JP2007270105A - Gas oil composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas oil composition for summer suitable for both diesel combustion and premixed compression ignition combustion. <P>SOLUTION: The gas oil composition comprises an FT synthetic base material and has a sulfur content of not more than 5 mass ppm, an oxygen content of not more than 100 mass ppm, a bulk modulus of 1,250 to 1,450 MPa, a Saybolt color of not less than +22, a lubrication ability of not more than 400 μm, an initial boiling point of not lower than 140°C and an end point of not higher than 380°C in the distillation properties, fraction ranges of (1) lower than 200°C, (2) 200°C to lower than 280°C, and (3) not lower than 280°C having specific cetane numbers, respectively, and constitution ratios of the fractions to the entire volume of 1 to less than 10 vol.%, 40 to less than 98 vol.%, and 1-59 vol.%, respectively, and is used in a supercharger and a diesel engine with EGR having a geometrical compression ratio of more than 16, and satisfies the JIS No.1 gas oil specifications in the quality item properties other than the sulfur content. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a light oil composition used in summer, and more particularly to a light oil composition for summer suitable for both diesel combustion and premixed compression ignition combustion.

  In diesel combustion, when this fuel injected into the engine combustion chamber evaporates and mixes with air to become a premixed gas with an appropriate fuel / air ratio, and ignition (premixed combustion) starts when the temperature reaches an appropriate temperature condition Has been. In many cases, this ignition is examined for its goodness or badness by evaporating performance due to the distillation properties of the fuel and the cetane number indicating self-igniting performance. When further output is required for diesel combustion (high load range), it is necessary to continue to inject fuel even after self-ignition has occurred. In this case, fuel spray is applied using air flow inside the engine combustion chamber. It is necessary to burn (diffusion combustion) while diffusing into the air atmosphere. Therefore, it can be said that what is required for fuel properties is a property that supports premixed combustion and a property that supports diffusion combustion.

  Premixed compression ignition combustion is a combustion form derived from these diesel combustions, and has recently received attention due to its low emission performance and excellent fuel efficiency. The difference from the above-mentioned diesel combustion is that the entire combustion stroke is premixed combustion and there is no diffusion combustion. However, as described above, since ignition starts due to the self-ignition performance of the fuel, it is difficult to control ignition particularly in a high load range. For this reason, many engines adopt a combustion concept that performs premixed compression ignition fuel only at low and medium loads and switches to normal diesel combustion in the high load range. Therefore, it can be said that what is required for fuel properties is both a factor that supports premixed compression ignition combustion in a low load region and a factor that supports diesel combustion in a high load region.

  Generally, gas oil compositions are obtained by hydrorefining or hydrodesulfurizing straight-run gas oil obtained from crude oil atmospheric distillation equipment, or hydrotreating straight-run kerosene obtained from crude oil atmospheric distillation equipment. It is manufactured by blending one or two or more substrates subjected to hydrodesulfurization treatment. In particular, in order to ensure low temperature fluidity in winter, the mixing ratio of the above kerosene base and gas oil base is often controlled, and cetane number improvers, detergents, and low temperature fluidity improvement as necessary. An additive such as an agent is blended (see, for example, Non-Patent Document 1).

  With regard to the above-mentioned fuel for premixed compression ignition combustion, for example, a diesel light oil composition characterized by blending a relatively light catalytic cracking light oil with Patent Document 1 and having a low cetane number, a high density, and a high aromatic content. Is disclosed. According to this document, it is described that it is possible to achieve both low temperature performance, low NOx, and low PM performance, which are excellent for premixed compression ignition combustion applications, but the disadvantages of premixed compression ignition combustion due to its extremely high aromatic content. It is easily expected that the amount of unburned fuel will increase. In addition, as described above, currently, premixed compression ignition combustion and general diesel combustion are often used in parallel, and in the fuel characterized by low cetane number, high density, and high aromatic content in this document It is clear that it is totally unsuitable for such combustion. Furthermore, because of the high aromatic content, it is easy to predict soot and deposit deposits on injection nozzles, EGR (exhaust gas recirculation) control valves, etc., so this document is fundamental as an environmentally friendly fuel. Not doing. Similarly, Patent Document 2, Patent Document 3, and Patent Document 4 show that the distillation property is defined as a function, and that it is effective for premixed compression ignition combustion. As described above, the distillation property is self-ignitability of fuel. It is thought that the effect of evaporation characteristics is still small, especially when premixed compression ignition combustion of the type that injects fuel early as in this document is presupposed. . Further, an index of temperature per distillate amount, such as T90, but not a distillate amount can be a guide for knowing the characteristics of the fuel, but it does not make sense because it is not an absolute quantitative definition. In addition, although the so-called cetane number itself is suppressed to a low value, the content of the saturated hydrocarbon compound required for active ignition control is on the other hand decreasing, so it is a fuel that cannot be controlled arbitrarily It can be said. Therefore, it is clear that these definitions cannot be said to be a fuel property that can control self-ignition, and it is considered that environmentally friendly fuel has not been realized.

In view of the usage environment, it is necessary for the environment-friendly fuel to optimize the fuel properties for each season. Assuming the use in summer, which is covered by the present invention, fuels with excessively light distillation properties often have problems with injection pump seizure, cavitation damage and high temperature restartability.
In other words, designing a high-quality fuel that can simultaneously achieve a high level of requirements required for a light oil composition that has both practical performance in an excellent summer environment and environmentally compatible performance that can also be applied to premixed compression ignition combustion. It is very difficult, and there are no examples or knowledge based on the examination of realistic production methods that sufficiently satisfy various performances required for other fuel oils.
JP 2006-28493 A JP 2005-343917 A JP 2005-343918 A JP 2005-343919 A Seiichi Konishi, “Introduction to Fuel Engineering”, Saika Hanafusa, March 1991, p. 136-144

  The present invention has been made in view of such a situation, and an object of the present invention is to provide a light oil composition for use in summer, and more specifically, summer suitable for both diesel combustion and premixed compression ignition combustion. The light oil composition for is provided.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, blended with an FT synthetic substrate, the sulfur content is 5 mass ppm or less, the oxygen content is 100 mass ppm or less, the volume modulus is 1250 MPa to 1450 MPa, the Saybolt color is +22 or more, and the lubrication performance is 400 μm or less. A supercharger having a distillation compression initial boiling point of 140 ° C. or more, an end point of 380 ° C. or less, and having the following characteristics (1) to (3) in each fraction range, and a geometric compression ratio exceeding 16: A diesel fuel composition that satisfies the JIS No. 1 diesel standard for quality items other than sulfur used in diesel engines with EGR.
(1) The cetane number in the fraction range of less than 200 ° C. is 20 or more and less than 40, and the composition ratio per volume in the whole fraction is 1% by volume or more and less than 10% by volume.
(2) The cetane number in the fraction range of 200 ° C. or more and less than 280 ° C. is 30 or more and less than 60, and the composition ratio per volume in the whole fraction is 40% by volume or more and 98% by volume or less.
(3) The cetane number in the fraction range of 280 ° C. or higher is 50 or more, and the composition ratio per volume in the whole fraction is 1 volume% or more and 59 volume% or less.

  Preferably, the peroxide value after the accelerated oxidation test is 50 mass ppm or less, the aromatic content is 15% by volume or less, and more preferably, the blending ratio of the FT synthetic substrate is 20% by volume or more. It is a light oil composition.

  The intent of the present invention is to consider not only the ignition phenomenon but also the evaporation phenomenon in the previous stage and the mixing phenomenon with air, and the light fraction that evaporates relatively early and the heavy fraction that evaporates relatively later. This is a balance of quality fractions including ignitability. Thereby, an optimal ignition state can be supported in both premixed compression ignition combustion and general diesel combustion. Since these ignition phenomena are highly dependent on the compression ratio and intake conditions on the engine side to be used, in order to exert the most excellent effect in the present invention, the conditions of the engine to be used are also restricted.

  According to the present invention, by using the light oil composition produced by the above production method, fraction regulation, etc., the practical performance and the premixing in the summer environment, which was difficult to realize with the conventional light oil composition, were achieved. It is possible to provide a high-quality fuel that can simultaneously achieve a high level of environmental performance that can be applied to compression ignition combustion.

Hereinafter, the present invention will be described in detail.
The light oil composition of the present invention needs to contain an FT synthesis base material. The FT synthesis base material is composed of a saturated hydrocarbon compound, and the light oil composition of the present invention can be easily produced by controlling the blending thereof. The properties of the FT synthetic substrate are not particularly limited in satisfying the properties of the light oil composition of the present invention. There are no particular restrictions on the base material other than the FT synthetic base material in satisfying the properties of the light oil composition of the present invention. It is preferable to blend the petroleum-based base material and the processed oil derived from animals and plants.

  The FT synthesis base material is equivalent to naphtha, kerosene, or light oil obtained by applying a Fischer-Tropsch (FT) reaction to a mixed gas (also referred to as synthesis gas) mainly composed of hydrogen and carbon monoxide. Liquid fraction, and hydrocarbon mixture obtained by hydrotreating and hydrocracking them, and liquid fraction and FT wax are produced by FT reaction, and obtained by hydrotreating and hydrocracking this. It shows the base material which consists of a hydrocarbon mixture.

The light oil composition of the present invention preferably contains 20% by volume or more of the FT synthetic base material. Further, for the purpose of reducing the frequency of increasing environmental loads such as sulfur and aromatics and more effectively performing the ignition control required for premixed compression ignition combustion, 25% by volume or more is more preferable. 30% by volume or more is more preferable, and 35% by volume or more is even more preferable.
The properties of the FT synthesis base material used in the present invention are not particularly limited as long as the light oil composition of the present invention has predetermined properties, but it is easy to produce the light oil composition of the present invention. From this point, the blending of a synthetic base material having a boiling range of 140 to 380 ° C. is preferable.

The mixed gas used as the raw material of the FT synthesis base material is obtained by oxidizing a carbon-containing substance using oxygen and / or water and / or carbon dioxide as an oxidizing agent, and further using a shift reaction using water as necessary. It is obtained by adjusting to a predetermined hydrogen and carbon monoxide concentration.
Substances containing carbon include natural gas, petroleum liquefied gas, methane gas, etc., gas components consisting of hydrocarbons that are gaseous at room temperature, petroleum asphalt, biomass, coal, waste such as building materials and garbage, sludge, In addition, mixed gas obtained by exposing heavy crude oil, unconventional petroleum resources, etc. that are difficult to process by ordinary methods to high temperatures is common, but mixed gas mainly composed of hydrogen and carbon monoxide As long as is obtained, the present invention does not limit the raw materials.

