JP5317605B2 - Light oil composition - Google Patents
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- 239000000203 mixture Substances 0.000 title claims abstract description 39
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- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 2
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
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- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
本発明は、軽油組成物、特には、排気ガス中の粒子状物質を低減させることができる軽油組成物に関する。 The present invention relates to a light oil composition, and more particularly to a light oil composition capable of reducing particulate matter in exhaust gas.
ディーゼルエンジンの排気ガスには粒子状物質（Particle Matter、以下、ＰＭという）が含まれ、近年、環境問題等の観点から、ディーゼルエンジンを搭載した自動車の排気系にフィルタを設けて大気に放出されるＰＭを構成する粒子の総粒子数や重量を低減する方法が提案されている。 Diesel engine exhaust gas contains particulate matter (hereinafter referred to as PM). Recently, from the viewpoint of environmental problems, etc., a diesel engine exhaust system equipped with a filter is released into the atmosphere. There has been proposed a method for reducing the total number and weight of particles constituting PM.
一方で、ＰＭ排出量の削減について燃料の面からも検討されており、排ガス中に含まれるＰＭ全体の量、ＰＭを構成する粒子の総粒子数及び当該粒子のうち直径の分布中心が５０nm付近である粒子の粒子数、並びにアルデヒド類の量を同時に且つ十分に低減することが可能な軽油組成物（特許文献１）や、粒子直径が５０nm以下の粒子の排出抑制が可能なディーゼルエンジン用燃料油組成物が提案されている（特許文献２及び３）。また、過渡運転時におけるエンジンから排出される窒素酸化物、炭化水素、一酸化炭素、二酸化炭素、ＰＭ、微小粒子、直径１００nm以下の粒子、アルデヒド類の低減、排ガス跡処理装置の負荷の低減、燃費の向上、運転性及び加速性の向上、燃料噴射ポンプの駆動力の低減、エンジン運転時の騒音の低減、なおかつエンジン始動性に優れ、酸化安定性に優れ、部材への影響を少なくすることができる軽油組成物が提案されている（特許文献４〜６）。 On the other hand, the reduction of PM emissions has also been studied from the aspect of fuel. The total amount of PM contained in the exhaust gas, the total number of particles constituting the PM, and the diameter distribution center of the particles is around 50 nm. A diesel fuel that can simultaneously and sufficiently reduce the number of particles and the amount of aldehydes (Patent Document 1), and a diesel engine fuel that can suppress emission of particles having a particle diameter of 50 nm or less Oil compositions have been proposed (Patent Documents 2 and 3). In addition, nitrogen oxides, hydrocarbons, carbon monoxide, carbon dioxide, PM, fine particles, particles with a diameter of 100 nm or less, reduction of aldehydes, reduction of the load of exhaust gas trace treatment equipment discharged from the engine during transient operation, Improved fuel economy, improved drivability and acceleration, reduced driving force of fuel injection pump, reduced noise during engine operation, excellent engine startability, excellent oxidation stability, and reduced impact on components A light oil composition that can be used has been proposed (Patent Documents 4 to 6).
ところで、最近、ＧＴＬ軽油がＰＭ排出削減の面でも注目されている。ＧＴＬ軽油は天然ガスや石炭等をガス化し、フィッシャートロプシュ合成によって得られた合成油を分留、必要により水素化分解や異性化等を行って、軽油留分を得たものである。このＧＴＬ軽油は、ＰＭ生成の原因のひとつとされている芳香族成分をほとんど含まないため、ＰＭ排出量は少ないものと考えられている。しかしながら、本発明者が調査したところ、確かに、ＧＴＬ軽油等の芳香族成分をほとんど含まない軽油留分をディーゼル燃料として用いると、排気ガス中の粒子の総粒子数は少ないが、驚くべきことに、直径が２２nm以下の非常に小さい粒子（以下、「微小粒子」という）は、比較的多いということがわかった。この微小粒子も、少ない方が環境上好ましい。
この微小粒子は上記の従来提案の燃料組成物としてもその個数を必ずしも減らすことはできず、ＰＭ全体の量が減っても微小粒子の個数が増えることもあったし、さらには燃費が低下するという問題もあった。
By the way, recently, GTL diesel oil has attracted attention in terms of reducing PM emissions. GTL gas oil is obtained by gasifying natural gas, coal, etc., fractionating a synthetic oil obtained by Fischer-Tropsch synthesis, hydrocracking, isomerization, etc. as necessary to obtain a gas oil fraction. Since this GTL light oil contains almost no aromatic component, which is one of the causes of PM generation, it is considered that the amount of PM emission is small. However, as a result of investigation by the present inventor, it is surprising that when a light oil fraction containing almost no aromatic components such as GTL light oil is used as diesel fuel, the total number of particles in the exhaust gas is small. Furthermore, it was found that there are relatively many very small particles (hereinafter referred to as “microparticles”) having a diameter of 22 nm or less. It is environmentally preferable that the number of fine particles is small.
