加剤は（第８頁９、１０行）オレイン酸アルカノールアミド及びアルコキシル化オレイン酸を含む。 In another aspect, the fuel is substantially free of alkoxylated compounds and long-chain alkyl alcohols, but is of the formula R—CO—NR 1 R 2 (wherein R is a C 6-21 saturated or unsaturated carbon atom). It contains a linear or branched alkyl group (representing a number average molecular weight of 85 to 295), and R 1 and R 2 each independently represents a C 1 to C 4 hydroxyalkyl group. Alternative additives (page 8, line 9, 10) include oleic alkanolamides and alkoxylated oleic acids.

更に、レブリン酸又はその官能性誘導体を窒素化合物の形態で窒素源と一緒に取り込んだ燃料組成物を提供している。窒素化合物は、アンモニア、ヒドラジン、アルキルヒドラジン、ジアルキルヒドラジン、尿素、エタノールアミン、モノアルキルエタノールアミン、及びジアルキルエタノールアミン（但し、アルキルは独立にメチル、エチル、ｎ−プロピル又はイソプロピルから独立に選ばれる）よりなる群から選ばれる。尿素が好ましい。この窒素含有化合物は、無水化合物又は含水化合物、例えば水溶液であってよく、また５％ｗ／ｗ水溶液までであってよい。   Further provided is a fuel composition incorporating levulinic acid or a functional derivative thereof in the form of a nitrogen compound with a nitrogen source. Nitrogen compounds are ammonia, hydrazine, alkyl hydrazine, dialkyl hydrazine, urea, ethanolamine, monoalkylethanolamine, and dialkylethanolamine (wherein alkyl is independently selected from methyl, ethyl, n-propyl or isopropyl) Selected from the group consisting of Urea is preferred. The nitrogen-containing compound may be an anhydrous compound or a hydrous compound, such as an aqueous solution, and may be up to a 5% w / w aqueous solution.

セタン増進剤、解乳化剤でバイオディーゼル型の燃料も存在してよい（第１０頁１〜２９行）。
またＷＯ ０３００２６９６は“以上は、以下の実施例で示す”（第１１頁３１行）と述べているが、組成及びテスト結果のデータは、以下の文章：
“レブリン酸エチル５．０％以下、水１．０％及びノニオン洗浄剤２．０％を含有する規格ガソリンブレンドは、ベースガソリンと同様なＲＶＰを有することが見い出された。”及び
“レブリン酸エチル５．０％以下、水１．０％及びノニオン洗浄剤２．０％を含有する規格ディーゼルブレンドは、ベースディーゼルと同様な引火点を有することが見い出された。”
で構成されている。
Ｚｈ．Ｐｒｉｋｌ．ｈｉｍ．（レニングラード）（１９６９）４２（４），９５８−９ ＷＯ ９４２１７５３ ＷＯ ０３００２６９６ ＵＳ特許５，８５５，６２９ ＷＯ ３２８１２ ＵＳ特許５，７２５，６１２ ＵＳ特許４，８３２，７０２ Ｃａｍｐｅｎ等、“Ｇｒｏｗｉｎｇ ｕｓｅ ｏｆ ｓｙｎｌｕｂｅｓ”，Ｈｙｄｒｏｃａｒｂｏｎ Ｐｒｏｃｅｓｓｉｎｇ，１９８２年２月、７５〜８２頁 Ｗ．Ｗ．Ｙａｕ，Ｊ．Ｊ．Ｋｉｒｋｌａｎｄ及びＤ．Ｄ．Ｂｌｙ，“Ｍｏｄｅｒｎ Ｓｉｚｅ Ｅｘｃｌｕｓｉｏｎ Ｌｉｑｕｉｄ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ”，Ｊｏｈｎ Ｗｉｌｅｙ ａｎｄ Ｓｏｎｓ，Ｎｅｗ Ｙｏｒｋ，１９７９ A cetane enhancer, demulsifier and biodiesel type fuel may also be present (page 10, lines 1 to 29).
WO 03002696 states that "the above is shown in the following examples" (page 11, line 31), but the composition and test result data are as follows:
“Standard gasoline blends containing up to 5.0% ethyl levulinate, 1.0% water and 2.0% nonionic detergent were found to have RVP similar to the base gasoline.” And “levulinic acid Standard diesel blends containing up to 5.0% ethyl, 1.0% water and 2.0% nonionic detergent were found to have similar flash points as the base diesel. "
It consists of
Zh. Prikl. him. (Leningrad) (1969) 42 (4), 958-9 WO 9421753 WO 0300396 US Patent 5,855,629 WO 32812 US Patent 5,725,612 US Patent 4,832,702 Campen et al., “Growing use of synrubes”, Hydrocarbon Processing, February 1982, 75-82. W. W. Yau, J .; J. et al. Kirkland and D.C. D. Bly, “Modern Size Exclusion Liquid Chromatography”, John Wiley and Sons, New York, 1979.

