JP2001303080A - Gas oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain gas oil composition capable of extremely reducing an exhaust of environmental pollution substances when using for a high performanced and electronic controlled diesel engine, and exhibiting an excellent fuel efficiency and engine output. SOLUTION: This gas oil composition is characterized in that the sulfur content is <=0.005 mass %, distillation properties satisfy a relation of formula (1) T50+T70+T90+T95<1,170 (1) [T50, T70, T90 and T95 are 50 vol.% distillation temperature ( deg.C), 70 vol.% distillation temperature ( deg.C), 90 vol.% distillation temperature ( deg.C) and 95 vol.% distillation temperature ( deg.C), respectively] and aromatic components satisfy a relation of formula (2) 10<=(1-Arom)+5×(2-Arom)+10×(3-Arom)<=45 (2) [1-Arom is a monocyclic aromatic component content (vol.%), 2-Arom is a bicyclic aromatic component content (vol.%) and 3-Arom is a tricyclic aromatic component content (vol.%), respectively].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a gas oil composition,
More specifically, it relates to a gas oil composition having a low sulfur content.

[0002]

2. Description of the Related Art In recent years, in diesel vehicles, PM (particulate matter), NOx (nitrogen oxide),
In response to the demand for drastic reduction of the emission of environmental pollutants such as HC (hydrocarbon), improvement of the engine and post-treatment such as oxidation catalyst, NOx reduction catalyst, DPF (diesel particulate filter), etc. Higher performance such as mounting of devices is being promoted. In order to improve the performance of such a diesel vehicle, electronic control is very important in order to optimize the entire system with respect to fuel injection, engine combustion, and functions of a post-processing device.

However, conventional light oils (light oil compositions)
However, it has not been possible to effectively bring out the performance of such a high-performance, electronically controlled diesel vehicle system as a whole, and there has been a limit in reducing the emission of environmental pollutants in diesel vehicles. In other words, in a high performance, electronically controlled diesel vehicle, although a stricter quality is required for the light oil composition as a fuel than in the past, in response to the high performance and electronic control of such a diesel vehicle, A gas oil composition capable of sufficiently reducing the emission of environmental pollutants by optimizing the entire system and, consequently, improving operation performance has not yet been developed.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and particularly when used in a high performance, electronically controlled diesel vehicle, emission of environmental pollutants. Enabling a significant reduction in volume,
It is an object of the present invention to provide a gas oil composition that is compatible with high performance and electronic control of diesel vehicles and that exhibits excellent performance in both fuel efficiency and output.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that the sulfur content is reduced and the distillation properties and the aromatic content satisfy specific conditions. By doing so, it is possible to significantly reduce the emission of environmental pollutants in response to higher performance and electronic control of diesel vehicles, and to obtain a gas oil composition exhibiting excellent performance in both fuel consumption and output. This led to the completion of the present invention.

That is, the gas oil composition of the present invention has a sulfur content of 0.005% by mass or less and a distillation property of the following formula (1): T ₅₀ + T ₇₀ + T ₉₀ + T ₉₅ <1170 (1) In the formula, T ₅₀ , T ₇₀ , T ₉₀ , and T ₉₅ are 50% by volume distillation temperature (° C.), 70% by volume distillation temperature (° C.), 90% by volume distillation temperature (° C.), and 95% by volume, respectively. And the aromatic content is represented by the following formula (2): 10 ≦ (1-Arom) + 5 × (2-Arom) + 10 × (3-Arom) ≦ 45 2) [In the formula, 1-Arom is a partial aromatic content (% by volume);
Arom indicates a bicyclic aromatic content (% by volume), and 3-Arom indicates a tricyclic or higher aromatic content (% by volume)].

[0007]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below in detail.

[0008] The gas oil composition of the present invention must have a sulfur content of 0.005% by mass or less, preferably 0.003% by mass or less, more preferably 0.001% by mass or less.
% By mass or less. If the sulfur content exceeds 0.005% by mass, the sulfur content affects the latest exhaust gas purification system of diesel vehicles, and the PM and NO in the exhaust gas
The emission of environmental pollutants such as x will increase. In addition, the sulfur content here refers to JIS K
2541 means the sulfur content measured by the "Sulfur Content Test Method".

Further, in the gas oil composition of the present invention, the distillation property is represented by the following formula (1): T ₅₀ + T ₇₀ + T ₉₀ + T ₉₅ <1170 (1) wherein T ₅₀ , T ₇₀ , T ₉₀ , T ₉₅ indicates a 50% by volume distillation temperature (° C.), a 70% by volume distillation temperature (° C.), a 90% by volume distillation temperature (° C.), and a 95% by volume distillation temperature (° C.), respectively. It is necessary to be. Less than,
The value of {T ₅₀ + T ₇₀ + T ₉₀ + T ₉₅ } is called “distillation property index”.

When the distillation property index is 1170 or more, the concentrations of NOx and PM contained in the exhaust gas may increase. Therefore, it is necessary that the distillation property index be less than 1170 as in the above equation (1). To preferably 1150
Less, more preferably 1120 or less, even more preferably 1100 or less. On the other hand, the distillation property index is 8
It is preferably at least 00.

