JPH09194859A - Fuel oil composition for diesel engine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fuel oil composition for diesel engines coping with environmental pollution problems reduced in the amount of particulate substances contained in the exhaust gases formed during combustion. SOLUTION: This composition comprises a mineral oil as a base and 1-15wt.% at least one maleic or fumaric ester represented by the formula: R1 OOCCH=CHCOOR2 (wherein R1 is H, an alkyl or an alkenyl or a phenyl which may be substituted by an alkyl; and R2 is an alkyl, an alkenyl or a phenyl which may be substituted by an alkyl).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel fuel oil composition for a diesel engine. More specifically, it relates to a fuel oil composition for a diesel engine, which comprises mineral oil as a main component and contains a specific ester compound in an amount of 1 to 15% by weight. Such a fuel oil composition for a diesel engine is an environmental pollution countermeasure diesel vehicle that reduces the emission amount of particulate matter (hereinafter, also referred to as particulates or Ptc.) In exhaust gas generated during combustion. Very useful as engine fuel oil.

[0002]

2. Description of the Related Art Airborne particulate matter is defined by the Air Pollution Control Act as being a particulate matter suspended in the atmosphere and having a particle size of 10 μm or less. On a global scale, most of these particulate matter are naturally-occurring, such as dust from sea salt particles and dust piled up, smoke from forest fires, and volcanic ash associated with volcanic eruptions.
However, suspended particulate matter that causes air pollution in densely populated areas such as urban areas is Ptc. A large percentage is derived from.

Ptc. Is a mixture of mainly carbides, unburned fuel oil and unburned lubricating oil, and sulfur compounds mainly composed of sulfuric acid mist. In addition, Ptc. The constituents such as carbides are also the causative substances of black smoke. Therefore, reducing the exhaust smoke concentration (hereinafter also referred to as smoke) of the exhaust gas is performed by Ptc. Will lead to the reduction of P
tc. In order to reduce the emission amount of Ptc., The structure of the combustion chamber, the mechanism of the engine, the exhaust gas purifying catalyst device, Ptc. Although efforts have been made from various aspects such as the collecting device, the fuel oil, and the lubricating oil, the effect of reducing the economical efficiency and the stability of the performance over a long period of time have not yet been obtained.

However, the method for improving the fuel oil is important as a method for reducing the fuel oil since it requires almost no modification of the diesel engine. For example, JP-A-59-1153
No. 90 describes a diesel fuel obtained by adding water and an aliphatic alcohol to a diesel fuel, which has excellent phase stability and thermodynamic stability and which reduces the generation of smoke particles and NOx. ing.

Japanese Patent Laid-Open No. 232176/1984 discloses a gas oil containing a specific polyoxyalkylene compound as an essential component.
Fuel compositions for diesel engines with reduced concentration and reduced amount of particulates are described. Here, the specific polyoxyalkylene compound contains an organic residue, an alkyl group and a hydrocarbon group in its molecular structure, and has an average molecular weight of 400 to 6000.

Japanese Unexamined Patent Publication No. 7-18271 discloses NOx and HC in combustion exhaust gas from a diesel engine.
As a fuel oil additive capable of significantly reducing odor and black smoke of combustion exhaust gas, a diesel engine fuel modifier containing a glycol ether compound is Have been described.

Japanese Patent Application No. 6-141192 discloses a diesel engine capable of remarkably reducing suspended particulate matter including black smoke discharged into the atmosphere from a diesel engine during operation under high load. As fuel oil,
2-hydroxy-2-methylaliphatic carboxylic acid or ester thereof, polyoxyalkylene glycol or a derivative thereof in which both terminal groups contain either ether bond, ester bond or acyl bond, polymethylene dicarboxylic acid Diester, β-alkoxyisobutyric acid ester, 1,3-dioxolane or its derivative, 1,4-
Described is a fuel composition for a diesel engine to which one or more kinds of dioxane or a derivative thereof, 1,3-dioxane or a derivative thereof, and an oxygen-containing compound having a polyoxyalkylene group or a polyoxyphenylalkylene group as a skeleton are added. .

