JP4926513B2 - Fuel oil composition for compression self-ignition engine - Google Patents

Fuel oil composition for compression self-ignition engine Download PDF

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JP4926513B2
JP4926513B2 JP2006081079A JP2006081079A JP4926513B2 JP 4926513 B2 JP4926513 B2 JP 4926513B2 JP 2006081079 A JP2006081079 A JP 2006081079A JP 2006081079 A JP2006081079 A JP 2006081079A JP 4926513 B2 JP4926513 B2 JP 4926513B2
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重行 田中
保 田中
康司 北野
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Cosmo Oil Co Ltd
Toyota Motor Corp
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Description

本発明は、圧縮自己着火エンジン用燃料油組成物に関し、さらに詳しくは、優れた排気ガス特性と燃焼騒音の低い予混合圧縮自己着火燃焼を達成することができる燃料油組成物に関する。   The present invention relates to a fuel oil composition for a compression self-ignition engine, and more particularly to a fuel oil composition capable of achieving premixed compression self-ignition combustion with excellent exhaust gas characteristics and low combustion noise.

近年、環境問題から自動車から排出される排気ガスの低減や熱効率の向上が求められている。ディーゼルエンジンは、ガソリンエンジンに比べ熱効率が高く、地球温暖化に関係があるといわれている二酸化炭素(CO)の排出量が低い特性を有する。しかしながら、通常の拡散燃焼によるディーゼルエンジンでは、部分的に燃料の濃度が濃すぎる、高温燃焼する領域が形成されるなどの理由により、スモークや酸化窒素(NOx)の排出が問題となっている。これを解決するための新技術として、予混合圧縮自己着火エンジンが注目されている(例えば、非特許文献1参照)。 In recent years, reduction of exhaust gas emitted from automobiles and improvement of thermal efficiency have been demanded due to environmental problems. Diesel engines have higher thermal efficiency than gasoline engines, and have low carbon dioxide (CO 2 ) emissions, which are said to be related to global warming. However, in a diesel engine based on normal diffusion combustion, smoke and nitrogen oxide (NOx) emissions are problematic due to the fact that the fuel concentration is partly too high and a high temperature combustion region is formed. As a new technique for solving this problem, a premixed compression self-ignition engine has attracted attention (for example, see Non-Patent Document 1).

上記予混合圧縮自己着火エンジンで行われる予混合圧縮自己着火燃焼は、燃料と空気が希薄予混合された状態で圧縮されることにより、燃料が自己着火し燃焼する現象であり、通常のディーゼルエンジンにおいても、燃料を早期に噴射することによる燃料噴射時期の調整によって希薄予混合気を形成し、それを圧縮着火させることにより、排気ガス中のNOxやスモークを同時に低減することが可能である。しかしながら、一般に、高負荷条件において予混合圧縮着火燃焼を応用すると、混合気形成の悪化や急速な燃焼形態により排出ガスが増加するだけでなく燃焼騒音の増大も発生する場合があり、予混合圧縮自己着火燃焼は比較的負荷の低い領域に限られている。したがって、高負荷領域での運転は、燃料噴射時期を変化させることにより通常の拡散燃焼を行う運転が必要となるため、予混合圧縮自己着火エンジンにおいても、一般的なディーゼルエンジンの燃料噴射ノズル(ホールノズル)や燃焼室形状が求められる。ここで、ホールノズルを用いた通常のディーゼルエンジンにおいて、一般的な軽油を用いて早期噴射による予混合圧縮自己着火燃焼により運転を行った場合、従来の一般的な軽油を用いた拡散燃焼に依存するディーゼル燃焼による運転の場合に比べれば、NOxやスモークの発生が抑制されて、排気ガスがこれらの含有量の少ない優れた特性を示すが、まだNOxやスモークの発生の抑制が満足できるものではなく、また、燃焼騒音の発生を招くなど、十分に優れた運転特性を示す予混合圧縮自己着火燃焼を達成することは困難であった。   The premixed compression self-ignition combustion performed in the above premixed compression self-ignition engine is a phenomenon in which fuel is self-ignited and burned when the fuel and air are compressed in a lean premixed state. However, it is possible to simultaneously reduce NOx and smoke in the exhaust gas by forming a lean premixed gas by adjusting the fuel injection timing by injecting the fuel at an early stage and igniting it with compression. However, in general, when premixed compression ignition combustion is applied under high load conditions, not only the exhaust gas but also the combustion noise may increase due to the deterioration of the mixture formation and the rapid combustion mode. Auto-ignition combustion is limited to areas with relatively low loads. Therefore, since the operation in the high load region requires the operation of performing normal diffusion combustion by changing the fuel injection timing, even in the premixed compression self-ignition engine, the fuel injection nozzle ( Hole nozzle) and combustion chamber shape are required. Here, in a normal diesel engine using a hole nozzle, when operating by premixed compression self-ignition combustion by early injection using general light oil, it depends on diffusion combustion using conventional general light oil Compared to the operation by diesel combustion, the generation of NOx and smoke is suppressed, and the exhaust gas has excellent characteristics with a small content of these, but the suppression of the generation of NOx and smoke is still not satisfactory. In addition, it has been difficult to achieve premixed compression self-ignition combustion exhibiting sufficiently excellent operation characteristics such as causing combustion noise.