As described above, the distillation properties of the gas oil composition of the present invention may be those that satisfy the relationship of the above formula (1), and the respective distillation properties are not particularly limited. Distillation point: 135 to 200 ° C. 10% by volume distillation temperature (T ₁₀ ): 155 to 230 ° C. 30% by volume distillation temperature (T ₃₀ ): 175 to 260 ° C. 50% by volume distillation temperature (T ₅₀ ): 190 to 190 ° C. 290 ° C. 70% by volume distillation temperature (T ₇₀ ): 230 to 310 ° C. 90% by volume distillation temperature (T ₉₀ ): 270 to 350 ° C. 95% by volume distillation temperature (T ₉₅ ): 290 to 360 ° C. Distillation end point: It preferably satisfies 280 to 370 ° C.

When the initial boiling point of the gas oil composition is too low,
The initial boiling point is preferably at least 135 ° C., more preferably, because some light fractions evaporate and the spray range becomes too wide, and the amount of hydrocarbons entrained in the exhaust gas tends to increase as unburned matter. 140 ° C. or higher, even more preferably 14 ° C.
5 ° C. or higher. On the other hand, if the initial boiling point is too high, there is a possibility of causing a problem in low-temperature startability and low-temperature operability. Therefore, the initial boiling point is preferably 200 ° C or lower, more preferably 190 ° C or lower, even more preferably 185 ° C. It is below ° C.

When T _{10 of the} gas oil composition is too low, there is a concern that the amount of hydrocarbons entrained in the exhaust gas will increase for the same reason as when the initial boiling point is too low, so T ₁₀ is preferably 155. ° C or higher, more preferably 160 ° C or higher, still more preferably 165 ° C or higher, and still more preferably 170 ° C or higher. On the other hand, if the T ₁₀ is too high,
T ₁₀ is preferably 230 ° C. or less, more preferably 220 ° C. or less, even more preferably 210 ° C. or less, and even more preferably 205 ° C. or less, since there is a possibility of causing a problem in low-temperature startability and low-temperature operation. It is.

[0014] Also when T ₃₀ of the gas oil composition is too low, for the same reason as initial boiling point is too low, since the increase in the amount of hydrocarbons entrained in the exhaust gas is concerned, T ₃₀ is preferably 175 ° C or higher, more preferably 185 ° C or higher, still more preferably 190 ° C or higher, and still more preferably 195 ° C or higher. On the other hand, if T ₃₀ is too high,
T ₃₀ is preferably 260 ° C. or lower, more preferably 240 ° C. or lower, still more preferably 230 ° C. or lower, and even more preferably 220 ° C. or lower, since there is a possibility of causing a problem in low-temperature startability and low-temperature operation. It is.

The T _{50 of the} light oil composition is preferably at least 190 ° C. from the viewpoints of ensuring lubricity of the fuel injection pump and the fuel injection valve, and from the viewpoint of fuel consumption rate and engine output.
More preferably 200 ° C. or higher, even more preferably 2 ° C.
10 ° C. or higher, even more preferably 220 ° C. or higher,
Most preferably, it is 225 ° C or higher. On the other hand, from the viewpoint of not increasing the PM concentration in the exhaust gas, T ₅₀ is preferably 290 ° C. or lower, more preferably 270 ° C. or lower, even more preferably 260 ° C. or lower, still more preferably 250 ° C. or lower, and particularly preferably. 240 or less.

T _{70 of the} light oil composition is preferably 230 ° C. or higher from the viewpoint of ensuring lubricity of the fuel injection pump and the fuel injection valve, and from the viewpoint of fuel consumption rate and engine output.
More preferably 240 ° C. or higher, even more preferably 2 ° C.
It is at least 45 ° C, even more preferably at least 250 ° C. On the other hand, from the viewpoint of not increasing the PM concentration in the exhaust gas, T ₇₀ is preferably 310 ° C. or lower, more preferably 290 ° C. or lower, still more preferably 280 ° C. or lower, and even more preferably 270 ° C. or lower.

T _{90 of the} gas oil composition is preferably 27 from the viewpoint of ensuring lubricity of the fuel injection pump and the fuel injection valve.
0 ° C or higher, more preferably 275 ° C or higher, even more preferably 280 ° C or higher, even more preferably 28 ° C or higher.
5 ° C. or higher. On the other hand, from the viewpoint of not increasing the PM concentration in the exhaust gas, T ₉₀ is preferably 350 ° C. or lower, more preferably 330 ° C. or lower, and even more preferably 320 ° C. or lower.
° C or lower, still more preferably 310 ° C or lower, particularly preferably 305 ° C or lower.

[0018] T ₉₅ of the gas oil composition, from the viewpoint of ensuring the lubricating properties of the fuel injection pump and fuel injection valve, preferably 27
5 ° C or higher, more preferably 280 ° C or higher, even more preferably 285 ° C or higher, even more preferably 29 ° C or higher.
0 ° C. or higher. On the other hand, from the viewpoint of not increasing the PM concentration in the exhaust gas, _T95 is preferably 360 ° C or lower, more preferably 340 ° C or lower, and even more preferably 330 ° C or lower.
° C or lower, still more preferably 325 ° C or lower.

The distillation end point of the gas oil composition is preferably 280 ° C. or higher, more preferably 290 ° C., from the viewpoint of not significantly deteriorating the lubricity of the fuel injection pump and the fuel injection valve.
The temperature is more preferably 300 ° C. or more. On the other hand, from the viewpoint of not increasing the PM concentration in the exhaust gas, the distillation end point is preferably 370 ° C. or lower, more preferably 36 ° C. or less.
0 ° C. or lower, even more preferably 355 ° C. or lower, and even more preferably 350 ° C. or lower.