レブリン酸エチルを特定の窒素含有洗浄剤と一緒に含有するガソリン組成物は、エンジンの清浄性能を驚異的に高めることができ、またレブリン酸エチルを含有するガソリン組成物は同様な濃度のレブリン酸メチルを含有するガソリン組成物よりも特定のエラストマーシール材料との適合性を驚異的に向上できることが今回、意外にも見い出された。   Gasoline compositions containing ethyl levulinate together with certain nitrogen-containing detergents can dramatically increase engine cleaning performance, and gasoline compositions containing ethyl levulinate have similar concentrations of levulinic acid. It has now been surprisingly found that compatibility with certain elastomeric seal materials can be dramatically improved over methyl-containing gasoline compositions.

本発明によれば、スパーク点火エンジン用に好適なガソリンを主要量で含むと共に、レブリン酸エチルを１〜１５容量％、及び数平均分子量が７５０〜６０００の範囲のヒドロカルビル基を有する窒素含有洗浄剤を２０〜２０００重量ｐｐｍ含むガソリン組成物が提供される。   According to the present invention, a nitrogen-containing detergent having a major amount of gasoline suitable for a spark ignition engine and having a hydrocarbyl group in the range of 1 to 15% by volume of ethyl levulinate and a number average molecular weight of 750 to 6000. Of 20 to 2000 ppm by weight is provided.

ガソリン組成物中のレブリン酸エチルの濃度は、以下のパラメーターと一致する。
（ｉ）濃度は少なくとも１．５容量％であり、
（ｉｉ）濃度は少なくとも２容量％であり、
（ｉｉｉ）濃度は少なくとも３容量％であり、
（ｉＶ）濃度は少なくとも４容量％であり、
（Ｖ）濃度は１２容量％以下であり、
（Ｖｉ）濃度は１０容量％以下であり、
（Ｖｉｉ）濃度は８容量％以下であり、
（Ｖｉｉｉ）濃度は６容量％以下であり、
特徴（ｉ）及び（ｖ）、（ｉｉ）及び（ｖｉ）、（ｉｉｉ）及び（ｖｉｉ）、並びに（ｖ）及び（ｖｉｉｉ）の範囲は、それぞれ順次、更に好ましい。 The concentration of ethyl levulinate in the gasoline composition is consistent with the following parameters:
(I) the concentration is at least 1.5% by volume;
(Ii) the concentration is at least 2% by volume;
(Iii) the concentration is at least 3% by volume;
(IV) concentration is at least 4% by volume;
(V) The concentration is 12% by volume or less,
(Vi) concentration is 10% by volume or less,
(Vii) the concentration is 8% by volume or less,
(Viii) concentration is 6% by volume or less,
The ranges of the characteristics (i) and (v), (ii) and (vi), (iii) and (vii), and (v) and (viii) are more preferable respectively.

ガソリン組成物は、窒素含有洗浄剤を好ましくは５０〜１５００重量ｐｐｍ、更に好ましくは５０〜５００重量ｐｐｍ含有する。８０〜２５０重量ｐｐｍ、例えば１００〜１５０重量ｐｐｍの範囲が非常に好適である。   The gasoline composition preferably contains 50 to 1500 ppm by weight of nitrogen-containing detergent, more preferably 50 to 500 ppm by weight. A range of 80 to 250 ppm by weight, for example 100 to 150 ppm by weight, is very suitable.

数平均分子量（Ｍｎ）が７５０〜６０００の範囲のヒドロカルビル基を有する窒素含有洗浄剤は、アミン、例えばポリイソブチレンエチレンジアミン又はＮ−ポリイソブテニル−Ｎ，Ｎ’−ジメチル−１，３−ジアミノプロパンのようなポリイソブチレンモノアミン又はポリアミン；或いはアミド、例えばポリイソブテニルスクシンイミドであってよく、例えばＵＳ特許５，８５５，６２９及びＷＯ ３２８１２に種々記載されている。或いは窒素含有洗浄剤は、ＵＳ特許５，７２５，６１２に記載されるようなマンニッヒアミン洗浄剤であってよい。   Nitrogen-containing detergents having hydrocarbyl groups with a number average molecular weight (Mn) in the range of 750-6000 are amines such as polyisobutylene ethylenediamine or N-polyisobutenyl-N, N′-dimethyl-1,3-diaminopropane. It may be a polyisobutylene monoamine or polyamine; or an amide, such as polyisobutenyl succinimide, which are variously described, for example, in US Pat. No. 5,855,629 and WO 32812. Alternatively, the nitrogen-containing detergent may be a Mannich amine detergent as described in US Pat. No. 5,725,612.

特に好ましい窒素含有洗浄剤は、式Ｒ１−ＮＨ２（但し、Ｒ１はＲ２基又はＲ２−ＣＨ２−基を表わし、Ｒ２は数平均分子量が７５０〜６０００の範囲、好ましくは９００〜３０００の範囲、更に好ましくは９５０〜２０００の範囲、最も好ましくは９５０〜１３５０の範囲のヒドロカルビル基、例えば数平均分子量が９５０〜１０５０の範囲のポリブテニル又はポリイソブテニル基を表わす）のヒドロカルビルアミンである。 Particularly preferred nitrogen-containing detergents are those of formula R 1 —NH 2 where R 1 represents an R 2 group or an R 2 —CH 2 — group, and R 2 has a number average molecular weight in the range of 750 to 6000, preferably 900 Hydrocarbyl amines in the range of ~ 3000, more preferably in the range of 950 to 2000, most preferably in the range of 950 to 1350, for example polybutenyl or polyisobutenyl groups having a number average molecular weight in the range of 950 to 1050).

