JP5142588B2 - Method for producing gasoline composition - Google Patents

Description

  The present invention relates to gasoline as a fuel for automobiles, and particularly includes a biomass-derived base material from the viewpoint of renewable, prevention of global warming and diversification of supply sources, and is excellent in exhaust gas purification performance, fuel consumption performance, and driving performance. Regarding gasoline.

Conventionally, gasoline is produced by blending one or more kinds of base materials of a gasoline fraction obtained by treating crude oil with various refining apparatuses such as a catalytic reforming apparatus and a catalytic cracking apparatus ( For example, refer nonpatent literature 1).
Biomass-derived base materials that can be blended with gasoline include ethanol (biomass-derived ethanol) produced by fermenting sugar-based sugar components such as sugarcane and corn in yeast (ethanol derived from biomass), and ethanol and oil production from this biomass ETBE produced by reacting with isobutylene obtained by separation from mixed butylene generated from a fluid catalytic cracker (FCC) or the like in a steam plant or a steam cracker (steam cracker) in an ethylene plant is known (for example, Non-Patent Document 2).
On the other hand, use of fatty acid alkyl ester mixtures made from natural animal and vegetable fats and oils as a fuel for diesel automobiles is being considered alone or mixed with existing light oil or the like (see, for example, Non-Patent Document 3). .
Fuel Association, “New Edition Fuel Handbook”, Corona, March 1974, p. 264-267 Handout 3 of the 3rd Renewable Fuel Promotion Conference (October 10, 2003), Ministry of the Environment Central Environmental Council 7th report, July 29, 2003

In recent years, automobiles have been required to reduce both harmful substances in exhaust gas for improving the air environment and to reduce CO ₂ emissions of greenhouse gases from the viewpoint of suppressing global warming. Although the amount of harmful substances in the exhaust gas is extremely low, reduction of CO ₂ emissions by improving thermal efficiency, improving fuel efficiency, and the like is an issue. In the medium and long term, diversification of transportation fuel supply sources and construction of sustainable mobility are desired.
Under these circumstances, the use of biomass-derived fuel, which can reduce CO ₂ increase in the life cycle, contribute to diversification of fuel supply sources and is also a renewable energy, is attracting attention as fuel for gasoline automobiles. .
Animal and vegetable fats and oils, which are biomass, have been studied for use as fuel for diesel vehicles by fatty acid methyl esterification. However, since gasoline engines and diesel engines have different ignition characteristics and fraction ranges required for fuel, it is difficult to use these fatty acid methyl esters derived from animal and vegetable oils as fuel for gasoline automobiles.

As a result of diligent research to solve the above problems, the present inventors have made it possible to use biomass such as animal and vegetable oils and fats by hydrocracking, so that the gasoline composition can be used as a specific property. As a result, it has been found that excellent exhaust gas purification performance, fuel efficiency performance, and driving performance of gasoline automobiles can be derived, and the present invention has been completed.
That is, the present invention contains an oil to be treated containing fats and oils derived from plants or animals, at least one metal selected from the group consisting of Pd, Pt, Rh, Ir, Au and Ni and a crystalline metallosilicate. And a carrier containing a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and A hydrocracking catalyst (B) containing one or more metals selected from Co, Mo, and Ni supported on a support, in the presence of hydrogen, a hydrogen pressure of 2 to 13 MPa, a liquid space velocity (LHSV) of 0. 1~3.0h ^-1, a hydrogen / oil ratio 150 to 1500 NL / L distillation temperature range obtained by contacting under conditions to hydrocracking treatment of 2 from 25 ° C. 0 ℃ fraction of whole or RON of 96.0 or more, characterized in that the containing portion composed from the base material 3 volume% to 20 volume% or less, sulfur content of less 10 ppm by weight The present invention relates to a method for producing an unleaded gasoline composition.

  According to the present invention, it is possible to use biomass as a gasoline composition by treating biomass such as animal and plant fats and oils by hydrocracking. By making the gasoline composition have specific properties, it is possible to obtain excellent exhaust gas from gasoline automobiles. Gasoline with excellent purification performance, fuel efficiency and driving performance will be provided.

