JP2011127083A - Multi-grade gas oil fuel composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a multi-grade gas oil fuel composition substantially constituted only by paraffin, suppressing the amount of a formulation compound other than paraffin such as a polycyclic aromatic compound and an oxidization stabilizer as much as possible while having both sufficient low temperature flowability and kinematic viscosity, and being excellent in oxidation stability. <P>SOLUTION: In the multi-grade gas oil fuel composition, the content of 14 and 15C normal paraffin relative to the whole content of the normal paraffin is 12.4% or higher, the pour point is -20.0°C or lower, the clogging point is -12.5°C or lower, the kinematic viscosity at 30°C is 2.7 mm<SP>2</SP>/s or higher, and the oxidization index OI=182.78-2.32×A-0.19×B-0.21×C is larger than 34.9. In the formula, A is, in proton nuclear magnetic resonance spectrum, the ratio(%) of the peak total area of a group of peaks at a chemical shift of 1.45-2.25 ppm relative to the peak total area of a group of peaks at a chemical shift of 1.00-1.45 ppm, B is 10% distillation temperature (°C), and C is 90% distillation temperature (°C). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a light oil fuel composition used for diesel engines and the like, particularly to a multi-grade light oil fuel composition that satisfies the quality of light oil defined in each of JIS K 2204.

  The distillation properties of the light oil fuel composition are appropriately adjusted depending on the region and season of use, and vary greatly depending on the application. For example, if it is used in a cold region, it will be light considering low temperature fluidity, while if it is used in summer, the restriction on low temperature fluidity will be relaxed. There is a tendency to use one that is as heavy as possible as long as it functions as a fuel. Since the light oil fuel compositions having different distillation properties depending on the use have different molecular weight distributions of the hydrocarbons constituting the composition, the properties are naturally expected to be different depending on the use. One of the properties that are considered to differ depending on the application is oxidation stability.

  It is known that when the diesel fuel composition is oxidized, discoloration, sludge formation, viscosity increase, etc. are observed, and peroxides generated by oxidation deteriorate the vehicle fuel system members (rubber materials, metals, etc.). ing. Therefore, oxidation stability is one of the important indexes for evaluating the quality stability of light oil fuel compositions, and a light oil fuel composition having excellent oxidation stability is desired.

  In particular, in a situation where a common rail fuel injection device is employed as a method for reducing particulates (particulate matter: hereinafter referred to as “PM”) in exhaust gas in recent diesel engines, light oil fuel is more than conventional. There is a need for higher oxidative stability of the composition. In the common rail fuel injection system, due to its structure, the remaining fuel that is not injected into the combustion chamber while being pumped to the injector is returned to the fuel tank through the return passage. The fuel returned to the fuel tank (return fuel) This is because oxidation of light oil fuel in the fuel tank is promoted due to the high temperature. The fuel supply pressure (common rail pressure) in this common rail fuel injection system is expected to increase further with the cleanliness of diesel engines in the future. In general, it is known that the higher the temperature of fuel oil, the easier it is to cause oxidative degradation. Therefore, about the light oil fuel composition used for the future diesel engine, there is a concern that the temperature of the fuel oil is increased due to the high pressure of the common rail, that is, the oxidation deterioration is accelerated. On the other hand, with respect to the oxidation stability of light oil fuel compositions, attempts have been made to improve it, and improvements are usually made by adding various oxidation stabilizers such as amines and phenols. Is widely practiced.

  In recent years, various studies have been conducted to use Fischer-Tropsch fuel (hereinafter referred to as FT fuel) as automobile fuel in Japan. FT fuel is a fuel obtained by synthesizing raw materials such as natural gas, coal, biomass, etc. by the Fischer-Tropsch method via carbon monoxide and hydrogen synthesis gas. Often. For example, natural gas as a raw material is often called GTL, coal as a raw material is called CTL, and biomass as a raw material is often called BTL. In some cases, the term GTL is used as a generic term for the fuel obtained by the Fischer-Tropsch method. In the present invention, the term FT fuel is used as a generic term for the fuel obtained by the Fischer-Tropsch method. It is assumed that GTL, CTL, BTL, etc. are included in the FT fuel.