予混合圧縮自己着火燃焼では、燃料がエンジンシリンダー内に噴射された後、空気と予混合され、燃料の酸化反応が逐次的に進行し着火・燃焼という過程を経るので、燃料と空気の予混合気の形成と着火時期が重要なポイントであって、燃料自体の物理特性や化学特性が大きく影響する。それ故、燃料の性状によっては、通常のホールノズルや燃焼室形状のディーゼルエンジンにおいても予混合圧縮自己着火燃焼を達成できる可能性があると考えられる。この考えに基づき、燃料組成物の蒸留性状やセタン価を制御することにより排出ガスの少ない予混合圧縮着火燃焼を可能にした予混合圧縮自己着火エンジン用燃料油組成物が提案されている(特許文献1参照)。しかしながら、この燃料油組成物では、まだ上述した燃焼騒音に関する課題は解決されておらず、予混合圧縮自己着火燃焼に用いる燃料の品質を更に改善して、低排出ガス特性と低燃焼騒音特性を両立させることが求められている。   In premixed compression self-ignition combustion, fuel is injected into the engine cylinder and then premixed with air. The fuel oxidation reaction proceeds sequentially and undergoes a process of ignition and combustion. Qi formation and ignition timing are important points, and the physical and chemical characteristics of the fuel itself are greatly affected. Therefore, depending on the nature of the fuel, it is considered that premixed compression self-ignition combustion may be achieved even in a normal hole nozzle or combustion chamber-shaped diesel engine. Based on this idea, a fuel oil composition for a premixed compression self-ignition engine that enables premixed compression ignition combustion with less exhaust gas by controlling the distillation property and cetane number of the fuel composition has been proposed (patent) Reference 1). However, this fuel oil composition has not yet solved the problems related to combustion noise described above, and further improves the quality of the fuel used for premixed compression self-ignition combustion, resulting in low exhaust gas characteristics and low combustion noise characteristics. It is demanded to make it compatible.

特開2004−315604号公報JP 2004-315604 A Rudolf H. Stanglemaier and Charles E. Roberts, SAE Paper NO.1999−01−3682Rudolf H.R. Stanglemaier and Charles E.M. Roberts, SAE Paper NO. 1999-01-3682

本発明は、上記従来の状況に鑑みてなされたものであり、予混合圧縮自己着火燃焼における燃料の性状の及ぼす影響の大きさに着目し、予混合圧縮自己着火燃焼と燃料の性状の関係を十分に究明して、十分に優れた排気ガス特性を示し、かつ燃焼騒音の低い予混合圧縮自己着火燃焼を達成することができる燃料油組成物を提供することを目的とする。   The present invention has been made in view of the above-described conventional situation, paying attention to the magnitude of the influence of the properties of fuel in premixed compression self-ignition combustion, and the relationship between premixed compression self-ignition combustion and fuel properties. It is an object of the present invention to provide a fuel oil composition that can be fully investigated and can exhibit premixed compression self-ignition combustion with sufficiently excellent exhaust gas characteristics and low combustion noise.

そこで、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、一定の沸点留分毎のセタン価をある特定の範囲に調整し、かつ燃料全体のセタン価を一定範囲とすることで、早期噴射により排出ガス濃度の少ない予混合圧縮着火燃焼を行う場合における燃焼騒音を低減することが可能であり、十分に優れた排気ガス特性を示し、かつ燃焼騒音の低い予混合圧縮自己着火燃焼を達成することができる燃料油組成物を調製し得ることを見出し、本発明を完成させるに至った。   Therefore, as a result of intensive studies to achieve the above object, the present inventors have adjusted the cetane number for each constant boiling fraction to a specific range, and set the cetane number of the entire fuel to be within a certain range. This makes it possible to reduce combustion noise when performing premixed compression ignition combustion with low exhaust gas concentration by early injection, exhibiting sufficiently excellent exhaust gas characteristics, and premixed compression with low combustion noise It has been found that a fuel oil composition capable of achieving self-ignition combustion can be prepared, and the present invention has been completed.