The number of these fine particles cannot always be reduced even as the above-described conventional fuel composition, and even if the total amount of PM is reduced, the number of fine particles may be increased, and the fuel consumption is further reduced. There was also a problem.
本発明は上記課題を解決するもので、ディーゼル排気ガス中のＰＭ全体の重量、構成する粒子の総個数、及び微小粒子の個数を少なくするとともに、燃費が良好な軽油組成物を提供することにある。 The present invention solves the above-mentioned problem, and provides a light oil composition with good fuel efficiency while reducing the total weight of PM in diesel exhaust gas, the total number of constituent particles, and the number of fine particles. is there.
本発明者は、軽油の成分および性状と、ＰＭ全体の重量、構成する粒子の総個数、及び微小粒子の個数の関係について鋭意研究を進めた結果、軽油の品質として、全芳香族分を５.０〜１０.０容量％、２環芳香族分を４.０容量％以下、３環以上の芳香族分を０.５容量％以下、１５℃における密度を０.８０g/cm3以上、３０℃における動粘度を２.７〜３.５mm2/s、９０％留出温度を３２０〜３５０℃とすることで、ディーゼル排気ガス中のＰＭ全体の重量、構成する粒子の総個数、及び微小粒子の個数を同時に低減することができ、かつ、燃費も良好であることを見出した。 As a result of intensive research on the relationship between the components and properties of light oil and the weight of the whole PM, the total number of particles constituting the light oil, and the number of fine particles, the inventor has found that the total aromatic content is 5 as the quality of light oil. 0.0-10.0% by volume, bicyclic aromatic content is 4.0% by volume or less, tricyclic or more aromatic content is 0.5% by volume or less, density at 15 ° C. is 0.80g / cm 3 or more, By setting the kinematic viscosity at 30 ° C. to 2.7 to 3.5 mm 2 / s and the 90% distillation temperature to 320 to 350 ° C., the total weight of PM in diesel exhaust gas, the total number of constituent particles, and It has been found that the number of fine particles can be reduced at the same time and the fuel consumption is also good.
すなわち、本発明は次の通りである。
（１）全芳香族分が５.０〜１０.０容量％、２環芳香族分が４.０容量％以下、３環以上の芳香族分が０.５容量％以下、１５℃における密度が０.８０g/cm3以上、３０℃における動粘度が２.７〜３.５mm2/s、９０％留出温度が３２０〜３５０℃である軽油組成物。
That is, the present invention is as follows.
(1) Total aromatic content is 5.0 to 10.0 vol%, bicyclic aromatic content is 4.0 vol% or less, tricyclic or higher aromatic content is 0.5 vol% or less, density at 15 ° C There 0.80 g / cm 3 or more, the gas oil composition is a kinematic viscosity at 30 ° C. is 2.7~3.5mm 2 / s, 90% distillation temperature of 320-350 ° C..
（２）硫黄分が１〜６質量ppm、流動点が−７℃以下、曇り点が−５℃以下、目詰まり点が−５℃以下、真発熱量４２８００〜４３３００kJ/kg、セタン指数が５４〜７５である上記（１）に記載の軽油組成物。 (2) Sulfur content is 1 to 6 ppm by mass, pour point is −7 ° C. or less, cloud point is −5 ° C. or less, clogging point is −5 ° C. or less, true heating value 42800 to 43300 kJ / kg, cetane index is 54 The light oil composition according to the above (1), which is ˜75.
