JP5121138B2 - Light oil composition - Google Patents

Description

The present invention contains an environmentally low load type light oil base material produced using raw materials of animal and vegetable oils and / or triglyceride-containing hydrocarbons that are derived from animal and vegetable oils and fats, life cycle CO ₂ emission characteristics and oxidative stability, member effects, The present invention relates to a light oil composition for cold regions having excellent low temperature startability.

Conventionally, as the base material for light oil, straight-run gas oil obtained from crude oil atmospheric distillation equipment is hydrorefined or hydrodesulfurized, and straight-run kerosene obtained from crude oil atmospheric distillation equipment is hydrogenated. Those subjected to hydrorefining treatment or hydrodesulfurization treatment are known. Conventional gas oil compositions are produced by blending one or more of the above gas oil base and kerosene base. Moreover, additives, such as a cetane number improver and a detergent, are mix | blended with these light oil compositions as needed (for example, refer nonpatent literature 1).
Seiichi Konishi, “Introduction to Fuel Engineering”, Saika Hanafusa, March 1991, p. 136-144

By the way, in recent years, reduction of sulfur content and aromatic content in light oil, which is a fuel for internal combustion engines, has been demanded with the aim of urgently improving the air environment and reducing the environmental load. At the same time, in order to cope with the global warming problem, there is a demand for fuel properties that contribute to further improvement in fuel efficiency and reduce carbon dioxide (CO ₂ ). Synthetic fuels and renewable energy are one of the solutions. The use of biodiesel fuel, which is energy (hereinafter also referred to as BDF), as an alternative fuel is being studied.

  BDF is mainly a mixture of fatty acid alkyl esters made from natural animal and plant oils and fats. Influence of poisoning on aromatic compounds and exhaust gas aftertreatment catalysts that are considered to have a large contribution to soot formation in exhaust gas Since it is an oxygen-containing compound that has almost no sulfur content and has oxygen in the molecule, it has attracted attention as a promising candidate for alternative fuels. In addition, because it is plant-derived, it is positioned as renewable energy, so the international carbon dioxide reduction protocol signed in 1997, the so-called Kyoto Protocol, does not count carbon dioxide derived from BDF as an emission amount. The BDF also has a policy merit.

  However, fatty acid alkyl esters using natural animal and vegetable oils and fats as raw materials are inherently heavy, and there is a concern that unburned hydrocarbon emissions during combustion may increase due to poor burn-off in engine combustion and the like. In the case of BDF containing many fatty acid alkyl esters having many saturated fatty acid groups, it is solid even at room temperature, so it is inferior in handling as a fuel and it is difficult to ensure fluidity at low temperatures. In the case of BDF containing a lot of unsaturated fatty acid groups, its chemical composition is inferior in oxidative stability, and there is concern about deterioration of hue, generation of sludge, and adverse effects on engine members. Furthermore, the fatty acid glyceride, the alkyl alcohol, and the glycerin mixture, which is a by-product, are raw materials used for refining the fatty acid alkyl ester, which are extremely concerned about adverse effects on engine members and fuel injection systems.

Especially when viewed as a light oil for cold regions, even if it is a BDF having many unsaturated fatty acid groups, the low temperature performance of −15 ° C. to −20 ° C., which is the usage range of No. 3 light oil stipulated in the JIS light oil usage guidelines Is difficult to maintain. Moreover, since the existing low temperature fluidity improver is premised on the action | operation with respect to a hydrocarbon, it is often ineffective with respect to BDF.
These tendencies are not seen in the existing light oil, etc., so not only when using BDF alone, but also when mixing with existing light oil, etc. In addition to paying attention to the properties of BDF itself, it is necessary to pay more attention to oxidation stability, low-temperature performance, combustibility, and the like when mixing with existing light oil.

Therefore, fatty acids derived from natural animal and vegetable fats and oils for the provision of a light oil composition that reduces harmful exhaust components and reduces CO ₂ in the life cycle, has little effect on components, and has excellent oxidation stability and low-temperature startability. These performance improvements cannot be achieved simultaneously with the use of BDF, an alkyl ester mixture. Furthermore, because these engine performances are closely related to other fuel properties, it is very difficult to design high-quality fuels that can simultaneously achieve these required performances at a high level, and are required as commercial fuel oils. There are no examples or knowledge based on the examination of practical manufacturing methods that satisfy the various performances.

The present invention has been made in view of such a situation, and the object thereof is to contain an environment-friendly light oil base material produced by using animal and vegetable oils and fats and triglyceride-containing hydrocarbons derived from animal and vegetable oils and fats as a raw material. An object of the present invention is to provide a light oil composition excellent in all of cycle CO ₂ emission characteristics and oxidation stability, member influence and low temperature startability.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the present invention provides an inorganic oxidation having a hydrocarbon fraction containing a component derived from animal and vegetable fats and / or animal fats and oils having at least one metal selected from Groups 6A and 8 of the periodic table and acid properties. A sulfur-containing content of 5 mass ppm or less, comprising an environmentally low load light oil base material of a hydrocarbon-containing mixed fraction obtained by contacting a hydrocracking catalyst containing a product under hydrogen pressure The present invention relates to a light oil composition for cold districts having a content of 1% by mass or less, a distillation property of 10% distillation temperature of 140 ° C. or more and 190 ° C. or less and satisfying JIS No. 3 diesel oil standard.

  The present invention also provides a mixed oil obtained by mixing a petroleum-based base material having a hydrocarbon fraction containing a component derived from animal and vegetable fats and / or animal fats and a kerosene fraction refined from crude oil at an arbitrary ratio, Hydrocarbon-containing mixed fraction obtained by contacting under pressure of hydrogen with a hydrocracking catalyst containing an inorganic oxide having acid properties and at least one metal selected from Groups 6A and 8 in the Table The sulfur content is 5 mass ppm or less, the oxygen content is 1 mass% or less, the distillation property 10% distillation temperature is 140 ° C. or higher and 190 ° C. or lower. In addition, the present invention relates to a light oil composition for cold regions that satisfies the JIS No. 3 diesel oil standard.

  Further, the present invention is a mixture of the gas oil composition described above and a hydrorefined oil refined from crude oil or the like, having a sulfur content of 5 mass ppm or less, an oxygen content of 1 mass% or less, and a distillation property. The present invention relates to a light oil composition for cold regions having a 10% distillation temperature of 140 ° C. or higher and 190 ° C. or lower and satisfying JIS No. 3 light oil standard.