[0008] Further, as an additive containing a combustion aid, Japanese Patent Application Laid-Open No. 4-213391 discloses an additive for diesel fuel in which an overbased calcium sulfonate is dispersed in an organic solvent. ing. JP-A-7-7057
In JP-A-0, the soot emission of fuel oil can be remarkably reduced with a small amount, and for the purpose of improving the cetane number, an organic peroxide and a metal salt of an organic acid are used. Those using fuel additives containing compounds that are basides are described. However, the metal-containing additive itself is discharged as ash, that is, as ash, into the exhaust gas, and harms the human body.

Further, in Japanese Patent Laid-Open No. 3-234793, an effective component is used as a fuel oil for diesel engines, which has a much smaller amount of black smoke and NOx in exhaust gas than conventional mineral oil fuels, and has good ignitability and thermal efficiency. A fuel oil which is dimethyl acetal, and a fuel oil containing 50 to 100% by volume of dimethyl acetal in mineral oil are described.
However, it is difficult from a economical point of view to use a diesel engine fuel oil containing a large amount of dimethyl acetal on a daily basis as a fuel oil for transportation vehicles.

In Japanese Patent Laid-Open No. 7-145390, a nonionic surfactant is added to a fuel oil such as gasoline, light oil or heavy oil to reduce the surface tension, and the fuel oil is injected into an engine room. By refining the particle size of oil, and because this nonionic surfactant is an oxygen-containing compound containing oxygen, it improves the combustion efficiency of fuel oil and improves the efficiency of combustion in exhaust gas during combustion. Described is a fuel oil additive characterized by reducing NOx, CO, and particulates.

However, in any of the above-mentioned conventional techniques, light oil is the main component, and Ptc.
It was not possible to obtain a fuel oil composition for a diesel engine with a further reduced emission amount of.

[0012]

DISCLOSURE OF THE INVENTION An object of the present invention is to improve the above-mentioned conventional technique and reduce the emission amount of particulate matter in exhaust gas generated during combustion for a diesel engine for environmental pollution countermeasures. To provide fuel oil.

[0013]

As a result of our intensive studies, we focused on oxygenated compounds as fuel oil additives.
By adding 1 to 15% by weight of a specific ester compound to mineral oil, it was found that the emission amount of particulate matter into exhaust gas generated during combustion was significantly reduced, and the present invention was completed. It was

That is, the present invention is mainly composed of mineral oil and has the chemical formula (1)

[0015]

Embedded image R ₁ OOCCH═CHCOOR ₂ (1) (wherein R ₁ is H, a phenyl group which may be substituted with an alkyl group, an alkenyl group or an alkyl group,
R ₂ is a phenyl group which may be substituted with an alkyl group, an alkenyl group or an alkyl group. The present invention provides a fuel oil composition for a diesel engine, which comprises 1 to 15% by weight of one or more ester compounds represented by the formula (1).

The present invention relates to the fuel oil composition for a diesel engine as described above, and the preferred embodiments thereof include the following. (1) The alkyl group is an alkyl group having 1 to 10 carbon atoms, the alkenyl group is an alkenyl group having 2 to 8 carbon atoms, and the phenyl group which may be substituted with the alkyl group is an alkyl group. The fuel oil composition for a diesel engine, which is a phenyl group which may be substituted with a group (total carbon number is 6 to 10). (2) The fuel oil composition for a diesel engine, wherein the blending ratio of the ester compound is 3 to 9% by weight, or the fuel oil composition for a diesel engine according to (1) above. (3) The fuel oil composition for a diesel engine, wherein the ester compound is ethyl maleate, or the fuel oil composition for a diesel engine according to the above (1) or (2).

Hereinafter, the present invention will be described in detail. (Fuel oil composition for diesel engine)
The fuel oil composition for a diesel engine is a mineral oil to which an ester compound is added. The amount of the ester compound added is 1 to 15% by weight, preferably 3 to 9% by weight. The ester compounds can be used alone or in combination of two or more kinds. Furthermore, when the addition amount of the ester compound is less than 1% by weight, Ptc. When the amount exceeds 15% by weight, the diesel fuel oil composition does not form a uniform liquid phase, and the reduction effect commensurate with the added amount cannot be obtained, which is economical. Not.