窒素含有洗浄剤は公知の材料で、公知の方法又は公知の方法に類似の方法により製造できる。例えばＵＳ特許４，８３２，７０２には適当なポリブテン又はポリイソブテンからヒドロホルミル化及び引き続き得られるオキソ生成物の水素化条件下でのアミノ化によりポリブテニルアミン又はポリイソブテニルアミンを製造する方法が記載されている。   The nitrogen-containing cleaning agent is a known material and can be produced by a known method or a method similar to the known method. For example, US Pat. No. 4,832,702 describes a process for producing polybutenylamine or polyisobutenylamine by hydroformylation from a suitable polybutene or polyisobutene and subsequent amination of the resulting oxo product under hydrogenation conditions. Are listed.

好適なヒドロカルビルアミンは、ＢＡＳＦから商標“Ｋｅｒｏｃｏｍ”で得られる。
レブリン酸エチル及び窒素含有洗浄剤の他、ガソリン組成物は更に１種以上の担体液、腐蝕防止剤、耐酸化剤、染料、かすみ防止剤（ｄｅｈａｚｅｒ）、金属失活剤、前記定義したヒドロカルビル基を有する窒素含有洗浄剤以外の洗浄剤（例えばポリエーテルアミン）、摩擦改良剤、希釈剤及び標識剤を含有してよい。 A suitable hydrocarbylamine is obtained from BASF under the trademark “Kerocom”.
In addition to the ethyl levulinate and nitrogen-containing detergents, the gasoline composition may further comprise one or more carrier fluids, corrosion inhibitors, oxidation inhibitors, dyes, dehaze agents, metal deactivators, hydrocarbyl groups as defined above. It may contain a cleaning agent (for example, polyetheramine) other than the nitrogen-containing cleaning agent, a friction modifier, a diluent and a labeling agent.

特に好適な担体液は、ポリオレフィン、例えばポリイソブチレン及びポリα−オレフィン、並びにポリオキシアルキレン化合物である。担体液は、２０〜８０００重量ｐｐｍ、例えば５０〜５００重量ｐｐｍの合計濃度で使用するのが都合よいかも知れない。   Particularly suitable carrier liquids are polyolefins such as polyisobutylene and polyalphaolefins, and polyoxyalkylene compounds. The carrier liquid may be conveniently used at a total concentration of 20 to 8000 ppm by weight, for example 50 to 500 ppm by weight.

ポリα−オレフィン担体液は、主として三量体、四量体及び五量体であり、これら材料の合成は、Ｃａｍｐｅｎ等、“Ｇｒｏｗｉｎｇ ｕｓｅ ｏｆ ｓｙｎｌｕｂｅｓ”，Ｈｙｄｒｏｃａｒｂｏｎ Ｐｒｏｃｅｓｓｉｎｇ，１９８２年２月、７５〜８２頁に概説されている。ポリα−オレフィンは水素化処理されていなくてもよいが、水素化処理したオリゴマーが好ましい。ポリα−オレフィンは、好ましくは炭素原子数８〜１２のα−オレフィンモノマーから誘導される。このポリα−オレフィンの１００℃での粘度は、６×１０−６〜１×１０−５ｍ２／ｓ（６〜１０ｃＳｔ）である。デセン−１から誘導したポリα−オレフィンは非常に好適である。１００℃での粘度が８×１０−６ｍ２／ｓ（８ｃＳｔ）のポリα−オレフィンは非常に好適である。 Poly α-olefin carrier liquids are primarily trimers, tetramers and pentamers, and the synthesis of these materials is described in Campen et al., “Growing use of synrubes”, Hydrocarbon Processing, February 1982, 75-82. Outlined on page. The poly α-olefin may not be hydrotreated, but a hydrotreated oligomer is preferred. The poly α-olefin is preferably derived from an α-olefin monomer having 8 to 12 carbon atoms. The viscosity of this poly α-olefin at 100 ° C. is 6 × 10 −6 to 1 × 10 −5 m 2 / s ( 6 to 10 cSt). Poly α-olefins derived from decene-1 are very suitable. Poly α-olefins with a viscosity at 100 ° C. of 8 × 10 −6 m 2 / s (8 cSt) are very suitable.

極めて効果的なポリオキシアルキレン担体液は、好ましくは式ＩＩ
Ｒ３−Ｏ−（Ｒ５）ｐ−Ｏ−Ｒ４ （ＩＩ）
を有する。ここでＲ３及びＲ４は独立に水素原子又はヒドロカルビル基、好ましくはＣ１〜４０ヒドロカルビル基、例えばアルキル、シクロアルキル、フェニル又はアルキル−フェニル基を表わし、各Ｒ５は独立にアルキレン基、好ましくはＣ２〜８アルキレン基を表わし、ｐはポリアルキレン化合物のＭｎが４００〜３０００、好ましくは７００〜２０００、更に好ましくは１０００〜２０００となるような値である。 A highly effective polyoxyalkylene carrier liquid is preferably of formula II
R 3 —O— (R 5 ) p —O—R 4 (II)
Have Wherein R 3 and R 4 independently represent a hydrogen atom or a hydrocarbyl group, preferably a C 1-40 hydrocarbyl group, such as an alkyl, cycloalkyl, phenyl or alkyl-phenyl group, and each R 5 is independently an alkylene group, preferably Represents a C 2-8 alkylene group, and p is a value such that Mn of the polyalkylene compound is 400 to 3000, preferably 700 to 2000, and more preferably 1000 to 2000.