  As described above, since this FT fuel is synthesized using natural gas, coal, biomass or the like as a raw material, it is used as an alternative fuel for petroleum, and since it does not contain sulfur or aromatic hydrocarbons, sulfur from the engine. It is expected to be used as an environmentally friendly light oil fuel that suppresses emissions of oxides and PM. For example, as reported in the energy economy November 2001 issue “Regarding the marketability of liquid fuel (GTL) from natural gas” (Non-Patent Document 1), commercialization has already been carried out in some areas. Some have been made.

  Further, various studies have been conducted on the practical use of this FT fuel in Japan. For example, in Japanese Patent Application Laid-Open No. 2008-214369 (Patent Document 1) by the present applicant, GTL is used as a conventional light oil fuel. Attempts have been made to mix a fraction corresponding to light oil (GTL light oil) and add a conventional oxidation stabilizer to the mixed oil. And here, it is described that the oxidation stability at high temperature can be enhanced by blending an antioxidant with a light oil fuel composition containing GTL light oil. However, the amount of antioxidant necessary to obtain the desired effect increases as the fuel with poor oxidation stability increases the manufacturing cost. Furthermore, as the amount of the antioxidant increases, the problem that the antioxidant easily precipitates due to a decrease in temperature, and conversely, if the amount of the additive is small, the antioxidant effect of the additive is consumed during oxidation. After that, there was a problem that the oxidation stability was remarkably deteriorated to adversely affect the metal members of the vehicle fuel system.

  On the other hand, Japanese Patent Application Laid-Open No. 2008-266617 (Patent Document 2) proposes maintaining the oxidation stability of light oil fuel without adding an antioxidant. Here, oxidation stability is obtained by blending one or more polycyclic aromatic compounds selected from the group consisting of anthracenes and dialkylnaphthalenes into a fraction corresponding to light oil of FT fuel (FT light oil). Yes.

JP 2008-214369 A JP 2008-266617 A

Energy Economy November 2001 "Marketability of liquid fuel (GTL) from natural gas"

  However, none of the above documents discusses oxidation stability in consideration of distillation properties that differ depending on the application, and in particular, low-temperature fluidity and kinematic viscosity that are affected by distillation properties. Moreover, one of the characteristics of FT gas oil is that it does not cause environmental problems related to aromatics and sulfur. This characteristic is due to the feature that it is composed only of paraffin. In the conventional technique which corresponds to the oxidation stability of the FT light oil by adding a fuel composition other than the FT light oil, there is a problem that the original characteristics of the FT light oil are not fully utilized.

  Furthermore, regarding the low temperature fluidity and kinematic viscosity that the distillation properties receive, there is a problem that they cannot be improved at the same time because they exhibit opposite behaviors to the distillation properties. The kinematic viscosity becomes smaller when the distillation property becomes lighter (when the distillation temperature decreases by 90%), whereas the low temperature fluidity becomes better. On the other hand, when the kinematic viscosity is low, it tends to be difficult to control the fuel injection timing on the fuel injection pump side, and the lubricity of each part of the fuel injection pump mounted on the engine may be impaired. However, in cold regions, in order to enable stable use, emphasis is placed on low-temperature fluidity, and the kinematic viscosity must be lower than that used in summer. .

  Therefore, the present invention is substantially composed only of paraffin, and both low temperature fluidity and kinematic viscosity affected by distillation properties that differ depending on the application are good, such as polycyclic aromatics and oxidation stabilizers, An object of the present invention is to provide a multi-grade light oil fuel composition excellent in oxidation stability, in which the amount of a compound other than paraffin is suppressed as much as possible.

The multigrade light oil fuel composition according to the present invention is substantially composed only of paraffin, and the content of normal paraffins having 14 and 15 carbon atoms with respect to the total normal paraffin content is 12.4% or more, and the pour point is −20. 0 ° C. or less, clogging point is −12.5 ° C. or less, kinematic viscosity at 30 ° C. is 2.7 mm ² / s or more, and oxidation index OI represented by the following formula is larger than 34.9.
OI = 182.78-2.32 × A−0.19 × B−0.21 × C
(A: In the proton nuclear magnetic resonance spectrum, the ratio of the total peak area of the peak group at a chemical shift of 1.45 to 2.25 ppm to the total peak area of the peak group at a chemical shift of 1.00 to 1.45 ppm,% B: distillation 10% distillation temperature, ° C., C: distillation 90% distillation temperature, ° C.)