  A Fischer-Tropsch reaction requires a metal catalyst. Preferably, the method uses a group 8 metal of the periodic table, for example, cobalt, ruthenium, rhodium, palladium, nickel, iron, etc., more preferably a group 8 group 4 metal as the active catalyst component. Moreover, the metal group which mixed these metals in an appropriate amount can also be used. These active metals are generally used in the form of a catalyst obtained by being supported on a support such as silica, alumina, titania or silica alumina. Further, by using these catalysts in combination with a second metal in addition to the above active metal, the catalyst performance can be improved. Examples of the second metal include zirconium, hafnium, titanium, and the like in addition to alkali metals and alkaline earth metals such as sodium, lithium, and magnesium, and a chain that serves as an index for improving the conversion rate of carbon monoxide and generating wax. It is used appropriately according to the purpose, such as an increase in growth probability (α).

  The Fischer-Tropsch reaction is a synthesis method that generates a liquid fraction and FT wax using a mixed gas as a raw material. In order to efficiently perform this synthesis method, it is generally preferable to control the ratio of hydrogen to carbon monoxide in the mixed gas. The molar mixing ratio of hydrogen to carbon monoxide (hydrogen / carbon monoxide) is preferably 1.2 or more, more preferably 1.5 or more, and even more preferably 1.8 or more. The ratio is preferably 3 or less, more preferably 2.6 or less, and even more preferably 2.2 or less.

  When performing the Fischer-Tropsch reaction using the catalyst, the reaction temperature is preferably 180 ° C. or higher and 320 ° C. or lower, and more preferably 200 ° C. or higher and 300 ° C. or lower. When the reaction temperature is less than 180 ° C., carbon monoxide hardly reacts and the hydrocarbon yield tends to be low. On the other hand, when the reaction temperature exceeds 320 ° C., the amount of gas such as methane increases, and the production efficiency of the liquid fraction and FT wax decreases.

No particular restriction on the gas hourly space velocity relative to the catalyst, but preferably 500h ^-1 or more 4000h ^-1 or less, 1000h ^-1 or more 3000h ^-1 or less is more preferable. If the gas space velocity is less than 500 h ⁻¹ , the productivity of the liquid fuel tends to decrease. If the gas space velocity exceeds 4000 h ⁻¹ , the reaction temperature must be increased, and gas generation increases, resulting in a yield of the target product. It will decline.

  The reaction pressure (partial pressure of synthesis gas composed of carbon monoxide and hydrogen) is not particularly limited, but is preferably 0.5 MPa or more and 7 MPa or less, and more preferably 2 MPa or more and 4 MPa or less. If the reaction pressure is less than 0.5 MPa, the yield of the liquid fuel tends to decrease, and if it exceeds 7 MPa, the amount of capital investment tends to increase, which is uneconomical.

  The FT synthesis substrate can be obtained by hydrorefining or hydrocracking the liquid fraction and FT wax produced by the above FT reaction by any method and adjusting them to the distillation properties, composition, etc. suitable for the purpose. Hydrorefining and hydrocracking may be selected in accordance with the purpose, and selection of only one or a combination of both methods is not limited in any way as long as the light oil composition of the present invention can be produced. .

The catalyst used for hydrorefining is generally a catalyst in which a hydrogenation active metal is supported on a porous carrier, but the present invention does not limit the form of the catalyst as long as the same effect can be obtained.
An inorganic oxide is preferably used as the porous carrier. Specific examples include alumina, titania, zirconia, boria, silica, zeolite, and the like.
Zeolite is a crystalline aluminosilicate, and includes faujasite, pentasil, mordenite, etc., preferably faujasite, beta, mordenite, particularly preferably Y type and beta type. Of these, the Y type is preferably ultra-stabilized.

As the active metal, the following two types (active metal A type and active metal B type) are preferably used.
The active metal A type is at least one metal selected from Group 8 metals of the Periodic Table. Preferably, it is at least one selected from Ru, Rh, Ir, Pd and Pt, and more preferably Pd or / and Pt. The active metal may be a combination of these metals. For example, Pt—Pd, Pt—Rh, Pt—Ru, Ir—Pd, Ir—Rh, Ir—Ru, Pt—Pd—Rh, Pt—Rh— Ru, Ir-Pd-Rh, Ir-Rh-Ru, and the like. When using a noble metal catalyst composed of these metals, it can be used after pre-reduction treatment in a hydrogen stream. In general, when a gas containing hydrogen is circulated and heat of 200 ° C. or higher is applied according to a predetermined procedure, the active metal on the catalyst is reduced, and hydrogenation activity is exhibited.
Further, as the active metal B type, it contains at least one metal selected from Group 6A and Group 8 metals of the periodic table, and preferably contains two or more metals selected from Groups 6A and 8 What you are doing can also be used. For example, Co-Mo, Ni-Mo, Ni-Co-Mo, and Ni-W can be mentioned. When using a metal sulfide catalyst made of these metals, it is necessary to include a preliminary sulfidation step.

  As the metal source, a general inorganic salt or a complex salt compound can be used, and as a supporting method, any method of a supporting method used in an ordinary hydrogenation catalyst such as an impregnation method or an ion exchange method can be used. When a plurality of metals are supported, they may be supported simultaneously using a mixed solution, or may be sequentially supported using a single solution. The metal solution may be an aqueous solution or an organic solvent.

The reaction temperature when hydrotreating using a catalyst composed of an active metal A type is preferably 180 ° C. or higher and 400 ° C. or lower, more preferably 200 ° C. or higher and 370 ° C. or lower, and 250 ° C. or higher and 350 ° C. or lower. More preferably, the temperature is 280 ° C. or lower and even more preferably 280 ° C. or higher and 350 ° C. or lower. When the reaction temperature in hydrorefining exceeds 370 ° C., side reactions that decompose into a naphtha fraction increase and the yield of the middle fraction is extremely reduced, which is not preferable. On the other hand, when the reaction temperature is lower than 270 ° C., the alcohol component cannot be completely removed and is not preferable.
The reaction temperature when hydrotreating using a catalyst comprising an active metal B type is preferably 170 ° C. or higher and 320 ° C. or lower, more preferably 175 ° C. or higher and 300 ° C. or lower, and 180 ° C. or higher and 280 ° C. More preferably, it is not higher than ° C. If the reaction temperature in the hydrorefining exceeds 320 ° C., side reactions that decompose into naphtha fractions increase, and the yield of middle fractions is extremely undesirably reduced. On the other hand, when the reaction temperature is lower than 170 ° C., the alcohol component cannot be completely removed and is not preferable.

The hydrogen pressure when hydrotreating using a catalyst composed of an active metal A type is preferably 0.5 MPa or more and 12 MPa or less, and more preferably 1.0 MPa or more and 5.0 MPa or less. The higher the hydrogen pressure, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.
The hydrogen pressure when hydrotreating using a catalyst composed of an active metal B type is preferably 2 MPa or more and 10 MPa or less, more preferably 2.5 MPa or more and 8 MPa or less, and 3 MPa or more and 7 MPa or less. More preferably. The higher the hydrogen pressure, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.

The liquid hourly space velocity which hydrorefining is carried out using a catalyst composed of the active metal A type (LHSV) is preferably at 0.1 h ^-1 or more 10.0H ^-1 or less, 0.3h ^-1 or 3 More preferably, it is 5 h ⁻¹ or less. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, an extremely large reaction tower volume is required, resulting in excessive capital investment, which is not economical.
The liquid hourly space velocity which hydrorefining is carried out using a catalyst composed of the active metal B type (LHSV) is preferably at 0.1 h ^-1 or more ^{2h -1} or less, 0.2 h ^-1 or more 1.5h more preferably ^{1 or} less, and more preferably 0.3h ^-1 or 1.2 h ^-1. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, an extremely large reaction tower volume is required, resulting in excessive capital investment, which is not economical.

The hydrogen / oil ratio is preferably 50 NL / L or more and 1000 NL / L or less, more preferably 70 NL / L or more and 800 NL / L or less when hydrotreating using a catalyst composed of an active metal A type. preferable. The higher the hydrogen / oil ratio, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.
The hydrogen / oil ratio when hydrotreating using a catalyst composed of an active metal B type is preferably 100 NL / L or more and 800 NL / L or less, more preferably 120 NL / L or more and 600 NL / L or less. Preferably, it is 150 NL / L or more and 500 NL / L or less. The higher the hydrogen / oil ratio, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.

The catalyst used for hydrocracking is generally one in which a hydrogenation active metal is supported on a carrier having a solid acid property, but the present invention does not limit the form of the catalyst as long as the same effect can be obtained. Absent.
Supports having a solid acid property include amorphous and crystalline zeolites. Specific examples include amorphous silica-alumina, silica-magnesia, silica-zirconia, silica-titania and zeolite faujasite type, beta type, MFI type, and mordenite type. Preferred are faujasite type, beta type, MFI type, and mordenite type zeolite, and more preferred are Y type and beta type. The Y type is preferably ultra-stabilized.

As the active metal, the following two types (active metal A type and active metal B type) are preferably used.
The active metal A type is at least one metal selected from Group 6A and Group 8 metals in the periodic table. Preferably, it is at least one metal selected from Ni, Co, Mo, Pt, Pd and W. When using a noble metal catalyst composed of these metals, it can be used after pre-reduction treatment in a hydrogen stream. In general, when a gas containing hydrogen is circulated and heat of 200 ° C. or higher is applied according to a predetermined procedure, the active metal on the catalyst is reduced, and hydrogenation activity is exhibited.
The active metal B type may be a combination of these metals, and examples thereof include Pt—Pd, Co—Mo, Ni—Mo, Ni—W, and Ni—Co—Mo. Moreover, when using the catalyst which consists of these metals, it is preferable to use after pre-sulfiding.

  As the metal source, a general inorganic salt or a complex salt compound can be used, and as a supporting method, any method of a supporting method used in an ordinary hydrogenation catalyst such as an impregnation method or an ion exchange method can be used. When a plurality of metals are supported, they may be supported simultaneously using a mixed solution, or may be sequentially supported using a single solution. The metal solution may be an aqueous solution or an organic solvent.