すなわち、本発明は、上記目的を達成するために、次の圧縮自己着火エンジン用燃料油組成物を提供する。
(1)初留点が20℃以上135℃以下、50%留出点が60℃以上250℃以下、終点が200℃以上350℃以下であり、30℃における動粘度が0.4mm /s以上3.0mm /s以下であり、硫黄分が10質量ppm以下であり、燃料全体のセタン価が30以上50以下であり、沸点が150℃未満の留分のセタン価が10以上45以下であり、沸点が150℃以上の留分のセタン価が30以上95以下であり、かつ沸点が150℃未満の留分のセタン価(150−CN)と沸点が150℃以上の留分のセタン価(150+CN)の比〔(150−CN)/(150+CN)〕が1以下であることを特徴とする圧縮自己着火エンジン用燃料油組成物。
)終点が200℃以上300℃以下であることを特徴とする上記()に記載の圧縮自己着火エンジン用燃料油組成物。
That is, this invention provides the following fuel oil composition for compression self-ignition engines, in order to achieve the said objective.
(1) The initial boiling point is 20 ° C to 135 ° C, the 50% distillation point is 60 ° C to 250 ° C, the end point is 200 ° C to 350 ° C, and the kinematic viscosity at 30 ° C is 0.4 mm 2 / s. The cetane number of the fraction having a boiling point of less than 150 ° C. is 10 or more and 45 or less, and is 3.0 mm 2 / s or less, the sulfur content is 10 mass ppm or less, the cetane number of the whole fuel is 30 or more and 50 or less. , and the boiling point of 0.99 ° C. or more distillate cetane number Ri der 30 or more 95 or less, and a fraction of the cetane number having a boiling point of less than 150 ℃ (150-CN) and a boiling point fraction above 0.99 ° C. A fuel oil composition for a compression self-ignition engine, wherein the ratio of cetane number (150 + CN) [(150-CN) / (150 + CN)] is 1 or less .
( 2 ) End point is 200 degreeC or more and 300 degrees C or less, The fuel oil composition for compression self-ignition engines as described in said ( 1 ) characterized by the above-mentioned.

本発明によれば、十分に優れた排気ガス特性を示し、かつ低い燃焼騒音を示す予混合圧縮自己着火燃焼を達成することができる燃料油組成物が提供される。   ADVANTAGE OF THE INVENTION According to this invention, the fuel oil composition which can achieve the premixing compression self-ignition combustion which shows the exhaust gas characteristic which was fully excellent, and shows low combustion noise is provided.

以下、本発明を詳細に説明する。
本発明の燃料油組成物は、原油を常圧蒸留して得られるナフサ留分、ナフサ留分を脱硫して得られる脱硫ナフサ、脱硫ナフサを接触改質して得られる改質ガソリン、および改質ガソリンからベンゼンを取り除いた脱ベンゼン改質ガソリン、原油を常圧蒸留して得られる灯軽油留分、灯軽油留分を脱硫して得られる脱硫灯軽油、重質油を接触分解、水素化分解、あるいは熱分解して得られる、ガソリン、灯軽油留分、オレフィンとイソブタンから生成されるアルキレート、ナフサ留分を接触処理し、異性化したアイソメレート、炭素数4あるいは5の炭化水素などを適宜配合して調製することができる。また、フィッシャートロプシュ合成によるパラフィン系炭化水素やアルコール燃料、種々の炭素数を有するパラフィン系溶剤、ナフテン系溶剤、芳香族系溶剤などを原料として用いることもできる。また、本発明の燃料油組成物は、上記のように各種の原料留分を適宜配合して好適に調整することができるが、必要に応じて、原油からの直留留分として取得することも可能である。
Hereinafter, the present invention will be described in detail.
The fuel oil composition of the present invention includes a naphtha fraction obtained by atmospheric distillation of crude oil, a desulfurized naphtha obtained by desulfurizing the naphtha fraction, a reformed gasoline obtained by catalytic reforming of the desulfurized naphtha, and a modified gasoline. Debenzene-modified gasoline with benzene removed from high-quality gasoline, kerosene fraction obtained by atmospheric distillation of crude oil, desulfurized kerosene obtained by desulfurizing kerosene fraction, and catalytic cracking and hydrogenation of heavy oil Gasoline, kerosene fraction obtained by cracking or pyrolysis, alkylate produced from olefin and isobutane, isomerized isomerate, hydrocarbon with 4 or 5 carbon atoms, etc. Can be appropriately blended and prepared. In addition, paraffinic hydrocarbons and alcohol fuels by Fischer-Tropsch synthesis, paraffinic solvents having various carbon numbers, naphthenic solvents, aromatic solvents, and the like can also be used as raw materials. Further, the fuel oil composition of the present invention can be suitably adjusted by appropriately blending various raw material fractions as described above, but if necessary, obtained as a direct fraction from crude oil. Is also possible.