(A) Mineral Oil The mineral oil used in the present invention comprises 5 petroleum fractions having a flash point of 40 ° C. or higher and a distillation property of 90% and a distillation temperature of 360 ° C. or lower.
Fuel oil for diesel engines containing 0% or more can be used. For example, kerosene, light oil specified in JIS K2204, heavy oil A specified in JIS K2205, and the like. The above petroleum fraction is a petroleum fraction produced by distilling crude oil under atmospheric pressure, or a petroleum fraction produced by distilling crude oil under atmospheric pressure is further hydrocracked or pyrolyzed. Etc. can be used.

(B) Ester Compound The ester compound used in the present invention has the chemical formula (1)

[0020]

Embedded image R ₁ OOCCH═CHCOOR ₂ (1) (wherein R ₁ is H, an alkyl group, an alkenyl group or a phenyl group which may be substituted with an alkyl group,
R ₂ is a phenyl group which may be substituted with an alkyl group, an alkenyl group or an alkyl group. ) A maleic acid ester or a fumaric acid ester represented by the formula (1) is included. R ₁ and R ₂ may be the same or different. Preferably, the alkyl group has 1 to 10 carbon atoms, the alkenyl group has 2 to 8 carbon atoms, and the phenyl group which may be substituted with an alkyl group has 6 to 10 carbon atoms. The alkyl group and alkenyl group may be linear or branched. Examples of such ester compounds include maleic acid ester and fumaric acid ester. For example, maleic acid dimethyl ester, maleic acid diethyl ester, maleic acid dibutyl ester, maleic acid monoethyl ester, maleic acid monophenyl ester, maleic acid 2-ethylhexyl ester, fumaric acid dimethyl ester, fumaric acid diethyl ester, fumaric acid dibutyl ester, Examples include fumaric acid monoethyl ester, fumaric acid monophenyl ester, fumaric acid 2-ethylhexyl ester and the like. Ethyl maleate is preferred and includes both monoesters and diesters.

The ester compound used in the present invention can be used by dissolving it in a diluent, if desired. As the diluent, a known organic solvent can be used, and examples thereof include saturated aliphatic hydrocarbons such as n-hexane and n-dodecane, aromatic hydrocarbons such as xylene and toluene, and fuel oil such as light oil. . The amount of these diluents used is not particularly limited as long as it does not impair the performance of the fuel oil composition for a diesel engine of the present invention, but is usually 10 parts by weight with respect to 100 parts by weight of the ester compound.
１０００1000 parts by weight.

(C) Fuel Oil Additives If desired, known fuel oil additives may be used within a range that does not impair the performance of the fuel oil composition for a diesel engine of the present invention. Examples include cetane number improvers, antioxidants, metal deactivators, detergents and corrosion inhibitors. These additives are described, for example, in "Petroleum Product Additives" edited by Toshio Sakurai (Koshobo). For example, in the case of a cetane number improver, the addition amount of these additives is 0.1
However, the amount is not limited to this. These additives can be used alone or in combination of two or more kinds.

The fuel oil composition for a diesel engine according to the present invention is extremely useful as a fuel oil for a diesel engine which is a measure against environmental pollution and which reduces the emission of particulate matter into the exhaust gas generated during combustion. is there.

[0024]

EXAMPLES The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following embodiments. The following mineral oils and ester compounds were used in the following examples. (1) Mineral Oil Mineral oil having the physical properties shown in Table 1 was used.

[0025]

[Table 1] (2) Ester compound DEM: Diethyl maleate (manufactured by Tokyo Chemical Industry Co., Ltd .: M0010) was used.

(Examples 1 to 5) DEM was added to mineral oil.
(Diethyl maleate) was added and mixed well to prepare a fuel oil. An engine test was conducted on each fuel oil to measure the smoke reduction rate. The amount of DEM added is as shown in Table 2. The measurement results are shown in Table 2.

[0027]

[Table 2]

The engine test method is as follows. (A) Test engine: A direct injection diesel engine (4D33 type) manufactured by Mitsubishi Motors Corporation was used. Table 3 shows the main specifications.