好ましくはＲ３はＣ８〜２０アルキル基を表わし、Ｒ４は水素原子を表わす。Ｒ３は好ましくはＣ８〜１８アルキル基、更に好ましくはＲ３はＣ８〜１５アルキル基を表わす。Ｒ３はＣ８〜１５アルキル基の混合物であるのが都合よいかも知れない。 Preferably R 3 represents a C 8-20 alkyl group and R 4 represents a hydrogen atom. R 3 preferably represents a C 8-18 alkyl group, more preferably R 3 represents a C 8-15 alkyl group. It may be convenient for R 3 to be a mixture of C 8-15 alkyl groups.

式ＩＩにおいて、Ｒ５は好ましくは１，２アルキレン基である。好ましくは各Ｒ５は独立にＣ２〜４アルキレン基、例えばエチレン、１，２−プロピレン又は１，２−ブチレン基である。極めて効果的な結果は、各Ｒ５基が１，２−プロピレン基を表わす場合に得られた。 In formula II, R 5 is preferably a 1,2 alkylene group. Preferably each R 5 is independently a C 2-4 alkylene group, such as an ethylene, 1,2-propylene or 1,2-butylene group. Very effective results have been obtained when each R 5 group represents a 1,2-propylene group.

例えばポリアルキレンのような炭化水素の数平均分子量は、極めて類似した結果を与える種々の方法により測定できる。Ｍｎは蒸気相浸透圧法（ＶＰＯ）（ＡＳＴＭ Ｄ３５９２）又は例えばＷ．Ｗ．Ｙａｕ，Ｊ．Ｊ．Ｋｉｒｋｌａｎｄ及びＤ．Ｄ．Ｂｌｙ，“Ｍｏｄｅｒｎ Ｓｉｚｅ Ｅｘｃｌｕｓｉｏｎ Ｌｉｑｕｉｄ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ”，Ｊｏｈｎ Ｗｉｌｅｙ ａｎｄ Ｓｏｎｓ，Ｎｅｗ Ｙｏｒｋ，１９７９に記載されるような最新ゲル透過クロマトグラフィー（ＧＰＣ）で測定するのが都合よいかも知れない。或る化合物の式が既知の場合、数平均分子量はその式の重量として計算できる。   The number average molecular weight of hydrocarbons such as polyalkylenes can be measured by various methods that give very similar results. Mn may be vapor phase osmotic pressure (VPO) (ASTM D3592) or W. Yau, J .; J. et al. Kirkland and D.C. D. It may be convenient to measure with modern gel permeation chromatography (GPC) as described in Bly, “Modern Size Exclusion Liquid Chromatography”, John Wiley and Sons, New York, 1979. If the formula for a compound is known, the number average molecular weight can be calculated as the weight of that formula.

極めて好適な摩擦改良剤は、ＤＥ−Ａ−１９９５５６５１（ＢＡＳＦ）（例えばその実施例１に記載される）に開示された、例えば５〜１０００重量ｐｐｍ、好ましくは２０〜４００重量ｐｐｍ、更に好ましくは５０〜２００重量ｐｐｍの範囲の量の脂肪酸塩摩擦改良剤である。   Highly suitable friction modifiers are disclosed in DE-A-19955651 (BASF) (for example described in Example 1 thereof), for example 5 to 1000 ppm by weight, preferably 20 to 400 ppm by weight, more preferably Fatty acid salt friction modifier in an amount ranging from 50 to 200 ppm by weight.

スパーク点火エンジン用に好適な通常のガソリンは、沸点が２５〜２３２℃の範囲で、飽和炭化水素、オレフィン系炭化水素及び芳香族系炭化水素の混合物を含む炭化水素混合物である。飽和炭化水素の含有量が４０〜８０容量％の範囲で、オレフィン系炭化水素の含有量が０〜３０容量％の範囲で、芳香族系炭化水素の含有量が１０〜６０容量％の範囲のガソリンブレンドが好ましい。このガソリンは、直留ガソリン、ポリマーガソリン、天然ガソリン、二量化又は三量化オレフィン、熱又は接触改質炭化水素から、或いは接触分解又は熱分解石油原料又はそれらの混合物から合成的に製造した芳香族系炭化水素混合物から誘導できる。ガソリンの炭化水素組成及びオクタン水準は臨界的ではない。オクタン水準（Ｒ＋Ｍ）／２は、一般に８５より高い。従来のガソリンのいずれも使用できる。例えばガソリン中の炭化水素は、ガソリン用に従来公知である従来のアルコール又はエーテルの相当量以下まで置換できる。   A typical gasoline suitable for a spark ignition engine is a hydrocarbon mixture having a boiling point in the range of 25 to 232 ° C. and comprising a mixture of saturated hydrocarbons, olefinic hydrocarbons and aromatic hydrocarbons. The saturated hydrocarbon content is in the range of 40 to 80% by volume, the olefinic hydrocarbon content is in the range of 0 to 30% by volume, and the aromatic hydrocarbon content is in the range of 10 to 60% by volume. A gasoline blend is preferred. This gasoline is an aromatic synthetically produced from straight run gasoline, polymer gasoline, natural gasoline, dimerized or trimerized olefins, heat or catalytically modified hydrocarbons, or catalytically cracked or pyrolyzed petroleum feedstocks or mixtures thereof. It can be derived from a hydrocarbon mixture. The hydrocarbon composition and octane level of gasoline are not critical. The octane level (R + M) / 2 is generally higher than 85. Any conventional gasoline can be used. For example, hydrocarbons in gasoline can be substituted to a substantial amount of conventional alcohols or ethers conventionally known for gasoline.

