JP5436041B2 - Light oil composition - Google Patents
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- JP5436041B2 JP5436041B2 JP2009120326A JP2009120326A JP5436041B2 JP 5436041 B2 JP5436041 B2 JP 5436041B2 JP 2009120326 A JP2009120326 A JP 2009120326A JP 2009120326 A JP2009120326 A JP 2009120326A JP 5436041 B2 JP5436041 B2 JP 5436041B2
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- 239000000203 mixture Substances 0.000 title claims description 40
- 239000007789 gas Substances 0.000 claims description 47
- 238000004821 distillation Methods 0.000 claims description 26
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003921 oil Substances 0.000 description 61
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 42
- 239000000446 fuel Substances 0.000 description 24
- 239000004071 soot Substances 0.000 description 24
- 238000012360 testing method Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 238000010998 test method Methods 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 239000013618 particulate matter Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 naphthene compound Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Description
本発明は、軽油組成物、特には、排出ガス中の煤、窒素酸化物、未燃焼炭化水素及び一酸化炭素等の環境負荷物質の排出量を低減させることが可能な軽油組成物に関するものである。 The present invention relates to a light oil composition, and more particularly to a light oil composition capable of reducing emissions of environmentally hazardous substances such as soot, nitrogen oxides, unburned hydrocarbons and carbon monoxide in exhaust gas. is there.
乗用車に搭載される小型ディーゼルエンジンの排出ガスは窒素酸化物及び煤を含むため、環境問題等の観点から、窒素酸化物吸蔵触媒で排出ガスに含まれる窒素酸化物を一旦吸蔵した後、還元雰囲気下で脱離した窒素酸化物により排出ガス中の未燃焼炭化水素や一酸化炭素を酸化し、更に、下流にフィルターを設けて大気に放出される煤を低減する方法が提案されている。 Since the exhaust gas of a small diesel engine installed in a passenger car contains nitrogen oxides and soot, from the viewpoint of environmental problems, etc., after the nitrogen oxides contained in the exhaust gas are temporarily stored by the nitrogen oxide storage catalyst, the reducing atmosphere A method has been proposed in which unburned hydrocarbons and carbon monoxide in exhaust gas are oxidized by nitrogen oxides desorbed below, and further, a filter is provided downstream to reduce soot released to the atmosphere.
一方で、環境負荷物質の排出量削減について燃料の面からも検討されており、例えば、３１０℃以上の高沸点留分が粒子状物質の生成に大きく影響することから、９０％留出温度を低下させることにより粒子状物質の生成を抑制した軽油組成物や、軽質化により特に粒子状物質を構成する溶剤可溶分を減少させた軽油組成物が提案されている（非特許文献１及び２）。また、粒子状物質の生成をエンジンの全負荷範囲で大幅に抑制する為にセタン価向上剤を含有し、９０％留出温度を低くしたディーゼルエンジン用燃料油組成物（特許文献１）や、９０％留出温度及び二環以上の芳香族含有量を低くしたディーゼルエンジン用燃料油組成物（特許文献２）が提案されている。また、排出ガス中の粒子状物質、窒素酸化物、未燃焼炭化水素といった環境汚染物質の排出量を大幅に低減する為に、硫黄分を低くし、蒸留性状と芳香族含有量が特定の条件を満たすディーゼルエンジン用燃料油組成物（特許文献３）が提案されている。 On the other hand, reduction of emissions of environmentally hazardous substances has been studied from the aspect of fuel. For example, a high boiling point fraction of 310 ° C. or higher greatly affects the generation of particulate matter. There have been proposed light oil compositions in which the generation of particulate substances is suppressed by lowering, and light oil compositions in which the solvent-soluble components constituting the particulate substances are reduced by lightening (Non-Patent Documents 1 and 2). ). In addition, a fuel oil composition for diesel engines (Patent Document 1) containing a cetane number improver in order to significantly suppress the generation of particulate matter in the entire load range of the engine and having a 90% lower distillation temperature, A fuel oil composition for a diesel engine with a 90% distillation temperature and a low aromatic content of two or more rings has been proposed (Patent Document 2). In addition, in order to significantly reduce the emission of environmental pollutants such as particulate matter, nitrogen oxides and unburned hydrocarbons in the exhaust gas, the sulfur content is lowered and the distillation properties and aromatic content are under certain conditions. A diesel engine fuel oil composition (Patent Document 3) that satisfies the above has been proposed.