[0029]

[Table 3]

(B) Engine test equipment and operating conditions:
The system diagram of the engine test apparatus is as shown in FIG. In FIG. 1, fuel oil is sent from a fuel tank (1) through a valve (2) to a engine (4) by a fuel pump (3). In the fuel pump (3), part of the fuel oil is returned to the fuel tank (1) via the return line (5) without being injected into the combustion chamber of the engine. Further, a part of the fuel oil can be collected from the middle of the return line (5). Fuel oil for engine tests is stored in different fuel tanks. Combustion air is taken into the engine (4) through the intake pipe (6). Part of the exhaust gas discharged from the exhaust pipe (7) of the engine is guided to the smoke meter (8), and the exhaust smoke concentration, that is, the smoke is measured. The engine operating conditions are
It is as shown in Table 4. The type of fuel oil sent to the engine (4) was switched by the valve (2). The engine speed and load (torque) were adjusted to predetermined operating conditions by a dynamometer (9).

[0031]

[Table 4]

(C) Smoke reduction rate measurement method: In the engine test apparatus, the engine was started using mineral oil to which DEM was not added as fuel oil, and the engine speed was 1920 rpm for the first 10 minutes, Torque 16kg
m, engine speed 1920 rpm for the next 60 minutes,
Warm-up operation was performed with a torque of 28 kg · m. Further, after performing steady operation for 15 minutes under the same operating conditions, the smoke was measured. At the start of measurement, after 5 minutes, 10 minutes, and 15 minutes, smoke was measured 3 times each, and the average value of all of them was used as the smoke of mineral oil. Next, with the same steady operation,
The fuel oil was switched to the fuel oil containing DEM, and when the recovery amount of the fuel oil from the return line reached 2 liters, the smoke of the fuel oil was measured in the same manner as above.
Then, the fuel was switched to another fuel oil having a different DEM addition amount, and the smoke was measured in the same manner. Finally, switching to mineral oil again, the smoke was measured in the same manner. The smoke reduction rate of the fuel oil was calculated according to the following equation.

[0033]

[Equation 1] (However, the smoke of mineral oil is the total average value of the smoke measured for mineral oil.) (D) Smoke measurement method: Measured according to JIS D8004 and JIS D1101.

As is clear from Table 2, the smoke reduction rate of the fuel oil containing DEM was superior to that of the fuel oil containing no DEM. That is, the fuel oil composition for a diesel engine of the present invention to which the ester compound is added is the Ptc. The amount was significantly reduced.

[0035]

As described above in detail and concretely,
According to the present invention, by adding 1 to 15% by weight of the ester compound represented by the chemical formula (1) to mineral oil,
A fuel oil composition for a diesel engine, in which the amount of particulate matter emitted into exhaust gas during combustion is remarkably reduced, is provided, and it is extremely useful as a fuel oil for a diesel engine against environmental pollution.

The reason why the fuel oil composition for a diesel engine of the present invention exhibits an excellent effect that the emission amount of the particulate matter into the exhaust gas generated during combustion as described above is remarkably reduced. About, we thought as follows.
That is, in a dynamic combustion reaction that changes with changes in engine operating conditions, substances that cause black smoke, such as generated and grown carbide, are effectively oxidized,
We thought. However, we do not insist on the propriety of such a reaction mechanism regarding the effect of the present invention. As a result, the fuel oil in which the ester compound is added to the mineral oil in an amount of 1 to 15% by weight has a significantly reduced discharge of particulate matter into the exhaust gas generated during combustion.

[Brief description of the drawings]

FIG. 1 is a system diagram of an engine test apparatus.

[Explanation of symbols]

 1 Fuel Tank 2 Valve 3 Fuel Pump 4 Engine 5 Return Line 6 Intake Pipe 7 Exhaust Pipe 8 Smoke Meter 9 Dynamometer

Claims (1)

[Claims] 1. A mineral oil as a main component, represented by the chemical formula (1): R ₁ OOCCH = CHCOOR ₂ ... (1) (wherein R ₁ is substituted with H, an alkyl group, an alkenyl group or an alkyl group). A phenyl group which may be
R ₂ is a phenyl group which may be substituted with an alkyl group, an alkenyl group or an alkyl group. 1 to 15% by weight of at least one ester compound represented by the formula (1).