JP2001303074A - Gas oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a gas oil composition capable of extremely reducing an exhaust of particulates from an diesel engine in the whole load range of the engine. SOLUTION: This gas oil composition comprises a base gas oil containing at least >=50 vol.% gas oil base having >=145 deg.C initial boiling point, <=270 deg.C 95 vol.% distillation temperature and <=80 mass ppm sulfur content, contains >=500 mass ppm based on the whole amount of the composition of cetane number improver and has >=45 cetane index, <=330 deg.C 90 vol.% distillation temperature, <=500 mass ppm sulfur content and >=1.7 mm2/s kinematic viscosity at 30 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas oil composition having a low sulfur content, and more particularly to a gas oil composition capable of significantly reducing the amount of particulates in diesel exhaust gas over the entire engine load range. It relates to a light oil composition.

[0002]

2. Description of the Related Art As components contained in diesel exhaust gas, nitrogen oxide (hereinafter referred to as NOx) and particulate matter (hereinafter referred to as PM) are mainly regarded as problems. NOx is a substance mainly generated by the reaction of nitrogen in the air with oxygen in the engine, and includes NO, NO _{2, and the} like. PM is fine particles in the exhaust gas, and is the one obtained by discharging soot (soot) by combustion and high-boiling high-molecular unburned components contained in fuel or lubricating oil. These substances cause air pollution and acid rain, and urgent reduction measures are required. In addition, recently, aldehydes including formaldehyde and acetaldehyde have also attracted attention because of their adverse effects on human health and odor.

[0003] Since October 1997, light oil used as fuel for diesel engines has been used in SOF for automobiles.
Assuming that a post-treatment device such as a catalyst (organic solvent-soluble component oxidation catalyst) and a NOx reduction catalyst is installed, the sulfur content is reduced to 500 mass ppm or less. However, these post-processing devices have problems such as low efficiency and durability, and at present, very few devices have been put to practical use. At present, vehicles with the latest emission reduction measures are being introduced to the market, but the replacement of already sold vehicles requires a lot of time, so the fundamental solution has not been reached. In addition, more stringent emission regulations will be introduced after 2003.

[0004]

As described above, in 2003,
Because of the strict emission regulations that will be enforced after the year 2010, and because it will take a lot of time for the market to adopt the latest emission reduction technologies, the reduction of emissions Improving the quality of the product has high immediate effect and is considered to be very effective. As fuel, not only is it effective for existing diesel vehicles, but also for vehicles that have advanced emission measures such as DPF installation, effective fuel is required. There are several possible ways to improve fuel to reduce exhaust gas.However, fuels containing oxygenated compounds may have adverse effects on engine components, etc. No. Accordingly, an object of the present invention is to provide a gas oil composition capable of greatly reducing the emission of particulates contained in diesel exhaust gas over the entire load range of the engine. In particular, it is also to provide a light oil composition effective for reducing exhaust gas (particularly, reducing PM concentration) even for a vehicle equipped with a DPF.

[0005]

According to the present invention, the first boiling point is 14 points.
5% or more, 95% by volume Distillation temperature is 270 ° C or less, and sulfur content is 80% by mass or less. Contains 500 mass ppm or more, has a cetane index of 45 or more, and a 90% by volume distillation temperature of 330 ° C.
Hereafter, the sulfur content is 500 ppm by mass or less;
The light oil composition has a kinematic viscosity at 0 ° C. of 1.7 mm ² / s or more.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The gas oil composition of the present invention contains a base gas oil and a cetane number improver. The base gas oil has an initial boiling point (IBP) of 145 ° C. or more and a 95% by volume distillation temperature (IBP). T
₉₅ ) is 270 ° C. or less and the sulfur content is 80 mass pp.
It contains a light oil base material having properties of not more than m. First, the light oil base will be described. Generally, when the initial boiling point (IBP) decreases, the amount of hydrocarbons in the exhaust gas tends to increase.
In the present invention, the amount of hydrocarbons in the exhaust gas can be reduced by using the light oil base material of 145 ° C. or higher. On the other hand, if the initial boiling point is too high, problems tend to occur in low-temperature startability and low-temperature stability (low-temperature operation). For this reason, the initial boiling point of the light oil base material of the present invention is preferably 150 ° C. or higher, more preferably 155 ° C. or higher. On the other hand, the upper limit of the initial boiling point is preferably 210 ° C. or lower, more preferably 200 ° C. or lower. 9
The 5 volume% distillation temperature (T _95), the generally T ₉₅ is too high, PM concentration reduction in the exhaust gas is hardly obtained sufficiently. In the present invention, by using a gas oil base material having a T ₉₅ of 270 ° C. or less, a greater effect of reducing the PM concentration in the exhaust gas can be obtained. On the other hand, if _T95 is too low, the lubrication performance tends to decrease. For this reason, the 95% by volume distillation temperature of the gas oil base material of the present invention is preferably 220 ° C. or higher, more preferably 230 ° C. or higher. On the other hand, the upper limit of the 95% by volume distillation temperature is preferably 265 ° C. or lower, more preferably 250 ° C. or lower.