  The reaction temperature when performing hydrocracking using a catalyst comprising an active metal A type and an active metal B type is preferably 200 ° C. or higher and 450 ° C. or lower, more preferably 250 ° C. or higher and 430 ° C. or lower. More preferably, it is 300 ° C. or more and 400 ° C. or less. If the reaction temperature in the hydrocracking exceeds 450 ° C., side reactions that decompose into a naphtha fraction increase and the yield of the middle fraction is extremely reduced, which is not preferable. On the other hand, when the temperature is lower than 200 ° C., the activity of the catalyst is remarkably lowered, which is not preferable.

  The hydrogen pressure when hydrocracking using a catalyst comprising an active metal A type and an active metal B type is preferably 1 MPa or more and 20 MPa or less, more preferably 4 MPa or more and 16 MPa or less, and 6 MPa or more and 13 MPa. More preferably, it is as follows. The higher the hydrogen pressure is, the more hydrogenation reaction is promoted. However, the decomposition reaction rather slows down and the progress of the reaction needs to be adjusted by increasing the reaction temperature, leading to a decrease in catalyst life. For this reason, there is generally an economical optimum for the reaction temperature.

The liquid hourly space velocity which hydrocracking is carried out using a catalyst composed of the active metal A type (LHSV) is preferably at 0.1 h ^-1 or more ^{10h -1} or less, 0.3h ^-1 over 3.5h More preferably, it is ⁻¹ or less. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, an extremely large reaction tower volume is required, resulting in excessive capital investment, which is not economical.
The liquid hourly space velocity which hydrocracking is carried out using a catalyst composed of the active metal B type (LHSV) is preferably at 0.1 h ^-1 or more ^{2h -1} or less, 0.2 h ^-1 or more 1.7h more preferably ^{1 or} less, and more preferably 0.3h ^-1 or 1.5 h ^-1. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, an extremely large reaction tower volume is required, resulting in excessive capital investment, which is not economical.

The hydrogen / oil ratio is preferably 50 NL / L or more and 1000 NL / L or less, more preferably 70 NL / L or more and 800 NL / L or less when hydrocracking using a catalyst composed of an active metal A type. Preferably, it is 400 NL / L or more and 1500 NL / L or less. The higher the hydrogen / oil ratio, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.
The hydrogen / oil ratio is preferably 150 NL / L or more and 2000 NL / L or less, more preferably 300 NL / L or more and 1700 NL / L or less when hydrocracking using a catalyst composed of an active metal B type. Preferably, it is 400 NL / L or more and 1500 NL / L or less. The higher the hydrogen / oil ratio, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.

The apparatus for hydrotreating may be of any configuration, the reaction towers may be used alone or in combination, hydrogen may be additionally injected between the reaction towers, gas-liquid separation operation, hydrogen sulfide removal equipment, hydrogen It may have a distillation column for fractionating the chemical product and obtaining the desired fraction.
The reaction format of the hydrotreating apparatus can take a fixed bed system. Hydrogen can take either a countercurrent or a cocurrent flow with respect to the feedstock, and may have a plurality of reaction towers and a combination of countercurrent and cocurrent flow. The general format is downflow, and there is a gas-liquid twin parallel flow format. Hydrogen gas may be injected into the middle stage of the reaction tower as a quench for the purpose of removing reaction heat or increasing the hydrogen partial pressure. The mixed gas used as the raw material of the FT synthesis base material is obtained by oxidizing a carbon-containing substance using oxygen and / or water and / or carbon dioxide as an oxidizing agent, and further using a shift reaction using water as necessary. It is obtained by adjusting to a predetermined hydrogen and carbon monoxide concentration. Substances containing carbon include natural gas, petroleum liquefied gas, methane gas, etc., gas components consisting of hydrocarbons that are gaseous at room temperature, petroleum asphalt, biomass, coal, waste such as building materials and garbage, sludge, In addition, mixed gas obtained by exposing heavy crude oil, unconventional petroleum resources, etc. that are difficult to process by ordinary methods to high temperatures is common, but mixed gas mainly composed of hydrogen and carbon monoxide As long as is obtained, the present invention does not limit the raw materials.

  The petroleum base material is a hydrocarbon base material obtained by processing crude oil. Generally, the straight base material obtained from the atmospheric distillation apparatus, the straight-run heavy oil obtained from the atmospheric distillation apparatus or the residue Depressurized base material obtained by treating inspection oil with a vacuum distillation apparatus, catalytic cracking base material or hydrocracking base material obtained by catalytic cracking or hydrocracking of a decompressed heavy base material or desulfurized heavy oil, and these petroleum systems Examples thereof include hydrorefining base materials or hydrodesulfurization base materials obtained by hydrorefining hydrocarbons. In addition to crude oil, non-conventional petroleum resources, such as oil shells, oil sands, orinocotal, etc., are treated appropriately, and the base materials finished to the same performance as the above base materials are also petroleum. It can be used according to the base material.

  The highly hydrogenated petroleum-based base material according to the present invention is a kerosene oil fraction obtained by hydrorefining a predetermined feedstock and further hydrotreating it. As raw material oil, straight-run kerosene oil obtained from atmospheric distillation equipment, straight-run heavy oil obtained from atmospheric distillation equipment and residual oil obtained by processing with vacuum distillation equipment, desulfurization Examples thereof include hydrorefined kerosene oil and hydrodesulfurized kerosene oil obtained by hydrotreating undesulfurized vacuum kerosene light oil, depressurized heavy gas oil, or catalytic cracked kerosene obtained by catalytic cracking of desulfurized heavy oil.

The hydrorefining conditions when the feedstock is a light oil fraction may be those that have been processed using a hydrodesulfurization apparatus common in petroleum refining. In general, the reaction is performed under the conditions of a reaction temperature of 300 to 380 ° C., a hydrogen pressure of 3 to 8 MPa, an LHSV of 0.3 to 2 h ⁻¹ , and a hydrogen / oil ratio of 100 to 500 NL / L. The hydrorefining conditions when the feedstock is a kerosene fraction may be those that have been processed using a hydrodesulfurization apparatus common in petroleum refining. In general, the reaction temperature is 220 to 350 ° C., the hydrogen pressure is ^{1 to} 6 MPa, the LHSV is 0.1 to 10 h ⁻¹ , and the hydrogen / oil ratio is 10 to 300 NL / L. Preferably, the reaction temperature is 250 ° C. to 340 ° C., the hydrogen pressure is 2 to 5 MPa, the LHSV is ^{1 to} 10 h ⁻¹ , and the hydrogen / oil ratio is 30 to 200 NL / L, more preferably the reactivity is 270 ° C. to 330 ° C., the hydrogen pressure is 2 to 4 MPa. , LHSV2~10h ^-1, a hydrogen / oil ratio 50~200NL / L.
The lower the reaction temperature, the more advantageous for the hydrogenation reaction, but not for the desulfurization reaction. The higher the hydrogen pressure and the hydrogen / oil ratio, the more the desulfurization and hydrogenation reactions are promoted, but there is an optimal point economically. The lower the LHSV is, the more advantageous the reaction is. However, when the LHSV is too low, a very large reaction tower volume is required, resulting in excessive capital investment.

The catalyst used for these hydrorefining can apply the general catalyst for hydrodesulfurization. The active metal is usually a sulfide of group 6A or group 8 metal, and examples thereof include Co—Mo, Ni—Mo, Co—W, and Ni—W. As the carrier, a porous inorganic oxide mainly composed of alumina is used. These conditions and the catalyst are not particularly limited as long as the properties of the raw material oil are satisfied.
The feedstock according to the present invention is obtained by the above-described hydrorefining treatment, and preferably has a sulfur content of 5 ppm to 10 ppm and a boiling point range of 130 ° C to 380 ° C. When the sulfur content and boiling point range of the feedstock oil are within the above ranges, the properties defined in the following advanced hydroprocessing can be achieved easily and reliably.

The advanced hydrogenation treatment can be obtained by using the above-described hydrorefined kerosene as a raw material and further hydrotreating in the presence of a hydrogenation catalyst.
Advanced hydrotreating conditions are a reaction temperature of 170 to 320 ° C., a hydrogen pressure of 2 to 10 MPa, an LHSV of 0.1 to 2 h ⁻¹ , and a hydrogen / oil ratio of 100 to 800 NL / L. Preferably, the reaction temperature is 175 ° C to 300 ° C, the hydrogen pressure is 2.5 to 8 MPa, the LHSV is 0.2 to 1.5 h ^-1 , and the hydrogen / oil ratio is 150 to 600 NL / L, more preferably the reaction temperature is 180 ° C to 280 ° C. The hydrogen pressure is 3 to 7 MPa, the LHSV is 0.3 to 1.2 h ⁻¹ , and the hydrogen / oil ratio is 150 to 500 NL / L. The lower the reaction temperature, the more advantageous for the hydrogenation reaction, but not for the desulfurization reaction. The higher the hydrogen pressure and hydrogen / oil ratio, the more the desulfurization and hydrogenation reactions are promoted. The lower the LHSV, the more advantageous for the reaction, but if it is too low, a very large reaction tower volume is required, resulting in excessive capital investment.

The apparatus for hydrotreating hydrorefined feedstock may be of any configuration, the reaction towers may be used alone or in combination, more hydrogen may be injected between the reaction towers, and gas-liquid separation You may have operation and hydrogen sulfide removal equipment.
The reaction format of the hydrotreating apparatus of the present invention can be a fixed bed system. Hydrogen can take either a countercurrent or a cocurrent flow with respect to the feedstock, and may have a plurality of reaction towers and a combination of countercurrent and cocurrent flow. The general format is downflow, and there is a gas-liquid twin parallel flow format. Hydrogen gas may be injected into the middle stage of the reaction tower as a quench for the purpose of removing reaction heat or increasing the hydrogen partial pressure.

  The catalyst used for the hydrotreatment is a catalyst in which a hydrogenation active metal is supported on a porous carrier. Examples of the porous carrier include inorganic oxides such as alumina. Specific inorganic oxides include alumina, titania, zirconia, boria, silica, or zeolite. In the present invention, at least one of titania, zirconia, boria, silica, and zeolite is composed of alumina. Is good. The production method is not particularly limited, but any preparation method can be employed using raw materials in various sols, salt compounds, and the like corresponding to each element. Furthermore, once the composite hydroxide or composite oxide such as silica alumina, silica zirconia, alumina titania, silica titania, and alumina boria is prepared, the preparation process in the state of alumina gel and other hydroxides or in an appropriate solution state It may be prepared by adding at any step. The ratio of alumina to other oxides can be any ratio with respect to the porous carrier, but preferably alumina is 90% or less, more preferably 60% or less, more preferably 40% or less.

