JP2002327185A - Biodiesel fuel oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a biodiesel fuel oil remarkably reducing particulate matter(PM) forming a black smoke in an exhaust gas and remarkably reducing the discharge of toxic sulfur oxides and nitrogen oxides and HCCO and to recycle and effectively utilize a waste edible oil discharged from home and the food service industry by using the waste edible oil together with kerosene as a fuel component of the diesel engines. SOLUTION: This diesel fuel oil comprises a cetane number improver or a chemical substance having >=45 deg.C flash point and <=300 deg.C ignition point in an amount of 0.01-0.5 based on 100 of a composition of 60-90% of the kerosene and 10-40% of a polyhydric alcohol alkyl ester. The waste edible oil is used as the polyhydric alcohol alkyl ester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a kerosene-based diesel fuel oil, and more particularly, to a mixture of kerosene with a polyhydric alcohol alkyl ester, particularly a waste cooking oil, or a waste cooking oil. The present invention relates to a diesel fuel oil obtained by mixing an ester.

[0002]

2. Description of the Related Art Light oils and heavy oils have been used as fuels for diesel vehicles. However, when these fuels are used for a diesel engine, fine carbon particles (hereinafter referred to as PM) are generated due to incomplete combustion of the fuel.
There is a problem of discharging black smoke consisting of. This PM
Uses a catalyst to effectively remove black smoke from exhaust gas generated by incomplete combustion of diesel engine fuel consisting of light oil and heavy oil because it is harmful to the environment and human health. Studies have been conducted to remove them, but no results have been seen yet, and as a result, the operation of diesel vehicles in densely populated areas, including the Tokyo metropolitan area, is being regulated. Diesel engines that use light oil and heavy oil as fuels scatter harmful sulfur oxides and nitrogen oxides in addition to PM in exhaust gas.
Colorless hydrocarbons resulting from incomplete combustion,
There is a problem that carbon monoxide (hereinafter referred to as HCCO) is released. Sulfur oxide in exhaust gas absorbs moisture when released into the air and turns into sulfurous acid and sulfuric acid, corroding metal structures and withering standing trees, so desulfurization from factory flue gas has advanced considerably. However, in diesel engines, diesel oil contains 200 ppm of sulfur compounds and heavy oil with low sulfur content also contains 1000 ppm of sulfur compounds. Is required.

[0003]

SUMMARY OF THE INVENTION The present invention has a problem when conventional light oil or heavy oil is used as a fuel for a diesel engine, that is, PM which forms black smoke in exhaust gas is significantly reduced from the exhaust gas. It provides a diesel engine fuel oil with significantly reduced emissions of harmful sulfur oxides, nitrogen oxides and HCCO. In order to solve this problem, the present invention has conducted various studies.As a result, kerosene was used in place of light oil and heavy oil, and a composition in which kerosene was mixed with a polyhydric alcohol alkyl ester and a certain compound to solve this problem. The present invention has been found that it can be solved.

[0004] As another environmental problem, used cooking oil (hereinafter referred to as waste cooking oil) discharged from the household and the food service industry is treated with a coagulant, or buried in soil as it is, or washed away into rivers. Has been pointed out as a pollution problem. Cooking oil has been oxidized as a result of being used in food processing at high temperatures, and its degree varies depending on the user and is not uniform. There is almost no. That is why it is thrown away in the environment. The present invention, as a fuel component of a diesel engine with kerosene,
By using waste cooking oil, it is possible to recycle and effectively use waste cooking oil.

[0005]

That is, the present invention is directed to solving the above-mentioned problems by providing white kerosene 60 to 90.
A diesel fuel oil composition comprising 10 parts by weight of a polyhydric alcohol alkyl ester and 0.01 to 10 parts of a cetane number improver. In particular, white kerosene 60-9
0 parts and 10 to 40 parts of a polyhydric alcohol alkyl ester,
And the flash point is 45 ° C. or higher and the flash point is 300
The present invention provides a diesel fuel oil composition comprising 0.01 to 10 parts of a chemical substance having a peroxide temperature of 60 to 90 parts and a peroxide value of 10 to 3000 parts.
A diesel fuel oil composition comprising 10 to 40 parts of a polyhydric alcohol alkyl ester, wherein the diesel engine uses a polyhydric alcohol alkyl ester from which salts or impurities have been removed as the polyhydric alcohol alkyl ester. A fuel oil composition is provided. As the invention of claim 5, 72 to 78 parts of white kerosene, 22 to 28 parts of a polyhydric alcohol alkyl ester, and a cetane improver 0.1
The present invention provides a diesel fuel oil composition comprising from 10 parts to 10 parts. The invention of claim 6 provides a diesel fuel oil composition using waste cooking oil as the polyhydric alcohol alkyl ester, and the invention of claim 7 uses waste cooking oil which is vegetable oil as the waste cooking oil of claim 6. It provides a diesel fuel oil composition.