[0007] The sulfur content in the gas oil base is preferably small in order to maintain the durability of the exhaust gas aftertreatment device. In the present invention, the sulfur content is preferably 50 mass ppm or less, more preferably 30 mass pp.
m, especially 10 ppm by mass or less.

[0008] The light oil base material used in the present invention has the above-mentioned properties, but other properties are preferably as follows. 10% by volume distillation temperature (T ₁₀ ): 170 to 250 ° C. 50% by volume distillation temperature (T ₅₀ ): 185 to 210 ° C. 90% by volume distillation temperature (T ₉₀ ): 210 to 260 ° C. Distillation end point (EP) : 230 to 280 ° C Density ＠ (15 ° C): 780 to 805 kg / cm ³ Aromatic content: 23% by volume or less Flash point: 40 to 55 ° C Smoke point: 23 ° C or more

The properties of the gas oil base material used in the present invention will be described in more detail. Distillation temperature of 10% by volume of gas oil base material (T ₁₀ )
If the temperature is too low, the amount of hydrocarbons in the exhaust gas tends to increase, while if the temperature is too high, problems tend to occur in low-temperature startability and low-temperature stability. For this reason, the distillation temperature of 10% by volume of the gas oil base material used in the present invention is preferably 170 ° C. or higher, more preferably 175 ° C. or higher. On the other hand, the upper limit of the distillation temperature of 10% by volume is preferably 250 ° C. or less,
More preferably, the temperature is 200 ° C. or lower. With respect to the distillation temperature (T ₅₀ ) of ₅₀ % by volume of the gas oil base, if this temperature is too low, the amount of hydrocarbons in the exhaust gas tends to increase, while if the temperature is too high, the exhaust gas PM concentration tends to increase. Therefore, the light oil base material 5 used in the present invention
The distillation temperature at 0% by volume is preferably 185 ° C. or higher, more preferably 195 ° C. or higher. On the other hand, the upper limit of the distillation temperature of 50% by volume is preferably 210 ° C. or lower, more preferably 205 ° C. or lower.

Distillation temperature of 90% by volume of gas oil base material (T ₉₀ )
If this temperature is too high, the PM in the exhaust gas
The concentration tends to increase. On the other hand, if the temperature is too low,
Lubrication performance tends to decrease. For this reason, the distillation temperature of 90% by volume of the gas oil base material used in the present invention is preferably 210 ° C. or higher, more preferably 220 ° C. or higher.
On the other hand, the upper limit of the 90% by volume distillation temperature is preferably 260 ° C. or lower, more preferably 240 ° C. or lower. Regarding the distillation end point (EP) of the gas oil base, if this temperature is too high, the PM concentration in the exhaust gas tends to increase. On the other hand, if the temperature is too low, the lubricating performance tends to decrease. For this reason, the distillation end point of the gas oil base material used in the present invention is preferably 230 ° C. or higher, more preferably 240 ° C. or higher. On the other hand, the upper limit of the distillation end point is 280
° C or lower, more preferably 260 ° C
It is as follows.

The aromatic content in the gas oil base material is related to the respective concentrations of NOx and PM contained in the exhaust gas. If the content is too large, the respective concentrations of NOx and PM in the exhaust gas increase. Easier to do. For this reason, the aromatic content is preferably 23% by volume or less, more preferably 15% by volume or less. Here, the aromatic content means the volume% of the aromatic content measured in accordance with the fluorescent indicator adsorption method of "Petroleum products-component test method" specified in JIS K 2536.

If the density of the gas oil base at 15 ° C. is too small, it is difficult to obtain a sufficient fuel consumption rate and acceleration. On the other hand, if the value is too large, the effect of reducing the PM concentration in the exhaust gas cannot be sufficiently obtained. Therefore, the density of the gas oil base material used in the present invention is 78
It is preferably 0 kg / m ³ or more. The upper limit of the density of the gas oil base material, is preferably 805kg / m ³ or less, more preferably 800 kg / m ³ or less. Here, the density means a density measured according to JIS K 2249 "Determination of density of crude oil and petroleum products and conversion table of density / mass / capacity".

If the value of the flash point of the light oil base material is too high, it is difficult to sufficiently obtain the effect of reducing the PM concentration in the exhaust gas. On the other hand, if this value is too low, the amount of hydrocarbons in the exhaust gas tends to increase. For this reason, the flash point of the gas oil base material used in the present invention is preferably 40 ° C. or higher, more preferably 45 ° C. or higher. On the other hand, the upper limit of the flash point of the gas oil base material is preferably 55 ° C. or less,
More preferably, it is 50 ° C. or lower. Here, the flash point is
Flash point measured according to JIS K 2265 "Crude oil and petroleum products-Flash point test method".