The distillation properties (initial boiling point,
_{T 10, T 30, T 50} , T 70, T 90, T 95, and the distillation end point), all JIS K 2254 - refers to a value measured according to "Petroleum products distillation test method".

In the gas oil composition of the present invention, the aromatic component contained is represented by the following formula (2): 10 ≦ (1-Arom) + 5 × (2-Arom) + 10 × (3-Arom) ≦ 45 (2 [Wherein, 1-Arom is a partial aromatic content (% by volume),
Arom indicates a bicyclic aromatic content (volume%), and 3-Arom indicates a tricyclic or higher aromatic content (volume%)]. Hereinafter, ｛(1-Arom) + 5 ×
The value of (2-Arom) + 10 × (3-Arom)｝ is called “aromatic index”.

When the aromatic index is less than 10, the fuel consumption rate and the output / torque of the engine are inferior. Therefore, it is necessary that the aromatic index be 10 or more as in the above formula (2). More preferably 15 or more, even more preferably 18 or more, particularly preferably 2 or more
0 or more. On the other hand, if the aromatic index exceeds 45, the emission amount of environmental pollutants such as PM in the exhaust gas may increase. Therefore, the aromatic index must be 45 or less as in the above equation (2). From the viewpoint of, it is preferably 40 or less, more preferably 36 or less, and still more preferably 3 or less.
It is 3 or less, still more preferably 30 or less, particularly preferably 27 or less.

In the gas oil composition of the present invention, the content of each of the one-membered aromatic component, the two-ringed aromatic component and the three- or more-ringed aromatic component satisfies the relationship of the above formula (2). Each content is not particularly limited, but from the viewpoint of fuel consumption rate and engine output / torque, the content of the aromatic component is preferably 8% by volume or more, more preferably 10% by volume or more. It is even more preferably at least 12% by volume. On the other hand, from the viewpoint of reducing each concentration of NOx and PM contained in the exhaust gas, the content of the partial aromatic component is as follows:
Preferably 30% by volume or less, more preferably 25% by volume
Or less, still more preferably 20% by volume or less. Further, the content of the bicyclic aromatic component in the gas oil composition of the present invention is preferably 4% by volume or less, more preferably 2% by volume or less, from the viewpoint of reducing each concentration of NOx and PM contained in the exhaust gas. It is even more preferably 1% by volume or less. Further, the content of the aromatic component having three or more rings in the gas oil composition of the present invention is determined by the NOx and PM contained in the exhaust gas.
From the viewpoint of lowering the respective concentrations, the concentration is preferably 2% by volume or less, more preferably 1% by volume or less, still more preferably 0.5% by volume or less.

The content of the one-membered aromatic component, the content of the two-ringed aromatic component, and the content of the three- or more-ringed aromatic component are measured in accordance with the Japan Petroleum Institute standard JPI-5S-49-97. Means the volume percentage (% by volume) of each aromatic component by the number of aromatic rings.

The total aromatic content in the gas oil composition of the present invention is preferably 9% by volume or more, more preferably 10% by volume or more, and still more preferably, from the viewpoint of fuel consumption rate and engine output / torque. It is at least 12% by volume, even more preferably at least 14% by volume, particularly preferably at least 16% by volume, most preferably at least 18% by volume. On the other hand, from the viewpoint of reducing the concentrations of NOx and PM contained in the exhaust gas, the total aromatic content is preferably 40% by volume or less, more preferably 35% by volume or less, still more preferably 30% by volume or less. , Even more preferably at most 27% by volume, most preferably at most 25% by volume.

The content of the saturated component in the gas oil composition of the present invention is preferably 60% by volume or more, more preferably 70% by volume or more, from the viewpoint of reducing the concentrations of NOx and PM in the exhaust gas. It is more preferably at least 73% by volume, still more preferably at least 75% by volume. On the other hand, from the viewpoint of maintaining good low-temperature startability and low-temperature operability, the saturated content is preferably 91% by volume or less, more preferably 90% by volume or less, still more preferably 88% by volume or less. It is preferably at most 86% by volume, particularly preferably at most 84% by volume, most preferably at most 82% by volume.

The olefin content of the gas oil composition of the present invention is preferably 5% by volume or less, more preferably 3% by volume or less, from the viewpoint of the stability of the gas oil composition.
It is even more preferably 1% by volume or less.

Here, the total aromatic content is defined as
It means the volume percentage (% by volume) of the total aromatic component measured according to the Japan Petroleum Institute standard JPI-5S-49-97. Also, the saturated content and the olefin content,
It means the volume percentage (volume%) of the saturated component and the olefin component measured in accordance with the fluorescent indicator adsorption method of "Petroleum products-component test method" defined in JIS K 2536, respectively.

In the light oil composition of the present invention,
Density is preferably 0.800 g / cm^ThreeThat's it
More preferably 0.802 g / cm^ThreeAbove, even better
0.804g / cm^ThreeAbove, even better
Preferably 0.806 g / cm^ThreeThat is all. Density is above
Below the lower limit, fuel consumption rate and engine output / torque
Tend to be inferior. On the other hand, the density at 15 ° C is preferable.
Or 0.850 g / cm ^ThreeBelow, more preferably 0.
840 g / cm^ThreeBelow, even more preferably 0.83
0 g / cm^ThreeBelow, even more preferably 0.82
5g / cm^ThreeOr less, particularly preferably 0.820 g / cm^Three
It is as follows. If the density exceeds the above upper limit,
The PM concentration in the media tends to increase. Note that here
Density refers to JIS K 2249 “Crude oil and petroleum products
Density test method and density / mass / volume conversion table "
Means the density measured.