[0006]

DETAILED DESCRIPTION OF THE INVENTION The diesel fuel composition according to the present invention uses kerosene as a main component instead of conventional light oil and heavy oil. By using kerosene, PM can be significantly reduced from exhaust gas of diesel engines,
Therefore, it can be made extremely small so that black smoke is hardly generated. Kerosene is obtained by fractionating from petroleum, and there are 1 kerosene and 2 kerosene according to JIS standards. No. 1 kerosene is called white kerosene, and No. 2 kerosene, which is a so-called kerosene for home use, is called brown kerosene and is used for industrial use. Kerosene used in the present invention,
It is white kerosene (hereinafter simply referred to as “kerosene”), and commercially available one is used. Kerosene is a result of technological advances,
Sulfur is 50 ppm or less, and therefore, even when burned, the generation of sulfur oxides is extremely small as compared with light oil and heavy oil, and environmental pollution can be prevented. The diesel fuel oil provided in the present invention uses 10 to 40 parts of a polyhydric alcohol alkyl ester with respect to 60 to 90 parts of white kerosene, so that the sulfur content is 45 ppm or less.

A typical example of the polyhydric alcohol alkyl ester used in the present invention is a chemical substance in which 1 mole of glycerin is esterified with 1 to 3 moles of a fatty acid. Synthetic fats and oils may be used. Natural fats and oils are easily available, and as typical examples,
Linseed oil, coconut oil, cottonseed oil, soybean oil, olive oil, safflower oil, coconut oil, almond oil, castor oil,
Sesame oil, palm oil, palm kernel oil, corn oil, peanut oil, tung oil, lard oil, butterfat, tallow, lard, wool oil, whale oil, sardine oil, mackerel oil, etc., but vegetable oil has a wide temperature range Since the liquid is maintained in the range, it is easier to use than animal oil and is preferable. Examples of the polyhydric alcohol alkyl ester include, in addition to glycerin, alkyl esters such as ethylene glycol, pentaerythritol, and propylene glycol butylene glycol.

In the present invention, waste edible oil is preferably used as the polyhydric alcohol alkyl ester. By using waste cooking oil, it is possible not only to suppress the pollution problem due to the disposal action such as the waste cooking oil being buried in the soil and being washed away in a river, but also to reuse it as a resource. Waste cooking oil is collected from households, the food service industry, prepared food stores, supermarkets, etc., but depending on its use history, it contains tempura slag or mixed with seasonings such as a slight amount of salt. It is preferable to remove contaminants so as not to generate dioxin or damage the engine. For this reason, it is preferable to wash with water before use, or to further filter, or It is preferable to perform a clay treatment. As the treatment, it is preferable to wash the waste edible oil with water to remove water-soluble foreign substances, and then to filter, or further, to absorb and remove foreign substances that cannot be removed by the water washing, by a clay treatment. In the present invention, when waste oil having a peroxide value of 10 to 3000 is used as the waste cooking oil, ignitability is good when used in combination with kerosene. In this case, a cetane number improver is unnecessary. The invention of claim 3 is constituted by waste cooking oil having a peroxide value of 10 to 3000. In terms of performance and availability, those having a peroxide value of 20 to 500 are preferable. Waste cooking oil having a peroxide value of 10 to 3000 can be obtained from ordinary waste cooking oil. However, in order to increase the peroxide value, air or ozone is blown into the waste cooking oil to promote oxidation and the peroxide value. May be 10 to 3000.

Another advantage of using a polyhydric alcohol alkyl ester in the present invention is that when kerosene is used as fuel, insufficient lubrication of the piston / cylinder for fuel supply can be compensated. Polyhydric alcohol alkyl esters improve the lubricity of the fuel supply piston / cylinder. Accordingly, it is not necessary to add a lubricating component such as spindle oil to compensate for insufficient lubrication.