If the value of the smoke point of the light oil base is too low, the effect of reducing the PM concentration in the exhaust gas cannot be sufficiently obtained. For this reason, the light oil base used in the present invention preferably has a smoke point of 23 ° C. or higher, more preferably 27 ° C. or more.
° C or higher. Here, the smoke point is defined by JIS K 2537
Means the smoke point measured by "Petroleum products-aviation turbine fuel oil and kerosene-Smoke point test method".

The light oil base material used in the present invention contains at least 50% by volume or more in the base light oil. The upper limit is adjusted depending on the gas oil composition having the desired performance. The upper limit is preferably 99% by volume, and more preferably 95% by volume.
%, Particularly preferably 90% by volume, most preferably 85% by volume.

The base gas oil used in the present invention can be prepared by mixing a gas oil base material having the above-mentioned properties as a main component and a gas oil base material having other properties so as to obtain properties of a final purpose. Further, the light oil base material and other light oil base materials of the present invention can be prepared using various light oils obtained by a known method. Examples of the gas oil base material include straight-run gas oil obtained from a normal-pressure distillation apparatus for crude oil; reduced-pressure gas oil obtained by subjecting a straight-run heavy oil or residue oil obtained from a normal-pressure distillation apparatus to a low-pressure distillation apparatus; Hydrorefined gas oil obtained by hydrorefining reduced-pressure gas oil obtained from the above; hydrodesulfurized gas oil obtained by hydrodesulfurizing straight-run gas oil in one or more stages under severer conditions than ordinary hydrorefining; Catalytic cracking gas oil obtained by catalytic cracking of desulfurized or undesulfurized vacuum gas oil, vacuum heavy gas oil or desulfurized heavy oil; straight kerosene obtained by atmospheric distillation of crude oil; hydrogen obtained by hydrorefining straight kerosene One or more kinds of refined kerosene; cracked kerosene obtained by cracking a gas oil fraction obtained by atmospheric distillation of crude oil can be used. When the sulfur content in the gas oil base material used in the present invention exceeds 80 mass ppm, the sulfur content is adjusted to a predetermined level by using an appropriate means such as hydrorefining (desulfurization treatment). Can be. In addition, when preparing the gas oil composition of the present invention, if the sulfur content of the base gas oil exceeds 500 ppm by mass, the desulfurization treatment as described above is performed prior to the addition of the cetane number improver and the like. To reduce the sulfur content to 500 ppm by mass or less.

The light oil composition of the present invention comprises the above-mentioned base light oil containing a cetane improver. As the cetane improver, various compounds known in the art as a cetane improver can be optionally used. For example, nitrate esters and organic peroxides can be mentioned. The cetane improver used in the present invention is preferably a nitrate ester. Examples of the nitrate include 2-chloroethyl nitrate, 2-ethoxyethyl nitrate, isopropyl nitrate, butyl nitrate, primary amyl nitrate, secondary amyl nitrate, isoamyl nitrate, and primary hexyl nitrate. , Second hexyl nitrate, n-heptyl nitrate, n-octyl nitrate, 2-ethylhexyl nitrate, cyclohexyl nitrate, and various nitrates such as ethylene glycol dinitrate. Among these, an alkyl nitrate having 6 to 8 carbon atoms is preferable. 1 as cetane number improver
One kind of compound may be used alone, 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 or more based on the total amount of the composition. If the content is less than 500 ppm by mass, the NOx concentration, PM concentration, aldehyde The concentration cannot be reduced to a satisfactory level. In the light oil composition of the present invention, the content of the cetane number improver defined on the basis of the total amount of the composition is preferably 600 mass ppm or more, more preferably 700 mass ppm or more, and 800 mass Particularly preferably, it is at least 900 ppm by mass.
Although the upper limit of the content of the cetane improver is not particularly limited in the present invention, it is 1400 mass p based on the total amount of the gas oil composition.
pm or less, more preferably 1250 mass ppm or less, particularly preferably 1100 mass ppm or less, and most preferably 1000 mass ppm or less.

Commercially available products called cetane number improvers are generally obtained in the form of an active ingredient that contributes to cetane number improvement, that is, the cetane number improver 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 of the active ingredient in the gas oil composition is 500 mass p based on the total amount of the composition.
It is important that the speed is at least pm.

The cetane index of the gas oil composition of the present invention is 45 or more. If the cetane index is less than 45, the concentrations of NOx, PM, and aldehyde in the exhaust gas may increase. In the present invention, the cetane index is preferably 47 or more, more preferably 48 or more, and most preferably 50 or more.

Here, the cetane index refers to JIS K22
80 means the value calculated by the "method of calculating cetane index using 8.4 variable equation" in "Petroleum products-fuel oil-Test method of octane number and cetane number and method of calculating cetane index". Note that the cetane index in the above JIS standard is not applied to the case where the cetane number improver is added, but in the present invention, the cetane index of the case where the cetane number improver is added is also calculated using the above “8.4 variable equation”. Calculation method of the calculated cetane index ".