本発明の燃料油組成物において、硫黄分は10質量ppm以下であって、好ましくは8質量ppm以下である。硫黄分が10質量ppmより多いと、排気ガス中の硫黄酸化物の含有量が多くなる場合があり、また該排気ガスを処理する触媒を被毒する場合がある。硫黄分は、JIS K 2541の微量電量滴定式酸化法により測定できる。   In the fuel oil composition of the present invention, the sulfur content is 10 mass ppm or less, preferably 8 mass ppm or less. When the sulfur content is more than 10 mass ppm, the content of sulfur oxide in the exhaust gas may increase, and the catalyst for treating the exhaust gas may be poisoned. The sulfur content can be measured by the microcoulometric titration method of JIS K2541.

本発明の燃料油組成物において、初留点は20℃以上135℃以下であって、好ましくは20℃以上100℃以下である。135℃より初留点が高いと、燃料油組成物の揮発性が乏しくなることから、燃料油組成物と空気の混合割合が低くなるため、予混合圧縮自己着火燃焼を行う場合、スモークや炭化水素が多く排出される場合がある。初留点が20℃より低いと、燃料ポンプや燃料パイプ中に燃料油組成物の蒸気が多量に発生して燃料油組成物の流通が妨げられる場合がある。 The fuel oil composition of the present invention, the initial boiling point equal to or less than 135 ° C. 2 0 ° C. or more, good Mashiku is 100 ° C. or less 20 ° C. or higher. When the initial boiling point is higher than 135 ° C., the volatility of the fuel oil composition becomes poor. Therefore, the mixing ratio of the fuel oil composition and air decreases, so when performing premixed compression self-ignition combustion, smoke or carbonization is performed. A lot of hydrogen may be discharged. When the initial boiling point is lower than 20 ° C., a large amount of vapor of the fuel oil composition is generated in the fuel pump or the fuel pipe, which may hinder the distribution of the fuel oil composition.

本発明の燃料油組成物において、50%留出点は60℃以上250℃ 以下であって、好ましくは80℃以上230℃以下であり、より好ましくは100℃以上200℃以下である。250℃より50%留出点が高いと、燃料の揮発性が乏しくなることから、燃料油組成物と空気の混合割合が低くなるため、予混合圧縮自己着火燃焼を行う場合、スモークや炭化水素が多く排出される場合がある。50%留出点が60℃より低いと、燃料ポンプや燃料パイプ中に燃料油組成物の蒸気が多量に発生して燃料油組成物の流通が妨げられる場合がある。 The fuel oil composition of the present invention, 50% distillation point or less 250 ° C. 6 0 ° C. or higher, good Mashiku is at 80 ° C. or higher 230 ° C. or less, more preferably at 100 ° C. or higher 200 ° C. or less . When the 50% distillation point is higher than 250 ° C., the volatility of the fuel becomes poor. Therefore, the mixing ratio of the fuel oil composition and air decreases, so when performing premixed compression self-ignition combustion, smoke and hydrocarbons are used. May be discharged. When the 50% distillation point is lower than 60 ° C., a large amount of vapor of the fuel oil composition is generated in the fuel pump or the fuel pipe, which may hinder the distribution of the fuel oil composition.

本発明の燃料油組成物において、終点は200℃以上350℃以下であって、好ましくは200℃以上300℃以下である。350℃より終点が高いと、燃料油組成物の揮発性が乏しくなることから、燃料油組成物と空気の混合割合が低くなるため、予混合圧縮自己着火燃焼を行う場合、スモークや炭化水素が多く排出される場合がある。終点が200℃より低いと、夏場などの高温時に燃料ポンプや燃料パイプ中に燃料油組成物の蒸気が多量に発生して燃料油組成物の流通が妨げられる場合があるのに加え、燃料としての蒸留範囲が極端に狭くなるために、得率が少なくなりすぎて効率的でない。
上記初留点や、50%留出点や、終点といった蒸留性状は、JIS K 2254の石油製品蒸留試験方法の常圧法により測定できる。
The fuel oil composition of the present invention, the endpoint is not more than 350 ° C. 2 00 ° C. or more, good Mashiku is 200 ° C. or higher 300 ° C. or less. When the end point is higher than 350 ° C., the volatility of the fuel oil composition becomes poor, and therefore, the mixing ratio of the fuel oil composition and air decreases, so when performing premixed compression self-ignition combustion, smoke and hydrocarbons are not generated. A lot may be discharged. When the end point is lower than 200 ° C., the fuel oil composition vapor may be generated in a large amount in the fuel pump or the fuel pipe at a high temperature such as in summer, and the distribution of the fuel oil composition may be hindered. The distillation range is extremely narrow, so that the yield is too low to be efficient.
The distillation properties such as the initial boiling point, 50% distillation point, and end point can be measured by the atmospheric pressure method of the petroleum product distillation test method of JIS K 2254.

