JP5684180B2 - Light oil composition - Google Patents

Description

  The present invention relates to a light oil composition.

  There is a social demand for reducing the content of particulate matter such as nitrogen oxides (NOx) and sulfate from exhaust gas from diesel vehicles. For this reason, in diesel oil fuel oil for diesel vehicles, There is a demand for reducing the content of sulfur, which is a substance that poisons the catalyst of an exhaust gas aftertreatment device, and is a source of sulfate.

  As a means for reducing the sulfur content of the gas oil composition, a method of hydrodesulfurizing the gas oil fraction is generally used. However, in the hydrodesulfurization treatment, not only the sulfur content in the gas oil fraction but also the gas oil fraction Antioxidants (e.g. amines, phenols, etc.) originally contained in water may be hydrotreated, and low sulfur gas oil compositions that have undergone hydrodesulfurization will produce peroxides. It is known that the oxidation stability is low (see, for example, Non-Patent Document 1 and Non-Patent Document 2).

  The oxidation stability of the gas oil composition is an important management item for the quality control of the gas oil composition. In particular, in the low-sulfurized gas oil composition in which the oxidation stability is likely to be reduced, the generation of peroxide should be suppressed. Is required.

  For this reason, the present applicant has come to propose a light oil composition with improved oxidation stability by adjusting the contents of naphthenebenzenes and fluorenes within a predetermined range (see Patent Document 1).

On the other hand, in order to reduce the CO ₂ emitted from automobiles, the introduction of biomass fuel, which is considered to have zero CO ₂ generation during combustion, is being promoted around the world. ing. As biomass fuel for diesel vehicles, those based on fatty acid alkyl esters such as FAME (fatty acid methyl ester) and FAEE (fatty acid ethyl ester) produced from animal and vegetable oils and waste cooking oil are known.

Hirohisa Taguchi, Idemitsu Technical Bulletin 39 No. 2 (1996) T. T. et al. Russell and D.C. Brown, World Refining, p. 40, April (2000)

JP 2006-137721 A

  However, in recent years, in order to further reduce NOx and particulate matter emitted from diesel vehicles, high-pressure fuel injection technology using a common rail fuel injection system has been introduced into many diesel vehicles in addition to exhaust aftertreatment devices. ing. In the above system, the light oil composition may be exposed to a high temperature of 130 ° C. or higher, and a part of the light oil composition exposed to the high temperature returns to the fuel tank without being injected from the injector, and again the above system Therefore, it is more important than ever to suppress a decrease in oxidation stability of the light oil composition under such severe conditions.

In particular, fatty acid alkyl esters often have unsaturated bonds derived from animal or vegetable oils and waste cooking oils as raw materials, and light oils obtained when fatty acid alkyl esters having a high content of unsaturated bonds are used as a light oil base. It tends to reduce the oxidation stability of the composition.
On the other hand, when a fatty acid alkyl ester having a low content of unsaturated bonds is used as a light oil base, the oxidation stability of the resulting light oil composition is improved, but the freezing temperature is likely to be lowered because the freezing point is increased.

  The present invention is highly suppressed with a sulfur content of 10 mass ppm or less, and exhibits excellent flammability to suppress the generation of particulate matter, and contains a substrate for biomass fuel containing an unsaturated fatty acid alkyl ester Nevertheless, an object of the present invention is to provide a light oil composition capable of suppressing a decrease in oxidation stability even under severe conditions.

  As a result of intensive studies by the inventor in order to solve the above technical problem, it surprisingly contains a biomass fuel base material containing an unsaturated fatty acid alkyl ester, and has a high sulfur content of 10 mass ppm or less. Diesel oil containing a predetermined amount of tricyclic to pentacyclic aromatic compounds that have been highly removed as causative substances to reduce the combustibility and generate particulate matter, and containing a predetermined amount of benzoanthracenes The present inventors have found that the above object can be achieved by a composition, and have completed the present invention based on this finding.

That is, the present invention
(1) Sulfur content is 10 mass ppm or less, total content of tricyclic aromatic compound, tetracyclic aromatic compound and pentacyclic aromatic compound is 700 to 3000 mass ppm, and content of benzoanthracene is 3 0.0 to 10.0 mass ppm, the content of unsaturated fatty acid alkyl ester is 0.5 to 5 mass%, and the content of fatty acid alkyl ester containing the unsaturated fatty acid alkyl ester is 1 to 10 mass%. (2) The sulfur content is 10 mass ppm or less, the benzoanthracene content is 3.5 to 15.0 ppm by mass, and the boiling point range is 170 to 380 ° C. Desulfurized gas oil fraction 55 to 94% by mass;
A sulfur content of 10 mass ppm or less and a desulfurized kerosene fraction having a boiling point range of 140 to 290 ° C of 5 to 40 mass%,
The light oil composition according to the above (1), which is obtained by mixing 1 to 10% by mass of a fatty acid alkyl ester,
Is to provide.

  According to the present invention, the sulfur content is suppressed to 10 ppm by mass or less, and excellent combustibility to suppress the generation of particulate matter is exhibited, and the biomass fuel base material containing unsaturated fatty acid alkyl ester is contained. Nevertheless, it is possible to provide a light oil composition capable of suppressing a decrease in oxidation stability even under severe conditions.

First, the light oil composition of the present invention will be described.
The gas oil composition of the present invention has a sulfur content of 10 mass ppm or less, a total content of tricyclic aromatic compounds, tetracyclic aromatic compounds and pentacyclic aromatic compounds of 700 to 3000 mass ppm, benzoanthracenes. The content of the unsaturated fatty acid alkyl ester is 3.0 to 10.0 mass ppm, the content of the unsaturated fatty acid alkyl ester is 0.5 to 5 mass%, and the content of the fatty acid alkyl ester containing the unsaturated fatty acid alkyl ester is 1 to 10 mass %.

In the light oil composition of the present invention, the content of the sulfur compound is 10 ppm by mass or less, preferably 9 ppm by mass or less, and more preferably 5 to 9 ppm by mass.
In the light oil composition of the present invention, the sulfur compound content is 10 mass ppm or less, thereby suppressing the poisoning of the catalyst of the exhaust gas aftertreatment device and the amount of particulate matter such as sulfate discharged from the diesel engine. Can be reduced.
In addition, in this application document, content of a sulfur compound means the value measured according to JISK2541 "Crude oil and petroleum products-sulfur content test method".

In the light oil composition of the present invention, the total content of the tricyclic aromatic component, the tetracyclic aromatic component, and the pentacyclic aromatic component is 700 to 3000 ppm by mass, preferably 750 to 2700 ppm by mass, 800 More preferably, it is ˜2500 mass ppm.
In the light oil composition of the present invention, the total content of the tricyclic aromatic component, the tetracyclic aromatic component, and the pentacyclic aromatic component is within the above range, so that the deterioration of the exhaust gas properties is suppressed and the harsh conditions are satisfied. Even under such conditions, a decrease in oxidation stability can be suppressed.