Then, in the light oil composition of the present invention,
The above density, total aromatic content, and 50% by volume distillation temperature are calculated by the following formula (3): {D− (0.001648 × TA + 0.000398 × T ₅₀ )} <0.705 (3) Density at 15 ° C. (g / cm ³ ), TA
Indicates the total aromatic content (% by volume), and T ₅₀ indicates the distillation temperature (° C.) of 50% by volume.]. Hereinafter, ΔD− (0.001648 × TA + 0.000398)
× T ₅₀ )｝ is referred to as “D-TA-T ₅₀ relation index”.

The above D-TA-T₅₀Relationship index is 0.705
In the case above, the fuel consumption rate and engine output / torque are
Since it tends to be inferior, the D-TA
-T ₅₀The relationship index is preferably less than 0.705, more preferably
0.700 or less, still more preferably 0.69
5 or less, even more preferably 0.690 or less.
You. On the other hand, the above D-TA-T₅₀Relationship index is 0.600 or more
It is preferably above.

The kinematic viscosity of the gas oil composition of the present invention is not particularly limited. However, from the viewpoint of control of the fuel injection timing and lubricity of the distribution type fuel injection pump attached to the engine, the kinematic viscosity at 30 ° C. is preferably 1.7 mm ² /.
s or more, more preferably 1.8 mm ² / s or more, even more preferably 1.9 mm ² / s or greater, even more preferably from at 1.95 mm ² / s or more. On the other hand, the kinematic viscosity at 30 ° C. is preferably 4.5 mm ² / s or less, more preferably 4.0 mm ² , from the viewpoint of not increasing the PM concentration in the exhaust gas and reducing the effect on the startability at low temperatures. / S or less, still more preferably 3.5 mm ² / s or less, even more preferably 3.
0 mm ² / s or less. In addition, the kinematic viscosity here means the kinematic viscosity measured based on JIS K2283 "Crude oil and petroleum products-Kinematic viscosity test method and viscosity index calculation method".

The cetane number and cetane index of the gas oil composition of the present invention are not particularly limited. However, from the viewpoint that each concentration of NOx, PM and aldehyde in the exhaust gas can be further reduced, the cetane number is preferably 45 or more,
More preferably 50 or more, even more preferably 51 or more, even more preferably 53 or more, particularly preferably 55 or more, the cetane index is preferably 45 or more,
It is more preferably 47 or more, still more preferably 48 or more, still more preferably 50 or more, and particularly preferably 52 or more. In addition, the cetane number here means J
It means the cetane number measured in accordance with "7. Cetane number test method" of IS K 2280 "Petroleum products-Fuel oil-Octane number and cetane number test method and cetane index calculation method". The cetane index is defined as JIS K 2
280 means a value calculated based on "Calculation method of cetane index using 8.4 variable equation" in "Petroleum products-Fuel oil-Test method of octane number and cetane number and calculation method of cetane index".

The gas oil composition of the present invention has a pour point (P
There is no particular limitation on P). However, from the viewpoint of low-temperature startability or low-temperature operation, the pour point is preferably −
7.5 ° C. or lower, more preferably −10 ° C. or lower, even more preferably −20 ° C. or lower, and still more preferably −30 ° C. or lower. The pour point here is J
It means the pour point measured in accordance with IS K 2269 "Pour point of crude oil and petroleum products and cloud point test method of petroleum products".

Similarly, the gas oil composition of the present invention has no particular restriction on its clogging point (CFPP). However, from the viewpoint of low-temperature startability or low-temperature operation, the clogging point is preferably −5 ° C. or less, more preferably −12 ° C.
Or less, still more preferably -15 ° C or less, still more preferably -19 ° C or less, and particularly preferably -24 ° C.
It is as follows. Note that the clogging point referred to here is JI
SK 2288 means the clogging point measured according to "Light Oil-Clogging Point Test Method".

The gas oil composition of the present invention has no particular limitation on its cloud point (CP). However, from the viewpoint of low-temperature startability or low-temperature operation, the cloud point is preferably 0 ° C or lower, more preferably -6 ° C or lower, still more preferably -8 ° C or lower, and still more preferably -12 ° C or lower.
° C or lower, particularly preferably -15 ° C or lower, most preferably -17 ° C or lower.

Further, the light oil composition of the present invention is preferably HF from the viewpoint of sufficiently maintaining the effect of adding a lubricity improver described later.
The wear scar diameter in the RR test is preferably 550 μm or less, more preferably 500 μm or less. In addition, the wear scar diameter in the HFRR test here means a wear scar diameter measured based on the Japan Petroleum Institute method JPI-5S-50-98 "light oil-lubricity test method".

The light oil composition of the present invention can be obtained by blending additives and the like as necessary with light oil (base light oil). The base gas oil according to the present invention is not particularly limited as long as the obtained gas oil composition satisfies the above conditions, and the production method and the like are not particularly limited, and one or more of the following gas oil base materials are appropriately selected and mixed. It is possible to get. Specific examples of the gas oil base material that can be used in the present invention include, for example, a straight-run gas oil obtained from an atmospheric distillation apparatus for crude oil;
Vacuum gas oil obtained by subjecting a straight-run heavy oil or residue obtained from an atmospheric distillation unit to a vacuum distillation unit; hydrorefined gas oil obtained by hydrorefining a vacuum gas oil obtained from a vacuum distillation unit; straight-run gas oil Hydrodesulfurized gas oil obtained by hydrodesulfurization in one or more stages under severer conditions than ordinary hydrorefining; obtained by catalytic cracking of desulfurized or undesulfurized vacuum gas oil, vacuum heavy gas oil or desulfurized heavy oil Catalytic cracked gas oil; straight kerosene obtained by atmospheric distillation of crude oil; hydrorefined kerosene obtained by hydrorefining straight kerosene; obtained by cracking a gas oil fraction obtained by atmospheric distillation of crude oil Decomposed kerosene and the like.