According to the present invention, it is difficult to realize with a conventional light oil composition by including an environmentally low load light oil base material produced using the above-described animal and vegetable oil and triglyceride-containing hydrocarbon as a component derived from animal and vegetable oil and fat. There is provided a light oil composition for cold districts excellent in all of the life cycle CO ₂ emission characteristics and oxidation stability, member influence and low temperature startability.

Hereinafter, the present invention will be described in detail.
As a constituent of the light oil composition of the present invention, a hydrocarbon fraction containing components derived from animal and vegetable oils and animal fats is used as a raw material oil, and at least one metal selected from Groups 6A and 8 of the periodic table, An environment-friendly light oil base material of a hydrocarbon-containing mixed fraction obtained by contacting a hydrocracking catalyst containing an inorganic oxide having acid properties under hydrogen pressure is used.

The environmentally low load gas oil base according to the present invention is a low sulfur gas oil fraction, a kerosene fraction, or a mixture thereof obtained by hydrotreating a predetermined raw material oil.
The raw oil must be a hydrocarbon fraction containing components derived from animal and vegetable oils and animal fats. In the present invention, the animal and plant oils and fats and the hydrocarbon fraction containing the components derived from animal and plant oils are produced and manufactured from natural or artificially produced and produced animal and plant oils and / or animal and vegetable fat components and / or these fats and oils. And components added for the purpose of maintaining and improving the performance of these oil and fat products. Examples of animal fats and animal oils include beef tallow, milk lipid (butter), pork tallow, sheep fat, whale oil, fish oil, liver oil, and the like. Vegetable oil and vegetable oil ingredients include coconut palm, palm palm, olives, Examples include rapeseed (rapeseed), rice bran, sunflower, cottonseed, corn, soybeans, sesame seeds, and other parts of the linseed, 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 a fraction having a boiling point of 250 ° C. or higher is not contained, the production of a gas component is increased during production, so that the yield of the liquid product is decreased and life cycle carbon dioxide may be increased.

  Moreover, as raw material oil, you may use what mixed the petroleum-type hydrocarbon fraction with the animal and vegetable oil and fat and the component derived from animal and vegetable oil and fat. When the feedstock is mixed, the ratio of the 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 based on 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.

  Examples of the petroleum hydrocarbon fraction include straight-run gas oil obtained from a crude oil atmospheric distillation apparatus, straight-run heavy oil obtained from an atmospheric distillation apparatus, and residual oil obtained by treating the crude oil with a vacuum distillation apparatus. Catalytic cracked diesel oil or hydrocracked diesel oil obtained by catalytic cracking or hydrocracking diesel oil, vacuum heavy diesel oil or desulfurized heavy oil, hydrorefined diesel oil obtained by hydrorefining these petroleum hydrocarbons or hydrogenated Desulfurized gas oil and the like can be mentioned, but heavy straight-run gas oil and vacuum gas oil are preferred from the viewpoint of reducing the life cycle carbon dioxide.

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. Conditions such as ~ 0.9h ^-1 and hydrogen / oil ratio 350-1600NL / L are even more desirable. All of these conditions are 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. When the pressure and the hydrogen / oil ratio exceed the upper limit values, there is a possibility that excessive equipment investment such as a compressor may be required. The lower the liquid space velocity, the more advantageous the reaction. However, if the liquid space velocity is less than the lower limit, a very large reaction tower volume is required, which tends to result in excessive capital investment. Tend not to progress sufficiently.

  The reactor type may be a fixed bed system. That is, hydrogen can take either a countercurrent or a cocurrent flow with respect to the raw material oil, or a combination of countercurrent and cocurrent flow having a plurality of reaction towers. As a general format, it is a down flow, and a gas-liquid twin parallel flow format can be adopted. In addition, the reactors may be used singly or in combination, and a structure in which one reactor is divided into a plurality of catalyst beds may be adopted. In the present invention, the distillate oil hydrorefined in the reactor is fractionated into predetermined fractions through a gas-liquid separation step, a rectification step and the like. At this time, there is a possibility that hydrogen sulfide may be generated if the moisture or raw material oil produced by the reaction contains sulfur, but gas-liquid separation equipment is used between the reactors or in the product recovery process. And other by-product gas removal devices may be installed.

  In general, hydrogen gas is introduced from the inlet of the first reactor before or after passing through the heating furnace, but separately from this, the temperature in the reactor is controlled and the reactor is as much as possible. It may be introduced between the catalyst beds or between a plurality of reactors in order to maintain the hydrogen pressure throughout. The hydrogen thus introduced is referred to as quench hydrogen. At this time, the ratio of quench hydrogen to hydrogen introduced accompanying the feedstock is desirably 10 to 60% by volume or more, more desirably 15 to 50% by volume or more. When the ratio of quench hydrogen is lower than the lower limit, the reaction at the subsequent reaction site may not proceed sufficiently, and when it exceeds the upper limit, the reaction near the reactor inlet may not proceed sufficiently.

  In the present invention, the feedstock may be treated with the hydrocracking catalyst alone, but in order to reduce the oxygen content contained in the distillate with the pretreatment catalyst for hydrogenation and obtain sufficient hydrocracking activity, The hydrogenation pretreatment catalyst capacity and the hydrocracking catalyst capacity can be set arbitrarily. The ratio of the hydrogenation pretreatment catalyst capacity to the total catalyst capacity is preferably 10 to 90% by volume, and more preferably 25 to 75% by volume. When the ratio of the hydrotreatment catalyst capacity is less than the lower limit, the oxygen content in the distillate treated with the pretreatment catalyst cannot be sufficiently reduced, and the upper limit is set. When exceeding, there exists a possibility that reaction may not fully advance.

  The oxygen content contained in the distillate treated with the pretreatment catalyst for hydrogenation is preferably reduced by 40% by weight or less, more preferably 30% by weight or less, in the feedstock. Since the oxygen content in the distillate oil that comes into contact with the hydrocracking catalyst poisons the catalytic activity point, sufficient activity is obtained when the oxygen content in the distillate oil after contact with the pretreatment catalyst exceeds 40% by weight. There is a tendency not to be obtained.

  In addition to the hydrotreating catalyst and hydrocracking catalyst, trap the scale that flows along with the feedstock as necessary, and support the pretreatment catalyst and hydrocracking catalyst at the partition of the catalyst bed. For the purpose, a guard catalyst, a metal removal catalyst, and an inert filler can be used alone or in combination. In addition, a catalyst having hydrogenation activity may be used after the hydrocracking catalyst for the purpose of stabilizing the cracked product by hydrogenation.