（３）１０％、５０％及び９０％留出温度の平均値が２５５〜２８０℃、９０％、９５％並びに９７％留出温度及び終点の平均値が３３０〜３７０℃である上記（１）又は（２）に記載の軽油組成物。 (3) The average value of 10%, 50% and 90% distillation temperatures is 255 to 280 ° C., 90%, 95% and 97% The average temperature of distillation temperature and end point is 330 to 370 ° C. (1) Or the light oil composition as described in (2).
（４）１環芳香族分が５.０〜１０.０容量％、ノルマルパラフィン分が１７〜２１重量％、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 above-mentioned (1) to (3) wherein the monocyclic aromatic component is 5.0 to 10.0% by volume, the normal paraffin component is 17 to 21% by weight, and the H / C ratio is 1.8 to 2.1. ).
本発明の軽油組成物は、ディーゼル排気ガス中のＰＭ全体の重量、構成する粒子の総個数、及び微粒子の個数を同時に低減することができ、かつ、燃費が良好であるという格別の効果を奏する。 The light oil composition of the present invention can reduce the weight of the whole PM in the diesel exhaust gas, the total number of constituent particles, and the number of fine particles at the same time, and has an extraordinary effect of good fuel consumption. .
（芳香族分）
本発明の軽油組成物においては、全芳香族分を５.０〜１０.０容量％の範囲にすることが必要である。全芳香族分をこの範囲にすることで、ＰＭ全体の重量、構成する粒子の総個数、及び微小粒子の個数を低減し、低温流動特性や燃費を維持できる。好ましくは６.０〜７.０容量％の範囲である。
また、２環芳香族分は、ＰＭ全体の重量、構成する粒子の総個数、及び微小粒子の個数を低減させるためには、４.０容量％以下にする必要があり、好ましくは２.０容量％以下、さらに好ましくは１.０容量％以下であり、０容量％、すなわち、含まれていなくてもよい。
さらには、同様に、３環以上の芳香族分は、０.５容量％以下にする必要があり、好ましくは０.３容量％以下、さらに好ましくは０.１容量％以下で、０容量％であってもよい。
なお、１環芳香族分は、発熱量の維持の観点から、５.０〜１０.０容量％の範囲にすることが好ましく、さらには５.５〜１０.０容量％の範囲が特に好ましい。
各芳香族分は、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 must be in the range of 5.0 to 10.0% by volume. By setting the total aromatic content within this range, the weight of the entire PM, the total number of constituent particles, and the number of fine particles can be reduced, and low-temperature flow characteristics and fuel consumption can be maintained. Preferably it is the range of 6.0-7.0 volume%.
In addition, the bicyclic aromatic component needs to be 4.0% by volume or less in order to reduce the weight of the entire PM, the total number of constituent particles, and the number of fine particles, and preferably 2.0% or less. The volume% or less, more preferably 1.0 volume% or less, and 0 volume%, that is, it may not be included.
Furthermore, similarly, the aromatic content of three or more rings must be 0.5% by volume or less, preferably 0.3% by volume or less, more preferably 0.1% by volume or less, and 0% by volume. It may be.
The monocyclic aromatic component is preferably in the range of 5.0 to 10.0% by volume, more preferably in the range of 5.5 to 10.0% by volume from the viewpoint of maintaining the calorific value. .
Each aromatic component is measured by the method defined in JPI-5S-49-97 “Petroleum products—Hydrocarbon type test method—High performance liquid chromatograph method”.