Hereinafter, the present invention will be described in detail.
The gasoline of this invention needs to contain the base material obtained by processing the to-be-processed oil containing biomass by hydrocracking.
Examples of biomass contained in the oil to be treated for hydrogenolysis of gasoline of the present invention include plant or animal-derived oils and fats. These are generally esters of higher fatty acids and glycerin, and examples include vegetable oils such as palm oil, rapeseed oil, corn oil, soybean oil, and grape seed oil, and animal oils such as lard. In the case of the present invention, these fats and oils may be used waste oil. The fats and oils used in the present invention are not particularly limited, but vegetable oils are preferable from the viewpoint of carbon neutral, and rapeseed oil, soybean oil, and palm oil are more preferable from the viewpoints of the number of fatty acid alkyl chain carbons and their reactivity. Moreover, in the case of this invention, these fats and oils may be 1 type, or 2 or more types of mixtures may be sufficient as them.

  The content of biomass contained in the hydrocracked oil of the present invention is not particularly limited, but more biomass is used from the viewpoints of renewable, prevention of global warming and diversification of fuel supply sources. 25 volume% or more is preferable, 50 volume% or more is more preferable, 75 volume% or more is more preferable, 90% capacity or more is further more preferable, and the whole quantity may be biomass.

  Oils and fats derived from animal and vegetable oils generally have a fatty acid triglyceride structure, but may contain other oils and fats processed into esters such as fatty acids and fatty acid methyl esters. However, since carbon dioxide is generated when producing fatty acids and fatty acid esters from vegetable oils and fats, it is preferable that the components having a triglyceride structure are mainly used as vegetable oils and fats from the viewpoint of reducing carbon dioxide emissions. . In the hydrocracking of the present invention, the proportion of the compound having a triglyceride structure in the biomass contained in the oil to be treated is preferably 90 mol% or more, more preferably 92 mol% or more, and 95 mol%. It is still more preferable that it is above.

  The oil to be treated for hydrocracking of the present invention may contain, in addition to biomass, a fraction obtained in a general petroleum refining process as a petroleum hydrocarbon fraction. For example, a fraction corresponding to a predetermined boiling range obtained from an atmospheric distillation apparatus or a vacuum distillation apparatus, or a predetermined obtained from a hydrodesulfurization apparatus, a hydrocracking apparatus, a residual oil direct desulfurization apparatus, a fluid catalytic cracking apparatus, etc. A fraction corresponding to the boiling point range can be used. In addition, you may use the fraction obtained from each said apparatus individually by 1 type or in mixture of 2 or more types. Furthermore, the oil to be treated of the present invention may contain chemical-derived compounds such as plastics and solvents, and is obtained via a Fischer-Tropsch reaction using a synthesis gas composed of carbon monoxide and hydrogen as a raw material. Synthetic oil may be included.

  In the hydrocracking to obtain the base material contained in the gasoline of the present invention, it is selected from the group consisting of oil to be treated containing biomass in the presence of hydrogen and a metal belonging to Group 8 of the periodic table. One preferred method is to treat the catalyst by bringing it into contact with a hydrocracking catalyst containing at least one metal and a support containing a crystalline metallosilicate (hereinafter referred to as hydrocracking A of the present invention).

Hereinafter, the hydrocracking A of the present invention will be described in detail.
The oxygen content contained in the oil to be treated of hydrocracking A of the present invention is preferably 0.1 to 15% by mass, more preferably 1 to 15% by mass, and still more preferably based on the total amount of the oil to be treated. It is 3-14 mass%, Most preferably, it is 5-13 mass%. If the oxygen content is less than 0.1% by mass, it tends to be difficult to stably maintain the deoxygenation activity and desulfurization activity. On the other hand, if the oxygen content exceeds 15% by mass, equipment required for the treatment of by-product water is required, the interaction between water and the catalyst carrier becomes excessive, and the activity decreases or the catalyst strength decreases. To do. The oxygen content can be measured with a general elemental analyzer. For example, the sample is converted to carbon monoxide on platinum carbon, or further converted to carbon dioxide, and then a thermal conductivity detector. Can be measured.