  In the present application documents, the tricyclic aromatic compound means a compound obtained by condensing three aromatic rings such as anthracene, phenanthrene, naphthenephenanthrene, or an alkyl-substituted derivative of any one of these compounds. The tetracyclic aromatic compound means a compound obtained by condensing four aromatic rings such as pyrene, chrysene, benzoanthracene or the like, or an alkyl-substituted derivative of any of these compounds, Means a compound obtained by condensing five aromatic rings such as perylene and dibenzoanthracene or an alkyl-substituted derivative of any one of these compounds.

In the light oil composition of the present invention, the ratio of the total content of the tetracyclic aromatic compound to the total content of the tricyclic aromatic compound, the tetracyclic aromatic compound and the pentacyclic aromatic compound (total content of the tetracyclic aromatic compound) Quantity / (total content of tricyclic aromatic compound, tetracyclic aromatic compound and pentacyclic aromatic compound)) is 0.30 to 0.40 by mass ratio, and is 0.32 to 0.39. It is preferable that it is 0.33 to 0.38.
According to the knowledge of the present inventors, the effect of improving the oxidative stability is higher in the 4-ring aromatic compound than in the 3-ring aromatic compound and 5 in comparison with the 4-ring aromatic compound when compared with the same content. Ring aromatic compounds are higher. However, since the total content of the pentacyclic aromatic compound in the light oil composition is very small, the contribution to the effect of improving the oxidative stability is dominated by the tetracyclic aromatic compound. That is, by controlling the ratio of the total content of the tetracyclic aromatic compound to the total content of the tricyclic aromatic compound, the tetracyclic aromatic compound and the pentacyclic aromatic compound within the above range, Moreover, the fall of oxidation stability can be suppressed more effectively.

  In the light oil composition of the present invention, the ratio of the total content of the pentacyclic aromatic compound to the total content of the tricyclic aromatic compound, the tetracyclic aromatic compound and the pentacyclic aromatic compound (total content of the pentacyclic aromatic compound) Amount / (total content of tricyclic aromatic compound, tetracyclic aromatic compound and pentacyclic aromatic compound)) is preferably 0.004 to 0.009 in terms of mass ratio, and preferably 0.005 to 0. 0.008 is more preferable, and 0.006 to 0.008 is even more preferable.

  In the light oil composition of the present invention, the total content of tricyclic aromatic compounds, tetracyclic aromatic compounds and pentacyclic aromatic compounds, and the total content of tricyclic aromatic compounds, tetracyclic aromatic compounds and pentacyclic aromatic compounds. The ratio of the total content of the 4-ring aromatic compound or the total content of the 5-ring aromatic compound to the content is the total content of the 3-ring aromatic compound in the gas oil base such as the desulfurized gas oil fraction. It can be calculated from the total content of the aromatic compound and the total content of the pentacyclic aromatic compound and the blending ratio of each light oil base.

  In the present application document, the total content of the tricyclic aromatic compound, the total content of the tetracyclic aromatic compound, and the total content of the pentacyclic aromatic compound mean values calculated by the following method.

First, an activated alumina concentrate is obtained by concentrating a measurement sample such as a desulfurized gas oil fraction on an activated alumina column by a method of sequentially performing the following (1) to (6).
<Method for preparing activated alumina concentrate>
(1) 1 L of measurement sample is passed through 500 g of activated alumina, the adsorbed components are adsorbed on the activated alumina, and the remaining components are directly discharged from the column.
(2) 1 L of n-heptane is flowed to the activated alumina to obtain an n-heptane solution from which the saturated components of the adsorbed components are eluted.
(3) Next, 500 mL of methanol is passed through the activated alumina to obtain a methanol recovery liquid from which all the remaining adsorbed components are eluted.
(4) Methanol is removed by evaporation from the methanol recovery solution, and the residue is dissolved in toluene to obtain a toluene solution.
(5) The toluene solution is passed through 50 g of activated alumina to adsorb the adsorbed components on the activated alumina, and the remaining components are allowed to flow out of the column as they are.
(6) Pour 500 mL of toluene into the above 50 g of activated alumina to elute and collect the adsorbate, and then evaporate and remove toluene to obtain an activated alumina concentrate.

The resulting activated alumina concentrate was then analyzed with a gas chromatograph-mass spectrometer (GC-MS, Agilent 6890N and 5975B) and in accordance with ASTM D 3239 a tricyclic aromatic compound, a tetracyclic aromatic compound and After calculating the content (volume%) of each of the pentacyclic aromatic substances, assuming that the density of all the compounds is 1, each content ratio is converted from volume% to mass%, and then obtained by the above operation. Multiplied by the mass of the activated alumina concentrate, and further divided by the mass of the desulfurized gas oil fraction passed through the activated alumina, etc., so that the total content of the tricyclic aromatic compound, the total content of the tetracyclic aromatic compound, The total content of the pentacyclic aromatic compound can be determined, and the content in the light oil composition can be determined from the blending ratio of each light oil base.
By the above method, the total content of tricyclic aromatic compounds, the total content of tetracyclic aromatic compounds, and the total content of pentacyclic aromatic compounds can be measured in ppm order.

In the light oil composition of the present invention, the content of benzoanthracene is 3.0 to 10.0 mass ppm, preferably 4.0 to 9.0 mass ppm, and 5.0 to 8.0 mass ppm. More preferred.
According to the study by the present inventors, surprisingly, among benzoanthracenes among tetracyclic aromatic compounds, the effect of improving oxidative stability is high, and the content of benzoanthracenes is within the above range. The inventors have found that a decrease in oxidation stability can be effectively suppressed even under severe conditions, and have completed the present invention.

  In this application document, benzoanthracene means benzo [a] anthracene or an alkyl-substituted derivative thereof.

  In this application document, the content ratio of benzoanthracene means a value calculated by the following method.

First, by the following methods (i) to (vi), a light oil base material such as a desulfurized gas oil fraction is used as a measurement sample in an activated alumina column, and the measurement sample is concentrated to obtain an activated alumina concentrate.
<Method for preparing activated alumina concentrate>
(I) 1 L of measurement sample is passed through 500 g of activated alumina, the adsorbed components are adsorbed on the activated alumina, and the remaining components are directly discharged from the column.
(Ii) 1 L of n-heptane is flowed to the activated alumina to obtain an n-heptane solution in which the saturated component of the adsorbed components is eluted.
(Iii) Flowing 500 mL of methanol to the activated alumina to obtain a methanol recovery liquid from which all remaining adsorbed components are eluted.
(Iv) Methanol is removed by evaporation from the methanol recovery solution, and the residue is dissolved in toluene to obtain a toluene solution.
(V) The toluene solution is passed through 50 g of activated alumina, the adsorbed components are adsorbed on the activated alumina, and the remaining components are directly discharged from the column.
(Vi) Flowing 4000 mL of a mixed solvent of n-heptane, toluene and methanol to 50 g of the activated alumina to elute and recover the adsorbed material, and then evaporating and removing the mixed solvent to obtain an activated alumina concentrate.

  Next, the obtained activated alumina concentrate was quantified by GC × GC TofMS under the following measurement conditions using a column connected in the following order, and then the obtained measurement value was multiplied by the concentration rate. Furthermore, the content ratio of benzoanthracenes can be determined by calculating using the blending ratio of each substrate.