  The reaction temperature can be arbitrarily set in order to obtain the desired decomposition rate of the feedstock heavy fraction or the desired fraction yield. Furthermore, in order to suppress the oxygen content contained in the distillate treated with the hydrotreating catalyst within the above upper limit, the reaction temperature of the hydrotreating catalyst portion and the reaction temperature of the hydrocracking catalyst portion are arbitrarily set, respectively. Can be set to The average temperature of the entire reactor is generally 330 to 480 ° C., preferably 350 to 450 ° C., and even more desirably, in order to sufficiently proceed the reaction and produce gasoline, kerosene, and light oil having the predetermined properties. Is set in the range of 360-430 ° C. When the reaction temperature is less than the lower limit, the reaction may not proceed sufficiently. When the reaction temperature exceeds the upper limit, decomposition proceeds excessively, and the liquid product fraction tends to decrease. is there.

  The active metal of the pretreatment catalyst for hydrogenation contains at least one metal selected from Group 6A and Group 8 metals of the periodic table, preferably two or more selected from Group 6A and Group 8 Contains metals. For example, Co-Mo, Ni-Mo, Ni-Co-Mo, and Ni-W can be mentioned. In the pretreatment for hydrogenation, these metals are converted into sulfides and used.

  A porous inorganic oxide is used as the support for the hydrogenation pretreatment catalyst. Generally, it is a porous inorganic oxide containing alumina, and examples of other carrier constituents include silica, titania, zirconia, and boria. Desirably, it is a complex oxide containing at least one selected from alumina and other constituent components. Moreover, phosphorus may be included as another component. The total content of components other than alumina is preferably 1 to 20% by weight, and more preferably 2 to 15% by weight. If the content is less than 1% by weight, a sufficient catalyst surface area cannot be obtained and the activity may be lowered. If the content exceeds 20% by weight, the acidity of the support will increase and coke formation will occur. May cause a decrease in activity. When phosphorus is included as a carrier constituent, the content is preferably 1 to 5% by weight, more preferably 2 to 3.5% by weight in terms of oxide.

  There are no particular limitations on the raw materials that are precursors of silica, titania, zirconia, and boria, which are carrier constituents other than alumina, and general solutions containing silicon, titanium, zirconium, and boron can be used. For example, silicic acid, water glass and silica sol for silicon, titanium sulfate, titanium tetrachloride and various alkoxide salts for titanium, zirconium sulfate and various alkoxide salts for zirconium, and boric acid for boron, etc. it can. As phosphorus, phosphoric acid or an alkali metal salt of phosphoric acid can be used.

  It is desirable that the raw materials for the carrier constituents other than alumina be added in any step prior to the firing of the carrier. For example, it may be added to an aluminum aqueous solution in advance and then an aluminum hydroxide gel containing these components, may be added to a prepared aluminum hydroxide gel, or water or an acidic aqueous solution may be added to a commercially available alumina intermediate or boehmite powder. Although it may be added to the step of adding and kneading, a method of coexisting at the stage of preparing aluminum hydroxide gel is more desirable. Although the mechanism of the effect of these carrier constituents other than alumina has not been elucidated, it is thought that they form a complex oxide state with aluminum, which increases the surface area of the carrier and some interaction with the active metal. It is considered that the activity is affected by producing the action.

  As for the content of the active metal, for example, the total supported amount of W and Mo is preferably 12 to 35% by weight, more preferably 15 to 30% by weight based on the catalyst weight in terms of oxide. If the total supported amount of W and Mo is less than the lower limit, the activity may decrease due to the decrease in the number of active points. If the upper limit is exceeded, the metal is not effectively dispersed, and similarly It may cause a decrease in activity. The total supported amount of Co and Ni is preferably 1.5 to 10% by weight, more preferably 2 to 8% by weight based on the catalyst weight in terms of oxide. If the total supported amount of cobalt and nickel is less than 1.5% by weight, a sufficient cocatalyst effect may not be obtained and the activity may be reduced. If more than 10% by weight, the metal is effective. In the same manner, there is a possibility of causing activity.

  The hydrocracking catalyst contains at least one kind of metal selected from Group 6A and Group 8 metals of the periodic table, and preferably contains two or more kinds of metals from Groups 6A and 8 . For example, Co-Mo, Ni-Mo, Ni-Co-Mo, and Ni-W are mentioned, and Ni-Mo, Ni-Co-Mo, and Ni-W are desirably selected. In hydrocracking, these metals are used after being converted to a sulfide state in the same manner as the pretreatment catalyst for hydrogenation.

  As the carrier of the hydrocracking catalyst, an inorganic oxide having an acid property is adopted, but it is desirable to contain at least two of silica, alumina, boria, zirconia, magnesia and zeolite. For example, silica-alumina, titania-alumina, boria-alumina, zirconia-alumina, titania-zirconia-alumina, silica-boria-alumina, silica-zirconia-alumina, silica-titania-alumina, silica-titania-zirconia-alumina Desirably, silica-alumina, boria-alumina, zirconia-alumina, titania-zirconia-alumina, silica-boria-alumina, silica-zirconia-alumina, silica-titania-alumina are more desirable, silica-alumina, silica-zirconia-alumina Is even more desirable. Most preferably, these composite oxides contain zeolite. When alumina is contained, the ratio of alumina to other components can be any ratio with respect to the support, but the content of alumina is preferably 96% by weight or less of the support weight, and 90% by weight or less. More desirable. When the alumina content exceeds 96% by weight, sufficient acid properties cannot be obtained and it tends to be difficult to exhibit a predetermined hydrocracking activity.