しかしながら、これらの提案は必ずしも軽油の物理性状と化学性状が排出ガス性状に及ぼす影響を分離出来ていない。言い換えれば、軽油を軽質化することにより揮発性の良化と高沸点成分量の低減が同時に達成される為、さらに踏み込んで軽油の揮発性と粘性に代表される物理性状が排出ガス性状に及ぼす影響と、軽油の着火性と燃焼性に代表される化学性状が排出ガス性状に及ぼす影響とをそれぞれ考慮し、これら性状を組み合わせて排出ガス性状を最適化することに着目してはいない。また、軽油を軽質化すると、動粘度の低下により燃料噴霧の貫通力が低下するため、噴射ノズル近傍に燃料混合気の濃い領域が生成し、酸素濃度不足により煤が発生し易くなる。また、軽質化により密度や発熱量が低下して、燃費の悪化を引き起こす。さらには、燃料組成分布によっては、軽質化により芳香族含有量が増加して、煤が発生し易くなる場合もある。 However, these proposals are not necessarily able to separate the influence of light oil physical and chemical properties on exhaust gas properties. In other words, lighter gas oil makes it possible to improve volatility and reduce the amount of high-boiling components at the same time. Therefore, the physical properties represented by the volatility and viscosity of light oil affect exhaust gas properties. Considering the influence and the influence of chemical properties typified by light oil ignitability and combustibility on the exhaust gas properties, there is no focus on optimizing the exhaust gas properties by combining these properties. Further, when the light oil is lightened, the penetration force of the fuel spray is reduced due to a decrease in kinematic viscosity, so that a region with a rich fuel mixture is generated in the vicinity of the injection nozzle, and soot is easily generated due to insufficient oxygen concentration. In addition, the lighter weight causes a decrease in density and calorific value, leading to a deterioration in fuel consumption. Furthermore, depending on the fuel composition distribution, the aromatic content may increase due to lightening, and soot may be easily generated.
また、エンジン出口からの排出ガスは、通常、後処理触媒の酸化触媒で酸化され、更に、煤はディーゼル・パーティキュレート・フィルター（ＤＰＦ）で除去されるが、この場合、ＮＯｘの量は触媒前後で変化しないことから、エンジン出口では、ＮＯｘの排出量を低く維持することが必要である。また、煤の排出量が多いと、ＤＰＦへの煤の堆積量が増加して、再生頻度が増加することから、エンジン出口では、煤の排出量も低いことが望ましい。しかしながら、前述のＮＯｘ排出量と煤排出量は、一般にトレードオフの関係にあり、一方の排出量を低減すると、もう一方の排出量が増加してしまう。 In addition, the exhaust gas from the engine outlet is usually oxidized by the oxidation catalyst of the aftertreatment catalyst, and the soot is removed by the diesel particulate filter (DPF). In this case, the amount of NOx is around the catalyst. Therefore, it is necessary to keep the NOx emission amount low at the engine outlet. In addition, if the amount of soot discharged is large, the amount of soot deposited on the DPF increases and the regeneration frequency increases. Therefore, it is desirable that the amount of soot discharged is low at the engine outlet. However, the aforementioned NOx emission amount and soot emission amount are generally in a trade-off relationship, and if one emission amount is reduced, the other emission amount is increased.
そこで、本発明の目的は、上記従来技術の問題を解決し、軽油の揮発性と粘性に代表される物理性状と、軽油の着火性と燃焼性に代表される化学性状とを適切に組み合わせることで、ＮＯｘ排出量を低く維持しつつ、該ＮＯｘ排出量とトレードオフの関係にある煤排出量を少なくすることが可能で、ディーゼルエンジンからの排出ガス性状を改善することが可能な軽油組成物を提供することにある。 Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art and appropriately combine physical properties typified by light oil volatility and viscosity with chemical properties typified by light oil ignitability and combustibility. Thus, while maintaining the NOx emission amount low, it is possible to reduce the soot emission amount that is in a trade-off relationship with the NOx emission amount, and to improve the exhaust gas properties from the diesel engine. Is to provide.
本発明者らは、軽油の揮発性と粘性に代表される物理性状が排出ガス性状に及ぼす影響と、軽油の着火性と燃焼性に代表される化学性状が排出ガス性状に及ぼす影響とをそれぞれ分離して鋭意研究を進めた結果、軽油の揮発性指標の９０％留出温度と粘性指標の動粘度を特定範囲にした上、軽油の着火性指標のセタン価を特定範囲にし、燃焼性指標の燃料組成を規定することにより、排出ガス性状を最適化できることを見出し、本発明を完成させるに至った。すなわち、本発明は次の通りである。 The inventors of the present invention described the effects of the physical properties typified by the volatility and viscosity of light oil on the exhaust gas properties and the effects of the chemical properties typified by the ignitability and combustibility of light oil on the exhaust gas properties, respectively. As a result of diligent research, the 90% distillation temperature of the gas oil volatility index and the kinematic viscosity of the viscosity index were set in a specified range, and the cetane number of the light oil ignitability index was set in a specified range, and the flammability index By defining the fuel composition, it was found that the exhaust gas properties can be optimized, and the present invention has been completed. That is, the present invention is as follows.