<Column connection order>
Columns connected in the following order (a) to (e-2) are used.
(A) Primary column (column for LTM (Low Thermal Mass)) DB-1ms manufactured by Agilent: length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm
(B) Guard column: length 30 cm, inner diameter 0.25 mm
(C) Guard column: length 30 cm, inner diameter 0.1 mm
(D) Secondary column (BPX-50 manufactured by SGE): length 1.25 m, inner diameter 0.1 mm, film thickness 0.1 μm
(E-1) Guard column (Guard column for TofMS (Time Of Flight-Mass Spectrometry)): length 57 cm, inner diameter 0.1 mm (including transfer line 21 cm)
(E-2) Guard column (FID (Frame Ionization Detector) guard column): length 34 cm, inner diameter 0.1 mm

<GC x GC measurement conditions>
Temperature rise conditions: Hold at 65 ° C. for 1 minute → Raise at 3 ° C./minute→Hold at 150 ° C. → Raise at 5 ° C./minute→Hold at 310 ° C. (secondary oven + 10 ° C. offset)
Carrier gas: helium, constant pressure mode, 43.93 psi (1.5 mL / min, 65 ° C.)
Inlet temperature: 310 ° C
Injection volume: 0.2 μL, split ratio 50: 1
Data reading: 200 spectra / second Modulation time: 8 seconds

  Conventionally, it has been known that when the content of the polycyclic aromatic compound is increased in the low-sulfur gas oil composition, the combustibility is lowered and the generation amount of the particulate matter is increased. As a causative substance that has reduced the combustibility so far and generated particulate matter while surprisingly suppressing the sulfur content to 10 mass ppm or less when the present inventors diligently studied. A diesel oil composition that contains a predetermined amount of highly-removed tricyclic to pentacyclic aromatic compounds and a predetermined amount of benzoanthracene is used to suppress the decrease in flammability and to maintain the generation of particulate matter. It has been found that the decrease in oxidation stability can be suppressed even under severe conditions while suppressing the degree, and further, this effect can be effectively exhibited even when a fatty acid alkyl ester is used as a light oil base. Find Which has led to the completion of the present invention.

  Since the tricyclic to pentacyclic aromatic compound in the light oil fraction is usually reduced and decomposed simultaneously when the sulfur content is highly removed, reducing the sulfur content in the light oil composition is In many cases, it was meant to reduce the content of tricyclic to pentacyclic aromatic compounds. On the other hand, when trying to simply increase the amount of the 3-ring to 5-ring aromatic compound in the gas oil composition, usually a gas oil fraction from which the sulfur content has not been sufficiently removed will be used. It becomes difficult to obtain a light oil composition having a content of 10 mass ppm or less.

  In the present invention, the reaction temperature, catalyst, hydrogen and the like are increased so that the content ratio of tricyclic to pentacyclic aromatic compounds, particularly benzoanthracenes which are highly effective in improving oxidation stability, is increased during the production of the gas oil fraction. By reducing the sulfur content by controlling the reaction conditions such as partial pressure, liquid space velocity, boiling range of distillation, etc., the sulfur content is reduced, especially the oxidation stability is improved. By obtaining a light oil fraction containing a benzoanthracene that is highly effective in a predetermined ratio and mixing the light oil fraction in a desired ratio, the intended light oil composition can be easily obtained.

In the present invention, as a light oil fraction containing the benzoanthracenes in a predetermined ratio, a tetracyclic aromatic compound or a pentacyclic aromatic compound is predetermined with respect to the total content of the tricyclic to pentacyclic aromatic compound. It is preferable to obtain a gas oil composition containing the desired gas oil fraction by mixing the gas oil fraction in a desired ratio.
According to the light oil composition of the present invention, the ratio of the content of the tetracyclic aromatic compound and the content of the pentacyclic aromatic compound to the total content of the tricyclic to pentacyclic aromatic compound is increased. By containing a predetermined amount, it is possible to more effectively reduce the decrease in oxidation stability of the light oil composition.

In the light oil composition of the present invention, the content of the fatty acid alkyl ester is 1 to 10% by mass, preferably 2 to 10% by mass, and more preferably 3 to 10% by mass. In the light oil composition of the present invention, when the content of the fatty acid alkyl ester is 1% by mass to 10% by mass, the combustion state in a diesel engine as an oxygen-containing fuel is suppressed while suppressing a decrease in oxidation stability and low-temperature fluidity. And the generation amount of particulate matter (PM) and the like can be reduced.
Fatty acid alkyl esters include both unsaturated fatty acid alkyl esters and saturated fatty acid alkyl esters.
In the light oil composition of the present invention, the fatty acid alkyl ester preferably contains 5-95% by weight of unsaturated fatty acid alkyl ester, more preferably 25-85% by weight, and even more preferably 45-80% by weight. .
When the content of the unsaturated fatty acid alkyl ester in the fatty acid alkyl ester is within the above range, the amount of the unsaturated fatty acid alkyl ester in the light oil composition can be easily controlled within a desired range.

  In the light oil composition of the present invention, the content of the unsaturated fatty acid alkyl ester is 0.5 to 5% by mass, preferably 1 to 5% by mass, and more preferably 1.5 to 5% by mass. In the light oil composition of the present invention, when the content of the unsaturated fatty acid alkyl ester is within the above range, a light oil composition exhibiting desired oxidation stability and low temperature fluidity can be obtained.

  In the light oil composition of the present invention, the content of the polyunsaturated fatty acid alkyl ester having two or more unsaturated bonds in one molecule is preferably 0.1 to 4% by mass, and 0.1 to 3% by mass. %, More preferably 0.1 to 2% by mass, and most preferably 0.1 to 1% by mass. In the light oil composition of the present invention, when the content of the polyunsaturated fatty acid alkyl ester is within the above range, a light oil composition exhibiting desired oxidation stability can be easily obtained.

  In addition, in this application document, content of fatty acid alkyl ester, unsaturated fatty acid alkyl ester, and polyunsaturated fatty acid alkyl ester is “the Japan Oil Chemists' Society standard oil analysis method 2.4.2.2-1996”. "Means the value measured.

In the light oil composition of the present invention, the fatty acid alkyl ester is preferably made from fats and oils such as animal and vegetable oils and waste cooking oils.
Fatty acid alkyl esters made from fats and oils such as animal and vegetable oils and waste edible oils do not contain sulfur, so mixing them with a light oil base makes it possible to control the sulfur content in the light oil composition to a lower level. Thus, the amount of sulfate that is a component of particulate matter (PM) discharged from the engine can be reduced, and the influence on the exhaust gas aftertreatment device can be reduced.

Examples of the animal and vegetable oils used as the raw material for the fatty acid alkyl ester include vegetable oils such as palm oil, rapeseed oil, soybean oil, coconut oil, and Jatropha oil.
These fatty acid alkyl esters derived from vegetable oil are considered to be carbon-neutral fuel base materials as renewable energy, and are preferably used from the viewpoint of reducing carbon dioxide emissions. Among them, fatty acid alkyl esters derived from non-food vegetable oils, such as Jatropha oil, can be cultivated in wasteland due to food issues due to competition between food and fuel. It is also suitable from the viewpoint.

  The reaction method and the purification method for producing fatty acid alkyl esters from raw oils and fats such as vegetable oils are not particularly limited, and an alkali catalyst method using a general alkali metal, an acid catalyst using an acid catalyst such as an organic acid And a lipase method using a lipase enzyme.