  In addition to silica, there are alumina, titania, boria, gallium, and the like as components constituting the zeolite crystal skeleton used in the hydrocracking catalyst. Zeolite containing silica and alumina, that is, aluminosilicate is preferable. Many types of crystal structures of zeolite have been reported, and examples thereof include faujasite type, beta type, mordenite type, and pentasil type. In the present invention, the faujasite type, the beta type, and the pentasil type are more preferable, and the faujasite type and the beta type are even more preferable in that sufficient hydrocracking activity is exhibited. As these zeolites, those having an alumina content adjusted according to the stoichiometric ratio of raw materials at the start of synthesis, or those subjected to a predetermined hydrothermal treatment and / or acid treatment can be used. Of these, the super-stabilized Y type that is super-stabilized by hydrothermal treatment and / or acid treatment is most desirable. This ultra-stabilized Y type has a fine pore structure called micropores of 20 cm or less, which is the original size of zeolite, and new pores are formed in the range of 20 to 100 cm to convert the oxygen content of the fat and oil component. It is presumed to provide a good reaction field, and the volume of the pores having the pore diameter is preferably 0.03 ml / g or more, more preferably 0.04 ml / g. The pore volume here can be generally determined by a mercury intrusion method. Known conditions can be used as the hydrothermal treatment conditions. As the physical property of the ultra-stabilized Y-type, the silica / alumina molar ratio is preferably 10 to 120, more preferably 15 to 70, and still more preferably 20 to 50. When the silica / alumina molar ratio is higher than 120, the acidity is low, and sufficient hydrocracking activity may not be exhibited. On the other hand, when the silica / alumina molar ratio is lower than 10, the acidity is too strong, and the coke generation reaction may be promoted to cause a rapid decrease in activity. The content of zeolite is preferably 2 to 80% by weight, more preferably 4 to 75% by weight, based on the weight of the carrier. If the zeolite content is less than the lower limit, the hydrocracking activity may not be exhibited, and if the zeolite content exceeds the upper limit, the acidity is too strong and the coke formation reaction may be accelerated. is there.

  In any of the hydrogenation pretreatment catalyst and the hydrocracking catalyst, the method of incorporating the active metal into the catalyst is not particularly limited, and a known method applied when producing a normal desulfurization catalyst may be used. it can. Usually, a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed. Further, an equilibrium adsorption method, a pore-filling method, an incident-wetness method, and the like are also preferably employed. For example, the pore-filling method is a method in which the pore volume of the support is measured in advance and impregnated with the same volume of the metal salt solution, but the impregnation method is not particularly limited, and the amount of metal supported Further, it can be impregnated by an appropriate method depending on the physical properties of the catalyst support.

Furthermore, in the present invention, a light oil composition satisfying a predetermined performance can be produced by mixing the environmentally low load light oil base produced above and a hydrorefined oil refined from crude oil or the like.
The hydrorefined oil refined from the crude oil, etc., is obtained by treating straight-run gas oil obtained from a crude oil atmospheric distillation device, straight-run heavy oil or residual oil obtained from an atmospheric distillation device with a vacuum distillation device. Hydrocracked gas oil, hydrocracked gas oil obtained by catalytic cracking or hydrocracking of vacuum gas oil, vacuum heavy gas oil or desulfurized heavy oil obtained by hydrocracking, and hydrorefining of these petroleum hydrocarbons Examples include light oil or hydrodesulfurized light oil.
These hydrorefined oils can be constituted by blending a plurality of light oil fraction base materials and kerosene fraction base materials in a category that satisfies a predetermined condition. In addition, synthetic light oil synthesized from natural gas, asphalt, coal, woody biomass and the like can be used.

The hydrorefining of the hydrorefined oil can be performed using a hydrodesulfurization apparatus common in petroleum refining. In general, in the case of a light oil fraction, the reaction is performed under the conditions of a reaction temperature of 300 to 380 ° C., a hydrogen pressure of 3 to 8 MPa, LHSV 0.3 to 2 h ⁻¹ , and a hydrogen / oil ratio of 100 to 500 NL / L.
As a catalyst used for hydrorefining, a general hydrodesulfurization catalyst can be applied. As the active metal, normally, Group 6A and Group 8 metals of the periodic table are preferably used, 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.

Moreover, the hydrorefined oil can use what hydrotreated the above-mentioned raw material oil in presence of a hydrogenation catalyst. The hydrotreating conditions are usually 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. The reaction temperature is preferably 175 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 190 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 the hydrogen / oil ratio, the more the desulfurization and hydrogenation reactions are promoted, but there is an optimal point economically. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, a very large reaction tower volume is required, resulting in an excessive capital investment.

The apparatus for hydrotreating the feedstock may be of any configuration, the reaction towers may be used alone or in combination, and hydrogen may be additionally injected between the reaction towers, gas-liquid separation operation or hydrogen sulfide. You may have the removal equipment.
A fixed bed system is preferably employed as the reaction mode of the hydrotreating apparatus. Hydrogen can take either a countercurrent or cocurrent flow with respect to the feedstock, and may have a plurality of reaction towers and a combination of countercurrent and cocurrent. As a general format, it is a down flow, and a gas-liquid twin parallel flow format is preferable. 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. An inorganic oxide is mentioned as a porous support | carrier. 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. Things are 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% by mass or less, more preferably 60% by mass or less, and more preferably 40% by mass 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 and mordenite, particularly preferably Y type and beta type are used. 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 of the periodic table. Preferably, it is at least one selected from Ru, Rd, Ir, Pd and Pt, 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, etc. can be employed. 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 is preferably 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.

  In the present invention, hydrorefined oil of the kerosene fraction can be used in addition to the hydrorefined oil of the light oil fraction. Such a kerosene fraction can be a kerosene fraction obtained by hydrotreating a predetermined feedstock. The raw oil is mainly straight-run kerosene obtained by atmospheric distillation of crude oil, but hydrocracked kerosene produced together with hydrocracked light oil and hydrogen obtained by hydrotreating the above kerosene fraction. Refined kerosene can be used. It is also possible to use synthetic kerosene made from natural gas, asphalt, coal, biomass and the like.

The hydrorefined oil kerosene fraction of the present invention can be obtained by hydrotreating (desulfurizing and refining) the above-described raw material oil in the presence of a hydrogenation catalyst.
The hydrotreating conditions are usually a reaction temperature of 220 to 350 ° C., a hydrogen pressure of ^{1 to} 6 MPa, an LHSV of 0.1 to 10 h ⁻¹ , and a hydrogen / oil ratio of 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. , LHSV 2 to 10 h ⁻¹ , hydrogen / oil ratio 50 to 200 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 the hydrogen / oil ratio, the more the desulfurization and hydrogenation reactions are promoted, but there is an optimal point economically. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, a very large reaction tower volume is required, resulting in an excessive capital investment.

The apparatus for hydrotreating the feedstock may be of any configuration, the reaction towers may be used alone or in combination, and hydrogen may be additionally injected between the reaction towers, gas-liquid separation operation or hydrogen sulfide. You may have the removal equipment.
A fixed bed system is preferably employed as the reaction mode of the hydrotreating apparatus. Hydrogen can take either a countercurrent or cocurrent flow with respect to the feedstock, and may have a plurality of reaction towers and a combination of countercurrent and cocurrent. As a general format, it is a down flow, and a gas-liquid twin parallel flow format is preferable. 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. As the porous carrier, a porous inorganic oxide mainly composed of alumina is used. 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. Things are 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% by mass or less, more preferably 60% by mass or less, and more preferably 40% by mass or less. . These conditions and the catalyst are not particularly limited as long as the properties of the raw material oil are satisfied.