In the light oil composition of the present invention, there is no particular limitation on the cetane number, but the cetane number is preferably adjusted to 45 or more by adding the cetane number improver. It is more preferably at least 50, and most preferably at least 50. By setting the cetane number to 45 or more, NOx, P
Each concentration of M and aldehyde can be further reduced. Here, the cetane number means a cetane number measured according to "7. Cetane number test method" in JIS K 2280 "Petroleum products-fuel oil-Octane number and cetane number test method and cetane index calculation method". .

The gas oil composition of the present invention has a 90% by volume distillation temperature (T ₉₀ ) of 330 ° C. or less. When the T ₉₀ exceeds 330 ° C., there is a possibility that the concentration of PM in exhaust gas is increased. In the present invention, T ₉₀ is preferably 325 ° C. or less, more preferably 320 ° C. or less, and particularly preferably 315 ° C. or less. There is no particular restriction on the lower limit of T _90, further improve the fuel economy, in order to increase the output of the engine, T ₉₀ 280
C. or higher, more preferably 285.degree. C. or higher.

The gas oil composition of the present invention is not particularly limited distillation characteristics other than T _90, it is desirable to satisfy the properties described below. Initial boiling point: 135 to 180 ° C. 10% by volume distillation temperature (T ₁₀ ): 155 to 210 ° C. 30% by volume distillation temperature (T ₃₀ ): 175 to 250 ° C. 50% by volume distillation temperature (T ₅₀ ): 190 ２270 ° C. 70% by volume distillation temperature (T ₇₀ ): 220-300 ° C. 95% by volume distillation temperature (T ₉₅ ): 290-360 ° C. Distillation end point: 320-360 ° C.

The distillation properties of the gas oil composition of the present invention will be described in more detail. If the initial boiling point of the gas oil composition is too low,
The initial boiling point is preferably 135 ° C. or higher because some light fractions are vaporized and the spray range becomes too wide, and the amount of hydrocarbons entrained in the exhaust gas may increase as unburned matter. , More preferably 140 ° C or higher, particularly preferably 145 ° 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 upper limit of the initial boiling point is preferably 180 ° C, more preferably 170 ° C.

[0026] For T ₁₀ of the gas oil composition may be too low, for the same reasons as in the case initial boiling point is too low, the increase in the amount of hydrocarbons entrained in the exhaust gas is concerned, T ₁₀ 155
℃ or more, more preferably 160 ℃
Above, particularly preferably 165 ° C. or higher. On the other hand, if it is too high, there is a fear that caused a problem in cold startability and low temperature operability, it is preferable that T ₁₀ is 210 ° C. or less, more preferably 205 ° C. or less, particularly preferably at 200 ° C. or less .

If T _{30 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 described above. Therefore, it is preferable that T ₃₀ is 175 ° C. or higher, more preferably 180 ° C. or higher, particularly preferably 185 ° C. or higher. On the other hand, if it is too high, since it can cause trouble in the low temperature startability and low temperature operability, T ₃₀ is preferably at 250 ° C. or less, more preferably 230 ° C. or less, particularly preferably 210 ° C. It is as follows.

The T _{50 of the} light oil composition is preferably 190 ° C. or higher, more preferably 195 ° C. or higher, particularly preferably 200 ° C. or higher, from the viewpoint of fuel efficiency and engine output. In reducing the PM concentration in the exhaust gas, T ₅₀ is preferably 270 ° C. or lower, more preferably 260 ° C. or lower, 250 ° C. or lower, and preferably 240 ° C. or lower, and particularly preferably 230 ° C. or lower. , Most preferably 225 ° C or lower.

[0029] Similarly as the T ₇₀ is also T ₅₀ of the gas oil composition, influence the fuel consumption and engine output. T ₇₀ is preferably 220 ° C. or more, more preferably 225 ° C. or more, and particularly preferably 230 ° C. or more, in order to further improve fuel efficiency and further increase the output of the engine. And the PM in the exhaust gas
In order to further reduce the concentration, T ₇₀ is preferably 300 ° C. or lower, more preferably 290 ° C. or lower, 280 ° C. or lower, and more preferably 270 ° C. or lower, particularly preferably 26 ° C. or lower.
The temperature is 5 ° C. or less, most preferably 260 ° C. or less.

[0030] It is desirable T ₉₅ of the gas oil composition is 290 ° C. or more, in order to further reduce the PM concentration in the exhaust gas is preferably T ₉₅ is 360 ° C. or less, further 355 ° C. or less , 350 ° C or below, and 345 ° C
It is preferably in the following order, particularly preferably 342 ° C or lower, and most preferably 340 ° C or lower.