The alkyl group of the fatty acid alkyl ester used in the present invention is various alkyl groups including isomers such as methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group. Table 1 below shows representative examples of fatty acid alkyl esters to which the alkyl group is bonded.
However, in the present invention, the type of fatty acid alkyl ester used is not limited to the following representative examples.

  The fatty acid alkyl ester used in the present invention and the fatty acid constituting the fat used in the raw material can be specified using a gas chromatograph (GC).

The fatty acid alkyl ester used in the present invention preferably has a density at 15 ° C. of 0.860 to 0.900 g / cm ³ , more preferably 0.865 to 0.900 g / cm ³ , and 0 More preferably, it is 870 to 0.900 g / cm ³ . When the density at 15 ° C. is within the above range, the fuel efficiency can be kept good when used in a diesel engine.
In addition, in this application document, the density in 15 degreeC means the value measured according to JISK2249 "Crude oil and petroleum products-density test method and density / mass conversion table".

The fatty acid alkyl ester used in the present invention preferably has a kinematic viscosity at 30 ° C. of 2.5 to 6.0 mm ² / s, more preferably 3.0 to 6.0 mm ² / s, More preferably, it is 3.5-6.0 mm < ² > / s.
When the kinematic viscosity at 30 ° C. is within the above range, the spray state can be kept good when used in a diesel engine.
In this application document, the kinematic viscosity at 30 ° C. means a value measured according to JIS K2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.

The fatty acid alkyl ester used in the present invention has an ester content of preferably 96.5% by mass or more, and more preferably 97.0% by mass or more. When the ester content is within the above range, impurities such as unreacted products and by-products when the fatty acid alkyl ester is produced are preferable.
In addition, in this application document, ester content of fatty-acid alkylester shall mean the value measured by EN14103 "Fatty Acid Methyl Esters (FAME) -Determination of ester and linear acid methyl esters."

The fatty acid alkyl ester used in the present invention preferably has an acid value of 0.00 to 0.50 mg KOH / g, more preferably 0.00 to 0.30 mg KOH / g, and still more preferably 0.00 to 0.00. 10 mg KOH / g. When the acid value is within the above range, corrosion of automobile members and sludge generation by the light oil composition containing the fatty acid alkyl ester can be suppressed, which is preferable.
In addition, in this application document, an acid value means the value measured according to JISK2501.

  The light oil composition of the present invention preferably has a Saybolt color of -16 to +6, more preferably -15 to +3, and still more preferably -14 to 0.

Many of the polycyclic aromatic compounds contained in the light oil composition are fluorescent substances. Generally, if the content of the polycyclic aromatic compound is large, the light oil composition is colored and the value of the Saebold color is lowered. Since the Saybolt color is within the above range, it contains a predetermined amount of polycyclic aromatic compounds and can exhibit sufficient oxidation stability, so that it is possible to easily suppress deterioration in oxidation stability even under severe conditions. Can do.
In this application document, the Saebold color means a value measured according to JIS K 2580 “Petroleum products—color test method”.

The light oil composition of the present invention preferably has an initial boiling point (IBP) of 140 to 210 ° C, more preferably 150 to 200 ° C, and further preferably 160 to 180 ° C.
The light oil composition of the present invention preferably has a 10% by volume distillation temperature (T10) of 170 to 260 ° C, more preferably 180 to 250 ° C, and further preferably 190 to 240 ° C.
The gas oil composition of the present invention preferably has a 50% by volume distillation temperature (T50) of 260 to 315 ° C, more preferably 265 to 305 ° C, and further preferably 280 to 300 ° C.
In the light oil composition of the present invention, the 90 vol% distillation temperature (T90) is preferably 295 to 360 ° C, more preferably 310 to 355 ° C, and further preferably 320 to 350 ° C.
In the light oil composition of the present invention, the end point (EP) is preferably 300 to 390 ° C, more preferably 325 to 385 ° C, and further preferably 350 to 380 ° C.

In the light oil composition of the present invention, when IBP, T10, T50, T90 and EP are within the above ranges, the spray state and the combustion state in the diesel engine are appropriately maintained, and the generation of deposits and the deterioration of exhaust gas properties are suppressed. It becomes easy to do.
In the present application documents, IBP, T10, T50, T90 and EP mean values measured according to JIS K2254 “Petroleum products-distillation test method”.

The light oil composition of the present invention preferably has a density at 15 ° C. of 0.800 to 0.860 g / cm ³ , more preferably 0.810 to 0.860 g / cm ³ , and 0.815 to More preferably, it is 0.860 g / cm ³ . When the density at 15 ° C. is within the above range, the fuel efficiency can be kept good when used in a diesel engine.
In addition, in this application document, the density in 15 degreeC means the value measured according to JISK2249 "Crude oil and petroleum products-density test method and density / mass conversion table".

The gas oil composition of the present invention is preferably a kinematic viscosity at 30 ° C. is 1.7~5.1mm ² / s, more preferably 2.3~4.6mm ² / s, 3.2 More preferably, it is -4.5 mm < ² > / s.
When the kinematic viscosity at 30 ° C. is within the above range, the spray state can be kept good when used in a diesel engine.
In this application document, the kinematic viscosity at 30 ° C. means a value measured according to JIS K2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.

The light oil composition of the present invention preferably has a flash point of 45 to 105 ° C, more preferably 50 to 105 ° C. When the flash point is in the above range, ignition due to static electricity or the like can be reduced when handling the light oil composition.
In addition, in this application document, flash point means the value measured according to JISK2265 "Crude oil and petroleum products-flash point test method".

The light oil composition of the present invention preferably has a cetane index of 50 to 67, more preferably 55 to 67, and still more preferably 58 to 67. When the cetane index is within the above range, it becomes easy to maintain good ignitability when used in a diesel engine.
In the present application documents, the cetane index means a value measured according to JIS K2280 “Petroleum products-fuel oil-octane number and cetane number test method and cetane index calculation method”.

  The gas oil composition of the present invention is a desulfurized gas oil having a sulfur content of 10 mass ppm or less, a benzoanthracene content of 3.5 to 15.0 mass ppm, and a boiling range of 170 to 380 ° C. A desulfurized kerosene fraction of 5 to 40% by mass and a fatty acid alkyl ester of 1 to 10% by mass with a fraction of 55 to 94% by mass, a sulfur content of 10 mass ppm or less and a boiling range of 140 to 290 ° C. What mixes is suitable, 65-90 mass% of the said desulfurized gas oil fraction, 10-30 mass% of the said desulfurized kerosene fraction, and 2.0-10 mass% of the said fatty-acid alkylester are mixed. More preferably, 70 to 85% by mass of the desulfurized gas oil fraction, 10 to 20% by mass of the desulfurized kerosene fraction, and 3.0 to 10% by mass of the fatty acid alkyl ester are mixed. Is more suitable A.

  The details of the fatty acid alkyl ester are as described above, the sulfur content is 10 ppm by mass or less, the benzoanthracene content is 3.5 to 15.0 ppm by mass, and the boiling point range is 170 to Specific examples of the desulfurized gas oil fraction at 380 ° C. and specific examples of the desulfurized kerosene fraction having a sulfur content of 10 mass ppm or less and a boiling point range of 140 to 290 ° C. are as described later.