  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 and mordenite, particularly preferably Y type and beta type are used. 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 6A metals of the periodic table. Preferably, it is at least one selected from Mo and W. The active metal may be a combination of a Group 6A metal and a Group 8 metal, specifically, a combination of Mo or W and Co or Ni. For example, Co—Mo, Co—W, Ni—Mo, Combinations such as Ni-W, Co-Ni-Mo, and Co-Ni-W can be employed. 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 is preferably 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 gas oil composition produced according to the present invention uses the above-mentioned environmentally low load gas oil base material of the hydrocarbon-containing mixed fraction, has a sulfur content of 5 mass ppm or less, an oxygen content of 1 mass% or less, and a distillation property. The gas oil composition must have a 10% distillation temperature of 140 ° C. or higher and 190 ° C. or lower and satisfy the JIS No. 3 diesel oil standard.

  The sulfur content of the gas oil composition of the present invention needs to be 5 mass ppm or less, preferably 4 mass ppm from the viewpoint of reducing harmful exhaust components discharged from the engine and improving the performance of the exhaust gas aftertreatment device. Below, more preferably 3 ppm by mass or less, still more preferably 2 ppm by mass or less, and even more preferably 1 ppm by mass 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 gas oil composition of the present invention needs to be 1% by mass or less, preferably 0.8% by mass or less, more preferably 0.6% by mass or less from the viewpoint of improving oxidation stability. More preferably, it is 0.4% by mass or less, and still more preferably 0.2% by mass or less. 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

The light oil composition of the present invention is required to satisfy the JIS No. 3 light oil standard. The JIS No. 3 diesel oil standard is a standard that satisfies “Type No. 3” defined in JIS K 2204 “Diesel Oil”. Specifically, the flash point is 45 ° C. or higher, the 90% distillation temperature is 330 ° C. or lower, and the pour point. −20 ° C. or less, clogging point (CFPP) −12 ° C. or less, 10% residual oil residual carbon content of 0.1% by mass or less, cetane index of 45 or more, kinematic viscosity at 30 ° C. of 2.0 mm ² / s or more, sulfur It is necessary that the content is 0.05% by mass or less. In addition, the diesel oil composition in the present invention is preferably used in accordance with the No. 3 diesel oil usage guideline shown in “Diesel Oil Usage Guidelines” shown in the explanation of JIS K 2204-1996. In addition, regarding the provision of sulfur content, it is necessary to apply the provision of the present invention as a higher concept rather than the provision of the JIS standard.

  The flash point of the light oil composition of the present invention must satisfy 45 ° C. or higher, which is a JIS No. 3 light oil standard. When the flash point is less than 45 ° C., it cannot be handled as a light oil composition for safety reasons. For the same reason, the flash point is preferably 49 ° C. or higher, and more preferably 53 ° 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 cetane index of the light oil composition of the present invention needs to satisfy 45 or more which is a JIS No. 3 light oil standard. When the cetane index is less than 45, the concentration of PM, aldehydes, or NOx in the exhaust gas tends to increase. For the same reason, the cetane index is preferably 48 or more, and most preferably 51 or more. 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 preferably 52 or more, more preferably 54 or more, and further preferably 55 or more. When the cetane number is less than 52, the concentrations of NOx, PM and aldehydes in the exhaust gas tend to be high. Further, from the viewpoint of reducing black smoke in the exhaust gas, the cetane number is preferably 90 or less, more preferably 88 or less, and even more preferably 85 or less. Moreover, in the light oil composition of this invention, a cetane number improver can be mix | blended with an appropriate quantity as needed, and the cetane number of the light oil composition obtained can be improved. 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.

Density at 15 ℃ of the gas oil composition of the present invention, in terms of calorific value ensuring, is preferably 740kg / ^{m 3} or more, more preferably 755kg / ^{m 3} or more, more preferably 750 kg / ^{m 3} or more. Further, the density, NOx, from the viewpoint of reducing the emission of PM, it is preferably 850 kg / ^{m 3} or less, more preferably 845 kg / ^{m 3} or less, more preferably 840 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”.

The light oil composition of the present invention desirably has a lubricating performance such that the HFRR wear scar diameter (WS1.4) is preferably 410 μm or less, more preferably 400 μm or less. When the HFRR wear scar diameter (WS1.4) exceeds 410 μm, especially in a diesel engine equipped with a distribution type injection pump, it causes an increase in the driving torque of the pump during operation and an increase in wear of each part of the pump. The engine itself may be destroyed as well as the performance deterioration. In addition, in an electronically controlled fuel injection pump capable of high-pressure injection, there is a concern about wear on the sliding surface.
The HFRR wear scar diameter (WS1.4) as used in the present invention is a value measured by the Petroleum Institute Standard JPI-5S-50-98 “Light Oil-Lubricity Test Method” issued by the Japan Petroleum Institute. Means.

  Although there is no restriction | limiting in particular in aromatic content in the light oil composition of this invention, it is preferable that it is 20 volume% or less from a viewpoint of improving an environmental impact reduction effect and NOx and PM reduction, More preferably, it is 19 volumes. % Or less, more preferably 18% by volume or less. The aromatic content in the present invention is measured in accordance with the Petroleum Institute Method JPI-5S-49-97 “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method” issued by the Japan Petroleum Institute. It means the volume percentage (volume%) of the aromatic content.

  The water content of the light oil composition of the present invention is preferably 300 ppm by volume or less, preferably 250 ppm by volume or less, from the viewpoint of adverse effects on members to fuel tanks and the like and suppression of hydrolysis of ester compounds. Is more preferable, and it is further more preferable that it is 200 volume ppm or less. In addition, the water | moisture content here is the water prescribed | regulated by JISK2275 "moisture test method (crude oil and petroleum products)."

  The clogging point (CFPP) of the light oil composition of the present invention needs to satisfy −12 ° C. or less, which is JIS No. 3 light oil standard. Furthermore, it is preferably −13 ° C. or less, and more preferably −14 ° C. or less, from the viewpoint of preventing the prefilter blockage of the diesel vehicle. Here, the clogging point refers to a clogging point measured according to JIS K 2288 “Light oil—clogging point test method”.

  Moreover, the pour point of the light oil composition of this invention needs to satisfy | fill -20 degrees C or less which is a JIS3 light oil specification. Furthermore, from the viewpoint of low temperature startability or low temperature drivability and maintaining the injection performance of the electronically controlled fuel injection pump, it is preferably −23 ° C. or lower. Here, the pour point means a pour point measured by JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.