（密度）
本発明の軽油組成物においては、１５℃における密度を０.８０g/cm3以上にすることが必要である。これにより燃費を良好に維持でき、ＰＭ全体の重量構成する粒子の総個数、及び微小粒子の個数を抑制できる。この密度は０.８０〜０.８３g/cm3が好ましく、特には、０.８０５〜０.８３g/cm3が好ましい。
この密度は、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 light oil composition of the present invention, the density at 15 ° C. needs to be 0.80 g / cm 3 or more. Thereby, fuel consumption can be maintained satisfactorily, and the total number of particles constituting the weight of the entire PM and the number of fine particles can be suppressed. The density is preferably from 0.80 to 0.83 g / cm 3 , particularly preferably from 0.805 to 0.83 g / cm 3 .
This density is measured by a method defined in JIS K2249 “Crude oil and petroleum product density test method”.
（動粘度）
また、３０℃における動粘度を２.７〜３.５mm2/sの範囲にする必要がある。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排出ガス性状を良好にすることができる。好ましくは３.０〜３.５mm2/s、さらに好ましくは３.４〜３.５mm2/sの範囲である。
この３０℃における動粘度は、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)
Further, the kinematic viscosity at 30 ° C. needs to be in the range of 2.7 to 3.5 mm 2 / s. By setting it within this range, the lubricity in the fuel injection pump can be maintained, the atomization of fuel during fuel injection can be promoted, and the exhaust gas properties can be improved. Preferably it is 3.0-3.5 mm < 2 > / s, More preferably, it is the range of 3.4-3.5 mm < 2 > / s.
The kinematic viscosity at 30 ° C. is measured at 30 ° C. by the method defined in JIS K2283 “Kinematic Viscosity Test Method”.
（硫黄分）
本発明の軽油組成物においては、硫黄分を１〜６質量ppmの範囲にすることが、排ガス中の硫黄酸化物の低減、排ガスの後処理装置の耐久性向上、および燃料噴射ポンプでの潤滑性維持、さらには燃料の酸化安定性維持の観点から好ましく、特には１〜５質量ppm、さらには２〜３質量ppmの範囲が好ましい。
この硫黄分は、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 the present invention, setting the sulfur content in the range of 1 to 6 ppm by mass reduces sulfur oxides in the exhaust gas, improves the durability of the exhaust gas aftertreatment device, and lubricates the fuel injection pump. From the viewpoint of maintaining the property, and further maintaining the oxidation stability of the fuel, it is particularly preferably in the range of 1 to 5 ppm by mass, more preferably 2 to 3 ppm by mass.
This sulfur content is measured by a method defined in JIS K2541-6 “Sulfur content test method (ultraviolet fluorescence method)”.
（流動点および曇り点）
本発明の軽油組成物においては、低温時の運転性向上および燃費を良好に維持する観点から、流動点を−７℃以下が好ましく、−９℃以下が、また−１８℃以上がより好ましい。
また、低温時の運転性向上および燃費を良好に維持する観点から、曇り点を−５℃以下にすることが好ましく、特には−７℃以下が、また−１０℃がより好ましい。
この流動点および曇り点は、ＪＩＳ Ｋ２２６９「原油及び石油製品の流動点並びに石油製品曇り点試験方法」に規定された方法で測定されるものである。
(Pour point and cloud point)
In the light oil composition of the present invention, the pour point is preferably −7 ° C. or lower, more preferably −9 ° C. or lower, and more preferably −18 ° C. or higher, from the viewpoint of improving drivability at low temperatures and maintaining good fuel efficiency.
Further, from the viewpoint of improving drivability at low temperatures and maintaining good fuel efficiency, the cloud point is preferably set to -5 ° C or lower, particularly -7 ° C or lower, and more preferably -10 ° C.
The pour point and cloud point are measured by the method defined in JIS K2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.
（目詰まり点）
本発明の軽油組成物においては、低温時の運転性向上、燃費の良好な維持、および低温流動性向上剤の添加に係るコストを抑制等の観点から、目詰まり点を−５℃以下にすることが好ましい。特には、−７℃以下が、また−１２℃以上がより好ましい。
この目詰まり点はＪＩＳ Ｋ２２８８「軽油−目詰まり点試験方法」に規定された方法で測定されるものである。
(Clogging point)
In the light oil composition of the present invention, the clogging point is set to −5 ° C. or less from the viewpoint of improving the drivability at low temperatures, maintaining good fuel economy, and suppressing the cost associated with the addition of the low-temperature fluidity improver. It is preferable. In particular, −7 ° C. or lower is more preferable, and −12 ° C. or higher is more preferable.