ガソリンは無鉛であることが好ましく、法規で要求されている可能性がある。許可されている場合、無鉛アンチノック化合物及び／又は弁座リセッション保護化合物（例えば公知のカリウム塩、ナトリウム塩又は燐化合物）が存在してもよい。   Gasoline is preferably unleaded and may be required by law. If allowed, lead-free antiknock compounds and / or valve seat recession protection compounds (eg, known potassium, sodium or phosphorus compounds) may be present.

最近のガソリンは、本来、例えば硫黄含有量２００ｐｐｍ未満の低硫黄燃料である。
この規格では、成分の量（濃度）（容量％）（重量ｐｐｍ）は活性分（ａｃｔｉｖｅ ｍａｔｔｅｒ）である（即ち、揮発性溶剤／希釈材料を除く）。 Modern gasoline is inherently a low sulfur fuel, for example, with a sulfur content of less than 200 ppm.
In this standard, the amount (concentration) (volume%) (weight ppm) of the component is the active matter (ie, excluding volatile solvent / diluent material).

本発明は更に、前述のガソリン、レブリン酸エチル及び窒素含有洗浄剤を添加混合することを特徴とする本発明ガソリン組成物の製造方法を提供する。   The present invention further provides a method for producing the gasoline composition of the present invention, which comprises adding and mixing the aforementioned gasoline, ethyl levulinate and a nitrogen-containing detergent.

所望ならば、脂肪酸塩、添加助剤、及び前述のような腐蝕防止剤、酸化防止剤等の追加成分を添加剤濃厚物中に、好ましくは好適な希釈剤と共に、一緒に混合し、次いでこの添加剤能鉱物を本発明組成物を得るのに好適な量でガソリン中に分散してよい。   If desired, fatty acid salts, additive auxiliaries, and additional ingredients such as corrosion inhibitors, antioxidants, and the like as described above are mixed together in the additive concentrate, preferably with a suitable diluent, and then mixed together. Additive minerals may be dispersed in gasoline in an amount suitable for obtaining the composition of the present invention.

本発明は、前述のような本発明のガソリン組成物をスパーク点火エンジンの燃焼室に導入することを特徴とする該エンジンの操作方法も提供する。   The present invention also provides a method of operating the engine characterized by introducing the gasoline composition of the present invention as described above into the combustion chamber of a spark ignition engine.

本発明方法は、エンジンの清浄保持性能が良好である等、特に吸気系統（ｉｎｌｅｔ ｓｙｓｔｅｍ）の付着物に関連して、多くの有利な効果のいずれかを引き出すことができる上、高濃度の窒素含有洗浄剤、有利なオクタン性能（ＲＯＮ及びＭＯＮ）及び有利なリード蒸気圧では、清浄化性能が達成できる。   The method of the present invention can bring out any of a number of advantageous effects, particularly in connection with deposits in the intake system, such as good cleanliness performance of the engine, and high nitrogen concentration. With the included detergent, advantageous octane performance (RON and MON) and advantageous reed vapor pressure, cleaning performance can be achieved.

本発明は、以下に例示の実施例から更に理解されよう。実施例中、特に断わらない限り、部及び％は重量基準であり、また温度は摂氏温度である。   The invention will be further understood from the following illustrative examples. In the examples, unless otherwise indicated, parts and percentages are by weight, and temperatures are in degrees Celsius.

実施例で使用したベース燃料は、ＲＯＮ ９８．９、ＭＯＮ ８６．６、硫黄含有量（ＡＳＴＭ Ｄ２６２２−４）１３８重量ｐｐｍ、芳香族含有量５０．７％ｖ／ｖ、オレフィン含有量７．５％ｖ／ｖ（ＡＳＴＭ Ｄ６６２３−０１（方法Ｃ）、密度（ＤＩＮ ５１７５７／Ｖ４）７７９．１ｋｇ／ｃｍ３、蒸留（ＩＳＯ ３４０５／８８）ＩＢＰ ３５．４℃、９５％ｖ／ｖ １７４．４、ＦＢＰ ２０３℃の無鉛ガソリン（９５ ＵＬＧ）である。 The base fuels used in the examples are RON 98.9, MON 86.6, sulfur content (ASTM D2622-4) 138 ppm by weight, aromatic content 50.7% v / v, olefin content 7.5 % V / v (ASTM D 6623-01 (Method C), density (DIN 51757 / V4) 779.1 kg / cm 3 , distilled (ISO 3405/88) IBP 35.4 ° C., 95% v / v 174.4, FBP 203 ° C. unleaded gasoline (95 ULG).