（１）セタン価が４０〜６０、全芳香族分が１９．０〜２３．９容量％、２環芳香族分が６．６容量％以下、３環以上の芳香族分が２．８容量％以下、ナフテン分が９．８〜１１．９容量％、イソパラフィン分が３８．０〜３９．７容量％、１５℃における密度が０．７９〜０．８２ｇ／ｃｍ3、３０℃における動粘度が１．８〜３．０ｍｍ2／ｓ、９０％留出温度が２５５〜３０５℃である軽油組成物。 (1) Cetane number of 40 to 60, total aromatic content of 19.0 to 23.9 vol%, bicyclic aromatic content of 6.6 vol% or less, tricyclic or higher aromatic content of 2.8 vol% %, Naphthene content is 9.8 to 11.9 % by volume, isoparaffin content is 38.0 to 39.7% by volume, density at 15 ° C. is 0.79 to 0.82 g / cm 3 , kinematic viscosity at 30 ° C. Is a light oil composition having a 1.8% to 3.0 mm 2 / s and a 90% distillation temperature of 255 to 305 ° C.
（２）硫黄分が１質量ｐｐｍ以下である上記（１）に記載の軽油組成物。 (2) sulfur content gas oil composition according to (1) not more than 1 mass ppm.
（３）５０％留出温度、７０％留出温度、９０％留出温度及び９５％留出温度の合計値が１０２０〜１１５０℃である上記（１）又は（２）に記載の軽油組成物。 (3) The light oil composition according to (1) or (2), wherein the total value of 50% distillation temperature, 70% distillation temperature, 90% distillation temperature, and 95% distillation temperature is 1020 to 1150 ° C. .
（４）水素／炭素比（Ｈ／Ｃ比）が１．８〜２．１である上記（１）〜（３）の何れかに記載の軽油組成物。 (4) The light oil composition according to any one of (1) to (3), wherein the hydrogen / carbon ratio (H / C ratio) is 1.8 to 2.1.
本発明の軽油組成物は、ディーゼルエンジンからのＮＯｘ排出量を低く維持しつつ、煤排出量を少なくすることができ、かつ、煤の排出量を低減することにより煤除去フィルターに堆積する煤の燃焼頻度を低減できるという格別の効果を奏する。 The light oil composition of the present invention can reduce soot emissions while maintaining low NOx emissions from diesel engines, and can reduce soot deposits on soot removal filters by reducing soot emissions. There is a special effect that the combustion frequency can be reduced.
（セタン価）
本発明の軽油組成物においては、セタン価を４０〜６０の範囲にすることが必要である。セタン価が低すぎると低温時の始動性が悪化し、未燃焼の炭化水素排出量が増加する為、セタン価は４０以上であり、好ましくは４２以上、更に好ましくは４３以上、より一層好ましくは４４以上、特には４５以上である。一方、セタン価が高すぎると高負荷時に着火し易くなり、予混合期間が十分に取れなくなって、煤の排出量が増加する為、セタン価は６０以下であり、好ましくは５８以下、更に好ましくは５６以下、特には５５以下である。ここで、セタン価は、ＪＩＳ Ｋ２２８０「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」に規定された方法で測定されるものである。
(Cetane number)
In the light oil composition of this invention, it is necessary to make a cetane number into the range of 40-60. If the cetane number is too low, startability at low temperatures deteriorates and the amount of unburned hydrocarbons increases, so the cetane number is 40 or more, preferably 42 or more, more preferably 43 or more, and still more preferably 44 or more, especially 45 or more. On the other hand, if the cetane number is too high, ignition is likely to occur at high loads, the premixing period cannot be sufficiently taken, and the amount of soot discharged increases, so the cetane number is 60 or less, preferably 58 or less, more preferably Is 56 or less, particularly 55 or less. Here, the cetane number is measured by a method defined in JIS K2280 “Petroleum products-fuel oil-octane number and cetane number test method and cetane index calculation method”.