  In the present application documents, the desulfurized gas oil fraction includes a mixture of a plurality of desulfurized gas oil fractions, and the desulfurized kerosene fraction is a mixture of a plurality of desulfurized kerosene fractions. Shall be included. In this case, a desulfurized kerosene fraction obtained by mixing a plurality of desulfurized gas oil fractions or a desulfurized kerosene fraction obtained by mixing a plurality of desulfurized kerosene fractions only needs to satisfy the above characteristics.

  In the present application documents, the boiling range of the desulfurized gas oil fraction or the desulfurized kerosene fraction means a value measured according to JIS K 2254 “Petroleum product-distillation test method”.

  According to the present invention, the sulfur content is suppressed to 10 ppm by mass or less, and excellent combustibility to suppress the generation of particulate matter is exhibited, and the biomass fuel base material containing unsaturated fatty acid alkyl ester is contained. Nevertheless, it is possible to provide a light oil composition capable of suppressing a decrease in oxidation stability even under severe conditions.

  The light oil composition of the present invention can be prepared by mixing the above-described fatty acid alkyl ester and two or more kinds of light oil bases so as to have the specific composition and physical properties described above.

Examples of the light oil base used in the preparation of the light oil composition of the present invention include a kerosene fraction or a light oil fraction obtained by atmospheric distillation of crude oil, and a desulfurized kerosene fraction obtained by desulfurizing the kerosene fraction or the light oil fraction. Or a desulfurized gas oil fraction.
In addition, desulfurized gas oil fractions such as direct desulfurized gas oil fraction obtained from direct desulfurization equipment, indirect desulfurization gas oil fraction obtained from indirect desulfurization equipment, light cycle oil fraction obtained from fluid catalytic cracking equipment, and desulfurization thereof. Gas oil fractions and light cycle oil fractions are mixed with gas oil fractions obtained from an atmospheric distillation unit and further desulfurized to obtain a desulfurized gas oil fraction that is normally used as a base material for light oil compositions. be able to.

  The gas oil composition of the present invention preferably uses a desulfurized gas oil fraction obtained by desulfurizing a gas oil fraction distilled from an atmospheric distillation apparatus and a desulfurized kerosene fraction as a base material. .

As the light oil base, those obtained by desulfurization using a catalyst containing cobalt, phosphorus, molybdenum and an organic acid are preferable.
In addition, as the light oil base material, the reaction temperature, hydrogen partial pressure, liquid space velocity, boiling point range, etc. are monitored while monitoring the benzoanthracene content, the amount of each aromatic compound, and the sulfur content in the obtained base material. What is produced while controlling is preferable.

  As a method for producing the light oil composition of the present invention, the sulfur content is 10 mass ppm or less, the content of benzoanthracene is 3.5 to 15.0 mass ppm, and the boiling range is 170 to 380 ° C. The desulfurized gas oil fraction is 55 to 94% by mass, the sulfur content is 10 mass ppm or less, the desulfurized kerosene fraction having a boiling point range of 140 to 290 ° C. is 5 to 40% by mass, and the fatty acid alkyl ester 1 to 10 And a method of mixing with mass% (hereinafter, a method for preparing a light oil composition according to the present method is referred to as a light oil composition production method A).

  In production method A of the light oil composition, the desulfurized gas oil fraction includes a mixture of a plurality of desulfurized gas oil fractions, and the desulfurized kerosene fraction includes a plurality of desulfurized kerosene fractions. It is assumed that a mixture of these is included. In this case, a desulfurized kerosene fraction obtained by mixing a plurality of desulfurized gas oil fractions or a desulfurized kerosene fraction obtained by mixing a plurality of desulfurized kerosene fractions only needs to satisfy the above characteristics.

  In the manufacturing method A of a light oil composition, the boiling range of a desulfurized light oil fraction is 170-380 degreeC, 180-380 degreeC is more preferable, and 185-380 degreeC is further more preferable. In the light oil composition of the present invention, when the boiling point range of the desulfurized light oil fraction is within the above range, the flash point and kinematic viscosity of the obtained light oil composition can be maintained in an appropriate range.

In the manufacturing method A of a light oil composition, the amount of sulfur compounds in the desulfurized gas oil fraction is 10 mass ppm or less, preferably 9 mass ppm or less, and more preferably 5 to 9 mass ppm.
When the content of the sulfur compound in the desulfurized gas oil fraction is within the above range, the content of the sulfur compound in the obtained gas oil composition can be easily controlled within a desired range.

In the production method A of the light oil composition, the total content of the tricyclic aromatic component, the tetracyclic aromatic component, and the pentacyclic aromatic component of the desulfurized gas oil fraction is preferably 850 to 4000 ppm by mass, and 900 to 3,500. The mass is more preferably ppm, and further preferably 1000 to 3200 mass ppm.
In production method A of the light oil composition, the total content of the tricyclic aromatic component, the tetracyclic aromatic component, and the pentacyclic aromatic component is within the above range, so that the deterioration of the exhaust gas properties is suppressed, and the harsh conditions A gas oil composition in which a decrease in oxidative stability is also suppressed can be provided.

In the production method A of the light oil composition, the content of benzoanthracene in the desulfurized light oil fraction is 3.5 to 15.0 mass ppm, more preferably 5.0 to 12.0 mass ppm. More preferably, it is 5-10.0 mass ppm.
When the content of the benzoanthracene in the desulfurized gas oil fraction is within the above range, the content of the benzoanthracene in the obtained gas oil composition can be easily controlled within a desired range.

  The desulfurized gas oil fraction is monitored at the time of production, while monitoring the benzoanthracene content, the amount of each aromatic compound, and the sulfur content in the resulting fraction, reaction temperature, hydrogen partial pressure, liquid space velocity, By performing desulfurization treatment while controlling the reaction conditions such as the boiling point range of distillation, the content of sulfur is suppressed and tricyclic to pentacyclic aromatic compounds, particularly benzoanthracenes which are highly effective in improving oxidation stability In the same manner, as a light oil fraction containing a high proportion of the above benzoanthracenes, a tetracyclic aromatic compound with respect to the total content of the tricyclic to pentacyclic aromatic compound can be obtained. And a light oil fraction containing a pentacyclic aromatic compound in a predetermined ratio can be easily obtained.

In preparation A gas oil composition, density at 15 ℃ of desulfurized gas oil fraction is preferably 0.800~0.860g / cm ^3, more to be 0.810~0.860g / cm ³ Preferably, it is 0.820-0.860. When the density at 15 ° C. is within the above range, the fuel efficiency can be kept good when the obtained light oil composition is used in a diesel engine.
In addition, in this application document, the density in 15 degreeC means the value measured according to JISK2249 "Crude oil and petroleum products-density test method and density / mass conversion table".

In preparation A gas oil composition preferably has a kinematic viscosity at 30 ° C. of desulfurized gas oil fraction is 2.5~6.5mm ² / s, more to be 3.0~6.0mm ² / s Preferably, it is 3.5-5.5 mm < ² > / s.
When the kinematic viscosity at 30 ° C. is within the above range, the sprayed state can be kept good when the obtained light oil composition is used in a diesel engine.
In this application document, the kinematic viscosity at 30 ° C. means a value measured according to JIS K2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.