The additives that can be used in the light oil composition of the present invention include lubricity improvers, cetane improvers, detergents and the like. Such additives are used alone or in combination of several kinds for the purpose of further enhancing the expected performance, and among them, it is preferable to contain at least a lubricity improver.

As the lubricity improver according to the present invention, for example, one or more of lubricity improvers of carboxylic acid type, ester type, alcohol type and phenol type can be arbitrarily used. Among these, carboxylic acid-based and ester-based lubricity improvers are preferred.

Examples of the carboxylic acid-based lubricity improver include linoleic acid, oleic acid, salicylic acid, palmitic acid, myristic acid, hexadecenoic acid and a mixture of two or more of the above carboxylic acids. Examples of the ester-based lubricity improver include carboxylate of glycerin. The carboxylic acid constituting the carboxylic acid ester may be one kind or two or more kinds, and specific examples thereof include linoleic acid, oleic acid,
Salicylic acid, palmitic acid, myristic acid, hexadecenoic acid and the like.

The content of such a lubricity improver is not particularly limited. However, in order to bring out the effect of the lubricity improver, specifically, in a diesel engine equipped with a distribution type injection pump, in order to suppress the increase in the driving torque of the running pump and reduce the wear of the pump, Is 35 mass ppm based on the total amount of the composition.
Or more, more preferably 50 mass ppm or more. On the other hand, the compounding amount of the lubricity improver is
Since an effect commensurate with the amount of addition cannot be obtained even if it is added more than 150 mass ppm or less is preferable.
More preferably, it is not more than 00 mass ppm.

It is to be noted that commercial products called lubricity improvers are generally obtained in a state where active ingredients contributing to lubricity improvement are diluted with an appropriate solvent. When such a commercially available product is blended with the light oil composition of the present invention, the blending amount described above for the lubricity improver means the blending amount as an active ingredient.

As the cetane number improver according to the present invention, various compounds known in the art as cetane number improvers can be optionally used. For example, nitrate esters and organic peroxides can be used. It is possible, and among them, it is preferable to use a nitrate ester. For nitrate ester, 2-
Chloroethyl nitrate, 2-ethoxyethyl nitrate, isopropyl nitrate, butyl nitrate, primary amyl nitrate, secondary amyl nitrate, isoamyl nitrate, primary hexyl nitrate, secondary hexyl nitrate, n- Various nitrates such as heptyl nitrate, n-octyl nitrate, 2-ethylhexyl nitrate, cyclohexyl nitrate and ethylene glycol dinitrate are included. Among these, alkyl nitrates having 6 to 8 carbon atoms are preferable. As the cetane number improver, one kind of a single compound may be used, or two or more kinds of compounds may be used in combination.

The content of the cetane number improver in the gas oil composition of the present invention is 500 ppm by mass based on the total amount of the composition because the NOx concentration, PM concentration, aldehyde concentration and the like of the exhaust gas of a diesel engine can be further reduced.
It is preferably at least 600 ppm by mass, more preferably at least 600 ppm by mass, still more preferably at least 700 ppm by mass, particularly preferably at least 800 ppm by mass, most preferably at least 900 ppm by mass. preferable.

The upper limit of the content of the cetane number improver is not particularly limited, but generally, the content of the cetane number improver is preferably 1400 ppm by mass or less based on the total amount of the gas oil composition, and 1250 ppm by mass. It is more preferably at most 1 ppm by mass, more preferably at most 1100 ppm by mass, most preferably at most 1000 ppm by mass.

Commercially available products called cetane improvers are usually obtained in the form of an active ingredient that contributes to cetane improve, that is, diluted with an appropriate solvent. is there. When the gas oil composition of the present invention is prepared using such commercially available products, the content described above with respect to the cetane number improver means the content as an active ingredient.

As the detergent according to the present invention, for example,
Imide compounds; alkenyl succinic derivatives such as polybutenyl succinimide synthesized from polybutenyl succinic anhydride and polyamines; synthesized from polyhydric alcohols such as pentaerythritol and polybutenyl succinic anhydride Succinates such as polybutenyl succinate; copolymers such as dialkylaminoethyl methacrylate, polyethylene glycol methacrylate, and copolymers of vinylpyrrolidone and alkyl methacrylate; reaction products of carboxylic acids and amines (salts, etc.) And the like. One or more arbitrarily selected ashless detergents can be used, and among these, it is preferable to use an alkenyl succinic acid derivative and / or an amine salt of a carboxylic acid.

The alkenyl succinic acid derivative is preferably a compound represented by the following general formulas (1) to (4).