The distillation end point of the gas oil composition is desirably 320 ° C. or higher. However, in order to further reduce the PM concentration in the exhaust gas, the distillation end point is preferably at most 360 ° C, more preferably at most 355 ° C, particularly preferably at most 355 ° C.
50 ° C. or less. Distillation properties (initial boiling point, T
₁₀ , T ₃₀ , T ₅₀ , T ₇₀ , T ₉₀ , T ₉₅ , distillation end point) are all values measured in accordance with JIS K 2254 “Petroleum Products-Distillation Test Method”.

The gas oil composition of the present invention has a sulfur content of 50
It is 0 mass ppm or less. If the sulfur content of the gas oil composition exceeds 500 ppm by mass, the durability of the exhaust gas after-treatment device may be deteriorated, or corrosion inside the engine may be caused. In the present invention, this value is preferably 350 mass ppm or less, more preferably 200 mass ppm or less, even more preferably 150 mass ppm or less, and particularly preferably 100 mass ppm or less. , 50 mass ppm or less. Here, the sulfur content refers to JIS K 2
541 means the sulfur content based on the total amount of the gas oil composition measured by the "sulfur content test method".

The kinematic viscosity at 30 ° C. of the light oil composition of the present invention is 1.7 mm ² / s or more. If it is less than 1.7 mm ² / s, there is a concern that the control of the fuel injection timing becomes difficult, and the lubricity of the distribution type fuel injection pump attached to the engine tends to be impaired. This kinematic viscosity is 1.72 m
m ² / s or more, preferably 1.73 mm ² / s
In further preferably more, even more preferably at 1.75 mm ² / s or more, 1.78 mm ² /
s or more is particularly preferable, and 1.80 mm ² / s
It is most preferred that this is the case.

The upper limit of the kinematic viscosity at 30 ° C. is not particularly limited, but is preferably 3.5 mm ² / s or less, since the PM concentration in the exhaust gas can be further reduced. still more preferably 0 mm ² / s or less, even more preferably at most 2.5 mm ² / s, particularly preferably not more than 2.4 mm ² / s, is 2.2 mm ² / s or less Is most preferred. Here, the kinematic viscosity is JIS K 2283.
It means the kinematic viscosity measured by "crude oil and petroleum products-kinematic viscosity test method and viscosity index calculation method".

Density of the gas oil composition of the present invention at 15 ° C.
There is no particular limitation on. However, the fuel consumption rate and
Acceleration can be further improved, so its value
Is 802 kg / m^ThreeIt is preferable that it is above. on the other hand,
The upper limit of the density at 15 ° C is the PM concentration in the exhaust gas.
840 kg / m ^Three
835 kg / m^ThreeBelow
More preferably, 830 kg / m^ThreeMust be
Is still more preferred, and 820 kg / m^ThreeIs less than
Is particularly preferred, and 815 kg / m^ThreeMust be
Is most preferred. Here, the density refers to JIS K224.
9 "Crude oil and petroleum products density test method, density and mass
-Means the density measured by the "capacity conversion table".

In the gas oil composition of the present invention, the content of each of the saturated component, the olefin component and the aromatic component is not particularly limited, but is preferably the following composition. Saturated content: 60 to 95% by volume Olefin content: 0 to 5% by volume Aromatic content: 5 to 40% by volume The saturated content of the gas oil composition is determined by the NOx and PM in the exhaust gas. For lowering the concentration, it is preferably at least 60% by volume, more preferably at least 65% by volume,
It is particularly preferably at least 70% by volume, most preferably at least 75% by volume. On the other hand, in order to maintain good low-temperature startability and low-temperature operation, the content of the saturated component is preferably 95% by volume or less, more preferably 90% by volume or less, and particularly preferably 85% by volume or less. .

The olefin content of the gas oil composition is preferably in the range of 0 to 5% by volume, more preferably 0 to 1% by volume, from the viewpoint of the stability of the composition.

The aromatic content of the gas oil composition is preferably 5% by volume or more, more preferably 8% by volume or more, more preferably 10% by volume or more, because it is related to the fuel consumption rate and the engine output. , Even more preferably 12
% Or more, most preferably 15% or more. On the other hand, the aromatic content is determined by the NOx contained in the exhaust gas.
The content is preferably 40% by volume or less, more preferably 35% by volume or less, particularly preferably 30% by volume or less, and most preferably 25% or less because it is related to the respective concentrations of PM and PM.

In the gas oil composition of the present invention, the content of aromatics having two or more rings is preferably 3% by volume or less among the above aromatics. Thereby, each concentration of hydrocarbon (HC), NOx, and PM contained in the exhaust gas can be further reduced. This content is 2% by volume
The content is more preferably at most 1%, particularly preferably at most 1% by volume, most preferably at most 0.5% by volume. For the same reason, the content of aromatics containing three or more rings is 1% by volume.
It is preferably at most 0.5% by volume, more preferably at most 0.5% by volume, particularly preferably at most 0.3% by volume.