ベース燃料に周囲温度（２０℃）で添加剤を添加し、次いで均質化することにより、燃料を添加剤とブレンドした。   The fuel was blended with the additive by adding the additive to the base fuel at ambient temperature (20 ° C.) and then homogenizing.

以下の添加剤を使用した。
レブリン酸エチル：
Ａｖｏｃａｄｏ ＣｈｅｍｉｃａｌｓからのカタログＮｏ．１５００１。
“ＤＰ”：
標準的な商用ガソリンの添加剤包装で、ポリイソブチレンアミン洗浄剤、合成担体油及び慣用の腐蝕防止剤を含有し、ＤＥ−Ａ−１９９５５６５１の実施例３の添加物包装ＰＩに相当する。ポリイソブチレンアミン洗浄剤は、ＢＡＳＦからの、ポリイソブチレン（ＰＩＢ）鎖の数平均分子量が約１０００のポリイソブチレン モノアミン（ＰＩＢＡ）である。合成担体油は、開始剤としてＣ５〜１５の範囲のアルコール混合物を用いて製造した、プロピレンオキシド単位を１５〜３０含み、Ｍｎが１０００〜２０００のポリオキシプロピレングリコールヘミエーテルからなるポリエーテル担体である。添加剤包装は、不揮発分を約６８％含有し、包装の約２７重量％がＰＩＢＡ、包装の約４０重量％が担体液である。
“ＰＩＢＡ”：
活性分が５０〜５５重量％で、残部が本質的に未反応のポリイソブチレンからなる“ＤＰ”のポリイソブチレンモノアミンに相当する工業用ポリイソブチレンモノアミンである。 The following additives were used.
Ethyl levulinate:
Catalog No. from Avocado Chemicals. 15001.
“DP”:
Standard commercial gasoline additive package, containing polyisobutylene amine detergent, synthetic carrier oil and conventional corrosion inhibitors, corresponding to additive package PI of Example 3 of DE-A-19955651. The polyisobutylene amine detergent is polyisobutylene monoamine (PIBA) from BASF with a polyisobutylene (PIB) chain number average molecular weight of about 1000. Synthetic carrier oil is a polyether carrier made of polyoxypropylene glycol hemiether containing 15-30 propylene oxide units and having Mn of 1000-2000, prepared using an alcohol mixture in the range of C5-15 as initiator. is there. The additive package contains about 68% non-volatile content, about 27% by weight of the package is PIBA, and about 40% by weight of the package is the carrier liquid.
“PIBA”:
It is an industrial polyisobutylene monoamine corresponding to the polyisobutylene monoamine of “DP” with an active content of 50 to 55% by weight and the balance consisting essentially of unreacted polyisobutylene.

テスト燃料に対し、以下の方法に従ってエンジンテストを行った。
トヨタ清浄保持：
吸気バルブの清浄性を評価するため、１９９２年型トヨタカリーナから外した１気筒当り４バルブのＩＶＤ ３Ｓ−ＦＥエンジンを用いて、ＩＶＤ清浄保持テストを行った。このエンジンは、多点噴射（ＭＰＩ）式で、ラムダセンサー及び排ガス再循環装置を備える。 An engine test was performed on the test fuel according to the following method.
Toyota cleanliness retention:
In order to evaluate the cleanliness of the intake valves, an IVD cleanliness test was conducted using a 4-valve IVD 3S-FE engine per cylinder removed from the 1992 Toyota Carina. This engine is a multi-point injection (MPI) type and includes a lambda sensor and an exhaust gas recirculation device.

テストを始める前に、吸気部品及び燃焼室を浄化した後、エンジンに予め秤量した新しい吸気バルブ及び新しいスパークプラグを取付け、新しいオイルフィルターを取付け、更にエンジンに新しいエンジンオイルを入れた。   Before starting the test, after cleaning the intake parts and the combustion chamber, the engine was fitted with a new pre-weighed valve and a new spark plug, a new oil filter was installed, and the engine was filled with new engine oil.

ＣＥＣ−Ｆ−０５−Ａ−９３の方法に規定されるメルセデスベンツＭ１０２Ｅエンジンの代りにトヨタ３Ｓ−ＦＥエンジンを用いると共に、メルセデスベンツＭ１０２Ｅエンジン及びトヨタ３Ｓ−ＦＥエンジンで得られる異なるBＭＥＰ（ｂｒｅａｋ ｍｅａｎ ｅｆｆｅｃｔｉｖｅ ｐｒｅｓｓｕｒｅ）（破壊平均有効圧）値を相殺するため、トルク値はＣＥＣ−Ｆ−０５−Ａ−９３に規定のトルク値とは異なる他は、ＣＥＣ−Ｆ−０５−Ａ−９３のテスト法に相当するテスト法に従って、エンジンを６９時間走行させた。   The Toyota 3S-FE engine is used in place of the Mercedes-Benz M102E engine specified in the method of CEC-F-05-A-93, and different BMEP (break mean effective) obtained with the Mercedes-Benz M102E engine and the Toyota 3S-FE engine are used. pressure) (crush average effective pressure) value is canceled out by the test method of CEC-F-05-A-93 except that the torque value is different from the torque value specified in CEC-F-05-A-93. The engine was run for 69 hours according to the corresponding test method.