This clogging point is measured by a method defined in JIS K2288 “Diesel Oil—Clogging Point Test 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４２８００〜４３３００kJ/kg、特には４３２００〜４３３００ｋＪ／ｋｇの範囲にすることが好ましい。
この真発熱量は、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 43300 kJ / kg, particularly 43200 to 43300 kJ / kg.
This true calorific value is obtained by the method defined in JIS K2279 “Crude oil and petroleum products—heat calorific value test method and calculation estimation method”.
（セタン指数）
本発明の軽油組成物においては、着火性を良好にするためには、セタン指数を５４〜７５の範囲にすることが好ましく、また、６０〜７２、さらには６５〜７０の範囲が特に好ましい。
このセタン指数は、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求められるものである。
(Cetane index)
In the light oil composition of the present invention, in order to improve ignitability, the cetane index is preferably in the range of 54 to 75, more preferably in the range of 60 to 72, and even more preferably 65 to 70.
This cetane index is obtained by a method defined in JIS K2280 “Petroleum products-fuel oil-octane number and cetane number test method and cetane index calculation method”.
（蒸留性状）
本発明による軽油組成物においては、ＰＭ全体の重量、構成する粒子の総個数、及び微小粒子の個数を低減や燃費を良好に維持する観点から、９０％留出温度を３２０〜３５０℃の範囲にする必要がある。この９０％留出温度は、３２０℃〜３４０℃の範囲内が好ましく、さらには３３０〜３３５℃の範囲内が特に好ましい。
この蒸留性状は、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 according to the present invention, the 90% distillation temperature is in the range of 320 to 350 ° C. from the viewpoint of reducing the weight of the entire PM, the total number of constituent particles, and the number of fine particles and maintaining good fuel economy. It is necessary to. The 90% distillation temperature is preferably in the range of 320 ° C to 340 ° C, more preferably in the range of 330 to 335 ° C.
This distillation property is obtained by the method defined in JIS K2254 “Distillation test method”.
また、燃焼及び排出ガスを良好に維持する観点から、この蒸留性状において、１０％、５０％及び９０％留出温度の平均値を２５５〜２８０℃の範囲にすることが好ましく、また特に、２６０〜２８０℃が好ましい。この１０％、５０％及び９０％留出温度の平均値とは、前記各留出温度を加算して、３で割ったものである。 Further, from the viewpoint of maintaining good combustion and exhaust gas, in this distillation property, the average value of 10%, 50% and 90% distillation temperatures is preferably in the range of 255 to 280 ° C. ˜280 ° C. is preferred. The average values of the 10%, 50% and 90% distillation temperatures are obtained by adding the above distillation temperatures and dividing by 3.
さらに、燃焼及び排出ガスを良好に維持する観点から、この蒸留性状において、９０％、９５％並びに９７％留出温度及び終点の平均値を３３０〜３７０℃の範囲にすることが好ましく、特には３４０〜３７０℃が好ましい。この９０％、９５％並びに９７％留出温度及び終点の平均値とは、前記各留出温度を加算し、４で割ったものである。 Further, from the viewpoint of maintaining good combustion and exhaust gas, in this distillation property, it is preferable that the average values of 90%, 95% and 97% distillation temperatures and end points are in the range of 330 to 370 ° C. 340-370 degreeC is preferable. The 90%, 95% and 97% distillation temperatures and the average value of the end points are obtained by adding the above distillation temperatures and dividing by 4.
（ノルマルパラフィン分）
本発明の軽油組成物においては、微小粒子の個数のさらなる低減のためには、ノルマルパラフィン分を１７〜２１重量％の範囲にすることが好ましく、特には１７〜２０重量％が好ましい。
このノルマルパラフィン分は、ＪＩＳ Ｋ２５３６「石油製品―成分試験方法」に規定された方法により測定されるものである。
(Normal paraffin content)
In the light oil composition of the present invention, in order to further reduce the number of fine particles, the normal paraffin content is preferably in the range of 17 to 21% by weight, particularly preferably 17 to 20% by weight.