In the production method A of the light oil composition, the cetane index of the desulfurized light oil fraction is preferably 50 to 70, more preferably 55 to 70, and still more preferably 58 to 70. When the cetane index is within the above range, it becomes easy to maintain good ignitability when the obtained light oil composition is used in a diesel engine.
In the present application documents, the cetane index means a value measured according to JIS K2280 “Petroleum products-fuel oil-octane number and cetane number test method and cetane index calculation method”.

In the production method A of the light oil composition, the flash point in the desulfurized light oil fraction is preferably 70 to 105 ° C, more preferably 80 to 105 ° C. When the flash point is within the above range, ignition due to static electricity or the like can be reduced when the obtained light oil composition is handled.
In addition, in this application document, flash point means the value measured according to JISK2265 "Crude oil and petroleum products-flash point test method".

In the production method A of the light oil composition, the saturated content of the desulfurized light oil fraction is preferably 72 to 90% by volume, more preferably 75 to 88% by volume, and 76 to 87% by volume. Further preferred.
In production method A of the light oil composition, the aromatic content of the desulfurized gas oil fraction is preferably 10 to 28% by volume, more preferably 12 to 25% by volume, and 15 to 22% by volume. More preferably.
In the production method A of the light oil composition, the saturated content and the aromatic content of the desulfurized light oil fraction are within the above ranges, so that the ignitability of the obtained light oil composition can be easily maintained, It becomes easy to keep good low temperature performance.
In the present application documents, the saturated content and aromatic content mean values measured according to JPI-5S-49-07 "Petroleum products-hydrocarbon type test method-high performance liquid chromatograph method". .

In the manufacturing method A of a light oil composition, the boiling range of a desulfurization kerosene fraction is 140-290 degreeC, 143-285 degreeC is more preferable, and 145-280 degreeC is more preferable.
When the boiling point range in the desulfurized kerosene fraction is within the above range, the flash point and kinematic viscosity of the obtained light oil composition can be maintained in an appropriate range.

In preparation A gas oil composition, density at 15 ℃ desulfurization kerosene fraction is preferably 0.780~0.815g / cm ^3, more to be 0.785~0.810g / cm ³ preferable. When the density at 15 ° C. is within the above range, the fuel efficiency can be kept good when the obtained light oil composition is used in a diesel engine.
In addition, in this application document, the density in 15 degreeC means the value measured according to JISK2249 "Crude oil and petroleum products-density test method and density / mass conversion table".

In the light oil composition production method A, the flash point of the desulfurized kerosene fraction is preferably 40 ° C. or higher, more preferably 40 to 53 ° C. When the flash point is within the above range, ignition due to static electricity or the like can be reduced when the obtained light oil composition is handled.
In addition, in this application document, flash point means the value measured according to JISK2265 "Crude oil and petroleum products-flash point test method".

In the production method A of the light oil composition, the saturated content of the desulfurized kerosene fraction is preferably 75 to 90% by volume, and more preferably 77 to 88% by volume.
In the production method A of the light oil composition, the aromatic content of the kerosene oil fraction is preferably 10 to 25% by volume, and more preferably 12 to 23% by volume.
In the light oil composition production method A, when the saturated content and aromatic content of the desulfurized kerosene fraction are within the above ranges, it becomes easy to maintain good ignitability of the obtained light oil composition, and at a low temperature. It becomes easy to maintain good performance.
In the present application documents, the saturated content and aromatic content mean values measured according to JPI-5S-49-07 "Petroleum products-hydrocarbon type test method-high performance liquid chromatograph method". .

In the manufacturing method A of a light oil composition, the amount of sulfur compounds in the desulfurized kerosene fraction is 10 ppm by mass or less, preferably 9 ppm by mass or less, and more preferably 5-9 ppm by mass or less.
When the content of the sulfur compound in the desulfurized kerosene fraction is within the above range, the content of the sulfur content in the obtained light oil composition can be easily controlled within the desired range.
In addition, the desulfurized kerosene fraction whose sulfur compound amount is 10 mass ppm or less usually does not contain a tricyclic aromatic compound, a tetracyclic aromatic compound such as benzoanthracene, or a pentacyclic aromatic compound.

  The desulfurized kerosene fraction has a sulfur content, etc. by performing a desulfurization process while controlling reaction conditions such as reaction temperature, catalyst, hydrogen partial pressure, liquid space velocity, boiling range of distillation, etc. What is suppressed can be easily obtained.

  As described above, the production method A of the light oil composition has a sulfur content of 10 ppm by mass or less, a benzoanthracene content of 3.5 to 15.0 ppm by mass, and a boiling range of 170 to 380 ° C. The desulfurized gas oil fraction is 55 to 94% by mass, the sulfur content is 10 mass ppm or less, the desulfurized kerosene fraction having a boiling point range of 140 to 290 ° C. is 5 to 40% by mass, and the fatty acid alkyl ester 1 to 10 In the production method A of the light oil composition, the desulfurized gas oil fraction 65 to 90% by mass, the desulfurized kerosene fraction 5 to 30% by mass, and the fatty acid alkyl ester 2.0 It is preferable to prepare a target gas oil composition by mixing ˜10.0 mass%, the desulfurized gas oil fraction 70 to 85 mass%, the desulfurized kerosene fraction 10 to 20 mass%, Fatty acid alk above By mixing the ester 3.0 to 10.0 wt%, and more preferred to prepare the gas oil composition of interest.

  In the production method A of the light oil composition, the total content of the tricyclic aromatic compound, the tetracyclic aromatic compound and the pentacyclic aromatic compound, the content of benzoanthracene, the unsaturated fatty acid alkyl ester of the obtained light oil composition The desulfurized gas oil fraction, the desulfurized kerosene fraction, and the fatty acid alkyl ester are mixed at a desired ratio while controlling the content and the content of the fatty acid alkyl ester within a desired range.

  By the above-described production method, the sulfur content is suppressed to 10 mass ppm or less, and excellent combustibility for suppressing the generation of particulate matter is exhibited, and the substrate for biomass fuel containing unsaturated fatty acid alkyl ester is contained. Nevertheless, the light oil composition of the present invention that can suppress the decrease in oxidation stability even under severe conditions can be easily produced.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, this invention is not limited at all by these examples.

(Example 1 to Example 3, Comparative Example 1 to Comparative Example 4)
(1) Light oil base material As a light oil base material, desulfurized light oil fractions ULGO-1 to ULGO-5, a desulfurized kerosene fraction UKERO-1, and a fatty acid alkyl ester FAME-A were prepared. These light oil base materials are obtained by the following methods, respectively.

(ULGO-1)
Using a catalyst containing Co, P, Mo and an organic acid, a reaction temperature of 350 is applied to a straight-run gas oil fraction having a boiling point range of 219 to 376 ° C. obtained by fractionating crude oil with an atmospheric distillation apparatus. Desulfurization while adjusting the reaction conditions such that the content of benzoanthracenes and the content of sulfur in the product are within a predetermined range at ℃, hydrogen partial pressure 4.5 MPa, liquid space velocity 0.9 h ⁻¹ By performing the reaction, ULGO-1 having a boiling point range of 193 to 372 ° C. was obtained.