  Zeolite is a crystalline aluminosilicate, such as faujasite, pentasil, mordenite, etc., which is ultra-stabilized by a predetermined hydrothermal treatment and / or acid treatment, or one whose alumina content in the zeolite is adjusted is used. be able to. Preferably, faujasite, beta, and mordenite are used, particularly preferably Y type and beta type. The Y-type is preferably ultra-stabilized, and the ultra-stabilized zeolite by hydrothermal treatment forms new pores in the range of 20 to 100% in addition to the original pore structure called micropores of 20 cm or less. . Known conditions can be used for the hydrothermal treatment conditions.

  The active metal of the catalyst used for the hydrotreatment is at least one metal selected from Group 8 metals. Preferably, it is at least one selected from Ru, Rh, Ir, Pd, and Pt, and more preferably Pd or / and Pt. The active metal may be a combination of these metals, for example, Pt-Pd, Pt-Rh, Pt-Ru, Ir-Pd, Ir-Rh, Ir-Ru, Pt-Pd-Rh, Pt-Rh-Ru. , Ir-Pd-Rh, Ir-Rh-Ru, and the like can be used. As the metal source, a general inorganic salt or a complex salt compound can be used, and as a supporting method, any method of a supporting method used in an ordinary hydrogenation catalyst such as an impregnation method or an ion exchange method can be used. When a plurality of metals are supported, they may be supported simultaneously using a mixed solution, or may be sequentially supported using a single solution. The metal solution may be an aqueous solution or an organic solvent.

Metal loading may be performed after the completion of the entire preparation process of the porous support, or after further preloading on an appropriate oxide, composite oxide, zeolite in the intermediate process of porous support preparation, Heat concentration and kneading may be performed.
The amount of the active metal supported is not particularly limited, but is 0.1 to 10% by mass, preferably 0.15 to 5% by mass, and more preferably 0.2 to 3% by mass with respect to the catalyst mass.
The catalyst according to the present invention is used after a preliminary reduction treatment in a hydrogen stream. In general, when a gas containing hydrogen is circulated and heat of 200 ° C. or higher is applied according to a predetermined procedure, the active metal on the catalyst is reduced, and hydrogenation activity is exhibited.

  The treatment oil derived from animals and plants is composed of hydrocarbons obtained by applying the chemical reaction treatment applied when obtaining the above-mentioned petroleum-based base material to the oils and fats produced and produced from the animal and plant raw materials. It is a substrate. More specifically, an inorganic material having at least one metal selected from Group 6A and Group 8 of the periodic table and acid properties using a hydrocarbon fraction containing components derived from animal and plant oils and animal fats as raw material oils. A hydrocarbon-containing mixed base material which is brought into contact with a hydrocracking catalyst containing an oxide under hydrogen pressure. The raw material oil for the processed oil derived from animals and plants needs to be a component derived from animal and vegetable oils and fats. The animal and vegetable oils and fats and components derived from animal and vegetable oils and fats in the present invention refer to animal and vegetable oils and fats and components derived from animal and vegetable oils and fats that are produced or manufactured naturally or artificially. Animal fats and oils are made from beef tallow, milk fat (butter), pork tallow, sheep fat, whale oil, fish oil, liver oil, etc. (Rapeseed flowers), rice bran, sunflower, cottonseed, corn, soybean, sesame, linseed and other seeds and other parts can be mentioned, but other fats and oils can be used without problems. These raw oils may be solid or liquid, but it is preferable to use vegetable oils and vegetable oils as raw materials because of ease of handling, high carbon dioxide absorption capacity and high productivity. Moreover, in this invention, the waste oil which used these animal oils and vegetable oils for consumer use, industrial use, food use etc. can also be used as a raw material after adding the removal process of miscellaneous matters.

As a typical composition of the fatty acid portion of the glyceride compound contained in these raw materials, butyric acid (C ₃ H ₇ COOH), which is a fatty acid having no unsaturated bond in the molecular structure called saturated fatty acid, caproic acid ( C ₅ H ₁₁ COOH), caprylic acid (C ₇ H ₁₅ COOH), capric acid (C ₉ H ₁₉ COOH), lauric acid (C ₁₁ H ₂₃ COOH), myristic acid (C ₁₃ H ₂₇ COOH), palmitic acid ( C ₁₅ H ₃₁ COOH), stearic acid (C ₁₇ H ₃₅ COOH), and oleic acid (C ₁₇ H ₃₃ COOH), which is an unsaturated fatty acid having one or more unsaturated bonds, linoleic acid (C ₁₇ H ₃₁ COOH) ), linolenic acid _{(C 17} H 29 COOH), ricinoleic acid _{(C 17 H 32 (OH)} COOH) Hitoshigakyo It is. The hydrocarbon part of these fatty acids in natural substances is generally linear, but it is used in the present invention even if it has a structure having a side chain, that is, an isomer, as long as the properties defined in the present invention are satisfied. be able to. Further, the position of the unsaturated bond in the molecule of the unsaturated fatty acid is not limited to those generally found in nature as long as the properties defined in the present invention are satisfied in the present invention. The set one can also be used.
The above-mentioned raw material oils (animal and vegetable oils and fats and components derived from animal and vegetable oils and fats) have one or more of these fatty acids, and the fatty acids they have differ depending on the raw materials. For example, coconut oil has a relatively large amount of saturated fatty acids such as lauric acid and myristic acid, while soybean oil has a large amount of unsaturated fatty acids such as oleic acid and linoleic acid.

  The feedstock oil preferably contains a fraction of 250 ° C or higher, more preferably contains a fraction of 300 ° C or higher, and contains a fraction of 360 ° C or higher. Further preferred. When the fraction having a boiling point of 230 ° C. or higher is not contained, the production of gas is increased during production, so that the yield of the liquid product is decreased, and the life cycle carbon dioxide may be increased.

  Moreover, as raw material oil of the process oil derived from animals and plants, what mixed the petroleum hydrocarbon fraction with the animal and plant oils and fats and animal fats and oils-derived components may be used. In this case, the ratio of petroleum hydrocarbon fraction is preferably 10 to 99% by volume, more preferably 30 to 99% by volume, and still more preferably 60 to 98% by volume with respect to the total volume of the feedstock. When the ratio of petroleum hydrocarbon fraction is less than the lower limit, equipment required for treatment of by-product water may be required, and the ratio of petroleum hydrocarbon fraction exceeds the upper limit. When exceeding, it is not preferable from a viewpoint of life-cycle carbon dioxide reduction.

The hydrocracking conditions in the hydrotreating of the feedstock oil are performed under conditions such as a hydrogen pressure of 6 to 20 MPa, a liquid space velocity (LHSV) of 0.1 to 1.5 h ⁻¹ , and a hydrogen / oil ratio of 200 to 2000 NL / L. More desirable are conditions such as a hydrogen pressure of 8 to 17 MPa, a liquid space velocity of 0.2 to 1.1 h ⁻¹ , a hydrogen / oil ratio of 300 to 1800 NL / L, a hydrogen pressure of 10 to 16 MPa, and a liquid space velocity of 0.3. The conditions of ~ 0.9h ^-1 and hydrogen / oil ratio 350-1600NL / L are more desirable. These conditions are all factors that influence the reaction activity. For example, when the hydrogen pressure and the hydrogen oil ratio are less than the lower limit values, there is a risk of causing a decrease in reactivity or a rapid decrease in activity. If the hydrogen oil ratio exceeds the upper limit, excessive equipment investment such as a compressor may be required. Liquid hourly space velocity tends to be more advantageous for the lower the reaction, if it is less than 0.1 h ^-1 tend to be extremely large reactor volume is required excessive capital investment, while the 1.5 h ^-1 If it exceeds, the reaction will not proceed sufficiently.

  The light oil composition of the present invention is a fuel used in a diesel engine with a supercharger and an EGR having a geometric compression ratio exceeding 16, and needs to have the following specific properties by blending an FT synthetic base material. It is.

The diesel oil composition of the present invention needs to be used in a turbocharger and EGR equipped diesel engine having a geometric compression ratio exceeding 16. Since the light oil composition of the present invention satisfies the JIS No. 1 standard, it can be used in a diesel engine having a geometric compression ratio of 16 or less and not equipped with a supercharger or EGR equipment. This is not preferable because the effect of reducing the environmental load, which is the purpose of the diesel oil composition, cannot be expected.
The geometric compression ratio is a compression ratio calculated from the physical specifications of the engine. In general, it indicates the value obtained by dividing the cylinder internal volume A with the piston in the lowest position by the cylinder internal volume B with the piston in the uppermost position. It is often a value. In the present electronically controlled diesel engine, the substantial compression ratio can be changed by controlling the intake and exhaust valves and the supercharging pressure. However, in the present invention, the influence of the substantial compression ratio is also taken into account. The application range is limited by the geometric compression ratio.

Moreover, the diesel engine which the light oil composition of this invention uses is equipped with the equipment of a supercharger and EGR (exhaust gas recirculation). Both are equipment used to improve exhaust gas performance, fuel consumption, and output performance. In particular, premixed compression ignition combustion is often used as an application for ignition control, and the light oil composition of the present invention is also designed on the premise thereof.
In addition, this invention does not add a restriction | limiting regarding the other specification of the diesel engine to which the light oil composition of this invention is applied, a use, and a use environment.

The light oil composition of the present invention is blended with an FT synthetic base, the sulfur content is 5 mass ppm or less, the oxygen content is 100 mass ppm or less, the volume modulus is 1250 MPa or more and 1450 MPa or less, the Saybolt color is +22 or more, The lubrication performance is 400 μm or less, the distillation property initial boiling point is 140 ° C. or higher, the end point is 380 ° C. or lower, and each fraction range has the following characteristics (1) to (3), and the geometric compression ratio is 16 It is a diesel oil composition that satisfies the JIS No. 1 diesel oil standard in terms of quality items other than the sulfur content used in the supercharger and diesel engine with EGR.
(1) The cetane number in the fraction range of less than 200 ° C. is 20 or more and less than 40, and the composition ratio per volume in the whole fraction is 1% by volume or more and less than 10% by volume.
(2) The cetane number in the fraction range of 200 ° C. or more and less than 280 ° C. is 30 or more and less than 60, and the composition ratio per volume in the whole fraction is 40% by volume or more and 98% by volume or less.
(3) The cetane number in the fraction range of 280 ° C. or higher is 50 or more, and the composition ratio per volume in the whole fraction is 1 volume% or more and 59 volume% or less.