本発明の燃料油組成物において、30℃における動粘度は0.4mm/s以上3.0mm/s以下であって、好ましくは0.4mm/s以上2.5mm/s以下であり、さらに好ましくは0.5mm/s以上2.0mm/s以下である。動粘度が3.0mm/sより高いと、燃料油組成物の噴霧角度が狭くなり、微粒化が促進されにくいことから、予混合気の形成が悪くなる。動粘度が低すぎる場合には、燃料ポンプなどの磨耗を生じる場合があり好ましくない。動粘度は、JIS K2283の石油製品動粘度試験方法により測定できる。 In the fuel oil composition of the present invention, the kinematic viscosity at 30 ° C. is 0 . A less 4 mm 2 / s or more 3.0 mm 2 / s, good Mashiku is less 0.4 mm 2 / s or more 2.5 mm 2 / s, more preferably 0.5 mm 2 / s or more 2.0mm 2 / s or less. If the kinematic viscosity is higher than 3.0 mm 2 / s, the spray angle of the fuel oil composition becomes narrow and the atomization is hardly promoted, so that the formation of the premixed gas becomes worse. If the kinematic viscosity is too low, the fuel pump or the like may be worn, which is not preferable. The kinematic viscosity can be measured by a petroleum product kinematic viscosity test method of JIS K2283.

本発明の燃料油組成物において、セタン価は30以上50以下であって、好ましくは35以上45以下である。予混合圧縮自己着火燃焼を行う場合において、セタン価が30より低いと、炭化水素の排出量が増加する場合がある。一方、セタン価が50より高いと、予混合圧縮自己着火燃焼をより高負荷で達成しようとする場合、急激な熱発生を伴う場合があることから、燃焼騒音が高くなる場合がある。   In the fuel oil composition of the present invention, the cetane number is 30 or more and 50 or less, preferably 35 or more and 45 or less. When premixed compression self-ignition combustion is performed, if the cetane number is lower than 30, hydrocarbon emissions may increase. On the other hand, when the cetane number is higher than 50, combustion noise may be high because premixed compression self-ignition combustion may be accompanied by a rapid heat generation when attempting to achieve a higher load.

本発明の燃料油組成物において、沸点が150℃未満の留分のセタン価(以下、150−CNとも表す)は10以上45以下であって、好ましくは10以上40以下である。予混合圧縮自己着火燃焼を行う場合において、沸点が150℃未満の留分のセタン価が10より低いと、炭化水素の排出量が増加する場合がある。一方、沸点が150℃未満の留分のセタン価が45より高いと、予混合圧縮着火燃焼を行う場合において燃焼騒音が大きくなる場合がある。   In the fuel oil composition of the present invention, the cetane number of the fraction having a boiling point of less than 150 ° C. (hereinafter also referred to as 150-CN) is 10 or more and 45 or less, preferably 10 or more and 40 or less. When premixed compression self-ignition combustion is performed, if the cetane number of the fraction having a boiling point of less than 150 ° C. is lower than 10, the amount of hydrocarbon emissions may increase. On the other hand, if the cetane number of the fraction having a boiling point of less than 150 ° C. is higher than 45, combustion noise may increase when premixed compression ignition combustion is performed.

本発明の燃料油組成物において、沸点が150℃以上の留分のセタン価(以下、150+CNとも表す)は30以上95以下であって、好ましくは35以上95以下である。予混合圧縮自己着火燃焼を行う場合において、沸点が150℃以上の留分のセタン価が35より低いと、炭化水素の排出量が増加する場合があり、さらに予混合圧縮着火燃焼において燃焼騒音が大きくなる場合がある。一方、沸点が150℃以上の留分のセタン価が95より高くなっても燃焼騒音が大きくなる場合がある。   In the fuel oil composition of the present invention, the cetane number of a fraction having a boiling point of 150 ° C. or higher (hereinafter also referred to as 150 + CN) is 30 to 95, preferably 35 to 95. In the case of premixed compression self-ignition combustion, if the cetane number of a fraction having a boiling point of 150 ° C. or higher is lower than 35, the amount of hydrocarbon emissions may increase, and combustion noise in premixed compression ignition combustion may increase. May be larger. On the other hand, even if the cetane number of a fraction having a boiling point of 150 ° C. or higher is higher than 95, combustion noise may increase.