This normal paraffin content is measured by the method defined in JIS K2536 “Petroleum products-component test method”.
（Ｈ／Ｃ比）
本発明の軽油組成物においては、微小粒子の個数のさらなる低減のためには、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が好ましい。
このＨ／Ｃ比は、有機元素分析によりＨ分とＣ分を測定して、Ｈ／Ｃ比を求めるものである。
(H / C ratio)
In the light oil composition of the present invention, in order to further reduce the number of fine particles, the H / C ratio is preferably in the range of 1.8 to 2.1, and particularly 1.9 to 2.1. Is preferred.
The H / C ratio is obtained by measuring the H and C components by organic elemental analysis to obtain the H / C ratio.
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必要がある。 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 the mixture using the components or by mixing after hydrodesulfurization. However, when processing raw material oils rich in aromatics, the sulfur content and aromatics of the product should be specified. In order to achieve this 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 necessary to use a catalyst that selectively removes sulfur in hydrodesulfurization.
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の条件から適宜選択して、上述の軽油組成物が得られる様にするとよい。 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. From the conditions of ˜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 hydrogen / oil ratio 130 to 300 Nm 3 / kL. It is good to select suitably so that the above-mentioned light oil composition 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る。１０〜５００ppm、好ましくは５０〜１００ppm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 (having 12 to 24 carbon atoms) or a fatty acid ester thereof is preferably used. Abrasion resistance is sufficiently improved with an addition amount of 10 to 500 ppm, preferably 50 to 100 ppm.
本発明をより具体的に実施例により説明する。なお、本発明は、以下の実施例によって限定されるものではない。 The present invention will be described more specifically with reference to examples. 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（供試軽油１〜６）を調製した。この供試軽油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。
Preparation of light oil composition First, light oils (test light oils 1 to 6) used for the evaluation test were prepared as follows. Table 1 shows analytical values such as the composition of the sample gas oils 1 to 6. Although the analysis was based on the method described above, the H / C ratio was determined by measuring the H and C components using an organic element analyzer (CHN-1000 model manufactured by LECO).
供試軽油１：市販１号軽油を３０容量％、ＧＴＬ軽油（モスガス社製）を３０容量％、蒸留範囲が２０９〜２３１℃のナフテン/パラフィン系溶剤であるエクゾールＤ８０（東燃ゼネラル石油株式会社製）を３２容量％ 、炭素数３０のイソパラフィンであるスクアラン（東京化成工業株式会社製）を５容量％、蒸留範囲が２９０〜３０５℃の芳香族系溶剤である日石ハイゾールＳＡＳグレード２９６（新日本石油化学株式会社製）を３容量％、それぞれ配合して調製した。 Test gas oil 1: 30% by volume of commercial No. 1 gas oil, 30% by volume of GTL gas oil (manufactured by Moss Gas), Exol D80 (manufactured by TonenGeneral Sekiyu KK), which is a naphthene / paraffin solvent having a distillation range of 209-231 ° Nisseki Hyzol SAS Grade 296 (New Japan), an aromatic solvent having a volatility of 32% by volume, 5% by volume of Squalane (Tokyo Chemical Industry Co., Ltd.), an isoparaffin having 30 carbon atoms, and a distillation range of 290-305 ° C. Petrochemical Co., Ltd.) was prepared by blending 3% by volume.
供試軽油２：市販１号軽油を３０容量％、ＧＴＬ軽油（モスガス社製）を４０容量％、エクゾールＤ８０（東燃ゼネラル石油株式会社製）を３０容量％、それぞれ配合して調製した。 Test gas oil 2: 30% by volume of commercially available No. 1 gas oil, 40% by volume of GTL gas oil (manufactured by Moss Gas Co., Ltd.), and 30% by volume of Exol D80 (manufactured by TonenGeneral Sekiyu KK) were prepared.