  In the present invention, “substantially only paraffin” means that styrene compounds, diene compounds, and condensed polycyclic aromatics are not included in the main components, and it is allowed that a composition other than paraffin is included as an impurity. Is done. For example, FT gas oil in which the total mass or volume of isoparaffin and normal paraffin is 99% or more excluding slight impurities is the gas oil fuel composition of the present invention substantially composed only of paraffin. In addition to the Fischer-Tropsch method, there is also a method for hydrotreating animal and plant fats and oils that are raw materials for biomass as a method for producing a fuel composed only of paraffin. Among the fuels produced in this way, those corresponding to light oil are called second-generation biodiesel fuels, etc., but this second-generation biodiesel fuel is also only paraffin in the practice of the present invention. It is the light oil fuel composition comprised by these. In addition, additives may be added as appropriate without departing from the scope of the present invention.

  Examples of the additive include a lubricity improver for preventing wear of fuel supply pump parts and the like. As the lubricity improver, any known lubricity improver can be used as long as it is compatible with paraffin. Typical lubricity improvers include commercially available lubricity improvers such as acid-based fatty acid-based esters and glycerin mono-fatty acid ester-based ester-based compounds. These compounds can be used alone or in combination of two or more. The fatty acid used in these lubricity improvers is mainly composed of an unsaturated fatty acid having about 12 to 22 carbon atoms, preferably about 18 carbon atoms, that is, a mixture of oleic acid, linoleic acid, linolenic acid and the like. Is preferred. The lubricity improver may be added so that the wear trace of WS1.4 value in the HFRR (High Frequency Reciprocating Rig) of the fuel oil composition after the addition of the lubricity improver is 500 μm or less, preferably 460 μm or less. Usually, it is 50 to 1000 ppm. Here, the WS1.4 value in HFRR means a value obtained by the Petroleum Institute Standard JPI-5S-50-98 “Light Oil-Lubricity Test Method”.

  Furthermore, other additives include detergents such as amine salts of alkenyl succinic acid derivatives, metal deactivators such as salicylidene derivatives, anti-icing agents such as polyglycol ethers, aliphatic amines, alkenyl succinic acid esters, etc. Corrosion inhibitors, anionic, cationic and amphoteric surfactants, anti-foaming agents such as silicon, and the like. These additives can be used alone or in combination of two or more. Although the addition amount can be selected as appropriate, it is, for example, 0.2% by mass or less with respect to the fuel oil composition.

  The multi-grade light oil fuel composition according to the present invention has a normal paraffin content of 14 and 15 carbon atoms with respect to the total normal paraffin content of 12.4% or more, a distillation property and a peak total area ratio of proton nuclear magnetic resonance as variables. By making the oxidation index OI represented by the predetermined formula larger than 34.9, the oxidation stability is excellent while satisfying the low temperature fluidity and kinematic viscosity of each item of JIS standard (JIS K 2204). Therefore, an additive such as a low-temperature fluidity improver, a kinematic viscosity improver, or an oxidation stabilizer becomes unnecessary. Therefore, it corresponds to light oil fuel that satisfies the quality of each item of JIS standard (JIS K 2204), and is substantially composed only of paraffin, and has excellent oxidation stability while minimizing the amount of compound other than paraffin. A multigrade diesel fuel composition can be obtained.

The light oil fuel composition is required to have low-temperature fluidity in consideration of use in cold regions and winter seasons. In general, from the viewpoint of improving this low-temperature fluidity, the smaller the normal paraffin having a large molecular weight, the better. However, from the viewpoint of kinematic viscosity, the more normal paraffin with a large molecular weight, the better. That is, when the light oil fuel composition is substantially composed only of paraffin, the low-temperature fluidity and kinematic viscosity, which are properties defined in JIS K 2204, tend to conflict with the composition. On the other hand, the present inventor presumed that the ratio of branching to the total length of the straight chain was related to oxidation stability, and made various attempts. As a result, the chemical shift of the proton nuclear magnetic resonance ( ¹ H-NMR) spectrum was found. The oxidation stability of a gas oil fuel composition substantially composed only of paraffin is related to the chemical peak relative to the peak total area of the peak group at a chemical shift of 1.00 to 1.45 ppm in the proton nuclear magnetic resonance spectrum. The fact that the shift is affected by the ratio of the total peak area of the peak group at 1.45 to 2.25 ppm and the distillation properties was confirmed.