  The sulfur content in the oil to be treated of hydrocracking A of the present invention is preferably 50 ppm by mass or less, more preferably 20 ppm by mass or less, and still more preferably 10 masses based on the total amount of the oil to be treated. ppm or less. When the sulfur content exceeds 50 mass ppm, it tends to be difficult to stably maintain the deoxygenation activity, and the sulfur content contained in the hydrocracked oil tends to increase. This is not preferable because the amount of gasoline blended is limited. In addition, the sulfur content in this invention means the mass content of the sulfur content measured based on the method of JISK2541 "Sulfur content test method" or ASTM-5453.

  The oil to be treated of hydrocracking A of the present invention preferably contains a fraction having a distillation temperature of 300 ° C. or higher, and preferably does not contain a heavy fraction having a distillation temperature exceeding 700 ° C. . When the oil to be treated that does not contain a fraction having a distillation temperature of 300 ° C. or higher is used, it tends to be difficult to obtain a sufficient yield due to excessive decomposition. On the other hand, when the oil to be treated contains a heavy fraction having a distillation temperature exceeding 700 ° C., carbon deposition in the catalyst is promoted by the heavy component, and the activity tends to decrease. In addition, the distillation temperature in this invention is a value measured based on the method as described in JISK2254 "distillation test method" or ASTM-D86.

  As the crystal structure of the crystalline metallosilicate contained in the catalyst used in the hydrocracking A of the present invention, each of FAU, AEL, MFI, MMW, TON, MTW, * BEA, MOR among the structures defined by the International Zeolite Society It preferably has a structure represented by a code, more preferably FAU, * BEA, MOR, or MFI, and even more preferably FAU. The FAU is also called a faujasite type, and in the present invention, the Y type that has been subjected to ultrastabilization treatment is particularly preferable. The ultra-stabilization treatment refers to a hydrothermal treatment and / or a washing treatment with an acidic aqueous solution, and by such an operation, the aluminum content contained in the structure is adjusted to obtain mesopores defined as pore diameters of 2 to 50 nm. The resulting pore volume can be imparted.

The SiO ₂ / Al ₂ O ₃ molar ratio contained in the crystalline metallosilicate contained in the catalyst used in the hydrocracking A of the present invention is preferably in the range of 10-100. If the molar ratio is less than 10, coke formation may be promoted and the activity may be significantly reduced. If the molar ratio exceeds 100, sufficient hydrocracking activity may not be exhibited.

  The method for synthesizing the crystalline metallosilicate contained in the catalyst used in the hydrocracking A of the present invention is not particularly limited, and a generally known method can be used. The constituent raw materials can be subjected to an operation such as heating in the presence of a structure indicator such as an amine compound if necessary. Examples of the constituent raw material include sodium silicate, colloidal silica, alkoxide silicate and the like in the case of a silicon-containing compound, and aluminum hydroxide and sodium aluminate in the case of aluminum. Examples of the structure directing agent include tetrapropylammonium salt.

  In the catalyst used for the hydrocracking A of the present invention, examples of the constituent other than the crystalline metallosilicate include inorganic oxides selected from aluminum, silicon, zirconium, boron, titanium and magnesium. These inorganic oxides can be used as a bonding agent when molding a crystalline metallosilicate, and can also function as an active component that promotes hydrodeoxygenation and hydroisomerization. Two or more kinds selected from zirconium, boron, titanium and magnesium are preferable.

  In the catalyst used in the hydrocracking A of the present invention, the content of the crystalline metallosilicate in the entire catalyst is preferably 2 to 90% by mass, more preferably 5 to 85% by mass, and even more preferably 10 to 80% by mass. preferable. When the content is less than 2% by mass, hydrodeoxygenation activity and hydroisomerization activity as a catalyst are not sufficient, and when the content exceeds 90% by mass, the catalyst moldability is not easy, There is a risk of hindrance to industrial production.