[0050]

Embedded image

(Wherein A represents an n-butyl group, a sec-butyl group or a tert-butyl group, and R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a methyl group or an ethyl group. A total number of carbon atoms of R ^{1 to} R ⁴ is 2,
⁵ represents an alkylene group having 1 to 36 carbon atoms, and m represents an integer of 1 to 100. )

[0052]

Embedded image

(Wherein A represents an n-butyl group, a sec-butyl group or a tert-butyl group, and R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a methyl group or an ethyl group. A total number of carbon atoms of R ^{1 to} R ⁴ is 2,
⁵ represents an alkylene group having 1 to 36 carbon atoms, and m represents 1 to 1
Represents an integer of 00, and n represents an integer of 1 to 10. )

[0054]

Embedded image

(In the formula, A represents an n-butyl group, a sec-butyl group or a tert-butyl group, and R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a methyl group or an ethyl group. A total number of carbon atoms of R ^{1 to} R ⁴ is 2,
⁵ represents an alkylene group having 1 to 36 carbon atoms, and m represents 1 to 1
Represents an integer of 00, and n represents an integer of 1 to 10. )

[0056]

Embedded image

(Where A represents an n-butyl group, a sec-butyl group or a tert-butyl group, and R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a methyl group or an ethyl group. A total number of carbon atoms of R ^{1 to} R ⁴ is 2,
⁵ represents an alkylene group having 1 to 36 carbon atoms, and m represents 1 to 1
Represents an integer of 00 and n represents an integer of 1 to 10. The alkenyl succinic acid derivatives represented by the general formulas (1) to (4) will be described in detail.

A represents an n-butyl group, a sec-butyl group or a tert-butyl group. A tert-butyl group is preferred because more excellent cleanliness can be obtained.

R ^{1 to} R ⁴ each represent a hydrogen atom, a methyl group or an ethyl group. The total number of carbon atoms in R ^{1 to} R ⁴ is 2.

In the present invention, since better cleanliness can be obtained, when R ¹ and R ³ are both hydrogen atoms and R ² and R ⁴ are both methyl groups, or when R ¹ and R ⁴ are both methyl groups. ^It is preferred that both ³ are methyl groups and both R ² and R ⁴ are hydrogen atoms.

R ⁵ represents an alkylene group having 1 to 36 carbon atoms. R ⁵ is preferably an alkylene group having 1 to 18 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms. Specific examples of the alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a propylene group (1-methylethylene group, a 2-methylethylene group), a trimethylene group, and a butylene group (1-ethylethylene group). , 2-ethylethylene group), 1,2-dimethylethylene group, 2,2-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group, tetramethylene group and the like. No. Among these, R ⁵ is most preferably a methylene group, an ethylene group, a propylene group (1-methylethylene group, 2-methylethylene group) or a trimethylene group.

In the general formulas (1) to (4), m is 1 to 1.
Indicates an integer of 00. m is preferably 5 or more, more preferably 10 or more, from the viewpoint of maintaining the dispersibility in the gas oil composition and maintaining the cleanliness. In addition, in terms of the effect on the valve stick due to the increase in viscosity and the combustion chamber deposit due to the deterioration of thermal decomposition,
It is preferably 50 or less, more preferably 40 or less.

In the general formulas (2) to (4), n represents an integer of 1 to 10. n is preferably an integer of 1 to 5, more preferably 1 to 3.

The group represented by the following formula (5) is a compound represented by the general formula (1) having a group represented by the following formula (6) as a structural unit.
1 shows a polymer skeleton of an alkenyl succinic acid derivative represented by any one of (1) to (4).

[0065]

Embedded image

(R ¹ in the above formulas (5) and (6),
R ^2, R ^3, R ⁴ and m represents the general formula (1) ~ (4) R 1, R 2, R 3, R 4 and m the same group, the integer. In the above formulas (1) to (4) and (5), the m groups represented by the above formula (6) may be the same or different in the same molecule. That is, the compounds represented by the above formulas (1) to (4) and the group represented by the above formula (5) may be a homopolymer or a copolymer. The copolymer is
Any of a random copolymer, an alternating polymer, and a block copolymer may be used.

The number average molecular weight of the alkenyl succinic acid derivative is not particularly limited, but is preferably 500 or more from the viewpoint of maintaining the dispersibility in the gas oil composition and maintaining the cleanliness. , 1000 or more, still more preferably 1500 or more, and most preferably 2000 or more. The number average molecular weight is preferably 6,000 or less from the viewpoint of the effect on the valve stick due to the increase in viscosity and the combustion chamber deposit due to the deterioration in thermal decomposition.
More preferably, it is not more than 00.

As the alkenyl succinic acid derivative, only one compound selected from the compounds represented by formulas (1) to (4) may be used alone, or two or more compounds may be used in combination. You may.

When two or more kinds are used, the general formula (2)
And a compound represented by the general formula (3). Mixing ratio at that time (mass ratio)
Is preferably (2) :( 3) = 1: 99-99: 1, more preferably 10: 90-90: 10, and even more preferably 20: 80-80: 20. Most preferably, it is 30:70 to 70:30.

Preferred specific examples of the alkenyl succinic acid derivative are shown below.

Compound 1 represented by the following formula (number average molecular weight: 2000-3000)

[0072]

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(A: tert-butyl group, R ¹ , R ³ : hydrogen atom, R ² , R ⁴ : methyl group, R ⁵ : trimethylene group)

Compound 2 represented by the following formula (number average molecular weight: 2,000 to 3,000)

[0075]

Embedded image

(A: tert-butyl group, R ¹ , R ³ : hydrogen atom, R ² , R ⁴ : methyl group, R ⁵ : ethylene group, n:
1-3).