  And in this way, in the light oil fuel composition substantially composed only of paraffin, the present inventor, while isoparaffin and normal paraffin affect the various properties required there in a complicated manner. , Low temperature fluidity, kinematic viscosity, and oxidative stability have a constant relationship with the normal paraffin content of carbon numbers 14 and 15 with respect to the total normal paraffin content, and the peak total area ratio of proton nuclear magnetic resonance and distillation properties Found the fact that That is, when the content of normal paraffins having 14 and 15 carbon atoms with respect to the total normal paraffin content is 12.4% or more, the chemical shift is 1.00 in the proton nuclear magnetic resonance spectrum indicating the hydrogen atom isotope species in the paraffin. The ratio of the total peak area of the peak group when the chemical shift is 1.45 to 2.25 ppm and the distillation properties (10% and 90% of each distillation temperature) with respect to the total peak area of the peak group at ˜1.45 ppm are variables. It has been found that the value obtained by the predetermined formula is an index of the oxidation stability of the light oil fuel composition defined in each item of JIS K 2204, which is substantially composed only of paraffin. The present invention is also based on these new findings.

  Examples of the light oil fuel composition according to the present invention will be described. However, the present invention is not limited to the following examples.

  A light oil fuel composition comprising a mixed oil of normal paraffin and isoparaffin produced by the SMDS (Shell Middle Distillate Synthesis) process, and an adjusted mixed oil whose distillation properties and composition were adjusted using an isoparaffin solvent and a normal paraffin solvent was obtained. . Table 1 shows the properties and composition of the obtained light oil fuel composition. The SMDS process means partial oxidation of natural gas, synthesis of heavy paraffin by Fischer-Tropsch synthesis, and hydrocracking and distillation of the resulting heavy paraffin oil to obtain naphtha, kerosene, and light oil fractions. Is a process. Table 1 also shows the properties of conventional FT gas oil as reference examples.

In addition, each property shown in Table 1 is measured by the following method.
<Density (@ 15 ℃)>
Density at 15 ° C. measured by JIS K 2249 “Crude oil and petroleum products—Density test method and density / mass / volume conversion table”.
<Distillation properties>
Distillation properties obtained by JIS K 2254 "Petroleum products-Distillation test method".
<Cetane index>
It means the cetane index measured by JIS K 2280 “Petroleum products—fuel oil—octane number and cetane number test method and cetane index calculation method 8.4 cetane index calculation method using variable equation”. However, FT gas oil is outside the recommended application range for cetane index calculation, so it is shown as a reference value.
<Sulfur content>
Sulfur content obtained by JIS K 2541-2 "Crude oil and petroleum products-Sulfur content test method Part 2: Micro coulometric titration method".
<Paraffin content>
Paraffin content measured by JPI-5S-49-97 "Petroleum products-Hydrocarbon type test method-High performance liquid chromatograph method".
<Aromatic content>
Sum of 1-ring aromatics, 2-rings aromatics and 3 or more-rings aromatic hydrocarbons measured by JPI-5S-49-97 "Petroleum products-Hydrocarbon type test method-High performance liquid chromatograph method" .
<Total normal paraffin content and C14 and C15 normal paraffin content>
The normal paraffin content of each carbon number was obtained from the gas chromatograph method of each carbon based on ASTM D 2887 “Standard Test Method for Boiling Range Distribution of Petroleum Fraction by Gas Chromatography”, and the carbon number of each carbon was determined. Obtained by calculating the amount. That is, the retention time was examined using a mixture of normal paraffins having different carbon numbers as a standard, and the content of normal paraffin was determined from the peak area value of normal paraffin. Since the gas chromatography detector is a flame ionization detector (FID), the measurement sensitivity is proportional to the carbon number of paraffin. Therefore, taking this sensitivity into consideration, the content molar ratio was determined from the area value, and finally each mass ratio was determined. The total normal paraffin content was the total value of the normal paraffin content of each carbon number.
The type of column in the gas chromatographic method is HP5 (length: 30 m, inner diameter: 0.32 mm, liquid layer thickness: 0.25 μm), and each analysis condition is as follows.
Column tank temperature rising condition: 35 ° C. (5 minutes) → 10 ° C./minute (temperature rising) → 320 ° C. (11.5 minutes)
Sample vaporization chamber condition: constant 320 ° C. split ratio 150: 1
Detector section: 320 ° C
<Peak total area ratio>
Proton nuclear magnetic resonance ( ¹ H-NMR) spectrum analysis was performed, and the obtained spectrum had a chemical shift of 1.45 to 2.25 ppm relative to the total peak area of the peak group at a chemical shift of 1.00 to 1.45 ppm. Percentage of the total peak area of the peak group at.
<Pour point>
Pour point obtained by JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.
<Clogging point>
A clogging point obtained by JIS K 2288 "Petroleum products-light oil-clogging point test method".
<Kinematic viscosity (@ 30 ° C)>
Kinematic viscosity obtained by JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity pour point test method and viscosity index calculation method”.