The light oil composition of the present invention is required to have quality item properties other than sulfur content, which are separately restricted, satisfy JIS No. 1 light oil standards. The JIS No. 1 diesel oil standard is a standard that satisfies “Class No. 1” defined in JIS K 2204 “Diesel Oil”. Specifically, the flash point is 50 ° C. or higher, the 90% distillation temperature is 360 ° C. or lower, and the pour point. −2.5 ° C. or less, clogging point (CFPP) −1 ° C. or less, 10% residual oil residual carbon content of 0.1% by mass or less, cetane index of 50 or more, kinematic viscosity at 30 ° C. of 2.7 mm ² / s or more The sulfur content must be 0.05% by mass or less. In addition, the light oil composition in the present invention is preferably used in accordance with the No. 1 light oil usage guideline shown in “Guideline for Using Light Oil” shown in the explanation of JIS K 2204-1996.

  The sulfur content of the light oil composition of the present invention is required to be 5 ppm by mass or less, preferably 3 ppm by mass or less from the viewpoint of reducing harmful exhaust components discharged from the engine and improving the performance of the exhaust gas aftertreatment device. More preferably, it is 1 mass ppm or less. In addition, the sulfur content here means the mass content of the sulfur content based on the total amount of the light oil composition measured by JIS K2541 “Sulfur content test method”.

The oxygen content of the light oil composition of the present invention is required to be 100 mass ppm or less, preferably 80 mass ppm or less, more preferably 60 mass ppm or less from the viewpoint of improving oxidation stability. The oxygen content can be measured with a general elemental analyzer. For example, the sample is converted to CO on platinum carbon, or further converted to CO ₂ and then measured using a thermal conductivity detector. You can also

  In the light oil composition of the present invention, the bulk modulus needs to be 1250 MPa or more and 1450 MPa or less. In general, when a high pressure is applied to a compressible fluid such as light oil, the fluid itself is compressed according to the temperature and pressure at that place, and the density (volume per flow rate) changes. The compression elastic modulus of this object is defined as the bulk elastic modulus (unit: MPa). Assuming diesel fuel injection, the volume modulus of elasticity for the fuel fluid changes at a constant rate according to the physical characteristics and composition of the fuel itself as well as the temperature and pressure of the atmosphere in which the fuel is placed. Therefore, in an injection system having high-pressure and high-precision injection characteristics, such as an electronically controlled fuel injection pump, in order to maintain the fuel injection amount and injection rate as set, the volume elastic modulus shows a stable value. Fuel is desirable. Therefore, in the light oil composition of the present invention, the volume modulus of elasticity needs to be 1250 MPa or more and 1450 MPa or less, preferably 1270 MPa or more and 1420 MPa or less, and more preferably 1300 MPa or more and 1400 MPa or less. Note that the bulk modulus is not governed by a single fuel physical property or composition, but is defined as a result of multiple effects of multiple physical properties and compositions. From the technical point of view, it is reasonable to think of it as a fuel characteristic that should be considered in parallel with the composition.

  There is no officially determined method for measuring the bulk modulus at this time, but the outline will be described with reference to FIG. The fuel to be measured is sealed in a constant volume container made of a material and structure that can prove that the volume change of the container itself due to temperature and pressure changes is sufficiently small with respect to the fuel volume change in the same environmental change. . At this time, the container needs to be filled only with the fuel to be measured. A constant volume piston made of a material and a structure capable of demonstrating that the volume change of the piston itself due to changes in temperature and pressure is sufficiently small with respect to the volume change of the fuel in the same environmental change is inserted into this constant volume container, Change the container volume. Since the fuel to be measured is compressed according to its compression elastic characteristic, the pressure in the container changes as a result. By measuring this pressure, the bulk modulus is calculated.

Here, the measuring method of the volume elastic modulus of a light oil composition is demonstrated concretely.
FIG. 1 is a schematic configuration diagram showing an example of a bulk modulus measuring apparatus. In FIG. 1, a supply valve 2 is provided on the upper surface of the constant volume container 1 so as to communicate with the constant volume container 1, and a discharge valve 3 is connected to a predetermined position of the supply valve 2. Further, a temperature sensor 4 and a pressure sensor 5 are provided on the side of the constant volume container 1, and a piston 6 is provided on the lower surface of the constant volume container 1 so as to communicate with the inside of the constant volume container 1. Here, the constant volume container 1 and the piston 6 are made of a material and a structure whose capacity change is sufficiently smaller than the volume change of the fuel when the temperature and pressure of the atmosphere change by a predetermined amount.
When the measuring apparatus shown in FIG. 1 is used, first, the light oil composition 100 to be measured is introduced into the constant volume container 1 from the supply valve 2, and the constant volume container 1 is filled with the light oil composition. Next, the volume in the constant volume container 1 is changed by the piston 6. At this time, the light oil composition is compressed according to its compression elastic characteristics, and as a result, the pressure in the constant volume container 1 changes. The temperature and pressure during the compression process are measured by the temperature sensor 4 and the pressure sensor 5, and the volume modulus can be calculated based on the obtained measurement value.

  The Saybolt color of the light oil composition of the present invention needs to be +22 or more, and is preferably +25 or more, and more preferably +27 or more from the viewpoint of removing the oxidation stability inhibitor. The Saebold color here means a value measured according to JIS K 2580 “Petroleum products—color test method—Saebold color test method”.

The light oil composition of the present invention is required to have an HFRR wear scar diameter (WS1.4) of 400 μm or less with respect to its lubricating performance. If the lubrication performance is low, especially in a diesel engine equipped with a distributed injection pump, the driving torque of the pump during operation and the wear of each part of the pump will increase, and the engine itself may be destroyed as well as the exhaust gas performance deteriorates. There is. Further, even in an electronically controlled fuel injection pump capable of high pressure injection, there is a concern about wear on the sliding surface and the like. Therefore, the light oil composition of the present invention needs to have a HFRR wear scar diameter (WS1.4) of 400 μm or less, preferably 380 μm or less, and more preferably 360 μm or less in terms of its lubricating performance. .
Here, the lubrication performance and the HFRR wear scar diameter refer to the lubrication performance measured by the Petroleum Institute Standard JPI-5S-50-98 “Light Oil—Lubricity Test Method” issued by the Japan Petroleum Institute.

  The gas oil composition of the present invention needs to be constrained with respect to the fractional fraction and its cetane number. The roles and restrictions of each fraction are described below.

Since the light oil composition of the present invention is premised on use in the summer, if there is too much (distillation property is a fraction having a temperature of less than 200 ° C.), the high temperature restartability is deteriorated. However, if some light fraction is not contained, the evaporation characteristics are deteriorated. In addition, when the cetane number of the light fraction that easily evaporates is too high, self-ignition begins before sufficient mixing with air, and premixed combustion cannot be realized. However, if the cetane number is too low, self-ignition tends to be greatly delayed.
As a result of various studies in view of the above tendency, the cetane number in the fraction range where the distillation property is less than 200 ° C. is 20 or more and less than 40, and the composition ratio per volume in the whole fraction is 1% by volume. It is necessary that the amount is less than 10% by volume. Further, the fraction has a cetane number of preferably 21 or more and 39 or less, and more preferably 22 or more and 38 or less. The composition ratio with respect to the total fraction is preferably 2% by volume or more and 9.5% by volume or less, and more preferably 3% by volume or more and 9% by volume or less.

In the light oil composition of the present invention, a middle fraction (a fraction having a distillation property of 200 ° C. or more and less than 280 ° C.) is a central composition. That is, as described above, the blending amount of the light fraction is limited, and in order to maintain the evaporation characteristic while suppressing the deterioration of the high temperature restartability, it is necessary to control the fraction to an appropriate amount. Similarly, since the main fraction is dominant in terms of ignition, it is preferable that the cetane number of the main fraction is set to be slightly higher in order to positively self-ignite.
As a result of various studies in view of the above tendency, the cetane number in the fraction range of 200 ° C. or more and less than 280 ° C. is 30 or more and less than 60, and the constituent ratio per volume in the whole fraction is 40% by volume. It is necessary to be 98 volume% or less. Further, the fraction has a cetane number of preferably 31 or more and 59 or less, and more preferably 32 or more and 58 or less. The composition ratio with respect to the total fraction is preferably 42 volume% or more and 97 volume% or less, and more preferably 45 volume% or more and 95 volume% or less.

In the light oil composition of the present invention, a heavy fraction (a fraction having a distillation property of 280 ° C. or higher) is a fraction having a large calorific value per capacity, and is important in terms of improving output and fuel consumption. However, the fraction has a possibility of generating soot or the like when the combustion atmosphere conditions (temperature, pressure, ratio with air, etc.) are not suitable. It is necessary to determine the blending ratio in consideration of the balance with the above-mentioned light and medium fractions. In addition, since the fraction has a slightly slow evaporation rate and needs to have a sufficient mixing time with air, a large amount cannot be blended, but it is necessary to have a structure excellent in self-ignitability. .
As a result of various studies in view of the above tendency, the cetane number in the fraction range of 280 ° C. or higher is 50 or more, and the composition ratio per volume in the whole fraction is 1 volume% or more and 59 volume% or less. It is necessary to be. The fraction has a cetane number of preferably 52 or more, and more preferably 54 or more. The composition ratio with respect to the total fraction is preferably 5% by volume to 55% by volume, more preferably 10% by volume to 50% by volume, and further preferably 15% by volume to 45% by volume. .

In addition, the composition ratio and cetane number of each fraction can be measured by the following two methods.
(1) Using a relatively high-precision fractionation apparatus having a fractionation accuracy of ± 1 ° C. with respect to the target temperature and a residual oil ratio of 1% by volume or less, the gas oil composition is treated at the initial boiling point to 200 ° C., 200 C. to 280.degree. C., divided into 280.degree. C. to end point fractions, and the constituent ratio and cetane number of each fraction are measured.
(2) The base material to be mixed is fractionated in advance into the fractions using the above fractionator, and the composition ratio and cetane number are measured at that time.
The test method is JIS K 2254 "Petroleum products-Distillation test method-Atmospheric pressure method". The distillation properties are determined according to JIS K 2280 "Petroleum products-Fuel oil-Octane number and cetane number test method and cetane index calculation method". The cetane number is measured by “Test method”.