Here, the content of the saturated component, the content of the olefin component, and the content of the aromatic component are defined as the saturated component measured in accordance with the fluorescent indicator adsorption method of “Petroleum products-component test method” specified in JIS K 2536. , Olefin content and aromatic content by volume (% by volume). The aromatic content of two or more rings is determined according to the Japan Petroleum Institute standard JIS 5S49-
“Petroleum products-Test methods for hydrocarbon types” specified in 97
% By volume of an aromatic component having two or more rings as measured by "high performance liquid chromatography".

The gas oil composition of the present invention has no particular restriction on its pour point. However, the pour point of the composition is preferably −5 ° C. or lower, more preferably −10 ° C. or lower, and particularly preferably −20 ° C. or lower, from the viewpoint of low-temperature startability or low-temperature operation. -30 ° C
It is most preferred that: Here, the pour point is J
It refers to the pour point measured by IS K 2269 "Pour point of crude oil and petroleum products and cloud point test method of petroleum products".

The gas oil composition of the present invention has no particular restriction on the clogging point. However, the clogging point of the composition is preferably -1C or lower, more preferably -5C or lower, even more preferably -12C or lower, and preferably -19C or lower. Most preferred. Here, the clogging point is defined in JIS K 2288.
It means the clogging point measured by "light oil-clogging point test method".

Additives other than the above-mentioned cetane number improver can be added to the light oil composition of the present invention, if necessary.
In particular, it is preferable to add a lubricity improver and / or a detergent. As the lubricity improver, for example, one or more of carboxylic acid type, ester type, alcohol type and phenol type lubricity improvers can be arbitrarily used. Of these, carboxylic acid-based and ester-based lubricity improvers are preferred. As the carboxylic acid-based lubricity improver, for example, linoleic acid, oleic acid, salicylic acid,
Palmitic acid, myristic acid, hexadecenoic acid and the above carboxylic acids can be mentioned. Examples of the ester-based lubricity improver include carboxylic acid esters 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, and hexadecenoic acid. Can be mentioned.

The amount of the lubricity improver is not particularly limited. However, in order to bring out the effects of the compounded lubricity improver, specifically, in a diesel engine equipped with a distribution type injection pump, the increase in the driving torque of the pump during operation is suppressed and the wear of the pump is reduced. Therefore, the compounding amount of the lubricity improver is 35 mass ppm based on the total amount of the composition.
Or more, more preferably 50 mass ppm or more. And since the upper limit of the compounding amount cannot obtain the effect corresponding to the adding amount even if it is added more,
It is preferably at most 140 mass ppm, more preferably at most 105 mass ppm.

Examples of the detergent include: imide compounds; alkenyl succinic acid derivatives such as polybutenyl succinimide synthesized from polybutenyl succinic anhydride and polyamines; and polyhydric alcohols such as pentaerythritol. Succinic esters such as polybutenylsuccinic esters synthesized from polybutenylsuccinic anhydrides; copolymers such as dialkylaminoethyl methacrylate, polyethylene glycol methacrylate, and copolymers of vinylpyrrolidone and alkyl methacrylate; carboxylic acids And amine reaction products (salts and the like). One or more of these ashless detergents can be arbitrarily selected, and among them, 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).

[0047]

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, provided that the total number of carbon atoms in R ^{1 to} R ⁴ is 2, and R ⁵ is an alkylene group having 1 to 36 carbon atoms. And m represents an integer of 1 to 100. )

[0049]

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, provided that the total number of carbon atoms in R ^{1 to} R ⁴ is 2, and R ⁵ is an alkylene group having 1 to 36 carbon atoms. And m represents an integer of 1 to 100, and n represents an integer of 1 to 10. )

[0051]

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, provided that the total number of carbon atoms in R ^{1 to} R ⁴ is 2, and R ⁵ is an alkylene group having 1 to 36 carbon atoms. Represents, m
Represents an integer of 1 to 100, and n represents an integer of 1 to 10. )

[0053]

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, provided that the total number of carbon atoms in R ^{1 to} R ⁴ is 2, and R ⁵ is an alkylene group having 1 to 36 carbon atoms. Represents, m
Represents an integer of 1 to 100, 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. Tert
-A butyl group is preferred. R ^{1 to} R ⁴ each represent a hydrogen atom, a methyl group or an ethyl group. And
The total carbon number of R ^{1 to} R ⁴ is 2. In the present invention, since better detergency is 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 ³ are both It is preferred that the compound is a methyl group and R ² and R ⁴ are both 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 them, 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. n is
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) has a structural unit represented by the following formula (1):
1 shows a polymer skeleton of an alkenyl succinic acid derivative represented by any one of (1) to (4).

[0059]

Embedded image

(R ¹ , R ² , R ³ , R ⁴ and m in the above formulas (5) and (6) are represented by the general formulas (1) to (4)
And the same groups and integers as those for R ¹ , R ² , R ³ , R ⁴ and m. )

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 above equations (1) to
The compound represented by (4) and the group represented by the above formula (5) may be a homopolymer or a copolymer. The copolymer may be any of a random copolymer, an alternating polymer, and a block copolymer.