Compound 3 represented by the following formula (number average molecular weight: 4000-5000)

[0078]

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(A: tert-butyl group, R ¹ , R ³ : hydrogen atom, R ² , R ⁴ : methyl group, R ⁵ : ethylene group, n:
1-3).

Compound 4 represented by the following formula (number average molecular weight: 2,000 to 3,000)

[0081]

Embedded image

(A: tert-butyl group, R ¹ , R ³ : hydrogen atom, R ² , R ⁴ : methyl group, R ⁵ : ethylene group, n:
1-3).

Next, the amine salt of a carboxylic acid will be described in detail.

The carboxylic acid preferably has 5 to 50 carbon atoms, more preferably has 7 to 30 carbon atoms, and particularly preferably has 9 to 20 carbon atoms. The carboxylic acid may be either a monocarboxylic acid or a polycarboxylic acid, but is preferably a monocarboxylic acid. The carboxylic acid may be any of a fatty acid, an alicyclic carboxylic acid, and an aromatic carboxylic acid, but is preferably a fatty acid. The fatty acid may be linear or branched, and may be saturated or unsaturated.

Specific examples of the fatty acids having 9 to 20 carbon atoms include the following. Linear or branched nonanoic acid, linear or branched decanoic acid, linear or branched undecanoic acid, linear or branched dodecanoic acid, linear or branched tridecanoic acid, linear or branched chain A linear or branched pentadecanoic acid, a linear or branched hexadecanoic acid, a linear or branched heptadecanoic acid, a linear or branched octadecanoic acid, a linear or branched nonadecanoic acid, Chain or branched chain icosanoic acid, straight or branched chain nonenoic acid, straight or branched chain decenoic acid, straight or branched chain undecenoic acid, straight or branched chain dodecenoic acid, straight or branched chain Tridecenoic acid, linear or branched tetradecenoic acid, linear or branched pentadecenoic acid, linear or branched hexadecenoic acid, linear or branched heptadecenoic acid, linear or branched octadecenoic acid (olein The included), straight-chain or nonadecenoic acids branched, such as icosenoic acid linear or branched. Further, fatty acids having a hydroxyl group such as linoleic acid are also included. As the above carboxylic acid, one kind of carboxylic acid may be used alone, or two or more kinds of carboxylic acids may be used in combination.

The amine preferably has 1 to 30 carbon atoms. More preferably, it has 5 to 20 carbon atoms, and particularly preferably 8 to 18 carbon atoms. Examples of the amine include a monoamine, a polyamine, and an alkanolamine, and a monoamine is preferable.

The monoamine includes mono-substituted amines having one hydrocarbon group, di-substituted amines having two hydrocarbon groups, and tri-substituted amines having three hydrocarbon groups. Mono-substituted amines are preferred. .

Examples of the monosubstituted amine include alkylamine, alkenylamine, aromatic-substituted alkylamine, cycloalkylamine, and alkylcycloalkylamine. Preference is given to alkylamines and alkenylamines.

Examples of the alkylamine having 8 to 18 carbon atoms include linear or branched octylamine, linear or branched nonylamine, linear or branched decylamine, and linear or branched undecylamine. Linear or branched dodecylamine, linear or branched tridecylamine, linear or branched tetradecylamine, linear or branched pentadecylamine, linear or branched hexadecylamine, A straight or branched heptadecylamine, a straight or branched octadecylamine and the like can be mentioned.

The alkenylamine having 8 to 18 carbon atoms includes, for example, linear or branched octenylamine, linear or branched nonenylamine, linear or branched decenylamine, linear or branched undecenylamine, Linear or branched dodecenylamine, linear or branched tridecenylamine, linear or branched tetradecenylamine, linear or branched pentadecenylamine, linear or branched hexadecenylamine And linear or branched heptadecenylamine, linear or branched octadecenylamine (including oleylamine), and the like.

As the amine, one kind of amine may be used alone, or a mixture of two or more kinds of amines may be used.

Preferred specific examples of the amine salt of a carboxylic acid include a mixed fatty acid having 13 to 20 carbon atoms and a monosubstituted amine having an alkyl group having 8 to 16 carbon atoms. And a salt with a mixture of monosubstituted amines having an alkenyl group.

The amount of the detergent in the light oil composition of the present invention is not particularly limited. However, in order to bring out the effect of blending the detergent, specifically, the effect of suppressing the clogging of the fuel injection nozzle, the blending amount of the detergent should be 30% based on the total amount of the composition.
Mass ppm or more, preferably 60 mass ppm
More preferably, it is more preferably 80 mass ppm or more. Even if an amount less than 30 mass ppm is added, there is a possibility that the effect is not exhibited. On the other hand, if the blending amount is too large, a corresponding effect cannot be expected. Conversely, NOx, P
Because it may increase M, aldehyde, etc.
The amount of the detergent added is preferably 300 ppm by mass or less, more preferably 180 ppm by mass or less.

As in the case of the cetane number improver,
Commercially available products called detergents are generally obtained in a state where active ingredients contributing to cleaning are diluted with an appropriate solvent. When such a commercially available product is blended with the light oil composition of the present invention, the blending amount described above for the detergent means the blending amount as an active ingredient.