As the distillation properties in the light oil composition of the present invention, the above-mentioned characteristics of each fraction are satisfied, the initial boiling point is 140 ° C. or higher, the end point is 380 ° C. or lower, and the 90% distillation temperature, which is JIS No. 1 light oil standard, is 360 ° C. It is necessary that:
When the 90% distillation temperature exceeds 360 ° C, the amount of PM and fine particles discharged tends to increase. Therefore, it is preferably 355 ° C or less, more preferably 350 ° C or less, and further preferably 345 ° C or less. Although there is no lower limit on the 90% distillation temperature, it is preferably 240 ° C. or more, more preferably 250 ° C. or more, because if it is significantly low, it leads to deterioration of fuel consumption and reduction of engine output. More preferably, it is 260 ° C. or higher, more preferably 270 ° C. or higher.
The initial boiling point must be 140 ° C. or higher. If the initial boiling point is less than 140 ° C., engine output and startability at high temperatures may be deteriorated. Therefore, the initial boiling point is preferably 145 ° C. or higher, and more preferably 150 ° C. or higher. The end point needs to be 380 ° C. or lower. When the end point exceeds 380 ° C., the discharge amount of PM and fine particles tends to increase. Therefore, the end point is preferably 375 ° C. or lower, and more preferably 370 ° C. or lower.
Although there is no restriction on the 10% distillation temperature, the lower limit is preferably 160 ° C. or higher, more preferably 170 ° C. or higher, more preferably 180 ° C. or higher in order to suppress deterioration of engine output and startability at high temperatures. is there. On the other hand, the upper limit is preferably 250 ° C. or lower, more preferably 245 ° C. or lower, and further preferably 230 ° C. or lower for the purpose of suppressing deterioration of exhaust gas performance.
Here, the initial boiling point, 10% distillation temperature, 90% distillation temperature, and end point all mean values measured by JIS K 2254 “Petroleum products—Distillation test method—Atmospheric pressure method”.

  The cetane index of the light oil composition of the present invention needs to satisfy 50 or more which is JIS No. 1 light oil standard. When the cetane index is less than 50, the concentration of PM, aldehydes, or NOx in the exhaust gas tends to increase. For the same reason, the cetane index is preferably 52 or more, more preferably 55 or more. Further, although there is no restriction on the upper limit of the cetane index, when it exceeds 75, soot emission during acceleration tends to deteriorate, so the cetane index is preferably 75 or less, more preferably 74 or less, and further 73 or less. preferable. The cetane index referred to in the present invention is defined by “Calculation method of cetane index using 8.4 variable equations” in JIS K 2280 “Petroleum products-fuel oil-octane number and cetane number test method and cetane index calculation method”. It means the calculated value. Here, the cetane index in the JIS standard is generally applied to light oil to which a cetane number improver is not added, but in the present invention, the above-mentioned " Applying “8.4 Calculation Method of Cetane Index Using Variable Equation”, a value calculated by the calculation method is expressed as a cetane index.

  The cetane number in the light oil composition of the present invention is not particularly limited as long as it satisfies the characteristics of each fraction described above. However, it prevents knocking during diesel combustion, and suppresses NOx, PM and aldehyde emissions in exhaust gas. From a viewpoint, Preferably it is 30 or more, More preferably, it is 35 or more, More preferably, it is 40 or more. Further, from the viewpoint of reducing black smoke in the exhaust gas, the cetane number is preferably 70 or less, more preferably 68 or less, and further preferably 66 or less. The cetane number referred to here is a cetane number measured in accordance with “7. Cetane number test method” in JIS K 2280 “Petroleum products—Fuel oil—Octane number and cetane number test method and cetane index calculation method”. Means.

  The flash point of the light oil composition of the present invention needs to satisfy JIS No. 1 light oil standard of 50 ° C. or higher. When the flash point is less than 50 ° C., it is not preferable from the viewpoint of safety. Therefore, the flash point is preferably 52 ° C. or higher, and more preferably 54 ° C. or higher. The flash point in the present invention is a value measured by JIS K 2265 “Crude oil and petroleum product flash point test method”.

  The clogging point of the light oil composition of the present invention needs to satisfy -1 ° C. or lower which is JIS No. 1 light oil standard. Furthermore, it is preferably −3 ° C. or less, more preferably −5 ° C. or less, from the viewpoint of preventing the prefilter blockage of the diesel vehicle and maintaining the injection performance of the electronically controlled fuel injection pump. Here, the clogging point means a clogging point measured by JIS K 2288 “Light oil—clogging point test method”.

  The pour point of the light oil composition of the present invention needs to satisfy −2.5 ° C. or less, which is JIS No. 1 light oil standard. Furthermore, from the viewpoint of ensuring low temperature startability or low temperature drivability, and maintaining the injection performance of the electronically controlled fuel injection pump, it is preferably −5 ° C. or lower, more preferably −7.5 ° C. or lower. preferable. Here, the pour point means a pour point measured according to JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.

Kinematic viscosity at 30 ° C. of the gas oil composition of the present invention is required to be 2.7 mm ² / s or more is JIS1 No. diesel standards, is preferably 2.75 mm ² / s or more, 2.8 mm More preferably, it is ² / s or more. If the kinematic viscosity is less than 2.7 mm ² / s, 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 is impaired. There is a fear. On the other hand, the upper limit of the kinematic viscosity at 30 ° C. is not limited, but the viewpoint of suppressing the increase in the NOx and PM concentrations in the exhaust gas by increasing the resistance in the fuel injection system and destabilizing the injection system. Therefore, it is preferably 5 mm ² / s or less, more preferably 4.8 mm ² / s or less, and even more preferably 4.5 mm ² / s or less. In addition, kinematic viscosity here means kinematic viscosity measured by JISK2283 "crude oil and petroleum products-kinematic viscosity test method and viscosity index calculation method".

  The 10% residual carbon content of the gas oil composition of the present invention is required to be not more than 0.1% by mass, which is JIS No. 1 gas oil standard. Furthermore, 0.08% by mass or less is preferable, and 0.05% by mass or less is preferable from the viewpoint of reducing fine particles and PM, maintaining the performance of the exhaust gas aftertreatment device mounted on the engine, and preventing filter clogging by sludge. More preferred. Here, the 10% residual carbon content means a value measured by JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.

  The peroxide value after the accelerated oxidation test (oxidation stability test) of the light oil composition of the present invention is preferably 50 ppm by mass or less, and 40 ppm by mass or less from the viewpoint of storage stability and compatibility with members. It is more preferable that it is 30 mass ppm or less. The peroxide value after the accelerated oxidation test referred to here is the Petroleum Institute Standard JPI- after conducting the accelerated oxidation test under conditions of 95 ° C. and oxygen bubbling for 16 hours in accordance with ASTM D2274-94. It means the value of peroxide value measured according to 5S-46-96. In order to reduce the peroxide value, additives such as an antioxidant and a metal deactivator can be appropriately added to the light oil composition of the present invention.

  The aromatic content of the gas oil composition of the present invention is preferably 15% by volume or less, more preferably 14% by volume or less, further preferably 13% by volume or less, and 12% by volume or less. Even more preferably. When the aromatic content is 15% by volume or less, the production of PM and the like can be suppressed, and environmental performance can be exhibited even in diesel combustion and premixed compression ignition combustion, and the light oil composition of the present invention The property defined in 1 can be achieved more easily and reliably. The aromatic content here was measured in accordance with JPI-5S-49-97 “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method” published by the Japan Petroleum Institute. Means the volume percentage (volume%) of the aromatic content.

Although there is no restriction | limiting in particular regarding the naphthene content of the light oil composition of this invention, It is preferable that it is 50 mass% or less, 45 mass% or less is more preferable, and 40 mass% or less is further more preferable. When the naphthene content is 50% by mass or less, the production of PM and the like can be suppressed, and the environment-responsive performance can be exhibited even in diesel combustion and premixed compression ignition combustion, and is specified in the light oil composition of the present invention. Can be achieved more easily and reliably. The naphthene content referred to here is a mass percentage (mass percentage of naphthene measured in accordance with ASTM D 2425 “Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry”).
The normal paraffin content (normal paraffin content) of the light oil composition of the present invention is not particularly limited, but it is preferably 5% by mass or more for the purpose of facilitating the ignition controllability of the premixed compression ignition combustion. 7 mass% or more is more preferable, and 10 mass% or more is further more preferable. It is a value (mass%) measured using GC-FID. That is, a capillary column of methyl silicon (ULTRAALLOY-1) is used for the column, helium is used for the carrier gas, a hydrogen ion detector (FID) is used for the detector, a column length of 30 m, a carrier gas flow rate of 1.0 mL / min, and a splitting. It is a value measured under the conditions of ratio 1:79, sample injection temperature 360 ° C., column temperature rising condition 140 ° C. → (8 ° C./min)→355° C., detector temperature 360 ° C.

There is no particular limitation with respect to density at 15 ℃ of the gas oil composition of the present invention, in terms of calorific value ensuring, is preferably 760 kg / ^{m 3} or more, 765kg / ^{m 3} or more, more preferably, 770 kg / ^{m 3} The above is more preferable. Further, the density, NOx, from the viewpoint of reducing the emission of PM, it is preferably 840 kg / ^{m 3} or less, more preferably 835 kg / ^{m 3} or less, more preferably 830 kg / ^{m 3} or less. In addition, the density here means the density measured by JIS K 2249 “Density test method and density / mass / capacity conversion table of crude oil and petroleum products”.

  Although there is no restriction | limiting in particular regarding the cloud point of the light oil composition of this invention, it is -1 degrees C or less from a viewpoint of ensuring low temperature startability or low temperature drivability, and the viewpoint of maintaining the injection performance in an electronically controlled fuel injection pump. Is preferable, it is more preferable that it is -3 degrees C or less, and it is still more preferable that it is -5 degrees C or less. The cloud point here means a pour point measured according to JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.

  Although there is no restriction | limiting in particular regarding the water content of the light oil composition of this invention, it is preferable that it is 100 volume ppm or less from a viewpoint of the freezing prevention under low temperature and the corrosion prevention inside an engine, More preferably, it is 50 volume. ppm or less, more preferably 20 volume ppm or less. The water content here means a value measured by JIS K 2275 “Crude oil and petroleum products—moisture test method—Karl Fischer coulometric titration method”.