  In the hydrocracking A of the present invention, the porous inorganic oxide as a support carries one or more metals selected from Group 8 elements of the periodic table. When at least one metal selected from Pd, Pt, Rh, Ir, Au, and Ni is used as an active metal, these metals can be used in combination. Suitable combinations include, for example, Pd—Pt, Pd—Ir, Pd—Rh, Pd—Au, Pd—Ni, Pt—Rh, Pt—Ir, Pt—Au, Pt—Ni, Rh—Ir, Rh— Au, Rh—Ni, Ir—Au, Ir—Ni, Au—Ni, Pd—Pt—Rh, Pd—Pt—Ir, Pt—Pd—Ni, and the like can be given. Of these, combinations of Pd—Pt, Pd—Ni, Pt—Ni, Pd—Ir, Pt—Rh, Pt—Ir, Rh—Ir, Pd—Pt—Rh, Pd—Pt—Ni, Pd—Pt—Ir Is more preferable, and a combination of Pd—Pt, Pd—Ni, Pt—Ni, Pd—Ir, Pt—Ir, Pd—Pt—Ni, and Pd—Pt—Ir is even more preferable. In hydrocracking, it is preferable to use these metals after reducing them.

  When one or more metals selected from Pd, Pt, Rh, Ir, Au, and Ni are used as the active metal, the total content of the active metal based on the catalyst mass is preferably 0.1 to 2% by mass. 0.2 to 1.5 mass% is more preferable, and 0.5 to 1.3 mass% is even more preferable. If the total supported amount of the metal is less than 0.1% by mass, the active sites tend to decrease and sufficient activity cannot be obtained. On the other hand, if it exceeds 2% by mass, the metal is not effectively dispersed and sufficient activity tends not to be obtained.

  The method for supporting these active metals on a carrier is not particularly limited, and a known method applied when producing an ordinary catalyst can be used. Usually, a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed. In addition, 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 carrier is measured in advance and impregnated with a metal salt solution having the same volume. The impregnation method is not particularly limited, and it can be impregnated by an appropriate method according to the amount of metal supported and the physical properties of the catalyst carrier.

When combining a plurality of catalysts having different support components, for example, the content of the crystalline metallosilicate is 2 in the subsequent stage of the catalyst having a crystalline metallosilicate content of 5% by mass or less based on the total mass of the support. What is necessary is just to use the catalyst which exists in the range of -90 mass%.
Furthermore, in addition to hydrocracking catalysts, guard catalysts and demetals are used to trap the scale that flows in along with the oil to be treated as needed and to support the hydrocracking catalyst at the separation part of the catalyst bed. Catalysts and inert packing may be used. In addition, these can be used individually or in combination.

In the hydrocracking A of the present invention, the conditions for contacting the oil to be treated and the catalyst in the presence of hydrogen are as follows: hydrogen pressure 2-13 MPa, liquid space velocity (LHSV) 0.1-3.0 h ^{− 1} , preferably a hydrogen oil ratio (hydrogen / oil ratio) of 150 to 1500 NL / L, a hydrogen pressure of 2 to 10 MPa, a liquid space velocity of 0.2 to 2.0 h ⁻¹ , and a hydrogen oil ratio of 200 to 1200 NL / L. More preferably, the hydrogen pressure is 2 to 6 MPa, the space velocity is 0.3 to 1.5 h ⁻¹ , and the hydrogen oil ratio is 250 to 1000 NL / L. These conditions are factors that influence the reaction activity. For example, when the hydrogen pressure and the hydrogen oil ratio are less than the above lower limit values, the reactivity tends to decrease or the activity rapidly decreases. is there. On the other hand, when the hydrogen pressure and the hydrogen oil ratio exceed the above upper limit values, there is a tendency that excessive equipment investment such as a compressor is required. Further, the lower the liquid space velocity tends to be advantageous for the reaction, but if the liquid space velocity is less than the above lower limit value, there is a tendency that an extremely large internal volume reactor is required and excessive equipment investment is required, When the liquid space velocity exceeds the above upper limit, the reaction tends not to proceed sufficiently.

  In the hydrocracking A of the present invention, a fixed bed system can be adopted as the reactor type. That is, hydrogen can adopt either a countercurrent or a parallel flow type with respect to the oil to be treated. Moreover, it is good also as a form which combined the countercurrent and the parallel flow using several reactors. As a general format, it is a down flow, and a gas-liquid twin parallel flow format can be adopted. Moreover, the reactor may be used alone or in combination, and a structure in which one reactor is divided into a plurality of catalyst beds may be adopted.