  As a distillation property in the light oil composition of the present invention, it is necessary to satisfy a 90% distillation temperature of 330 ° C. or less which is a JIS No. 3 light oil standard. Preferably it is 325 degrees C or less, More preferably, it is 320 degrees C or less, More preferably, it is 315 degrees C or less. When the 90% distillation temperature exceeds the upper limit, the amount of PM and fine particles discharged tends to increase. The 90% distillation temperature is preferably 270 ° C. or higher, more preferably 275 ° C. or higher, and further preferably 280 ° C. or higher. If the 90% distillation temperature is less than the lower limit, the fuel efficiency improvement effect becomes insufficient and the engine output tends to decrease.

The 10% distillation temperature must satisfy 140 ° C or higher, more preferably 145 ° C or higher, further preferably 150 ° C or higher, and still more preferably 155 ° C or higher. If the 10% distillation temperature is less than the lower limit, engine output and startability at high temperatures tend to deteriorate. The 10% distillation temperature must satisfy 190 ° C. or lower, preferably 185 ° C. or lower, more preferably 180 ° C. or lower. If the 10% distillation temperature exceeds the upper limit, the exhaust gas performance tends to deteriorate.
The 10% distillation temperature and 90% distillation temperature here mean values measured by JIS K 2254 “Petroleum product-distillation test method”.

The kinematic viscosity at 30 ° C. of the light oil composition of the present invention is required to be 2.0 mm ² / s or more, which is JIS3 light oil standard, and preferably 2.2 mm ² / s or more. More preferably, it is 4 mm ² / s or more. When the kinematic viscosity is less than 2.4 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. It is preferable that kinematic viscosity at 30 ° C. of the gas oil composition of the present invention is less than 4.5 mm ² / s, more preferably not more than ^{4.3mm 2 / s, 4.0mm 2 /} s or less More preferably it is. If the kinematic viscosity exceeds 4.5 mm ² / s, the resistance inside the fuel injection system increases, the injection system becomes unstable, and the concentrations of NOx and PM in the exhaust gas increase. 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 residual carbon content of 10% residual oil in the light oil composition of the present invention needs to satisfy 0.1 mass% or less which is JIS No. 3 light oil standard. Furthermore, it is preferably 0.08% by mass or less and more preferably 0.06% by mass or less from the viewpoint of reducing fine particles and PM and maintaining the performance of the exhaust gas aftertreatment device mounted on the engine. preferable. The residual carbon content of 10% residual oil here means the residual carbon content of 10% residual oil measured by JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.

  In the light oil composition of the present invention, the ash content is preferably less than 0.01% by mass. If the ash content exceeds the upper limit, the ash becomes the core of PM during the combustion process in the engine, and the total amount of PM and the amount of nanoparticles increase. Further, even when the ash is discharged as it is, the ash is deposited on the exhaust gas post-processing device, and the performance of the post-processing device may be deteriorated. Furthermore, an adverse effect on the fuel injection system can be considered. The ash content in the present invention means a value measured by JIS K 2272 “Crude oil and petroleum product ash content and sulfate ash test method”.

  Moreover, although the electrical conductivity in the light oil composition in this invention is not specifically limited, From the point of safety, it is preferable that it is 50 pS / m or more. In order to improve the electrical conductivity, an antistatic agent or the like can be appropriately added to the light oil composition of the present invention. Here, the conductivity means a value measured in accordance with JIS K 2276 “Petroleum products—aviation fuel oil test 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, the peroxide value after the oxidation stability test is preferably 10 ppm by mass or less, more preferably 8 ppm by mass or less, and further preferably from the viewpoint of storage stability and compatibility with members. Is 5 ppm by mass or less. Here, the peroxide value means a value measured in accordance with the Petroleum Institute Standard JPI-5S-46-96. To the light oil composition of the present invention, additives such as an antioxidant and a metal deactivator can be appropriately added in order to reduce the total insoluble matter and the peroxide value.

  Moreover, it is preferable that the total acid value of the light oil composition of this invention is 1.0 mgKOH / g or less. Since the total acid value indicates the amount of free fatty acid in the mixture, if this value is large, there is a concern that the acidic compound may adversely affect the member. Therefore, the total acid value is preferably 1.0 mgKOH / g or less, more preferably 0.9 mgKOH / g or less, and further preferably 0.8 mgKOH / g or less. The total acid value referred to here means the total acid value measured by JIS K 2501 “Petroleum products and lubricating oils—neutralization number test method”.

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.

  In the present invention, it is preferable to use a nitrate ester among the cetane number improvers described above. 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 ppm by mass or more based on the total amount of the composition, more preferably 600 ppm by mass or more, further preferably 700 ppm by mass or more, and 800 ppm by mass or more. Even more preferably, it is most preferably 900 ppm by mass or more. When the content of the cetane number improver is less than 500 ppm by mass, a sufficient cetane number improving effect cannot be obtained, and PM, aldehydes, and further 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 mass ppm or less, more preferably 1250 mass ppm or less, based on the total amount of the light oil composition, and 1100 mass ppm or less. It is more preferable that it is 1000 mass ppm 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.

  In the light oil composition of the present invention, additives other than the cetane number improver can be blended as necessary, and in particular, a lubricity improver and / or a detergent is preferably blended.

As the lubricity improver, for example, one or more of carboxylic acid-based, ester-based, alcohol-based, and phenol-based lubricity improvers can be arbitrarily used. 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.

  The blending amount of the lubricity improver is not particularly limited as long as the HFRR wear scar diameter (WS1.4) is within the above-mentioned preferable range, but is preferably 35 ppm by mass or more based on the total amount of the composition, and 50 ppm by mass. More preferably. When the blending amount of the lubricity improver is within the above range, the effectiveness of the blended lubricity improving agent 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. Further, the upper limit of the blending amount is preferably 150 mass ppm or less on the basis of the total amount of the composition, and more preferably 105 mass ppm or less because an effect commensurate with the addition amount cannot be obtained even if it is added more. preferable.