本発明の燃料油組成物において、沸点が150℃未満の留分のセタン価(150−CN)と沸点が150℃以上の留分のセタン価(150+CN)の比〔(150−CN)/(150+CN)〕は、1以下であり、好ましくは0.8以下である。この比が1以下であれば、予混合圧縮着火燃焼における燃焼騒音を一層抑制することが可能となる。
セタン価は、JIS K 2280の燃料油セタン価試験方法により測定できる。留分別のセタン価については、それぞれの留分に該当する燃料調製用基材のセタン価を測定してもよいし、本発明の燃料油組成物を蒸留により分留し、それぞれの留分のセタン価を測定してもよい。
In the fuel oil composition of the present invention, the ratio of the cetane number (150-CN) of the fraction having a boiling point of less than 150 ° C. to the cetane number (150 + CN) of the fraction having a boiling point of 150 ° C. or more [(150-CN) / ( 0.99 + CN)] is 1 or less, good Mashiku is 0.8 or less. If this ratio is 1 or less, it becomes possible to further suppress combustion noise in premixed compression ignition combustion.
The cetane number can be measured by the fuel oil cetane number test method of JIS K 2280. Regarding the cetane number by fractionation, the cetane number of the fuel preparation base material corresponding to each fraction may be measured, or the fuel oil composition of the present invention may be fractionated by distillation, The cetane number may be measured.

本発明の燃料油組成物には、必要に応じて公知の燃料添加剤、例えば、酸化防止剤、氷結防止剤、助燃剤、帯電防止剤、防錆剤、識別剤、着色剤、清浄剤、セタン価向上剤、消泡剤、酸化防止剤、流動性向上剤、潤滑性向上剤などを、適量添加することができる。   In the fuel oil composition of the present invention, known fuel additives such as antioxidants, anti-icing agents, auxiliary agents, antistatic agents, rust preventives, discriminating agents, colorants, detergents, if necessary, An appropriate amount of a cetane number improver, an antifoaming agent, an antioxidant, a fluidity improver, a lubricity improver and the like can be added.

次に、本発明を実施例および比較例によりさらに具体的に説明する。なお、本発明は、これらの例によって何ら制限されるものではない。   Next, the present invention will be described more specifically with reference to examples and comparative examples. In addition, this invention is not restrict | limited at all by these examples.

実施例1〜3 および比較例1〜5
表1に示す性状を有する燃料油組成物を下記のようにして調製し、その評価を下記の方法により行った。
実施例1:イソオクタンを50容量%、沸点範囲206〜257℃のイソパラフィン溶剤を20容量%、炭素数14のノルマルパラフィンを30容量%の割合で混合して調製した。
実施例2:原油を常圧蒸留して得られる重質ナフサ留分(沸点範囲80℃〜140℃)と灯油留分(沸点範囲145℃〜245℃)をそれぞれ水素化脱硫処理した基材を等容量混合して調製した。
実施例3:沸点範囲104℃〜177℃の重質リフォーメートを43容量%、70℃〜103℃の沸点範囲のn−パラフィンを13容量%、169℃〜257℃の沸点範囲のn−パラフィンを35容量%、166℃〜266℃の沸点範囲のイソパラフィン溶剤を9容量%の割合で混合して調製した。
Examples 1-3 and Comparative Examples 1-5
A fuel oil composition having the properties shown in Table 1 was prepared as described below and evaluated by the following method.
Example 1: 50% by volume of isooctane, 20% by volume of isoparaffin solvent having a boiling point range of 206 to 257 ° C., and 30% by volume of normal paraffin having 14 carbon atoms were mixed.
Example 2: Substrates obtained by hydrodesulfurizing a heavy naphtha fraction (boiling range 80 ° C to 140 ° C) and a kerosene fraction (boiling range 145 ° C to 245 ° C) obtained by atmospheric distillation of crude oil, respectively. Prepared by mixing equal volumes.
Example 3: 43% by volume of heavy reformate having a boiling range of 104 ° C to 177 ° C, 13% by volume of n-paraffin having a boiling range of 70 ° C to 103 ° C, and n-paraffin having a boiling range of 169 ° C to 257 ° C Was prepared by mixing an isoparaffin solvent having a boiling point of 166 ° C. to 266 ° C. in a proportion of 9% by volume.