（芳香族分）
本発明の軽油組成物においては、全芳香族分が１９．０〜２３．９容量％である。全芳香族分が高すぎると、煤の排出量が増加し、また発熱量が増加することで窒素酸化物排出量も増加する為、全芳香族分は２３．９容量％以下である。一方、芳香族分が低すぎても発熱量が低下することで燃料消費量が増加する為、全芳香族分は１９．０容量％以上であり、好ましくは２０．０容量％以上、更に好ましくは２１．０容量％以上、特には２２．０容量％以上である。また、２環芳香族分は、煤の排出量を減少させるためには、６．６容量％以下であり、好ましくは５．０容量％以下である。さらには、同様に煤の排出量を減少させるためには、３環以上の芳香族分は、２．８容量％以下であり、好ましくは１．０容量％以下である。なお、これら芳香族分は、ＪＰＩ−５Ｓ−４９−９７「石油製品−炭化水素タイプ試験方法−高速液体クロマトグラフ法」に規定された方法で測定されるものである。
(Aromatic content)
In the light oil composition of the present invention, the total aromatic content is 19.0 to 23.9 % by volume. If the total aromatic content is too high, increased emissions of soot, also for also increases nitrogen oxides emissions by heat generation amount increases, the total aromatic content is not more than 23.9 volume%. On the other hand, even if the aromatic content is too low, the fuel consumption increases as the calorific value decreases, so the total aromatic content is 19.0% by volume or more, preferably 20.0% by volume or more, more preferably Is 21.0% by volume or more, particularly 22.0% by volume or more. Further, the bicyclic aromatic content is 6.6 % by volume or less , preferably 5.0% by volume or less, in order to reduce the amount of soot discharged. Furthermore, similarly, in order to reduce the discharge amount of soot, the aromatic content of three or more rings is 2.8 % by volume or less , preferably 1.0% by volume or less. These aromatic components are measured by the method defined in JPI-5S-49-97 “Petroleum products—Hydrocarbon type test method—High performance liquid chromatograph method”.
（ナフテン分）
本発明の軽油組成物においては、煤の排出量を低減し、また、燃費を良好に維持する観点から、ナフテン分が９．８〜１１．９容量％である。該ナフテン分は、煤排出量及び燃費の観点から、好ましくは９．８〜１０．０容量％、更に好ましくは９．８〜９．９容量％、特に好ましくは９．８容量％である。なお、該ナフテン分の分析には、Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ社製ＨＰ−６８９０Ｎ型ＦＩＤ検出器付きＧＣ及び日本電子社製ＡｃｃｕＴＯＦ ＪＭＳ−Ｔ１００ＧＣ飛行時間型質量分析計からなるＧＣシステムを用いた。詳細な分析条件は次の通りである。
(For naphthenic)
In the light oil composition of the present invention, the naphthene content is 9.8 to 11.9 % by volume from the viewpoint of reducing soot discharge and maintaining good fuel economy. The naphthene, from the viewpoint of soot emissions and fuel economy, it is preferably 9.8 to 10.0 volume%, more preferably 9.8 to 9.9% by volume, particularly preferably 9.8% by volume. For analysis of the naphthene content, a GC system consisting of GC with HP-6890N type FID detector manufactured by Agilent Technologies and AccuTOF JMS-T100GC time-of-flight mass spectrometer manufactured by JEOL Ltd. was used. Detailed analysis conditions are as follows.
１次カラム：微極性カラム（Ｓｕｐｅｌｃｏ社製ＰＴＥ−５、長さ３０ｍ、内径０．２５ｍｍ、フィルム厚０．２５μｍ）、モジュレータ中空カラム：長さ２ｍ、内径０．１ｍｍ
２次カラム：高極性カラム（Ｓｕｐｅｌｃｏ社製ＳｐｅｌｃｏＷＡＸ１０、長さ２ｍ、内径０．２５ｍｍ、フィルム厚０．２５μｍ）
昇温条件：１０℃／分（５０℃（５分保持）から２８０℃（２７分保持））
注入口温度：２８０℃
注入量：１．０μｌ
スプリット比：１００：１
キャリアガス：ヘリウム（Ｈｅ）、１．０ｍｌ／分
モジュレータ温度：下記のコールド温度、ホット温度を繰り返す。
ホットジェットガス温度：１５０℃（５分保持）から３２０℃（３３分保持）に１０℃／分で昇温。
コールドジェットガス温度：約−１４０℃
モジュレータ頻度：６秒間で０．３秒間ホット温度、その後５．７秒間コールド温度。
インターフェイス中空カラム：長さ０．５ｍ、内径０．２５ｍｍ
ＦＩＤガス条件：水素（４５ｍＬ／分）、空気（４５０ｍＬ／分）、メークアップヘリウム（２５ｍＬ／分）
Primary column: Micropolar column (PTE-5 manufactured by Supelco, length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm), modulator hollow column: length 2 m, inner diameter 0.1 mm
Secondary column: High-polarity column (SpelcoWAX10 from Supelco, length 2 m, inner diameter 0.25 mm, film thickness 0.25 μm)
Temperature rising condition: 10 ° C./min (from 50 ° C. (5 min hold) to 280 ° C. (27 min hold))
Inlet temperature: 280 ° C
Injection volume: 1.0 μl
Split ratio: 100: 1
Carrier gas: helium (He), 1.0 ml / min Modulator temperature: The following cold temperature and hot temperature are repeated.
Hot jet gas temperature: The temperature was raised from 150 ° C. (5 minutes hold) to 320 ° C. (33 minutes hold) at 10 ° C./min.
Cold jet gas temperature: about -140 ° C
Modulator frequency: 6 seconds for 0.3 seconds hot temperature, then 5.7 seconds for cold temperature.