  In the light oil composition of the present invention, from the viewpoint of storage stability, the total insoluble content after the oxidation stability test is preferably 2.0 mg / 100 mL or less, more preferably 1.5 mg / 100 mL or less. Preferably, it is 1.0 mg / 100 mL or less, more preferably 0.5 mg / 100 mL or less. The oxidation stability test here is conducted under conditions of 95 ° C. and oxygen bubbling for 16 hours in accordance with ASTM D2274-94. The total insoluble matter after the oxidation stability test here means a value measured in accordance with the oxidation stability test.

  In the light oil composition of the present invention, an appropriate amount of additives such as a low temperature fluidity improver, a lubricity improver, a cetane number improver, and a detergent can be blended as necessary.

A low temperature fluidity improver can be added to the diesel oil composition of the present invention from the viewpoint of prevention of filter blockage in a diesel vehicle. Moreover, the addition amount is preferably 200 mg / L or more and 1000 mg / L or less, more preferably 300 mg / L or more and 800 mg / L or less in terms of active ingredient concentration.
The type of the low-temperature fluidity improver is not particularly limited. For example, ethylene-unsaturated ester copolymer represented by ethylene-vinyl acetate copolymer, alkenyl succinic acid amide, dibehenate ester of polyethylene glycol Linear compounds such as phthalic acid, ethylenediaminetetraacetic acid, nitriloacetic acid and the like, or polar nitrogen compounds consisting of reaction products of hydrocarbyl-substituted amines, alkyl fumarate or alkyl itaconate-unsaturated esters One kind or two or more kinds of low-temperature fluidity improvers such as a comb polymer made of a copolymer can be used. Further, a copolymer of ethylene and methyl methacrylate, a copolymer of ethylene and α-olefin, a chlorinated methylene-vinyl acetate copolymer, an alkyl ester polymer of unsaturated carboxylic acid, a nitrogen-containing compound having a hydroxyl group And esters synthesized from saturates and saturated fatty acids, esters and amide derivatives synthesized from polyhydric alcohols and saturated fatty acids, esters synthesized from polyoxyalkylene glycols and saturated fatty acids, alkylene oxides of polyhydric alcohols or partial esters thereof Low temperature fluidity improver combining one or more selected from esters synthesized from adducts and saturated fatty acids, chlorinated paraffin / naphthalene condensates, alkenyl succinic acid amides, amine salts of sulfobenzoic acid, etc. can do. Among these, from the viewpoint of versatility, an ethylene-vinyl acetate copolymer additive can be preferably used. In addition, since a commercial product referred to as a low temperature fluidity improver may be diluted with an appropriate solvent for an active ingredient (active ingredient) that contributes to low temperature fluidity, such a commercial product may be used in the present invention. In the case of adding to a light oil composition, the above-mentioned addition amount means the addition amount (active ingredient concentration) as an active ingredient.

The addition of the lubricity improver to the light oil composition of the present invention is not particularly limited as long as the lubricating performance falls within the above-mentioned preferred range, but is preferably added for the reason of preventing wear of the fuel injection pump. Moreover, the addition amount is preferably 20 mg / L or more and 200 mg / L or less, more preferably 50 mg / L or more and 180 mg / L or less in terms of active ingredient concentration. When the addition amount of the lubricity improver is within the above range, the effect of the added lubricity improver can be effectively extracted. For example, in a diesel engine equipped with a distributed injection pump, An increase in driving torque can be suppressed and pump wear can be reduced.
The type of the lubricity improver is not particularly limited. For example, one or more of carboxylic acid-based, ester-based, alcohol-based and phenol-based lubricity improvers can be used arbitrarily. . Among these, carboxylic acid-based and ester-based lubricity improvers are preferable. Examples of the carboxylic acid-based lubricity improver include linoleic acid, oleic acid, salicylic acid, palmitic acid, myristic acid, hexadecenoic acid and a mixture of two or more of the above carboxylic acids. Examples of ester-based lubricity improvers include carboxylic acid esters of glycerin. The carboxylic acid constituting the carboxylic acid ester may be one kind or two or more kinds, and specific examples thereof include linoleic acid, oleic acid, salicylic acid, palmitic acid, myristic acid, hexadecenoic acid and the like. There is.

In the light oil composition of the present invention, if necessary, an appropriate amount of a cetane number improver can be blended to improve the cetane number of the resulting light oil composition.
As the cetane number improver, various compounds known as light oil cetane number improvers can be arbitrarily used, and examples thereof include nitrate esters and organic peroxides. These cetane number improvers may be used alone or in combination of two or more. Among the above cetane number improvers, it is preferable to use a nitrate ester. Such nitrate esters include 2-chloroethyl nitrate, 2-ethoxyethyl nitrate, isopropyl nitrate, butyl nitrate, primary amyl nitrate, secondary amyl nitrate, isoamyl nitrate, primary hexyl nitrate, Various nitrates such as secondary hexyl nitrate, n-heptyl nitrate, n-octyl nitrate, 2-ethylhexyl nitrate, cyclohexyl nitrate, and ethylene glycol dinitrate are included. An alkyl nitrate of 6-8 is preferred.

The content of the cetane improver is preferably 500 mg / L or more, more preferably 600 mg / L or more, further preferably 700 mg / L or more, and more preferably 800 mg / L or more based on the total amount of the composition. Even more preferably, it is most preferably 900 mg / L or more. When the content of the cetane number improver is less than 500 mg / L, a sufficient cetane number improving effect cannot be obtained, and PM, aldehydes, and NOx in diesel engine exhaust gas tend not to be sufficiently reduced. Further, the upper limit of the content of the cetane number improver is not particularly limited, but is preferably 1400 mg / L or less, more preferably 1250 mg / L or less, based on the total amount of the light oil composition, and 1100 mg / L or less. More preferably, it is most preferably 1000 mg / L or less.
As the cetane number improver, one synthesized according to a conventional method may be used, or a commercially available product may be used. In addition, what is marketed as a cetane number improver is usually obtained in a state where an active ingredient contributing to cetane number improvement (that is, cetane number improver itself) is diluted with an appropriate solvent. When preparing the light oil composition of this invention using such a commercial item, it is preferable that content of the said active ingredient in a light oil composition becomes in the above-mentioned range.

  A detergent can be added to the light oil composition of the present invention as necessary. The component of the detergent is not particularly limited, but examples thereof include imide compounds; alkenyl succinimides such as polybutenyl succinimide synthesized from polybutenyl succinic anhydride and ethylene polyamines; penta Succinic acid esters such as polybutenyl succinic acid esters synthesized from polyhydric alcohols such as erythritol and polybutenyl succinic anhydrides; such as copolymers of dialkylaminoethyl methacrylate, polyethylene glycol methacrylate, vinyl pyrrolidone and alkyl methacrylates Examples thereof include ashless detergents such as copolymerized polymers and reaction products of carboxylic acids and amines, among which alkenyl succinimides and reaction products of carboxylic acids and amines are preferred. These detergents can be used alone or in combination of two or more. Examples of using an alkenyl succinimide include a case where an alkenyl succinimide having a molecular weight of about 1000 to 3000 is used alone, an alkenyl succinimide having a molecular weight of about 700 to 2000, and an alkenyl succinimide having a molecular weight of about 10,000 to 20000. May be used in combination. The carboxylic acid constituting the reaction product of the carboxylic acid and the amine may be one type or two or more types. Specific examples thereof include fatty acids having 12 to 24 carbon atoms and carbon atoms having 7 to 24 carbon atoms. An aromatic carboxylic acid etc. are mentioned. Examples of the fatty acid having 12 to 24 carbon atoms include linoleic acid, oleic acid, palmitic acid, myristic acid and the like, but are not limited thereto. In addition, examples of the aromatic carboxylic acid having 7 to 24 carbon atoms include benzoic acid and salicylic acid, but are not limited thereto. Moreover, the amine which comprises the reaction product of carboxylic acid and an amine may be 1 type, or may be 2 or more types. The amine used here is typically oleylamine, but is not limited thereto, and various amines can be used.

  The blending amount of the cleaning agent is not particularly limited, but in order to bring out the effect of blending the cleaning agent, specifically, the effect of suppressing the clogging of the fuel injection nozzle, the blending amount of the cleaning agent is 30 mg / L based on the total amount of the composition. It is preferable to set it as the above, It is more preferable to set it as 60 mg / L or more, It is further more preferable to set it as 80 mg / L or more. Even if an amount less than 30 mg / L is added, the effect may not appear. On the other hand, if the blending amount is too large, an effect commensurate with it cannot be expected, and conversely there is a risk of increasing NOx, PM, aldehydes, etc. in the exhaust gas of the diesel engine. L or less is preferable, and 180 mg / L or less is more preferable. In general, commercially available detergents are obtained in a state where an active ingredient contributing to cleaning is diluted with an appropriate solvent. When such a commercial product is blended in the light oil composition of the present invention, the content of the active ingredient in the light oil composition is preferably within the above range.

Further, for the purpose of further improving the performance of the light oil composition in the present invention, other known fuel oil additives (hereinafter referred to as “other additives” for convenience) described later may be added alone or in combination of several kinds. it can. Other additives include, for example, phenol-based and amine-based antioxidants; metal deactivators such as salicylidene derivatives; corrosion inhibitors such as aliphatic amines and alkenyl succinic acid esters; anionic-based, cationic-based, Antistatic agents such as amphoteric surfactants; coloring agents such as azo dyes; antifoaming agents such as silicones; antifreezing agents such as 2-methoxyethanol, isopropyl alcohol, and polyglycol ether.
The addition amount of other additives can be arbitrarily determined, but the addition amount of each additive is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, based on the total amount of the light oil composition. is there.

  As described above, according to the present invention, by using the light oil composition produced by the above production method, fraction regulation, etc., it is difficult to realize with a conventional light oil composition in a summer environment. It is possible to provide high-quality diesel oil that can simultaneously achieve practical performance and environmentally compatible performance that can be applied to premixed compression ignition combustion at a high level.