供試軽油３：ＧＴＬ軽油（モスガス社製）４０容量％、蒸留範囲２１３〜２６２℃のイソパラフィン系溶剤であるＩＰソルベント２０２８（出光興産株式会社製）を３０容量％、蒸留範囲が２５５〜３４０℃のイソパラフィン系溶剤であるＮＡソルベントＮＡＳ−５Ｈ（日油株式会社製）を３０容量％、混合して調製した。 Test gas oil 3: 40% by volume of GTL gas oil (manufactured by Moss Gas), 30% by volume of IP solvent 2028 (manufactured by Idemitsu Kosan Co., Ltd.), an isoparaffin solvent having a distillation range of 213 to 262 ° C., and a distillation range of 255 to 340 ° C. 30% by volume of NA solvent NAS-5H (manufactured by NOF Corporation), which is an isoparaffinic solvent, was prepared.
供試軽油４：市販の２号軽油。 Test gas oil 4: Commercially available No. 2 gas oil.
供試軽油５：炭素数１４〜１６のノルマルパラフィンＳＨＮＰ（株式会社ジャパンエナジー製）を５０容量％，ＮＡソルベントＮＡＳ−５Ｈ（日油株式会社製）を２５容量％、ＩＰソルベント２０２８（出光興産株式会社製）を１７容量％、日石ハイゾールＳＡＳグレード２９６（新日本石油化学株式会社製）を５容量％、蒸留範囲が３５０〜４００℃の高沸点芳香族系溶剤である日石ハイゾールＳＡＳグレードＬＨ（新日本石油化学株式会社製）を３容量％混合して調製した。 Test gas oil 5: C14-C16 normal paraffin SHNP (manufactured by Japan Energy Co., Ltd.) 50% by volume, NA solvent NAS-5H (manufactured by NOF Corporation) 25% by volume, IP solvent 2028 (Idemitsu Kosan Co., Ltd.) Nisseki Hyzol SAS Grade LH, a high-boiling aromatic solvent with a distillation range of 350-400 ° C. (Made by Nippon Petrochemical Co., Ltd.) was prepared by mixing 3% by volume.
供試軽油６：ＧＴＬ軽油（モスガス社製）を６９容量％、市販の灯油を１０容量％、蒸留範囲が１６０〜１９５℃のＮＡソルベントＮＡＳ−３（日油株式会社製）を９容量％、日石ハイゾールＳＡＳグレード２９６（新日本石油化学株式会社製）を６容量％、日石ハイゾールＳＡＳグレードＬＨ（新日本石油化学株式会社製）を６容量％混合して調製した。 Test gas oil 6: 69% by volume of GTL gas oil (manufactured by Moss Gas), 10% by volume of commercially available kerosene, 9% by volume of NA solvent NAS-3 (manufactured by NOF Corporation) having a distillation range of 160-195 ° C. 6% by volume of Nisseki Hyzol SAS Grade 296 (manufactured by Nippon Petrochemical Co., Ltd.) and 6% by volume of Nisseki Hyzol SAS Grade LH (manufactured by Shin Nippon Petrochemical Co., Ltd.) were prepared.
次に上記供試軽油について、ＰＭ全体の重量、構成する粒子の総個数、微小粒子の個数並びに前記総個数に対する微小粒子の個数の割合（以後、単に微小粒子の割合という。）、及び燃費を、以下に示す車両を用い、国内認証試験モードである１０・１５モードで測定した。 Next, with respect to the test diesel oil, the weight of the entire PM, the total number of constituent particles, the number of microparticles, the ratio of the number of microparticles to the total number (hereinafter simply referred to as the ratio of microparticles), and the fuel consumption. Using the following vehicle, measurements were made in the 10.15 mode, which is the domestic certification test mode.