Interface hollow column: 0.5m length, 0.25mm inner diameter
FID gas conditions: hydrogen (45 mL / min), air (450 mL / min), make-up helium (25 mL / min)
ここで、上記ＧＣシステムは、炭素数７〜４４の化合物を測定することが可能であり、測定したピーク（山形）の溶出時間とマススペクトルから、それぞれのピーク（山形）に対応する化合物を同定する。同定された全ピーク（山形）の合計を含有量合計（１００ピーク体積％）とし、それぞれのピーク（山形）から対応するそれぞれの化合物の含有量をピーク体積％として算出し、これを容量％とする。ナフテン分（容量％）は、ナフテン環を骨格に持つ成分の合計含有量として求められる。 Here, the GC system can measure a compound having 7 to 44 carbon atoms, and the compound corresponding to each peak (yamagata) is identified from the elution time and mass spectrum of the measured peak (yamagata). To do. The sum of all identified peaks (yamagata) is defined as the total content (100 peak volume%), and the content of each corresponding compound is calculated as the peak volume% from each peak (yamagata). To do. The naphthene content (volume%) is determined as the total content of components having a naphthene ring in the skeleton.
（密度）
本発明の軽油組成物においては、１５℃における密度を０．７９ｇ／ｃｍ3〜０．８２ｇ／ｃｍ3にすることが必要である。密度をこの範囲にすることにより、燃費を良好に維持でき、排出ガス性状を最適化することが出来る。該密度は、燃費及び排出ガス性状を更に向上させる観点から、０．７９５〜０．８１５ｇ／ｃｍ3が好ましい。該密度は、ＪＩＳ Ｋ２２４９「原油及び石油製品密度試験方法」に規定された方法で測定されるものである。
(density)
In the gas oil composition of the present invention, it is necessary that the density at 15 ℃ to 0.79g / cm 3 ~0.82g / cm 3 . By setting the density within this range, it is possible to maintain good fuel efficiency and optimize exhaust gas properties. The density is preferably 0.795 to 0.815 g / cm 3 from the viewpoint of further improving fuel consumption and exhaust gas properties. The density is measured by a method defined in JIS K2249 “Crude oil and petroleum product density test method”.
（動粘度）
また、本発明の軽油組成物においては、３０℃における動粘度を１．８〜３．０ｍｍ2／ｓの範囲にする必要がある。動粘度をこの範囲にすることにより、燃料噴射ポンプでの潤滑性を保持することができ、また、燃料噴射時の燃料の微粒化を促進して排出ガス性状を良好にすることができる。該動粘度は、潤滑性及び排出ガス性状を更に向上させる観点から、好ましくは２．０〜２．８ｍｍ2／ｓ、更に好ましくは２．１〜２．６ｍｍ2／ｓの範囲である。ここで、該動粘度は、ＪＩＳ Ｋ２２８３「動粘度試験方法」に規定された方法により、３０℃で測定されるものである。
(Kinematic viscosity)
Moreover, in the light oil composition of this invention, it is necessary to make kinematic viscosity in 30 degreeC into the range of 1.8-3.0 mm < 2 > / s. By setting the kinematic viscosity within this range, the lubricity in the fuel injection pump can be maintained, and the atomization of the fuel during fuel injection can be promoted to improve the exhaust gas properties. Kinematic viscosity, from the viewpoint of further improving the lubricity and exhaust gas property, and preferably in the range of 2.0~2.8mm 2 / s, more preferably 2.1~2.6mm 2 / s. Here, the kinematic viscosity is measured at 30 ° C. by the method defined in JIS K2283 “Kinematic Viscosity Test Method”.
（蒸留性状）
本発明の軽油組成物においては、揮発性を良好にすることにより煤の排出量を低減し、また、燃費を良好に維持する観点から、９０％留出温度を２５５〜３０５℃の範囲にする必要がある。なお、該９０％留出温度は、揮発性及び燃費の更なる向上の観点から、２６０℃〜３００℃の範囲内が好ましく、２６５〜２９５℃の範囲内が特に好ましい。また、５０％留出温度、７０％留出温度、９０％留出温度及び９５％留出温度の合計値は、煤の排出量を低減し、燃費を良好に維持する観点から、好ましくは１０２０〜１１５０℃、より好ましくは１０２５〜１１３０℃、特に好ましくは１０３０〜１１２５℃である。なお、これら蒸留性状は、ＪＩＳ Ｋ２２５４「蒸留試験方法」に規定された方法により求められるものである。
(Distillation properties)
In the light oil composition of the present invention, the 90% distillation temperature is set in the range of 255 to 305 ° C. from the viewpoint of reducing soot emission by improving volatility and maintaining good fuel economy. There is a need. The 90% distillation temperature is preferably in the range of 260 ° C to 300 ° C, particularly preferably in the range of 265 to 295 ° C, from the viewpoint of further improving the volatility and fuel consumption. The total value of 50% distillation temperature, 70% distillation temperature, 90% distillation temperature and 95% distillation temperature is preferably 1020 from the viewpoint of reducing soot discharge and maintaining good fuel efficiency. It is -1150 degreeC, More preferably, it is 1025-1130 degreeC, Most preferably, it is 1030-1125 degreeC. These distillation properties are obtained by the method defined in JIS K2254 “Distillation test method”.