In the present invention, a part of the polyhydric alcohol alkyl ester can be replaced with a monohydric alcohol alkyl ester. Less than half of the polyhydric alcohol alkyl ester can be substituted with a monohydric alcohol alkyl ester and used together with kerosene to produce diesel fuel oil. When replacing a part of the polyhydric alcohol alkyl ester with the monohydric alcohol alkyl ester,
50% or less of the polyhydric alcohol alkyl ester is suitable. For example, 40% of a polyhydric alcohol alkyl ester of a diesel fuel oil comprising 80 parts of kerosene, 20 parts of a polyhydric alcohol alkyl ester and 0.5 part of a cetane number improver
Is replaced with lauryl methyl ester, and kerosene 80
Parts, 12 parts of a polyhydric alcohol alkyl ester, 8 parts of lauryl methyl ester and 0.5 part of a cetane improver. The monohydric alcohol alkyl ester used is an organic acid ester of a monohydric alcohol such as methyl alcohol, ethyl alcohol, or propyl alcohol, and the organic acid is a carboxylic acid having 8 to 20 carbon atoms, which may be a synthesized organic acid. Usually obtained from natural fats and oils. A preferred monohydric alcohol alkyl ester is a methyl ester, and more preferably a methyl ester of waste cooking oil.

In the present invention, a cetane number improver is used as another component. This is to improve the ignitability of the fuel. As the cetane improver that can be used, specifically,
Isopropyl nitrate, butyl nitrate, amyl nitrate, octyl nitrate, cyclohexyl nitrate, etc., alkyl nitrates, polysulfides such as diethyl tetrasulfide, nitropropane,
Nitro compounds such as nitroethane, oxygenated compounds such as diethyl ether, acetone, butylcarbinol, diethylcarbinol, organic peroxides such as ditertiary butyl peroxide, tertiary butyl hydroperoxide, etc., azobisisobutyro Any aliphatic hydrocarbon such as a diazo compound such as nitrile and divinyl acetylene can be mentioned, and preferred are chemical substances having a flash point of 45 ° C. or higher and an ignition point of 300 ° C. or lower. The flash point is preferably 45 ° C. or higher in view of the danger of handling in firefighting, and the flash point is preferably 300 ° C. or lower from the viewpoint of easy ignition. From the viewpoint of suppressing the generation of NOx and SOx, peroxide is preferable. The cetane number improver is used in an amount of 0.01 to 10 parts.
Preferably it is 0.01 to 0.5 part. Heavy oils contain 1000 ppm of sulfur compounds even if they have a low sulfur content, and light oils contain about 200 ppm of sulfur compounds. The kerosene and polyhydric alcohol alkyl ester mixture according to the present invention does not contain such a large amount of a sulfur compound, and has a flash point of 45 ° C. or higher to supplement the ignitability function of the sulfur compound, and has a flash point of not less than 45 ° C. 300
By using a chemical substance having a temperature of not more than ℃, the ignitability of a mixture of kerosene and a polyhydric alcohol can be remarkably improved.

The diesel fuel oil according to the present invention is kerosene 6
0-90 parts and polyhydric alcohol alkyl ester 10-4
0 parts of the composition are used. Kerosene is less than 60 parts,
If the polyhydric alcohol alkyl ester is 40 parts or more, the viscosity as a fuel becomes too high and cannot be used. As the viscosity is low in summer and high in winter,
Since it varies depending on the season, the content of kerosene is preferably 70 parts or more, and the content of the polyhydric alcohol alkyl ester is preferably 30 parts or less. Also, kerosene 60 to 9 constituting the diesel fuel oil according to the present invention.
A composition of 0 parts and 10 to 40 parts of a polyhydric alcohol alkyl ester may have insufficient lubricating properties of the fuel supply piston / cylinder if the kerosene is more than 90 parts and the polyhydric alcohol alkyl ester is less than 10 parts. become. From the viewpoint of such lubricity, the kerosene content is preferably 80%.
Or less, and the content of the polyhydric alcohol alkyl ester is preferably at least 20 parts. Therefore, the composition comprising 60 to 90 parts of kerosene and 10 to 40 parts of a polyhydric alcohol alkyl ester constituting the diesel fuel oil according to the present invention is preferably 70 to 80 parts of kerosene and 20 to 30 parts of a polyhydric alcohol alkyl ester as a preferable range. Further, a composition which is preferably easy to use is a composition comprising 72 to 78 parts of kerosene and 22 to 28 parts of a polyhydric alcohol alkyl ester.

In the diesel fuel oil according to the present invention, a chemical substance having a flash point of 45 ° C. or higher and a flash point of 300 ° C. or lower is a generally known chemical substance used for improving ignitability. The amount used is 10 parts or less, but it is usually sufficient to use it in a proportion of 0.01 to 0.5 part, preferably 0.1 to 0.3 part, more preferably 0.2 part. is there.