  In hydrocracking A of the present invention, hydrocracked oil hydrocracked in the reactor is fractionated into hydrocracked oil containing a predetermined fraction through a gas-liquid separation process, a rectification process, and the like. . For example, it is fractionated into gas, naphtha fraction, kerosene fraction, light oil fraction and residual fraction. In addition, water, carbon monoxide, carbon dioxide, hydrogen sulfide, etc. may be generated due to the reaction of oxygen and sulfur contained in the oil to be treated. A gas-liquid separation facility or other by-product gas removal device may be installed in the recovery process.

In the hydrocracking A of the present invention, hydrogen gas is generally introduced from the inlet of the first reactor in association with the oil to be treated before or after passing through the heating furnace. Hydrogen gas may be introduced from between the catalyst beds or between a plurality of reactors for the purpose of controlling the temperature in the reactor and maintaining the hydrogen pressure throughout the reactor. The hydrogen thus introduced is generally called quench hydrogen. The ratio of quench hydrogen to hydrogen gas introduced along with the oil to be treated is preferably 10 to 60% by volume, and more preferably 15 to 50% by volume. If the rate of quench hydrogen is less than 10% by volume, the reaction at the subsequent reaction site tends not to proceed sufficiently. If the rate of quench hydrogen exceeds 60% by volume, the reaction proceeds sufficiently near the reactor inlet. There is a tendency not to.
The kerosene fraction and / or gas oil fraction and / or residue obtained by the hydrocracking A of the present invention may be mixed with the oil to be treated, or may be subjected to a recycling treatment. Thereby, the yield of a gasoline fraction can be raised more.

  In hydrocracking to obtain a base material contained in the gasoline of the present invention, in the presence of hydrogen, an oil to be treated containing biomass and a sulfur-containing hydrocarbon compound, aluminum, silicon, zirconium, boron, titanium, and A porous inorganic oxide composed of two or more elements selected from magnesium, and one or more elements selected from Group 6A and Group 8 elements of the periodic table supported by the porous inorganic oxide The treatment (hereinafter referred to as hydrocracking B of the present invention) by contacting with a metal-containing catalyst is one preferred method.

Hereinafter, the hydrocracking B of the present invention will be described in detail.
The oxygen content contained in the oil to be treated of hydrocracking B of the present invention is preferably 0.1 to 15% by mass, more preferably 1 to 15% by mass, and still more preferably based on the total amount of the oil to be treated. It is 3-14 mass%, Most preferably, it is 5-13 mass%. If the oxygen content is less than 0.1% by mass, it tends to be difficult to stably maintain the deoxygenation activity and desulfurization activity. On the other hand, if the oxygen content exceeds 15% by mass, equipment required for the treatment of by-product water is required, the interaction between water and the catalyst carrier becomes excessive, and the activity decreases or the catalyst strength decreases. To do. The oxygen content can be measured with a general elemental analyzer. For example, the sample is converted to carbon monoxide on platinum carbon, or further converted to carbon dioxide, and then a thermal conductivity detector. Can be measured.

  Although the sulfur-containing hydrocarbon compound contained in the oil to be treated of hydrocracking B of the present invention is not particularly limited, specifically, sulfide, disulfide, polysulfide, thiol, thiophene, benzothiophene, dibenzothiophene, and derivatives thereof, etc. Is mentioned. The sulfur-containing hydrocarbon compound contained in the oil to be treated may be a single compound or a mixture of two or more. Furthermore, a petroleum hydrocarbon fraction containing a sulfur content may be mixed with the oil to be treated. As the petroleum hydrocarbon fraction, a fraction obtained in a general petroleum refining process can be used. For example, a fraction corresponding to a predetermined boiling range obtained from an atmospheric distillation apparatus or a vacuum distillation apparatus, or obtained from a hydrodesulfurization apparatus, a hydrocracking apparatus, a residual oil direct desulfurization apparatus, a fluid catalytic cracking apparatus, etc. A fraction corresponding to a predetermined boiling range may be used. In addition, you may use the fraction obtained from each said apparatus individually by 1 type or in mixture of 2 or more types.