比較例1:ノルマルヘプタンを50容量%、沸点範囲206〜257℃のイソパラフィン溶剤を45.5容量%、炭素数14のノルマルパラフィンを4.5容量%の割合で混合して調製した。
比較例2:161℃〜245℃の沸点範囲を有する芳香族溶剤を31容量%、αメチルナフタレンを2.8容量%、75℃〜150℃の沸点範囲を有するn−パラフィン混合物を55容量%、炭素数14のn−パラフィンを11.2容量%の割合で混合して調製した。
比較例3:原油を常圧蒸留して得られる灯軽油留分(沸点範囲170℃〜360℃)を水素化脱硫処理した基材に沸点範囲が200℃〜330℃のイソパラフィン溶剤を47容量%配合して調製した。
比較例4:原油を常圧蒸留して得られる灯油留分(145℃〜245℃)を水素化脱硫処理した基材に、沸点範囲が80℃〜240℃のイソパラフィン溶剤を80容量%配合して調製した。
比較例5:一般的な2号軽油を用いた。
Comparative Example 1: Prepared by mixing 50% by volume of normal heptane, 45.5% by volume of isoparaffin solvent having a boiling range of 206 to 257 ° C., and 4.5% by volume of normal paraffin having 14 carbon atoms.
Comparative Example 2: 31% by volume of an aromatic solvent having a boiling point range of 161 ° C. to 245 ° C., 2.8% by volume of α-methylnaphthalene, 55% by volume of n-paraffin mixture having a boiling point range of 75 ° C. to 150 ° C., carbon Several 14 n-paraffins were mixed at a ratio of 11.2% by volume.
Comparative Example 3: A kerosene fraction (boiling range: 170 ° C. to 360 ° C.) obtained by atmospheric distillation of crude oil was subjected to hydrodesulfurization, and 47% by volume of an isoparaffin solvent having a boiling range of 200 ° C. to 330 ° C. Prepared by blending.
Comparative Example 4: A kerosene fraction (145 ° C to 245 ° C) obtained by atmospheric distillation of crude oil was mixed with 80% by volume of isoparaffin solvent having a boiling point range of 80 ° C to 240 ° C. Prepared.
Comparative Example 5: A general No. 2 light oil was used.

Figure 0004926513
Figure 0004926513

評価試験エンジンとして、直列4気筒、排気量2L、コモンレール方式の燃料噴射装置およびインタークーラー付のターボ加給機、クールド排ガス再循環装置が搭載されているディーゼルエンジンを使用した。本試験エンジンの主要緒元を表2に示す。本試験エンジンにおいて、圧縮比を15とし、燃料の噴射時期を、通常のディーゼル燃焼の場合に比べ早期に設定することにより、予混合圧縮自己着火燃焼を可能にしている。   As an evaluation test engine, a diesel engine equipped with an in-line 4-cylinder, displacement 2L, common rail fuel injection device, turbocharger with intercooler, and cooled exhaust gas recirculation device was used. Table 2 shows the main specifications of the test engine. In this test engine, premixed compression self-ignition combustion is enabled by setting the compression ratio to 15 and setting the fuel injection timing earlier than in the case of normal diesel combustion.

Figure 0004926513
Figure 0004926513

上記試験エンジンを用いて、エンジン回転数:2000rpm、燃料噴射圧力:50MPa、噴射時期:上死点30°前、トルク:60Nmの条件で、各実施例、各比較例で調製した燃料油組成物の予混合圧縮着火燃焼時の燃焼騒音、炭化水素排出量(THC)、NOx排出量、スモーク排出量(FNS)を測定した。なお、NOx、CO、THCなど排ガス測定については、自動車排ガス分析計で排気管から直接測定した。燃焼騒音については、燃焼騒音計を用いて、エンジン筒内圧力波形から導出した。評価結果を表3に示す。   Fuel oil compositions prepared in each Example and each Comparative Example using the above test engine under the conditions of engine speed: 2000 rpm, fuel injection pressure: 50 MPa, injection timing: 30 ° top dead center, torque: 60 Nm Combustion noise, hydrocarbon emissions (THC), NOx emissions, smoke emissions (FNS) during premixed compression ignition combustion were measured. Note that NOx, CO, THC and other exhaust gas measurements were made directly from the exhaust pipe with an automobile exhaust gas analyzer. The combustion noise was derived from the in-cylinder pressure waveform using a combustion noise meter. The evaluation results are shown in Table 3.

Figure 0004926513
Figure 0004926513

*1:Filter Smoke Number;紙を通して所定量の排気ガスを吸引し、付着したスモークの反射率を測定する評価方法。評価は、真っ白=0、真っ黒=10とし、真っ白と真っ黒の間を0〜10で評価する。すなわち、測定用紙に光を照射し、その反射光を反射率計で計測することにより、次式で与えられる。
FSN=(Rf−Rs)/Rf×10
式中:Rf:排気ガスを吸引する前の用紙の反射率計値
Rs:排気ガスを吸引し、スモークが付着した用紙の反射率計値
* 1: Filter Smoke Number: An evaluation method in which a predetermined amount of exhaust gas is sucked through paper and the reflectance of the attached smoke is measured. Evaluation is made with white = 0 and black = 10, and a value between 0 and 10 is evaluated between white and black. That is, by irradiating the measurement paper with light and measuring the reflected light with a reflectometer, the following equation is given.
FSN = (Rf−Rs) / Rf × 10
In formula: Rf: Reflectance meter value of paper before sucking exhaust gas
Rs: Reflectometer value of paper that sucks exhaust gas and adheres smoke

燃料油組成物の評価に当たり、好適に排出ガスの少ない状態で予混合圧縮着火燃焼が達成されていると判断できる排出ガスレベルを、スモーク排出量:0.3以下、NOx排出量:30ppm以下、炭化水素排出量:3000ppm以下であるときとした。   In the evaluation of the fuel oil composition, the exhaust gas level at which premixed compression ignition combustion can be determined to be achieved preferably with a small amount of exhaust gas, smoke emission: 0.3 or less, NOx emission: 30 ppm or less, The amount of hydrocarbon emissions was assumed to be 3000 ppm or less.