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 a mixture of two or more compounds may be used. You may. When two or more kinds are used, a mixture of a compound represented by the general formula (2) and a compound represented by the general formula (3) is preferable. The mixing ratio (mass ratio) at that time is preferably (2) :( 3) = 1: 99-99: 1, more preferably 10: 90-90: 10, and 20: 80- The ratio is even more preferably 80:20, and most preferably 30:70 to 70:30.

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

[0065]

Embedded image Compound 1 represented by the following formula (number average molecular weight: 2
000-3000) (A: tert-butyl group, R ¹ , R ³ : hydrogen atom,
R ² , R ⁴ : methyl group, R ⁵ : trimethylene group)

[0066]

[Image Omitted] Compound 2 represented by the following formula (number average molecular weight: 2
000-3000) (A: tert-butyl group, R ¹ , R ³ : hydrogen atom,
R ² , R ⁴ : methyl group, R ⁵ : ethylene group, n: 1 to 3)

[0067]

Embedded image Compound 3 represented by the following formula (number average molecular weight: 4)
000-6000) (A: tert-butyl group, R ¹ , R ³ : hydrogen atom,
R ² , R ⁴ : methyl group, R ⁵ : ethylene group, n: 1 to 3)

[0068]

Embedded image Compound 4 represented by the following formula (number average molecular weight: 2
000-3000) (A: tert-butyl group, R ¹ , R ³ : hydrogen atom,
R ² , R ⁴ : methyl group, R ⁵ : ethylene group, n: 1 to 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 7 to 30 carbon atoms,
Particularly preferred are those having 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 is a fatty acid, an alicyclic carboxylic acid,
Any of aromatic carboxylic acids may be used, but fatty acids are preferred. The fatty acid may be linear or branched, and may be saturated or unsaturated.

Specific examples of the fatty acid having 9 to 20 carbon atoms include the following. Linear or branched nonanoic acid, linear or branched decanoic acid,
Straight or branched undecanoic acid, straight or branched dodecanoic acid, straight or branched tridecanoic acid, straight or branched tetradecanoic acid, straight or branched pentadecanoic acid, straight or branched chain Hexadecanoic acid, linear or branched heptadecanoic acid, linear or branched octadecanoic acid, linear or branched nonadecanoic acid, linear or branched icosanoic acid, linear or branched nonenic acid, Linear or branched undecenoic acid, linear or branched dodecenoic acid, linear or branched 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 (including oleic acid), Nonadecenoic acid chain or branched chain, such as icosenoic acid straight or branched chain. Further, a fatty acid containing a hydroxyl group such as linoleic acid is 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. Examples of the monoamine include a mono-substituted amine having one hydrocarbon group, a di-substituted amine having two hydrocarbon groups, and a tri-substituted amine having three hydrocarbon groups, and a mono-substituted amine is preferable.

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, linear or branched undecylamine, and linear Or branched dodecylamine, straight or branched tridecylamine, straight or branched tetradecylamine, straight or branched pentadecylamine, straight or branched hexadecylamine, straight or Examples include branched heptadecylamine, linear or branched octadecylamine, and the like.

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 , 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 containing oleic acid as a main component, a monosubstituted amine having an alkyl group having 8 to 16 carbon atoms, and a monosubstituted amine having 8 to 16 carbon atoms. And a salt with a mixture of monosubstituted amines having an alkenyl group.

There is no particular limitation on the amount of the detergent. 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 is preferably 20 ppm by mass or more based on the total amount of the gas oil composition. It is more preferably at least 80 ppm by mass, particularly preferably at least 80 ppm by mass. Even if the amount is less than 20 ppm by mass, the effect may not be exhibited. On the other hand, if the amount is too large, a corresponding effect cannot be expected, and conversely, each concentration of NOx, PM, aldehyde, etc. in the exhaust gas of the diesel engine may be increased. It is preferably at most 300 mass ppm, more preferably 2
50 mass ppm or less, particularly preferably 200 mass ppm or less, most preferably 180 mass ppm.
It is as follows.

As in the case of the cetane number improver,
Commercially available products referred to as lubricity improvers or detergents are generally obtained in a state where active ingredients contributing to lubricity improvement or cleaning are diluted with a suitable solvent. When such a commercially available product is blended with the light oil composition of the present invention, the above-mentioned blending amount of the lubricity improver and the detergent means the blending amount as an active ingredient.