（硫黄分）
本発明の軽油組成物においては、排出ガス中の硫黄酸化物の低減、及び排出ガスの後処理装置の耐久性向上の観点から、硫黄分を１質量ｐｐｍ以下の範囲にすることが好ましい。なお、該硫黄分は、ＪＩＳ Ｋ２５４１−６「硫黄分試験方法（紫外蛍光法）」に規定された方法で測定されるものである。
(Sulfur content)
In the light oil composition of this invention, it is preferable to make sulfur content into the range of 1 mass ppm or less from a viewpoint of the reduction | decrease of the sulfur oxide in exhaust gas, and the durable improvement of the exhaust gas aftertreatment apparatus. The sulfur content is measured by the method defined in JIS K2541-6 “Sulfur content test method (ultraviolet fluorescence method)”.
（真発熱量）
本発明の軽油組成物においては、燃費を良好にするために、真発熱量を好ましくは４２８００〜４３３５０ｋＪ／ｋｇ、更に好ましくは４３１００〜４３３００ｋＪ／ｋｇの範囲とする。ここで、該真発熱量は、ＪＩＳ Ｋ２２７９「原油及び石油製品−発熱量試験方法及び計算による推定方法」に規定された方法により求められるものである。
(True calorific value)
In the light oil composition of the present invention, in order to improve fuel efficiency, the true calorific value is preferably in the range of 42800 to 43350 kJ / kg, more preferably 43100 to 43300 kJ / kg. Here, the true calorific value is obtained by a method defined in JIS K2279 “Crude oil and petroleum products—a calorific value test method and a calculation estimation method”.
（イソパラフィン分）
本発明の軽油組成物においては、煤の排出量を低減し、また、燃費を良好に維持する観点から、イソパラフィン分が３８．０〜３９．７容量％であり、好ましくは３８．０容量％である。該イソパラフィン分の分析は、上述のナフテン分の分析と同様にして行うことができる。
(Isoparaffin content)
In the light oil composition of the present invention, the isoparaffin content is 38.0 to 39.7 % by volume, preferably 38.0% by volume, from the viewpoint of reducing soot emissions and maintaining good fuel economy. It is . The analysis of the isoparaffin content can be performed in the same manner as the analysis of the naphthene content described above.
（Ｈ／Ｃ比）
本発明の軽油組成物においては、微小粒子の個数をさらに低減する観点から、水素／炭素比（Ｈ／Ｃ比）を１．８〜２．１の範囲にすること好ましく、特には１．９〜２．１の範囲にすることが好ましい。該Ｈ／Ｃ比は、有機元素分析により水素（Ｈ）分と炭素（Ｃ）分を測定して、Ｈ／Ｃ比（モル比）を求めるものである。
(H / C ratio)
In the light oil composition of the present invention, from the viewpoint of further reducing the number of fine particles, the hydrogen / carbon ratio (H / C ratio) is preferably in the range of 1.8 to 2.1, particularly 1.9. It is preferable to be in the range of -2.1. The H / C ratio is obtained by measuring the hydrogen (H) content and carbon (C) content by organic elemental analysis to obtain the H / C ratio (molar ratio).