  Examples of the detergent include imide compounds; alkenyl succinimides such as polybutenyl succinimides synthesized from polybutenyl succinic anhydrides and ethylene polyamines; polyhydric alcohols such as pentaerythritol and polybutyls. Succinic acid esters such as polybutenyl succinic acid ester synthesized from tenyl succinic anhydride; copolymer polymers such as dialkylaminoethyl methacrylate, polyethylene glycol methacrylate, vinyl pyrrolidone and alkyl methacrylate copolymers, carboxylic acids and amines Ashless detergents such as reaction products of alkenyl succinic acid imide and reaction products of carboxylic acid and amine 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 clogging of the fuel injection nozzle, the blending amount of the cleaning agent is 30 mass ppm 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 mass ppm or more, It is further more preferable to set it as 80 mass ppm or more. Even if an amount less than 30 ppm by mass is added, the effect may not appear. On the other hand, if the amount is too large, an effect commensurate with that cannot be expected, and conversely, NOx, PM, aldehydes, etc. in the diesel engine exhaust gas may increase, so the amount of detergent contained is 300 mass. It is preferably not more than ppm, and more preferably not more than 180 mass ppm.

  As in the case of the above cetane improver, those commercially available as lubricity improvers or detergents are in a state where the active ingredients contributing to lubricity improvement or cleaning are diluted with an appropriate solvent, respectively. It is usually obtained at 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) to be described later are added alone or in combination of several kinds. You can also. Other additives include, for example, low-temperature fluidity improvers such as ethylene-vinyl acetate copolymer and alkenyl succinic acid amide; antioxidants such as phenols and amines; metal deactivators such as salicylidene derivatives; Anti-icing agents such as polyglycol ethers; corrosion inhibitors such as aliphatic amines and alkenyl succinic acid esters; antistatic agents such as anionic, cationic and amphoteric surfactants; colorants such as azo dyes; Antifoaming agents and the like.
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.

The light oil composition for cold regions containing an environmentally low load type light oil base material produced from the animal and vegetable oil and fat of the present invention and the triglyceride-containing hydrocarbon that is a component derived from the animal and vegetable oil and fat has life cycle CO ₂ emission characteristics and oxidation stability. It is excellent in member influence and low temperature startability.

  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 1-5 and Comparative Examples 1-4)
The reduced pressure light oil and vegetable oils and fats having the properties shown in Table 1 were reacted under the reaction conditions shown in Table 2 to prepare environmentally low load light oil base materials shown in Table 3 (Examples 1 to 3). In addition, the environmental low load type light oil base material 1 is vegetable oil and fat 1, the environmental low load type light oil base material 2 is vegetable oil and fat 2, and the environmental low load type light oil base material 3 is vacuum gas oil and vegetable oil and fat 1, 80:20. In this case, the mixture is reacted as a raw material oil.
Moreover, the property of the fatty-acid alkylester obtained by esterifying the vegetable oil shown in Table 1 is shown (Comparative Examples 2-4). These fatty acid alkyl esters are methyl ester compounds obtained by reaction with methanol. Here, they are stirred at 70 ° C. for about 1 hour in the presence of an alkali catalyst (sodium methylate) to directly react with alkyl alcohol. Thus, an ester exchange reaction for obtaining an ester compound was used.
A light oil composition was prepared by blending the environmentally low load type light oil base material shown in Table 3, the methyl ester value of vegetable oil and fat, and the hydrorefined oil which is a petroleum base material (Examples 1 to 5 and Comparative Examples). 1-4).
In addition, the additive used was as follows.
・ Lubricity improver: Carboxylic acid mixture based on linoleic acid ・ Detergent: Carboxylic acid mixture based on oleic acid and oleylamine
Reaction product Low temperature fluidity improver: ethylene-vinyl acetate copolymer

  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, aromatic content Content, cetane number and cetane index, pour point, clogging point, residual carbon content of 10% residual oil, bulk modulus, ash content, moisture, total insoluble matter after oxidation stability test, peroxide value, conductivity The results of measuring the wear scar diameter are shown in Table 4.

The properties of the fuel oil were measured by the following method.
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 sulfur content refers to the mass content of the sulfur content based on the total amount of light oil composition measured by JIS K2541 “Sulfur content test method”.
The oxygen content was measured by elemental analysis.

All the distillation properties are values measured by JIS K 2254 "Petroleum products-Distillation test method".
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%).
Moisture means the moisture specified by JIS K 2275 “Moisture test method (crude oil and petroleum products)”.
The flash point indicates a value measured according to JIS K 2265 “Crude oil and petroleum product flash point test method”.
The total acid value means the total acid value measured according to JIS K 2501 “Petroleum products and lubricating oils—neutralization number test method”.

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”.

Lubrication performance and 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. .
The clogging point refers to a clogging point measured by JIS K 2288 “Light oil—clogging point test method”.
The pour point refers to a pour point measured according to JIS K 2269 “Crude point of petroleum and petroleum products and a cloud point test method of petroleum products”.
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”.
Ash content means a value measured by JIS K 2272 “Crude oil and petroleum product ash and sulfate ash test method”.
The total insoluble matter after the oxidation stability test means a value measured under conditions of 95 ° C. and oxygen bubbling for 16 hours in accordance with ASTM D2274-94.
The peroxide value means a value measured according to the Petroleum Institute Standard JPI-5S-46-96.
The conductivity means a value measured in accordance with JIS K 2276 “Petroleum product-aviation fuel oil test method”.

  As shown in Table 4, the light oil compositions used in the examples and comparative examples are a specific ratio of water environment low load type light oil base material, methyl ester value of vegetable oil and fat, and hydrorefined oil which is a petroleum base material. It was prepared by blending with.

  As is clear from Table 2, the environmentally low load type light oil base material, and the environmental low load type light oil base material and the hydrorefined oil were mixed and used, and were blended within the range defined by the present invention. In 1-5, it is possible to easily and reliably obtain a light oil composition for cold regions that satisfies a sulfur content of 5 mass ppm or less, an oxygen content of 1 mass% or less, and satisfies the properties of JIS No. 3 diesel oil standard. did it. On the other hand, in Comparative Examples 1 to 4 in which a light oil composition was prepared without using the above-mentioned specific environment-friendly light oil base material, the light oil composition for cold regions 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 5 and Comparative Examples 1 to 4. All test results are shown in Table 5. As can be seen from the results in Table 5, the light oil compositions of Examples 1 to 5 have less carbon dioxide emissions in the life cycle than the light oil compositions of Comparative Examples 1 to 4, and are excellent in low-temperature startability. It is clear that it has excellent oxidation stability and no adverse effects on the material.

  The test method related to the vehicle test conforms to “27 Standards for Diesel Vehicle 10/15 Mode Exhaust Gas Measurement”, “Appendix 27, New Automobile Examination Standards Supervised by the Ministry of Land, Infrastructure, Transport and Tourism”.