表3から明らかなように、本発明に規定する要件、すなわち初留点が20℃以上135℃以下、50%留出点が60℃以上250℃以下、終点が200℃以上350℃以下であり、30℃における動粘度が0.4mm /s以上3.0mm /s以下であり、硫黄分が10質量ppm以下であり、燃料全体のセタン価が30以上50以下、沸点が150℃未満の留分のセタン価が10以上45以下であり、沸点が150℃以上の留分のセタン価が30以上95以下であり、かつ沸点が150℃未満の留分のセタン価(150−CN)と沸点が150℃以上の留分のセタン価(150+CN)の比〔(150−CN)/(150+CN)〕が1以下であるという要件を満たす実施例1〜3の燃料油組成物は、好適に排出ガスの少ない状態で予混合圧縮自己着火燃焼を達成することができ、その燃焼騒音は、比較例1〜5の当該要件を満たさない燃料油組成物の燃焼騒音より遥かに良好な騒音特性を示す。 As is apparent from Table 3, the requirements stipulated in the present invention, that is, the initial boiling point is 20 ° C to 135 ° C, the 50% distillation point is 60 ° C to 250 ° C, and the end point is 200 ° C to 350 ° C. The kinematic viscosity at 30 ° C. is 0.4 mm 2 / s or more and 3.0 mm 2 / s or less, the sulfur content is 10 mass ppm or less, the cetane number of the whole fuel is 30 or more and 50 or less, and the boiling point is less than 150 ° C. the cetane number of distillate is 10 or more 45 or less and a boiling point Ri der cetane number of 0.99 ° C. or more fractions of at least 30 95 or less, and a fraction of the cetane number having a boiling point of less than 150 ℃ (150-CN ) And the cetane number (150 + CN) of the fraction having a boiling point of 150 ° C. or higher [(150−CN) / (150 + CN)] satisfying the requirement that the ratio is 1 or less , Preliminarily with low emissions Mixed compression self-ignition combustion can be achieved, and the combustion noise exhibits much better noise characteristics than the combustion noise of fuel oil compositions that do not meet the requirements of Comparative Examples 1-5.

Claims (2)

初留点が20℃以上135℃以下、50%留出点が60℃以上250℃以下、終点が200℃以上350℃以下であり、30℃における動粘度が0.4mm /s以上3.0mm /s以下であり、硫黄分が10質量ppm以下であり、燃料全体のセタン価が30以上50以下であり、沸点が150℃未満の留分のセタン価が10以上45以下であり、沸点が150℃以上の留分のセタン価が30以上95以下であり、かつ沸点が150℃未満の留分のセタン価(150−CN)と沸点が150℃以上の留分のセタン価(150+CN)の比〔(150−CN)/(150+CN)〕が1以下であることを特徴とする圧縮自己着火エンジン用燃料油組成物。 2. Initial boiling point is 20 ° C. or higher and 135 ° C. or lower, 50% distillation point is 60 ° C. or higher and 250 ° C. or lower, end point is 200 ° C. or higher and 350 ° C. or lower, and kinematic viscosity at 30 ° C. is 0.4 mm 2 / s or higher. 0 mm 2 / s or less, the sulfur content is 10 mass ppm or less, the cetane number of the whole fuel is 30 or more and 50 or less, and the cetane number of the fraction having a boiling point of less than 150 ° C. is 10 or more and 45 or less, boiling point Ri der cetane number of 0.99 ° C. or more fractions of at least 30 95 or less, and a fraction of the cetane number having a boiling point of less than 150 ℃ (150-CN) and a boiling point of 0.99 ° C. or more fractions of cetane number ( 150 + CN) ratio [(150-CN) / (150 + CN)] is 1 or less, The fuel oil composition for compression self-ignition engines characterized by the above-mentioned. 終点が200℃以上300℃以下であることを特徴とする請求項に記載の圧縮自己着火エンジン用燃料油組成物。 The fuel oil composition for a compression self-ignition engine according to claim 1 , wherein the end point is 200 ° C or higher and 300 ° C or lower.
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