（軽油組成物の調製）
本発明の軽油組成物は、原料油として、例えば、常圧蒸留装置、接触分解装置、熱分解装置等から得られる各種の軽油留分、すなわち沸点が１４０〜４００℃の範囲で留出する留分を用いて、適宜混合して水素化脱硫するか、水素化脱硫後に適宜混合することにより得られるが、芳香族を多く含む原料油を処理する場合は、製品の硫黄分や芳香族分を所定範囲にするために、反応温度や水素分圧を高くし、また水素／オイル比を高くすることが有効である。なお、芳香族を多く含む原料油は難脱硫成分も多く含むことから、水素化脱硫にあたっては硫黄分を選択的に除去する触媒を用いることが好ましい。水素化脱硫は、Ｃｏ、Ｍｏ及びＮｉの１種以上を含有し、又所望によりＰを担持した水素化触媒を用い、反応温度２７０〜３８０℃、好ましくは２９５〜３６０℃、反応圧力２．５〜８．５ＭＰａ、好ましくは２．７〜７．０ＭＰａ、ＬＨＳＶ０．９〜６．０ｈ-1、好ましくは０．９〜５．４ｈ-1、水素／オイル比１３０〜３００Ｎｍ3／ｋＬの条件の範囲で適宜選択して、上述した本発明の軽油組成物が得られる様にするとよい。
(Preparation of light oil composition)
The gas oil composition of the present invention is a distillate distilled as a raw material oil, for example, various gas oil fractions obtained from an atmospheric distillation apparatus, a catalytic cracking apparatus, a thermal cracking apparatus, or the like, that is, a boiling point of 140 to 400 ° C. It can be obtained by mixing and hydrodesulfurizing and mixing appropriately after hydrodesulfurization, or when processing raw material oils rich in aromatics, the sulfur content and aromatic content of the product should be reduced. In order to make it within a predetermined range, it is effective to increase the reaction temperature and hydrogen partial pressure and to increase the hydrogen / oil ratio. In addition, since the raw material oil containing a lot of aromatics contains a lot of difficult desulfurization components, it is preferable to use a catalyst that selectively removes sulfur in hydrodesulfurization. Hydrodesulfurization uses a hydrogenation catalyst containing one or more of Co, Mo and Ni, and optionally carrying P, with a reaction temperature of 270 to 380 ° C., preferably 295 to 360 ° C., a reaction pressure of 2.5. To 8.5 MPa, preferably 2.7 to 7.0 MPa, LHSV 0.9 to 6.0 h −1 , preferably 0.9 to 5.4 h −1 , and a hydrogen / oil ratio of 130 to 300 Nm 3 / kL. It is good to select suitably in the range so that the light oil composition of the present invention mentioned above may be obtained.
本発明では、上記水素化脱硫した軽油留分に、灯油留分、ＧＴＬ、ＢＴＸを製造する際の副生成留分、潤滑油を製造する際の副生成留分、ノルマルパラフィン化合物、ノルマルパラフィン系溶剤、イソパラフィン化合物、イソパラフィン系溶剤、芳香族化合物、芳香族系溶剤、バイオマス由来の燃料基材、ナフテン化合物、ナフテン系溶剤、等を適宜配合して、上述の性状、品質に合った軽油組成物を調製することができる。 In the present invention, the hydrodesulfurized gas oil fraction is a kerosene fraction, a by-product fraction when producing GTL, BTX, a by-product fraction when producing a lubricating oil, a normal paraffin compound, a normal paraffin series. Light oil composition suitable for the above-mentioned properties and quality by appropriately blending solvent, isoparaffin compound, isoparaffin solvent, aromatic compound, aromatic solvent, biomass-derived fuel base material, naphthene compound, naphthenic solvent, etc. Can be prepared.
なお、上記方法で得られた軽油組成物には、低温流動性向上剤、耐摩耗性向上剤、セタン価向上剤、酸化防止剤、金属不活性化剤、腐食防止剤等の公知の燃料添加剤を添加してもよい。低温流動性向上剤としては、エチレン共重合体などを用いることができるが、特には、酢酸ビニル、プロピオン酸ビニル、酪酸ビニルなどの飽和脂肪酸のビニルエステルが好ましく用いられる。耐摩耗性向上剤としては、例えば長鎖脂肪酸（炭素数１２〜２４）又はその脂肪酸エステルが好ましく用いられ、１０〜５００質量ｐｐｍ、好ましくは５０〜１００質量ｐｐｍの添加量で十分に耐摩耗性が向上する。 In addition, to the light oil composition obtained by the above method, known fuel additions such as a low temperature fluidity improver, an abrasion resistance improver, a cetane number improver, an antioxidant, a metal deactivator, and a corrosion inhibitor are added. An agent may be added. As the low temperature fluidity improver, an ethylene copolymer or the like can be used. In particular, a vinyl ester of a saturated fatty acid such as vinyl acetate, vinyl propionate or vinyl butyrate is preferably used. As the wear resistance improver, for example, a long-chain fatty acid (carbon number 12 to 24) or a fatty acid ester thereof is preferably used, and the wear resistance is sufficient with an addition amount of 10 to 500 ppm by mass, preferably 50 to 100 ppm by mass. Will improve.
以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
＜軽油組成物の調製＞
まず以下のようにして、評価試験のために用いる軽油組成物（供試軽油１〜６）を調製した。これら供試軽油１〜６の組成等の分析値を表１に示す。分析は、上述した方法によるが、Ｈ／Ｃ比については、有機元素分析装置（ＬＥＣＯ社製ＣＨＮ−１０００型）を用いて、Ｈ分とＣ分を測定して、その比を求めた。また、セタン指数はＪＩＳ Ｋ２２８０「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」に規定された方法で測定し、１環芳香族分はＪＰＩ−５Ｓ−４９−９７「石油製品−炭化水素タイプ試験方法−高速液体クロマトグラフ法」に規定された方法で測定した。
<Preparation of light oil composition>
First, light oil compositions (test light oils 1 to 6) used for the evaluation test were prepared as follows. Table 1 shows analytical values such as the compositions of these test diesel oils 1 to 6. The analysis was performed according to the method described above, and the H / C ratio was determined by measuring the H and C fractions using an organic element analyzer (CHN-1000 model manufactured by LECO). The cetane index is measured by the method defined in JIS K2280 “Petroleum products-fuel oil-octane number and cetane number test method and cetane index calculation method”, and the monocyclic aromatic component is determined by JP-5S-49-97 It was measured by the method defined in “Product—Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method”.