(Fuel consumption test)
Fuel consumption was measured using a diesel engine-equipped vehicle (vehicle 1) shown below. The test mode is a transient operation mode that simulates the actual driving shown in FIG. 1, and the fuel consumption is corrected for the fuel volume flow rate consumed during the test mode and replaced with the weight value. Each result was compared and quantified relative to 100 as the result of the test.

(Vehicle specifications): Vehicle 1
Engine type: Supercharged inline 4 cylinder diesel engine with intercooler Displacement: 3L
Compression ratio: 18.5
Maximum output: 125kW / 3400rpm
Maximum torque: 350Nm / 2400rpm
Regulatory compliance: 1997 exhaust gas regulatory compliance Vehicle weight: 1900 kg
Mission: 4AT
Exhaust gas aftertreatment device: oxidation catalyst

(Life cycle CO ₂ calculation)
Life Cycle CO ₂ includes a CO ₂ generated due to combustion of the gas oil compositions in a vehicle equipped with a diesel engine, is calculated by dividing the CO ₂ generated from mining to the fuel oil supply to the vehicle tank.
CO ₂ generated by combustion (hereinafter referred to as “Tank to Wheel CO ₂ ”).
) Was calculated as the emission amount per unit calorific value of each light oil composition based on the CO ₂ emission amount, the running fuel consumption and the fuel density when the vehicle test was conducted.
In addition, CO ₂ generated from mining to fueling the vehicle tank (hereinafter referred to as “Well to Tank CO ₂ ”) is used for mining, transporting, processing, distributing, and refueling the vehicle. It was calculated as the sum of CO ₂ emissions in a series of flows. In calculating “Well to Tank CO ₂ ”, calculation was performed in consideration of the carbon dioxide emission shown in the following (1B) to (5B). As data necessary for such calculation, refinery operation performance data possessed by the present inventors was used.
(1B) Carbon dioxide emissions associated with the use of fuel in various processing equipment, boilers and other facilities.
(2B) In the treatment using hydrogen, the amount of carbon dioxide emission accompanying the reforming reaction in the hydrogen production apparatus.
(3B) Carbon dioxide emission associated with catalyst regeneration when passing through an apparatus with continuous catalyst regeneration, such as a catalytic cracker.
(4B) Carbon dioxide emissions when a light oil composition is manufactured or unloaded in Yokohama, delivered from Yokohama to Sendai, and refueled in Sendai.
(5B) The amount of carbon dioxide emitted when animal and vegetable oils and fats and components derived from animal and vegetable oils and fats are produced in Malaysia and the surrounding area and manufactured in Yokohama.
In addition, when using animal and vegetable oils and fats and components derived from animal and vegetable oils and fats, the so-called Kyoto Protocol applies the rule that carbon dioxide resulting from these fuels is not counted as emissions. In this calculation, this was applied to “Tank to Wheel CO ₂ ” generated during combustion.
Table 5 shows “Tunk to Wheel CO ₂ ” and “Well to Tank CO ₂ ” calculated in this way, and the respective emissions of life cycle CO ₂ (LC), which is the sum of these. In addition, the comparative example 1 is set to 100, and the numerical value which comparatively compared and quantified each result is also shown collectively.

(Low temperature startability)
(1) Flushing (cleaning) the fuel system of the test diesel vehicle with the evaluation fuel on the chassis dynamometer capable of controlling the environmental temperature using the vehicle 1 and (2) extracting the flushing fuel (3 ) Replacing the main filter with a new one, (4) Placing the prescribed amount of evaluation fuel (1/2 of the fuel tank capacity of the test vehicle) into the fuel tank. Thereafter, (5) the ambient temperature is rapidly cooled from room temperature to -5 ° C, (6) held at -5 ° C for 1 hour, and (7) to a predetermined temperature (-18 ° C) at a cooling rate of 1 ° C / h. (8) Hold the engine at a predetermined temperature for 1 hour, and then start the engine. If the engine does not start even after 10 seconds of cranking is repeated twice at 30 second intervals, it is not possible (x), and if the engine is started between two times of cranking is repeated (O).

(Oxidation stability test)
In accordance with ASTM D2274-94, the fuel is accelerated and deteriorated under conditions of 95 ° C. and oxygen bubbling for 16 hours, and the change in hue before and after the test is observed. If not, it was judged as “Yes”.

(Rubber swelling test)
In order to confirm the influence on the rubber member used in the O-ring of the engine parts, a soaking test was performed according to the following procedure. Acrylonitrile, one of the compounds composing rubber, has a combined acrylonitrile mass center value of nitrile rubber (medium nitrile rubber) that is 25% or more and 35% or less of the total as a rubber member to be evaluated, and conforms to MIL R6855 Then, the test fuel is heated and held at 100 ° C., and the test rubber member is immersed in it for 70 hours. Evaluation is made by comparing and quantifying the volume change of the test rubber member after 70 hours. Judgment of member stability is rejected (x) when the volume change rate absolute value before and after the test is ± 20% or more, border line (△), ± 10% or less when it is ± 10% or more and ± 20% or less In case of, pass (◯).

This is a transient operation mode that simulates actual driving in a fuel consumption test.

Claims (1)

A mixed oil obtained by mixing a petroleum-based base material having a hydrocarbon fraction containing animal and vegetable fats and / or animal and vegetable fat-derived components and a kerosene fraction refined from crude oil at an arbitrary ratio, Co-Mo, Ni-Mo , A hydrogenolysis catalyst containing a metal selected from Ni-Co-Mo and Ni-W and a support containing at least two of silica, alumina, boria, zirconia, magnesia and zeolite, and a hydrogen pressure of 6 to 20 MPa, liquid Hydrogenation of environmentally low load gas oil base and crude oil of hydrocarbon- containing mixed fraction obtained by contacting at a space velocity (LHSV) of 0.1 to 1.5 h ⁻¹ and a hydrogen / oil ratio of 200 to 2000 NL / L by mixing the hydrotreated oil obtained by refining, sulfur content is 5 ppm by mass or less, an oxygen content of 1 wt% or less, 10% distillation temperature of the distillation characteristics are 1 And at 0 ℃ than 190 ° C. or less, and a flash point 45 ° C. or higher, 90% distillation temperature 330 ° C. or less, a pour point -20 ° C. or less, plugging point (CFPP) -12 ° C. or less, 10% residual oil residual carbon A light oil composition for cold regions, which satisfies the JIS No. 3 light oil standard having a min content of 0.1% by mass or less, a cetane index of 45 or more, and a kinematic viscosity at 30 ° C. of 2.0 mm ² / s or more, is obtained. A method for producing the composition.

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