Next, the PetroOXY method was used as an index of oxidation stability in Examples 1 to 5, Comparative Examples 1 to 5, and Reference Example. The measurement conditions are as shown below.
<PetroOXY value>
Using an oxidation stability test apparatus PetroOXY (registered trademark, product name, Petrotest), the elapsed time until the pressure is reduced by 10% from the maximum pressure is measured. In this test, a test temperature of 140 ° C. was adopted in order to evaluate oxidation stability at high temperatures.
Moreover, the oxidation index OI was calculated | required from the ratio of the peak total area shown in Table 1, and distillation property. These results are shown together in Table 2.

  As shown in Table 2, each of Examples 1 to 5 is composed only of paraffin, and satisfies both the most severe standards of low-temperature fluidity and kinematic viscosity in each item of JIS standard (JIS K 2204). However, the PetroOXY value was larger than that of the reference example which is a conventional FT light oil, and it was confirmed that the oxidation stability was excellent. On the other hand, the oxidation stability of Comparative Example 1 is worse than that of the conventional FT light oil. In Comparative Examples 2 to 5, the PetroOXY value is higher than that of the reference example and the oxidation stability is improved, but the quality of any one of No. 1, No. 2, No. 3 of JIS standard (JIS K 2204) is provided. Absent. That is, Comparative Example 2 has a small kinematic viscosity, and Comparative Examples 3 to 5 have high clogging points.

Furthermore, in all of Examples 1 to 5, it was confirmed that the distillation 90% distillation temperature was JIS K 2204 No. 3 standard, that is, 330 ° C. or lower. That is, while having a higher kinematic viscosity than light oil fuel that satisfies the standard of JIS K 2204 No. 3, the distillation 90% distillation temperature is 330 ° C. or less, so that a good spray is formed in the engine. It was also confirmed that while maintaining a good combustion state and avoiding a decrease in output, it was possible to reduce PM emissions and to have performance superior to conventional light oil fuel.

Claims (1)

Substantially composed only of paraffin, the normal paraffin content of 14 and 15 carbon atoms with respect to the total normal paraffin content is 12.4% or more, the pour point is −20.0 ° C. or less, and the clogging point is −12.5. A multigrade light oil fuel composition having a kinematic viscosity at 30 ° C. or lower and 2.7 mm ² / s or higher and an oxidation index OI represented by the following formula of greater than 34.9.
OI = 182.78-2.32 × A−0.19 × B−0.21 × C
(A: In the proton nuclear magnetic resonance spectrum, the ratio of the total peak area of the peak group at a chemical shift of 1.45 to 2.25 ppm to the total peak area of the peak group at a chemical shift of 1.00 to 1.45 ppm,% B: distillation 10% distillation temperature, ° C., C: distillation 90% distillation temperature, ° C.)