供試軽油１：市販灯油を９５容量％、接触改質ガソリンの沸点１８０〜２２０℃の留分を５容量％混合して調製した。 Test gas oil 1: 95% by volume of commercial kerosene and 5% by volume of a fraction of catalytic reformed gasoline having a boiling point of 180 to 220 ° C. were prepared.
供試軽油２：市販灯油を２０容量％、常圧蒸留装置の１７０〜３６０℃の留分に含まれるパラフィン分を除去した後に脱硫した、脱ろう脱硫軽油８０容量％をそれぞれ配合して調製した。 Test gas oil 2: 20% by volume of commercially available kerosene and 80% by volume of dewaxed desulfurized gas oil that was desulfurized after removing the paraffin contained in the fraction of 170-360 ° C. of the atmospheric distillation unit .
供試軽油３：韓国油公製の市販水素化分解軽油 Test gas oil 3: Commercial hydrocracked gas oil manufactured by Korea Oil Corporation
供試軽油４：市販の１号軽油 Test gas oil 4: Commercially available No. 1 gas oil
供試軽油５：市販の１号軽油（供試軽油４より重質） Test gas oil 5: Commercially available No. 1 gas oil (heavier than test gas oil 4)
供試軽油６：市販の灯油 Test diesel 6: Commercial kerosene
次に上記供試軽油について、以下に示す市販ディーゼルエンジンを用い、定常条件におけるエンジン出口直後の排出ガス性状としてスモーク（煤）値（％）を司測研社製反射型スモークメータで測定し、また、窒素酸化物（ＮＯｘ）、一酸化炭素（ＣＯ）、未燃焼炭化水素（ＴＨＣ）、二酸化炭素（ＣＯ2）それぞれの排出量（ｇ／ｋＷｈ）をベスト測器社製排ガス分析計で測定した。数値は比較例２の供試軽油４（市販の１号軽油）を基準にして相対値（％／％、ｇ／ｋＷｈ ／ ｇ／ｋＷｈ、又は、ｋｇ／ｋＷｈ ／ ｋｇ／ｋＷｈ）で示した。これらの結果を表２に示す。 Next, for the above test diesel oil, using a commercially available diesel engine shown below, the smoke (煤) value (%) as an exhaust gas property immediately after the engine exit in a steady condition was measured with a reflective smoke meter manufactured by SHIKENKEN, In addition, emissions (g / kWh) of nitrogen oxides (NOx), carbon monoxide (CO), unburned hydrocarbons (THC), and carbon dioxide (CO 2 ) are measured with an exhaust gas analyzer manufactured by Best Sokki Co., Ltd. did. The numerical values are shown as relative values (% /%, g / kWh / g / kWh, or kg / kWh / kg / kWh) based on the test diesel oil 4 (commercially available No. 1 diesel oil) of Comparative Example 2. These results are shown in Table 2.
＜供試エンジン諸元と運転条件＞
気筒数： ４気筒
総排気量： 約２Ｌ
圧縮比： 約１７
定常条件： １５００ｒｐｍ、１／４負荷
<Test engine specifications and operating conditions>
Number of cylinders: 4 cylinders Total displacement: Approximately 2L
Compression ratio: about 17
Steady condition: 1500rpm, 1/4 load
これらの結果から、本発明の軽油組成物である実施例１及び２の供試軽油は、比較例１、２、３及び４の供試軽油に比較してＮＯｘ排出量が同等以下に抑えられており、また、スモーク排出量も同等以下に抑えられており、ＣＯ2排出量も同等であることが分かる。なお、比較例４の供試軽油は、ＮＯｘ排出量及びスモーク排出量が実施例と同等であるものの、ＴＨＣ排出量が非常に多かった。 From these results, the sample gas oils of Examples 1 and 2 that are the gas oil composition of the present invention have NOx emissions reduced to the same level or less as compared to the sample gas oils of Comparative Examples 1, 2, 3, and 4. In addition, it is understood that the smoke emission amount is suppressed to the same level or less, and the CO 2 emission amount is also equivalent. In addition, although the test diesel oil of Comparative Example 4 had the same NOx emission amount and smoke emission amount as the Example, the THC emission amount was very large.
本発明の軽油組成物は、ディーゼルエンジン用燃料又はその混合基材として好適に利用できる。 The light oil composition of the present invention can be suitably used as a diesel engine fuel or a mixed base material thereof.
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