[0014]

According to the present invention, there is a problem when conventional light oil or heavy oil is used as fuel for a diesel engine, that is, PM which forms graphite in exhaust gas caused by incomplete combustion is significantly reduced from the exhaust gas. You can do it. The content of sulfur oxide is 50 ppm in kerosene.
Even if it is contained, it is diluted by the polyhydric alcohol alkyl ester, so it is at most 45 ppm or less, preferably 40 ppm or less, and the sulfur oxide concentration of the current diesel fuel of 500 ppm or less is greatly reduced. 50pp which is strongly demanded from the viewpoint of catalyst maintenance attached to the exhaust pipe of
m or less. Further, the emission concentration of nitrogen oxides can be reduced by about 10% or more. The reason depends on the combustion temperature. Light oil and heavy oil have a high combustion temperature, so they also oxidize nitrogen in the air and emit nitrogen oxides.
The composition comprising kerosene, which is a diesel fuel oil according to the present invention, as a main component and a polyhydric alcohol alkyl ester added thereto has a low combustion temperature and a small nitrogen oxidation rate. Further, the diesel fuel oil according to the present invention uses a polyhydric alcohol alkyl ester as a component, and the molecule of the polyhydric alcohol alkyl ester contains an oxygen atom and is consumed by its own combustion. There is an excellent effect that combustion is easy and the amount of HCCO generated as a result of incomplete combustion is significantly reduced. Furthermore, when waste cooking oil is used as the polyhydric alcohol alkyl ester of the diesel fuel oil of the present invention, the used waste cooking oil discharged from the home and the food service industry is treated with a coagulant or buried in soil as it is. It is not only a solution to environmental problems that are being swept away, but also the effective use of resources. When the diesel fuel oil according to the present invention is compared with light oil, kerosene has higher ignitability than light oil, but is slightly inferior in power. Polyhydric alcohol alkyl esters have higher power than light oil, but are inferior in ignitability. However, by mixing the kerosene and the polyhydric alcohol alkyl ester, the present invention has the effect of improving the ignitability and maintaining the power. In addition, since the monohydric alcohol alkyl ester has an intermediate performance between kerosene and the polyhydric alcohol alkyl ester in ignitability and power, when 50% or less of the polyhydric alcohol alkyl ester is replaced with the monohydric alcohol alkyl ester, This has the effect of improving the balance between ignitability and power.

[0015]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. (Preparation of Materials) Commercially available kerosene was mixed with used tempura oil and hexyl alcohol to prepare test fuel A, test fuel B, test fuel C and test fuel D, and a commercial light oil was tested for the comparative example. It was used as fuel E and evaluated.

(Evaluation of Engine Operation) The test fuel shown in Table 2 was supplied to the diesel engine shown in Table 1, and the diesel engine was operated under the operating conditions shown in Table 1, and the PM in the exhaust gas was reduced by mini-diluting. Hydrocarbon (HC), carbon monoxide (C)
O) and nitrogen oxides (NOx) were measured by an automobile exhaust gas measuring device MEXA-4000 (manufactured by Horiba, Ltd.).

[Table 1]

[Table 2]

[Table 3]

Table 3 shows the measurement results. The measured value was expressed as a relative value when the test oil E was 100. As can be seen from these results, A to F of the test fuel for the product of the present invention are P
It can be confirmed that M is greatly reduced. Also, H
It can be seen that C, CO and NOx are also significantly reduced.
In addition, knocking occurred even when test oil E was used as a fuel.

EXAMPLES [0018] Used tempura oil having various peroxide values (hereinafter referred to as [POV]), tempura oil b, tempura oil c, and tempura oil d were added to commercially available kerosene and evaluated as diesel fuel oil. did. Tempura oil c and tempura oil d are obtained by passing ozone through tempura oil A at normal temperature to increase the POV.

[Table 4]

[Table 5]

Claims (7)

[Claims] (1) 60 to 90 parts of white kerosene, 10 to 40 parts of a polyhydric alcohol alkyl ester, and a cetane number improver.
Diesel fuel oil composition comprising 01 to 10 parts 2. 60 to 90 parts of white kerosene and 10 to 40 parts of a polyhydric alcohol alkyl ester, and a chemical substance having a flash point of 45.degree. C. or more and a flash point of 300.degree.
Diesel fuel oil composition consisting of 10 parts 3. A kerosene of 60 to 90 parts and a peroxide value of 10 to 10.
3000 polyhydric alcohol alkyl ester 10 to 40
Diesel fuel oil composition comprising 4. The diesel fuel oil composition according to claim 1, wherein the polyhydric alcohol alkyl ester has been subjected to a treatment for removing salts or contaminants. 5. Kerosene (72 to 78 parts), a polyhydric alcohol alkyl ester (22 to 28 parts), and a cetane number improver.
2. The diesel fuel oil composition according to claim 1, comprising 1 to 10 parts. 6. The diesel fuel oil composition according to claim 1, wherein the polyhydric alcohol alkyl ester is waste cooking oil. 7. The diesel fuel composition according to claim 6, wherein the waste cooking oil is a vegetable oil.