各サイクルでの特定条件は、次のとおりである。
段階 時間（秒） 回転数 トルク（Ｎｍ）
１ ３０ ８５０ アイドリング
２ ６０ １３００ ２６
３ １２０ １８５０ ２８
４ ６０ ３０００ ３０
テストを終了すると、エンジンを分解し、バルブを再び秤量して、吸入バルブの付着物（ＩＶＤ）重量を求めた。 Specific conditions in each cycle are as follows.
Stage Time (seconds) Speed Torque (Nm)
1 30 850 Idling 2 60 1300 26
3 120 1850 28
4 60 3000 30
At the end of the test, the engine was disassembled and the valve was weighed again to determine the intake valve deposit (IVD) weight.

実施例１
本例では、レブリン酸エチル ５容量％及びＤＰ ３８０重量ｐｐｍ（実施例１）；ＤＰ ３８０重量ｐｐｍ（比較例Ａ）；レブリン酸エチル ５容量％（比較例Ｂ）；をそれぞれ含むガソリン組成物を製造し、これら組成物をベース燃料（比較例Ｃ）と比較して前記方法でテストした。結果を第１表に示す。 Example 1
In this example, gasoline compositions containing 5% by volume of ethyl levulinate and 380 ppm by weight of DP (Example 1); 380 ppm by weight of DP (Comparative Example A); 5% by volume of ethyl levulinate (Comparative Example B); Manufactured and tested in the manner described above in comparison with the base fuel (Comparative Example C) The results are shown in Table 1.

以上の結果から明らかなように、レブリン酸エチル及びポリイソブチレンアミンの両方を含む燃料は、レブリン酸エチル及びポリイソブチレンアミンの一方又は他方を含む燃料、或いはこれら材料のいずれも含まない燃料に比べて、清浄保持性能が極めて驚異的に優れている。   As is clear from the above results, the fuel containing both ethyl levulinate and polyisobutylene amine is compared with the fuel containing one or the other of ethyl levulinate and polyisobutylene amine, or the fuel containing none of these materials. Clean maintenance performance is extremely amazing.

実施例２
清浄保持性能の顕著な向上はレブリン酸エチル及びポリイソブチレンアミンの同時存在によるものであることを確認し、証明するため、実施例１と同じ処方で製造したベース燃料を用いて、レブリン酸エチル ５容量％及びＰＩＢＡ ２２５重量ｐｐｍ（実施例２）；ＰＩＢＡ ２２５重量ｐｐｍ（比較例Ｄ）；をそれぞれ含むガソリン組成物を製造し、これら組成物を前記方法でテストした。結果を第２表に示す。 Example 2
To confirm and prove that the significant improvement in clean retention performance is due to the simultaneous presence of ethyl levulinate and polyisobutylene amine, the base fuel produced in the same formulation as Example 1 was used to produce ethyl levulinate 5 Gasoline compositions, each containing% by volume and 225 ppm by weight of PIBA (Example 2); 225 ppm by weight of PIBA (Comparative Example D), were prepared and tested in the manner described above. The results are shown in Table 2.

第２表に示す結果から、実施例２の燃料ブレンドにおける清浄保持性能の顕著で驚異的な向上は、レブリン酸エチル及びポリイソブテニルアミンの両方の存在によるものであることが実際に確認された。   From the results shown in Table 2, it was actually confirmed that the significant and surprising improvement in clean retention performance in the fuel blend of Example 2 was due to the presence of both ethyl levulinate and polyisobutenyl amine. It was.

実施例３
レブリン酸エチル含有燃料のシール材料との適合性を、ベース燃料と比較し、更にレブリン酸メチル含有燃料（ＡｌｄｒｉｃｈからのカタログＮｏ．６１４０５）と比較して調べるため、テストを行った。 Example 3
Tests were conducted to examine the compatibility of the ethyl levulinate containing fuel with the sealing material compared to the base fuel and further compared to the methyl levulinate containing fuel (Catalog No. 61405 from Aldrich).