Further, in the light oil composition of the present invention,
For the purpose of further enhancing other performances, other known fuel oil additives can be added alone or in combination of several kinds. Examples of such additives include low-temperature fluidity improvers such as ethylene-vinyl acetate copolymer and alkenyl succinamide; antioxidants such as phenol and amine; metal deactivators such as salicylidene derivatives Anti-icing agents such as polyglycol ether; corrosion inhibitors such as aliphatic amines and alkenyl succinates;
Antistatic agents such as cationic and amphoteric surfactants; coloring agents such as azo dyes; defoaming agents such as silicones;
The amount of these other additives is not particularly limited,
The amount of each additive is 0.5% by mass based on the total amount of the gas oil composition.
Or less, more preferably 0.2% by mass or less.

[0096] Among the above additives, the antistatic agent is an additive that is rarely used in conventional light oils. However, as in the present invention, the sulfur content is reduced to 0.005% by mass or less. In this case, it is preferable to use an antistatic agent in order to more reliably prevent ignition due to charging.

Further, the above-mentioned lubricity improver, cetane number improver, detergent, low-temperature fluidity improver, antioxidant, metal deactivator, anti-icing agent, corrosion inhibitor,
Each additive such as an antistatic agent, (10) a coloring agent, and (11) an antifoaming agent may be used alone or in combination of two or more. Specific examples of the combination when the additives are used in combination include:
, (11) ,,,, (11) ,,,
(11) ,, (11) ,,,,
(11) ,,, (11), (11),
(11) ,,, (11), (1
1), (11), (11), (11), (1
1) ,,, (11) ,,
(11), (11), (11), (1
1), (11), (11), (11),
(11), (11), (11),
(11), (11), (11),
(11) and (11), but are not limited thereto.

[0098]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Examples 1 to 6 Light oil compositions having the compositions, distillation properties and various properties shown in Table 1 were prepared, and the following exhaust gas tests, lubricity tests, and output / fuel efficiency tests were performed on each light oil composition. The results obtained are shown in the table. In addition, as the lubricity improver, a mixture containing glycerin, linoleic acid, and oleic acid as main components, mono- and diesters was used.

(1) Exhaust gas test Diesel 13 by bench test using the following engine
A mode test was performed, and the emission amount of particulate matter (PM) was measured as emission performance evaluation. PM in the exhaust gas was collected on a filter using a dilution tunnel manufactured by Horiba, and the weight of the collected PM was measured. Then, the case where the PM emission amount was 0.20 g / kWhr or less was evaluated as “very small”, and the case where the PM emission amount was 0.18 g / kWhr or less was evaluated as “extremely small”.

(Test Engine) Engine: In-line 4-cylinder Displacement: 5.3 L Injection system: Direct injection type Injection pump: Row type electronically controlled injection pump Post-processing: Oxidation catalyst Catalyst capacity: 2 L (platinum catalyst).

(2) Lubricity Test The wear scar diameter in the HFRR test was measured in accordance with the Japan Petroleum Institute method JPI-5S-50-98, "Diesel Oil-Lubricity Test Method". Then, the case where the wear scar diameter was 460 μm or less was regarded as good, and evaluated as acceptable (合格).

(3) Output / fuel efficiency test An engine output test (JIS D1001) was carried out by a bench test using the following engine, and the maximum output under the full load condition was obtained.
The maximum torque and the minimum fuel consumption were measured. Maximum output,
The maximum torque was evaluated as “no problem” when it increased or decreased by less than 3% compared to the specification value of the engine. In addition, the minimum fuel consumption rate was evaluated as “no problem” when it was reduced or increased by less than 3% as compared with the specification value of the engine.

(Test engine) Engine: In-line 4-cylinder engine Displacement: 5.3 L Injection system: Direct injection type Injection pump: Row type injection pump Maximum output = 107 kW / 2900 rpm Maximum torque = 373 Nm / 1700 rpm Minimum fuel consumption rate at full load = 208g / kWh.

[0104]

[Table 1]

As is clear from the results shown in Table 1, when the light oil composition according to the present invention is used in electronically controlled diesel engines and diesel vehicles, the emission of environmental pollutants is greatly reduced. In addition, excellent performance was exhibited in both fuel efficiency and output.

[0106]

As described above, according to the gas oil composition of the present invention, when used in a diesel vehicle which has high performance and is electronically controlled, the emission of environmental pollutants is greatly reduced, especially, and Can exhibit excellent performance in both fuel consumption and output, and can sufficiently achieve improved driving performance. Therefore, according to the present invention, it is possible to obtain an optimal light oil composition corresponding to high performance and electronic control of a diesel vehicle.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takashi Kaneko 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Prefecture Inside the Central Research Laboratory, Nishiishi Mitsui Co., Ltd. (72) Inventor Sanshiro Matsubara Chidori, Naka-ku, Yokohama-shi, Kanagawa Prefecture No. 8 Machi Nishiishi Central Research Laboratory Co., Ltd. F-term (reference) 4H013 CB02

Claims (1)

[Claims] 1. The sulfur content is 0.005% by mass or less, and the distillation property is the following formula (1): T ₅₀ + T ₇₀ + T ₉₀ + T ₉₅ <1170 (1) [wherein T ₅₀ , T ₇₀ , T ₉₀ and T ₉₅ indicate a 50% by volume distillation temperature (° C.), a 70% by volume distillation temperature (° C.), a 90% by volume distillation temperature (° C.), and a 95% by volume distillation temperature (° C.), respectively. And the aromatic component has the following formula (2): 10 ≦ (1-Arom) + 5 × (2-Arom) + 10 × (3-Arom) ≦ 45 (2) Arom is one aromatic content (% by volume), 2-
Arom indicates a bicyclic aromatic content (volume%), and 3-Arom indicates a tricyclic or higher aromatic content (vol%)].