To the gas oil composition of the present invention, other known fuel oil additives can be added alone or in combination of several kinds in order to further enhance the performance. These additives include, for example, low-temperature fluidity improvers such as ethylene-vinyl acetate copolymer and alkenyl succinamide; phenol-based and amine-based antioxidants; metal deactivators such as salicylidene derivatives; Anti-freezing agents such as polyglycol ethers; Corrosion inhibitors such as aliphatic amines and alkenyl succinates; Antistatic agents such as anionic, cationic and amphoteric surfactants; Colorants such as azo dyes; And the like. The addition amount of these additives can be arbitrarily determined, but the addition amount of each additive is usually 0.5% by mass or less, preferably 0.2% by mass or less based on the total amount of the gas oil composition. .

The gas oil composition of the present invention can be produced by using a known method. Usually, it is manufactured by blending a predetermined amount of a cetane number improver and, if necessary, a lubricating oil improver, a detergent, and other additives with the base gas oil.

[0079]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

Light oil bases having the following properties (light bases,
Formulation base materials) A to E were prepared.

[0081]

[Table 1]

Preparation of Light Oil Composition Each light oil composition having the properties and compositions shown in Table 2 was prepared using the base material shown in Table 1 above. The following additives were used. Cetane number improver: 2-ethylhexyl nitrate Lubricity improver: Carboxylic acid mixture containing linoleic acid as a main component Detergent: C13 containing oleic acid as a main component
Of a mixed fatty acid having from 20 to 20 and a mixture of a monosubstituted amine having an alkyl group having 8 to 16 carbon atoms and a monosubstituted amine having an alkenyl group having 8 to 16 carbon atoms

Using each gas oil composition shown in Table 2, (1)
Engine test 1, (2) Engine test 2, (3) Lubricity test and (4) Nozzle cleanliness test were performed. Table 2 shows the test results. (1) Engine test 1 The following engine was used to measure PM, hydrocarbon (HC) and NOx in exhaust gas under three conditions simulating actual running. PM was collected on a filter using a mini-dilution tunnel manufactured by Horiba, and the weight of the PM was measured. HC and NOx were measured by sampling directly from the exhaust pipe. (Engine specifications) Engine type: naturally-aspirated in-line 6-cylinder diesel Displacement: 7.1 L Inner diameter x stroke: 110 mm x 125 mm Compression ratio: 17.5 Maximum output: 260 ps / 2700 rpm Maximum torque: 77 kgf (754.6 N) / 2700 rpm (Conditions) Condition 1: TRIAS 24-5-1993 Condition 2: Mode simulating low-speed running Condition 3: Mode simulating high-speed running

(2) Engine test 2 The exhaust pipe of the following engine was led to the DPF device, and the PM in the exhaust gas discharged from the DPF device was measured by TRIAS 24.
It measured under the conditions of -5-1993. PM was collected on a filter using a mini-dilution tunnel manufactured by Horiba, and the weight of the PM was measured. (Engine specifications) Engine type: Natural-intake in-line 4-cylinder diesel Displacement: 4.985L Inner diameter x stroke: 115mm x 125mm Compression ratio: 19.5 Maximum output: 150ps / 3100rpm Maximum torque: 37kgf (362.6N) / 1600 rpm

(3) Lubricity test An HFRR test was performed under the following conditions, and the diameter of a circular scratch on the test ball after the test in the vibration direction and the diameter in the direction perpendicular to the vibration direction were measured, and the average value was obtained. Was defined as a wear scar diameter (WSD). Test ball Material: ANSI 52100 Hardness: 645HV30 Surface roughness: 0.1 μmRa or less Diameter: 6.25 nm Test plate Material: ANSI 52100 Hardness: 180HV30 Surface roughness: 0.1 μmRa or less Load: 2N Test temperature: 60 ° C. Stroke: 1 .0mm Frequency: 50Hz Time: 75 minutes

(4) Nozzle cleanliness test A 4-cylinder engine with a displacement of 2 L was used,
Continuous operation was performed for 48 hours under the conditions of pm and torque of 36.4 Nm, and the residual flow rate of the nozzle after the test was measured. The remaining nozzle flow rate indicates the ratio of the nozzle flow rate after the test to the flow rate of the new nozzle before the test. The nozzle flow rate was measured at a needle valve lift of 0.1 mm. In this test, the larger the value of the nozzle residual flow rate ratio, the better the cleanliness.

[0087]

[Table 2]

Continuing on the front page (72) Inventor Hiroaki Watanabe 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Prefecture Inside the Nippon Central Research Laboratory (72) Inventor Chikako Kaise 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Prefecture F-term in Mitsubishi Technical Research Institute (reference) 4H015 AA23 AB05

Claims (1)

[Claims] 1. An initial boiling point of 145 ° C. or higher, 95% by volume distillation
Temperature of 270 ° C or less and sulfur content of 80 mass pp
m at least 50% by volume of light oil base material
A cetane number improver is added to the base gas oil at 500 based on the total amount of the composition.
9 ppm or more by mass, and a cetane index of 45 or more, 9
0% by volume distillation temperature is 330 ° C or less, sulfur content is 50%
0 ppm by mass or less and a kinematic viscosity at 30 ° C. of 1.
7mm ^Two/ S or more.