(ULGO-2)
Using a catalyst containing Co, P, Mo and an organic acid, a reaction temperature of 345 is applied to a straight-run gas oil fraction having a boiling range of 211 to 384 ° C. obtained by fractionating crude oil with an atmospheric distillation apparatus. Desulfurization while adjusting the reaction conditions such that the content of benzoanthracenes and the content of sulfur in the product are within a predetermined range at ℃, hydrogen partial pressure 5.5 MPa, liquid space velocity 0.8 h ⁻¹ By carrying out the reaction, ULGO-2 having a boiling point range of 208 to 377 ° C. was obtained.

(ULGO-3)
Using a catalyst containing Co, P, Mo and an organic acid, a reaction temperature of 340 is applied to a straight-run gas oil fraction having a boiling range of 225 to 368 ° C. obtained by fractionating crude oil with an atmospheric distillation apparatus. Desulfurization while adjusting the reaction conditions such that the content of benzoanthracenes and the content of sulfur in the product are within a predetermined range at ℃, hydrogen partial pressure 6.5 MPa, liquid space velocity 0.7 h ⁻¹ By performing the reaction, ULGO-3 having a boiling point range of 205 to 364 ° C. was obtained.

(ULGO-4)
Using a catalyst containing Co, P, Mo and an organic acid, a reaction temperature of 340 is applied to a straight-run gas oil fraction having a boiling range of 221 to 360 ° C. obtained by fractionating crude oil with an atmospheric distillation apparatus. Desulfurization while adjusting the reaction conditions such that the content of benzoanthracenes and the content of sulfur in the product are each within a predetermined range at ℃, hydrogen partial pressure 6.6 MPa, liquid space velocity 0.6 h ⁻¹ By performing the reaction, ULGO-4 having a boiling point range of 197 to 356 ° C. was obtained.

(ULGO-5)
Using a catalyst containing Co, P, Mo, and an organic acid, a reaction temperature of 355 is applied to a straight-run gas oil fraction having a boiling point range of 219 to 377 ° C. obtained by fractionating crude oil with an atmospheric distillation unit. Desulfurization while adjusting the reaction conditions such that the content of benzoanthracenes and the content of sulfur in the product are within a predetermined range at ℃, hydrogen partial pressure 4.5 MPa, liquid space velocity 0.9 h ⁻¹ By performing the reaction, ULGO-5 having a boiling point range of 186 to 380 ° C. was obtained.

(UKERO-1)
Using a catalyst containing Co, P, Mo, and an organic acid, a reaction temperature of 310 is applied to a straight kerosene fraction having a boiling point range of 150 to 268 ° C. obtained by fractionating crude oil with an atmospheric distillation unit. By carrying out the desulfurization reaction while adjusting the reaction conditions so that the sulfur content of the product falls within a predetermined range at a temperature of ° C, a hydrogen partial pressure of 4.4 MPa, and a liquid space velocity of 8.5 h ⁻¹ , UKERO-1 with a range of 152-266 ° C. was obtained. The properties of UKERO-1 are shown in Table 1.

(FAME-A)
As fatty acid alkyl ester, FAME-A containing palm oil as a raw material and 50 mass% of unsaturated fatty acid alkyl ester was prepared. Table 2 shows the properties of FAME-A.

(2) Preparation of light oil composition The above light oil base material, that is, the desulfurized light oil fractions ULGO-1 to ULGO-5, the desulfurized kerosene fraction UKERO-1, and the fatty acid alkyl ester FAME-A are in the proportions shown in Table 3. The light oil compositions according to Examples 1 to 3 were added to the obtained base material mixture by adding 300 ppm by volume of a low-temperature fluidity improver of an ethylene-vinyl acetate copolymer system, respectively. And gas oil compositions according to Comparative Examples 1 to 4 were obtained.
In addition, of the desulfurized gas oil fraction (any one of ULGO-1 to ULGO-5 or a mixture thereof) contained in the light oil compositions according to Examples 1 to 3 and Comparative Examples 1 to 4 The fraction names are ULGO-A to ULGO-F, and the properties of these fractions are shown in Table 4.

Desulfurized gas oil fraction, desulfurized kerosene fraction, fatty acid alkyl ester and the obtained diesel oil composition used in Examples 1 to 3 and the desulfurized gas oil fraction and desulfurized kerosene fraction used in Comparative Examples 1 to 4 The sulfur content was measured in accordance with JIS K 2541 in the minute, fatty acid alkyl ester and the obtained light oil composition. The results are shown in Table 1, Table 2, Table 4, and Table 5.
Further, in each of the above desulfurized gas oil fraction and desulfurized kerosene fraction, by measuring the amount of the tricyclic aromatic compound, the amount of the tetracyclic aromatic compound, and the amount of the pentacyclic aromatic compound by measuring the amount of the tricyclic aromatic compound. Total content of compound, 4-ring aromatic compound and 5-ring aromatic compound (in the table, expressed as 3-ring + 4-ring + 5-ring) of 3-ring aromatic compound, 4-ring aromatic compound and 5-ring aromatic compound Mass ratio of content of tetracyclic aromatic compound to total content (total mass of tetracyclic aromatic compound / total mass of tricyclic aromatic compound, tetracyclic aromatic compound and pentacyclic aromatic compound; "4 ring aromatic compound amount / 3 ring + 4 ring + 5 ring"), and the total content of 3-ring aromatic compound, 4-ring aromatic compound and 5-ring aromatic compound, Content mass ratio (total mass of pentacyclic aromatic compound / tricyclic aroma It was determined notation) in the "5-ring aromatic compound content / tricyclic +4 ring +5 ring" in the table; compound, the total weight of 4-ring aromatics and 5 ring aromatics. The results are shown in Tables 1 and 4.
Further, the total content of the tricyclic aromatic compound, the tetracyclic aromatic compound and the pentacyclic aromatic compound in the obtained light oil composition (indicated in the table as “3 ring + 4 ring + 5 ring”), tricyclic aromatic Ratio of the content of the tetracyclic aromatic compound to the total content of the tetracyclic aromatic compound and the pentacyclic aromatic compound (total mass of the tetracyclic aromatic compound / tricyclic aromatic compound, tetracyclic aromatic compound) The total mass of the compound and the 5-ring aromatic compound; in the table, expressed as “amount of 4-ring aromatic compound / 3-ring + 4-ring + 5-ring”), and the 3-ring aromatic compound, 4-ring aromatic compound and 5-ring aromatic Mass ratio of content of pentacyclic aromatic compound to total content of aromatic compound (total mass of pentacyclic aromatic compound / total mass of tricyclic aromatic compound, tetracyclic aromatic compound and pentacyclic aromatic compound; In the table, “represented by the amount of 5-ring aromatic compound / 3 ring + 4 ring + 5 ring”), Desulfurized gas oil fraction, obtained from the blending ratio of the desulfurizing kerosene fraction and the fatty acid alkyl esters. The results are shown in Table 5.
Further, in each desulfurized gas oil fraction and desulfurized kerosene fraction, the content of benzoanthracenes is determined by the above-described method, and the content of benzoanthracenes in the obtained gas oil composition is determined as each desulfurized gas oil fraction, It calculated | required from the compounding ratio of a desulfurization kerosene fraction and a fatty-acid alkylester. The results are shown in Table 1, Table 4, and Table 5.