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

(Examples 1-3 and Comparative Examples 1-3)
The light oil composition shown in Table 2 was prepared by preparing a base material having the properties shown in Table 1 (Examples 1 to 3 and Comparative Examples 1 to 3). The FT synthesis substrates 1 to 3 are hydrocarbon mixtures obtained by subjecting natural gas to wax and middle distillation by FT reaction and hydrotreating it, but the reaction conditions (degrees of isomerization) are different. Therefore, it is a base material with different saturated hydrocarbon contents. The advanced hydrotreatment base material is a hydrocarbon base material obtained by further subjecting a light oil base material to hydrogenation treatment to further reduce sulfur and aroma. Processed oil derived from animals and plants is obtained by performing hydrogenation using palm oil (hole component) as a raw material and removing miscellaneous components. Hydrorefined diesel oil is equivalent to commercially available diesel oil used in summer. The high compression ratio fuel is prepared for a high compression ratio diesel engine by blending an appropriate amount of an FT synthesis base material, a hydrorefining base material, an advanced hydroprocessing base material, and the like. Therefore, except for the mixing ratio of each fraction and the cetane number of each fraction, the other specifications satisfy the items required for the light oil composition of the present invention. Examples 1 to 3 and Comparative Examples 1 to 3 were produced using appropriate amounts or all of these.
In addition, the additive used by this example is as follows.
Lubricant improver: Carboxylic acid mixture based on linoleic acid Detergent: Alkenyl succinimide mixture

  The blending ratio of the blended diesel oil composition, and the blended diesel oil composition, density at 15 ° C., kinematic viscosity at 30 ° C., flash point, sulfur content, oxygen content, distillation properties, cetane index, Cetane number, aromatic content, naphthene compound content, bulk modulus, cloudiness point, clogging point, pour point, hue, residual carbon content of 10% residual oil, total insoluble content after oxidation stability test and Table 2 shows the results of measuring the peroxide value, wear scar diameter, and moisture.

The properties of the light oil composition were measured by the following method. In addition, about the component ratio and cetane number of each fraction, it fractionates after base-material preparation and is measuring.
The density refers to a density measured according to JIS K 2249 “Determination method of density of crude oil and petroleum products and density / mass / capacity conversion table”.
The kinematic viscosity refers to a kinematic viscosity measured according to JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.
The flash point indicates a value measured according to JIS K 2265 “Crude oil and petroleum product flash point test method”.
The sulfur content (sulfur content) refers to the mass content of the sulfur content based on the total amount of the light oil composition measured by JIS K2541 “Sulfur content test method”.
The oxygen content (oxygen content) indicates a value measured using a thermal conductivity detector after the sample is converted to CO on platinum carbon or further converted to CO ₂ .
All the distillation properties are values measured by JIS K 2254 "Petroleum products-Distillation test method". E200-Eibp, E280-E200, and Eep-E280 are the distillate volume (volume%) from the distillation initial distillation point to 200 ° C., and the distillate volume (volume%) from distillation 200 ° C. to 280 ° C., respectively. ), Distillation amount of distillate (volume%) from 280 ° C. to the end point.
Normal paraffin content means the value (mass%) measured using the above-mentioned GC-FID.
The aromatic content is measured according to the Japan Petroleum Institute method JPI-5S-49-97 “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method” published by the Japan Petroleum Institute. Means the capacity percentage (volume%).
Naphthenic compound content refers to mass percentage (%) of naphthene content measured in accordance with ASTM D2524 “Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry”.

As described above, the volume elastic modulus was calculated based on the change in the pressure in the container when the fuel to be measured was sealed in the constant volume container and the constant volume piston was inserted therein.
The cloud point means the cloud point measured according to JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.
The clogging point means a clogging point measured by JIS K 2288 “Light oil—clogging point test method”.
The pour point means a pour point measured in accordance with JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.
The cetane index refers to a value calculated according to “Method for calculating cetane index using 8.4 variable equation” in JIS K 2280 “Petroleum products—fuel oil—octane number and cetane number test method and cetane index calculation method”. The cetane index in the JIS standard is not applied to the cetane number improver added, but the cetane index of the cetane index added with the cetane number improver also uses the above “8.4 variable equation”. It shall represent the value calculated by “Calculating method of cetane index”.
The cetane number means a cetane number measured according to “7. Cetane number test method” of JIS K 2280 “Petroleum products—fuel oil—octane number and cetane number test method and cetane index calculation method”.

Hue (Saebold) means the Saebold color measured according to the Saebold color test method described in JIS K 2580 “Petroleum products—color test method”.
The residual carbon content of 10% residual oil means the residual carbon content of 10% residual oil as measured by JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.
The peroxide value (peroxide value) after the oxidation stability test is accelerating oxidation under conditions of 95 ° C. and oxygen bubbling for 16 hours in accordance with ASTM D2274-94, and then the Petroleum Institute Standard JPI-5S- It means a value measured according to 46-96.
The total insoluble content after the oxidation stability test (total insoluble content) means a value measured after accelerated oxidation under conditions of 95 ° C. and oxygen bubbling for 16 hours in accordance with ASTM D2274-94. .
The lubrication performance and the HFRR wear scar diameter (WS1.4) refer to the lubrication performance measured by the Petroleum Institute Standard JPI-5S-50-98 “Diesel Oil-Lubricity Test Method” issued by the Japan Petroleum Institute.
Moisture refers to moisture measured by the Karl Fischer coulometric titration method described in JIS K 2275 “Crude oil and petroleum products—moisture test method”.

  As shown in Tables 1 and 2, the light oil composition used in the examples is produced by blending 20% by volume or more of the FT synthetic base material. Further, as apparent from Table 2, in Examples 1 to 3 in which the FT synthetic base material was blended within the range defined in the present invention, a light oil composition satisfying the defined properties was easily and reliably obtained. I was able to. On the other hand, although the specific base material is used as in Comparative Example 2 and Comparative Example 1 in which the light oil composition was prepared without using the specific light oil base material, the fractional composition ratio and the like satisfied the specified properties. If not, the light oil composition targeted by the present invention is not necessarily obtained.

  Next, various tests shown below were performed using the light oil compositions of Examples 1 to 3 and Comparative Examples 1 and 2. All test results are shown in Table 3. As can be seen from the results in Table 3, the light oil compositions of Examples 1 to 3 are more NOx, Smoke, fuel efficiency, and effective ignition delay period during premixed compression ignition combustion than the light oil compositions of Comparative Examples 1 and 2. , NOx, smoke, fuel efficiency, high temperature startability during normal combustion, and good results have been obtained. Practical performance and premixed compression in an excellent summer environment that was difficult to achieve with conventional diesel oil compositions It is possible to provide high-quality diesel oil that can simultaneously achieve a high level of environmental performance that can also be applied to ignition and combustion.

(Premixed compression ignition combustion test)
Based on a commercially available engine 1 shown below, a test was conducted with an experimental engine that made it possible to control the injection timing by partially improving the control unit of an electronically controlled common rail fuel injection pump. The test is performed under steady conditions (1200 rpm, 25% load equivalent condition (the amount of heat input between fuels is constant), fuel injection timing: 30 ° CA before top dead center, intake conditions: constant room temperature), along with NOx, smoke, and fuel consumption measurements. The effective ignition delay period was measured. The effective ignition delay period is a value obtained by subtracting the ignition start timing from the fuel injection end timing. If this value is positive, it means that almost all of the injected fuel has time to mix with air, and premix combustion Will proceed more effectively. On the other hand, if this value becomes negative, combustion has started before the end of fuel injection, and therefore combustion has been performed without sufficient premixing with significant Smoke generation. The fuel consumption was expressed as a relative value for each fuel, with Comparative Example 1 set to 100 (smaller values indicate better results).
The test method related to the engine test is in accordance with Annex 29 “Technical Standards for Diesel Vehicle 13 Mode Emission Measurement” supervised by the former Ministry of Transport.

(Engine specifications): Commercial engine 1
Engine type: Inline 6-cylinder diesel engine with supercharged EGR Displacement: 1.4L
Inner diameter x process: 73 mm x 81.4 mm
Compression ratio: 18.5
Maximum output: 72kW / 4000rpm
Regulatory compliance: 2002 exhaust gas regulatory compliance Exhaust gas aftertreatment device: None

(Diesel combustion test)
Using a commercially available engine 1 with no improvement in the injection system or the like, it was operated under a condition corresponding to a load of 3200 rpm 80% load (the amount of heat input between fuels was constant), and NOx, smoke, and fuel consumption were measured. The results were evaluated by relatively comparing each result with the result obtained when the fuel of Comparative Example 1 was used as 100 (a smaller value indicates a better result).

(High temperature startability test)
After performing the diesel combustion test described above, the temperature in the test chamber becomes constant at around 35 ° C. for a while. After completion of the diesel combustion test, the engine is held at idling for about 1 minute. Thereafter, the engine is stopped and left for 5 minutes to restart the engine. At this time, if the engine starts normally, it passes (○), if it does not start or if it takes more than 10 seconds to start, or a malfunction after starting (hunting, stumble, vehicle speed drop, engine stop, etc.) The case of failure is regarded as rejected (x).

It is a schematic block diagram which shows an example of the apparatus used for the measurement of the volume elastic modulus of a light oil composition.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Constant volume container 2 Supply valve 3 Discharge valve 4 Temperature sensor 5 Pressure sensor 6 Piston 100 Light oil composition

Claims (3)

Formulated with FT synthetic substrate, sulfur content is 5 mass ppm or less, oxygen content is 100 mass ppm or less, volume modulus is 1250 MPa to 1450 MPa, Saebold color is +22 or more, lubrication performance is 400 μm or less, distillation property With a supercharger and EGR with a geometric compression ratio of more than 16 and having an initial boiling point of 140 ° C. or higher, an end point of 380 ° C. or lower, and each fraction range having the following characteristics (1) to (3) A diesel fuel composition that satisfies the JIS No. 1 diesel oil standard for quality items other than sulfur used in diesel engines.
(1) The cetane number in the fraction range of less than 200 ° C. is 20 or more and less than 40, and the composition ratio per volume in the whole fraction is 1% by volume or more and less than 10% by volume.
(2) The cetane number in the fraction range of 200 ° C. or more and less than 280 ° C. is 30 or more and less than 60, and the composition ratio per volume in the whole fraction is 40% by volume or more and 98% by volume or less.
(3) The cetane number in the fraction range of 280 ° C. or higher is 50 or more, and the composition ratio per volume in the whole fraction is 1 volume% or more and 59 volume% or less.   The light oil composition according to claim 1, wherein the peroxide value after the accelerated oxidation test is 50 ppm by mass or less and the aromatic content is 15% by volume or less. The gas oil composition according to claim 1, wherein the blending ratio of the FT synthetic base material is 20% by volume or more.

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