テスト法はＩＳＯ １８１７：１９９８の改訂版である。２つのエラストマー材料として、水素化ニトリルエラストマー（Ｊａｍｅｓ Ｗａｌｋｅｒ ＆ Ｃｏ．Ｌｔｄ．，ＵＫからの“Ｅｌａｓｔ−ｏ−Ｌｉｏｎ”２８０（商標））及びフルオロカーボンテトラポリマーエラストマー（Ｊａｍｅｓ Ｗａｌｋｅｒ ＆ Ｃｏ．Ｌｔｄ．，ＵＫからの“Ｖｉｔｏｎ”（商標）ＬＲ ６３１０）をテストした。テスト前に、大きさ５０ｍｍ×２５ｍｍ×３ｍｍのエラストマーサンプルの容積及びショアー硬度を測定し、またテスト液１００ｍｌに周囲温度（２０℃）で１６８時間浸漬した後、再び測定した。テスト液に１６８時間浸漬後、サンプルを急いで乾燥し、空器中及び水中で秤量し（テスト液から取り出して８時間以内）、容積変化％を計算した。硬度は、“Ａ型ショアー押込み硬度計”（商標）（Ｓｈｏｒｅ Ｉｎｓｔｒｕｍｅｎｔｓ，ＩｎｓｔｒｏｎＣｏｒｐ．，米国）を用いて周囲温度で測定した。
結果を第３表に示す。 The test method is a revised version of ISO 1817: 1998. Two elastomeric materials include hydrogenated nitrile elastomers (“Elast-o-Lion” 280 ™ from James Walker & Co. Ltd., UK) and fluorocarbon tetrapolymer elastomers (from James Walker & Co. Ltd., UK). “Viton” ™ LR 6310). Before the test, the volume and Shore hardness of an elastomer sample having a size of 50 mm × 25 mm × 3 mm were measured, and the sample was immersed in 100 ml of the test solution at ambient temperature (20 ° C.) for 168 hours and then measured again. After immersing in the test solution for 168 hours, the sample was quickly dried, weighed in an empty container and in water (within 8 hours after removal from the test solution), and the volume change% was calculated. The hardness was measured at ambient temperature using a “Type A Shore Indentation Hardness Tester” (trademark) (Shor Instruments, Instron Corp., USA).
The results are shown in Table 3.

以上の結果から判るように、％変化が高いほど、シール漏れの恐れが増大することと関連することから、レブリン酸エチルは、いずれの所定濃度に対してもレブリン酸メチルに比べて著しく害が少ない。   As can be seen from the above results, ethyl levulinate is significantly more harmful than methyl levulinate for any given concentration because the higher% change is associated with an increased risk of seal leakage. Few.

Claims (10)

スパーク点火エンジン用に好適なガソリンを主要量で含むと共に、レブリン酸エチルを１〜１５容量％、及び数平均分子量が７５０〜６０００の範囲のヒドロカルビル基を有する窒素含有洗浄剤を２０〜２０００重量ｐｐｍ含むガソリン組成物。  20 to 2000 ppm by weight of a nitrogen-containing detergent containing a major amount of gasoline suitable for a spark ignition engine and having a hydrocarbyl group of 1 to 15% by volume of ethyl levulinate and a number average molecular weight in the range of 750 to 6000 Contains gasoline composition. レブリン酸エチルを１．５〜１２容量％含む請求項１に記載のガソリン組成物。  The gasoline composition according to claim 1, comprising 1.5 to 12% by volume of ethyl levulinate. レブリン酸エチルを２〜１０容量％含む請求項１に記載のガソリン組成物。  The gasoline composition according to claim 1, comprising 2 to 10% by volume of ethyl levulinate. レブリン酸エチルを３〜８容量％含む請求項１に記載のガソリン組成物。  The gasoline composition according to claim 1, comprising 3 to 8% by volume of ethyl levulinate. レブリン酸エチルを４〜６容量％含む請求項１に記載のガソリン組成物。  The gasoline composition according to claim 1, comprising 4-6% by volume of ethyl levulinate. 前記窒素含有洗浄剤を５０〜１５００重量ｐｐｍ含む請求項１〜５のいずれか１項に記載のガソリン組成物。  The gasoline composition according to any one of claims 1 to 5, comprising 50 to 1500 ppm by weight of the nitrogen-containing cleaning agent. 前記窒素含有洗浄剤を５０〜５００重量ｐｐｍ含む請求項１〜５のいずれか１項に記載のガソリン組成物。  The gasoline composition according to any one of claims 1 to 5, comprising 50 to 500 ppm by weight of the nitrogen-containing cleaning agent. 前記窒素含有洗浄剤が、式Ｒ１−ＮＨ２（但し、Ｒ１はＲ２基又はＲ２−ＣＨ２−基を表わし、Ｒ２は数平均分子量が９５０〜１３５０の範囲のヒドロカルビル基を表わす）のヒドロカルビルアミンである請求項１〜７のいずれか１項に記載のガソリン組成物。The nitrogen-containing cleaning agent has the formula R 1 —NH 2 (where R 1 represents an R 2 group or an R 2 —CH 2 — group, and R 2 represents a hydrocarbyl group having a number average molecular weight in the range of 950 to 1350). The gasoline composition according to claim 1, which is a hydrocarbylamine. 前記ガソリン、前記レブリン酸エチル及び前記窒素含有洗浄剤を添加混合することを特徴とする請求項１〜８のいずれか１項に記載のガソリン組成物の製造方法。  The method for producing a gasoline composition according to any one of claims 1 to 8, wherein the gasoline, the ethyl levulinate, and the nitrogen-containing cleaning agent are added and mixed. 請求項１〜８のいずれか１項に記載のガソリン組成物をスパーク点火エンジンの燃焼室に導入することを特徴とする該エンジンの操作方法。  A method for operating the engine, comprising introducing the gasoline composition according to any one of claims 1 to 8 into a combustion chamber of a spark ignition engine.
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