車両諸元
車両名：トヨタエスティマ
エンジン型式：３Ｃ−ＴＥ
総排気量：２１８４ｃｃ
圧縮比：２２．６
最高出力：６９ｋＷ／４０００ｒｐｍ
最大トルク：２０６Ｎｍ／２２００ｒｐｍ
規制適合：短期規制適合（平成５−６年）
Vehicle specifications Vehicle name: Toyota Estima Engine Model: 3C-TE
Total displacement: 2184cc
Compression ratio: 22.6
Maximum output: 69kW / 4000rpm
Maximum torque: 206Nm / 2200rpm
Regulatory compliance: Short-term regulatory compliance (1993-5)
（ＰＭ全体の重量測定）
ＴＲＩＡＳ ２４−４−１９９９「ディーゼル自動車１０・１５モード排出ガス試験方法」に規定された方法により測定した。この結果を表２に示した。
(Weighing the entire PM)
Measured by the method specified in TRIAS 24-4-1999 “Diesel vehicle 10/15 mode exhaust gas test method”. The results are shown in Table 2.
（ＰＭを構成する粒子の個数の測定）
車両からの排出ガスを１次希釈器（MD19−2E． Matter Engineering社製）、及び２次希釈器（ASET15−1． Matter Engineering社製）にて、空気で希釈及び加熱した。
その希釈ガスの総粒子数をCondensation Particle Counter（ＴＳＩ社製）で測定した。この結果を表２に示した。
(Measurement of the number of particles constituting PM)
The exhaust gas from the vehicle was diluted and heated with air in a primary diluter (MD19-2E, manufactured by Matter Engineering) and a secondary diluter (ASET15-1, manufactured by Matter Engineering).
The total number of particles of the dilution gas was measured with a Condensation Particle Counter (manufactured by TSI). The results are shown in Table 2.
この結果から、本発明の軽油組成物は、比較例２の市販の軽油や比較例３，４の供試軽油に比較してＰＭ全体の重量、構成する粒子の総個数が少ないことが分かる。なお、比較例１の芳香族分をほとんど含まない軽油組成物もＰＭ全体の重量、粒子の総個数が少ないことが分かる。 From these results, it can be seen that the light oil composition of the present invention has a smaller total PM weight and total number of constituting particles than the commercially available light oil of Comparative Example 2 and the test light oil of Comparative Examples 3 and 4. In addition, it turns out that the light oil composition which hardly contains the aromatic part of the comparative example 1 also has few weight of the whole PM, and the total number of particle | grains.
そこで、本発明に係る軽油組成物と比較例１の芳香族分をほとんど含まない供試軽油について、６.０４―２２.１nmの範囲の粒子数を微小粒子個数と定義し、Engine Exhaust Particle Sizer Spectrometer（ＴＳＩ社製）で、微小粒子の個数の測定を行なった。また、この微小粒子の個数が上記の総粒子数に占める割合も算出した。この結果を表３に示した。
なお、希釈条件は以下の通りである。
希釈率：１０５倍（１次希釈）、７倍（２次希釈）
加熱温度：１５０℃（１次希釈）、３００℃（２次希釈）
Therefore, the number of particles in the range of 6.04 to 22.1 nm is defined as the number of fine particles for the light oil composition according to the present invention and the test light oil containing almost no aromatic component of Comparative Example 1, and Engine Exhaust Particle Sizer The number of fine particles was measured with a Spectrometer (manufactured by TSI). The ratio of the number of fine particles to the total number of particles was also calculated. The results are shown in Table 3.
The dilution conditions are as follows.
Dilution rate: 105 times (primary dilution), 7 times (secondary dilution)
Heating temperature: 150 ° C. (primary dilution), 300 ° C. (secondary dilution)
（燃費の測定）
また、同様の供試軽油について、ＴＲＩＡＳ ５−４−１９９９「ディーゼル自動車１０・１５モード燃料消費試験方法」に規定された方法（カーボンバランス法）により、燃費を測定した。この結果を表３に示した。
(Measurement of fuel consumption)
In addition, fuel economy was measured for the same test diesel oil by the method (carbon balance method) defined in TRIAS 5-4-1999 “Diesel Vehicle 10/15 Mode Fuel Consumption Test Method”. The results are shown in Table 3.
これらの結果から、本発明に係る軽油組成物が、微小粒子も少なく、また燃費にも優れていることが分かる。 From these results, it can be seen that the light oil composition according to the present invention has few fine particles and is excellent in fuel efficiency.
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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