Further, the desulfurized gas oil fraction, the desulfurized kerosene fraction according to Examples 1 to 3, the desulfurized gas oil fraction according to Comparative Example 1 to Comparative Example 4, the desulfurized kerosene fraction saturated content and the aromatic content. Measured according to JPI-5S-49-07 “Petroleum products—Hydrocarbon type test method—High performance liquid chromatograph method”, the density at 15 ° C. was measured according to JIS K 2249, and the kinematic viscosity at 30 ° C. Measured according to JIS K 2283, flash point measured according to JIS K 2265, cetane index measured according to JIS K 2280, cetane index measured according to JIS K 2280, Saybolt The color was measured according to JIS K 2580.
Further, IBP, T10, T50, T90 and EP were measured according to JIS K2254 “Petroleum products-distillation test method”. The results are shown in Table 1, Table 4, and Table 5.

  In order to evaluate the oxidation stability of the light oil compositions according to Examples 1 to 3 and the light oil compositions according to Comparative Examples 1 to 4, JIS K2287 “Gasoline-oxidation stability test method—induction period method” The test period was changed from 100 ° C. to 140 ° C., and the induction period was determined as an index of oxidation stability under more severe conditions. The induction period in this test was the time until the pressure in the container dropped by 10% from the maximum value. The results are shown in Table 6.

In addition, in order to evaluate the oxidation stability of the light oil composition according to Example 1 to Example 3 and the light oil composition according to Comparative Example 1 to Comparative Example 4, storage at 100 ° C. for a certain period in the container. The amount of peroxide (peroxide) in the light oil composition after the measurement was measured. The peroxide amount was measured in accordance with JPI-5S-46-96 “Testing method for kerosene peroxide”. The amount of peroxide after the test was measured at a test temperature of 100 ° C. and 140 ° C., which is higher than the conventional test method. The results are shown in Table 6.
Test temperature: 100 ° C or 140 ° C
Sample volume: 300ml
Container material: Borosilicate glass Container capacity: 500ml
Atmosphere: Oxygen normal pressure sealed Light presence: Dark steel piece (SPCC): 1 x 20 x 50 mm Test period: 20 hours

  Furthermore, in order to evaluate the combustibility of the light oil compositions according to Examples 1 to 3 and the light oil compositions according to Comparative Examples 1 to 4, an exhaust gas test was conducted using a diesel engine, We measured the black smoke concentration, which is an indicator of the amount of material discharged. The exhaust gas test is based on TRIAS 24-5-1999 “Diesel vehicle 13 mode exhaust gas test method”, and is a diesel engine (model: 4HL1) manufactured by Isuzu Motors Co., Ltd. GSM (registered trademark) -10) was used under steady conditions with an engine speed of 1800 rpm and a load of 60%. Regarding the black smoke density obtained by the measurement, Table 6 shows the relative black smoke density when the measurement result in Example 3 is 1.0.

  Furthermore, in order to evaluate the low temperature fluidity of the light oil composition according to Examples 1 and 2 and the light oil composition according to Comparative Examples 1 and 2, in accordance with JIS K2288 "Petroleum products-light oil-clogging point test method". Sought clogging point. The results are shown in Table 6.

From Table 6, the light oil compositions obtained in Examples 1 to 3 all have a long induction period of 98 minutes or more, and the peroxide amount is less than 1 ppm by mass even after a storage test at 100 ° C. I understand. Moreover, even after a storage test at 140 ° C., which is a harsher condition, it is understood that the amount of peroxide is a low level of 29 mass ppm or less.
The long induction period means that there are few substances that easily react with oxygen at the beginning of the decrease in oxidation stability, and that the light oil composition is hardly deteriorated by radical chain reaction. When the amount of oxide is small, it is difficult to generate peroxide over a long period of time. Generation of acid by decomposition of the light oil composition component that has become peroxide, and gum and sludge by polymerization of the light oil composition component that has become peroxide This means that the diesel oil compositions obtained in Examples 1 to 3 are all excellent in oxidation stability and oxidation stability even under severe conditions in recent diesel engines. It can be seen that it is possible to suppress the decrease of the.
Moreover, it turns out that the light oil composition obtained in Example 1, 2 shows the outstanding low-temperature fluidity | liquidity in spite of containing predetermined amount of saturated fatty-acid alkylester in a light oil composition. .
Further, from Table 6, the light oil compositions obtained in Examples 1 to 3 exhibit excellent combustibility that suppresses the generation of particulate matter because the relative graphite concentration in the engine test is low. I understand that there is.

On the other hand, from Table 6, the light oil compositions obtained in Comparative Examples 1 to 3 have a shorter induction period than Examples 1 to 3, and the amount of peroxide after the storage test at 100 ° C and 140 ° C is More than in Examples 1 to 3. In Comparative Example 3, the amount of peroxide after the storage test at 100 ° C. is equal to or less than 1 ppm by mass, but the amount of peroxide after the storage test at 140 ° C. is larger than that in Examples 1 to 3. It can be seen that the peroxide produced with the decrease in the oxidation stability is an oxidizing agent itself and promotes further oxidation of the light oil composition, so that the light oil obtained in Comparative Examples 1 to 3 is used. It can be seen that all the compositions are prone to decrease in oxidation stability.
Further, since the light oil composition obtained in Comparative Example 1 has a fatty acid alkyl ester content as high as 16% by mass, the low-temperature fluidity performance is higher than that of the light oil composition obtained in Example 1 or Example 2. It turns out that it has fallen.
Moreover, it can be seen from Table 6 that the light oil composition obtained in Comparative Example 4 has a significantly increased relative black smoke concentration and low combustibility that increases the amount of particulate matter generated.

  According to the present invention, the sulfur content is suppressed to 10 ppm by mass or less, and excellent combustibility to suppress the generation of particulate matter is exhibited, and the biomass fuel base material containing unsaturated fatty acid alkyl ester is contained. Nevertheless, it is possible to provide a light oil composition capable of suppressing a decrease in oxidation stability even under severe conditions.

Claims (2)

  The sulfur content is 10 mass ppm or less, the total content of tricyclic aromatic compounds, tetracyclic aromatic compounds and pentacyclic aromatic compounds is 700 to 3000 mass ppm, and the content of benzoanthracenes is 3.0 to 10.0 mass ppm, content of unsaturated fatty acid alkyl ester is 0.5 to 5 mass%, content of fatty acid alkyl ester including the unsaturated fatty acid alkyl ester is 1 to 10 mass% Light oil composition. Desulfurized gas oil fraction having a sulfur content of 10 mass ppm or less, a benzoanthracene content of 3.5 to 15.0 mass ppm, and a boiling range of 170 to 380 ° C.
A sulfur content of 10 mass ppm or less and a desulfurized kerosene fraction having a boiling point range of 140 to 290 ° C of 5 to 40 mass%,
The light oil composition of Claim 1 formed by mixing 1-10 mass% of fatty-acid alkylesters.