  The sulfur content contained in the oil to be treated of hydrocracking B of the present invention is preferably 1 mass ppm to 1 mass%, more preferably 15 mass ppm to 0.5 mass%, based on the total amount of the oil to be treated. More preferably, it is 30 mass ppm to 0.1 mass%. If the sulfur content is less than 1 ppm by mass, it tends to be difficult to stably maintain the deoxygenation activity. On the other hand, if the sulfur content exceeds 1% by mass, the sulfur content contained in the hydrorefined oil tends to increase, and the blending amount in gasoline is restricted. In addition, the sulfur content in this invention means the mass content of the sulfur content measured based on the method of JISK2541 "Sulfur content test method" or ASTM-5453. The sulfur-containing hydrocarbon compound may be mixed in advance with the oil to be treated, and the mixture may be introduced into the reactor of the hydrorefining apparatus. Alternatively, when introducing the oil to be treated into the reactor, You may supply.

  The oil to be treated of hydrocracking B of the present invention preferably contains a fraction having a boiling point of 300 ° C. or higher, and preferably does not contain a heavy fraction having a boiling point exceeding 700 ° C. When the oil to be treated that does not contain a fraction having a boiling point of 300 ° C. or higher is used, it tends to be difficult to obtain a sufficient yield due to excessive decomposition. On the other hand, when the oil to be treated contains a heavy fraction having a boiling point higher than 700 ° C., carbon deposition in the catalyst is promoted by the heavy components, and the activity tends to decrease. In addition, the boiling point in this invention is a value measured based on the method as described in JISK2254 "distillation test method" or ASTM-D86.

In the hydrocracking B of the present invention, one or more selected from elements of Group 6A and Group 8 of the periodic table supported on a carrier comprising crystalline metallosilicate and the porous inorganic oxide A catalyst containing these metals is used.
As the crystal structure of the crystalline metallosilicate contained in the catalyst used in the hydrocracking B of the present invention, each of FAU, AEL, MFI, MMW, TON, MTW, * BEA, MOR among the structures defined by the International Zeolite Society It preferably has a structure represented by a code, more preferably FAU, * BEA, MOR, or MFI, and even more preferably FAU. The FAU is also called a faujasite type, and in the present invention, the Y type that has been subjected to ultrastabilization treatment is particularly preferable. The ultra-stabilization treatment refers to a hydrothermal treatment and / or a washing treatment with an acidic aqueous solution, and by such an operation, the aluminum content contained in the structure is adjusted to obtain mesopores defined as pore diameters of 2 to 50 nm. The resulting pore volume can be imparted.

The SiO ₂ / Al ₂ O ₃ molar ratio contained in the crystalline metallosilicate contained in the catalyst used for the hydrocracking B of the present invention is preferably in the range of 10-100. If the molar ratio is less than 10, coke formation may be promoted and the activity may be significantly reduced. If the molar ratio exceeds 100, sufficient hydrocracking activity may not be exhibited.

  The method for synthesizing the crystalline molecular sieve contained in the catalyst used in the hydrocracking B of the present invention is not particularly limited, and a generally known method can be used. The constituent raw materials can be subjected to an operation such as heating in the presence of a structure indicator such as an amine compound if necessary. Examples of the constituent raw material include sodium silicate, colloidal silica, alkoxide silicate and the like in the case of a silicon-containing compound, and aluminum hydroxide and sodium aluminate in the case of aluminum. Examples of the structure directing agent include tetrapropylammonium salt.

  In the catalyst used for the hydrocracking B of the present invention, examples of the constituent other than the crystalline metallosilicate include inorganic oxides selected from aluminum, silicon, zirconium, boron, titanium and magnesium. These inorganic oxides can be used as a bonding agent when molding a crystalline metallosilicate, and can also function as an active component that promotes hydrodeoxygenation and hydroisomerization. Two or more kinds selected from zirconium, boron, titanium and magnesium are preferable.

  In the catalyst used for hydrocracking B of the present invention, the content of crystalline metallosilicate in the entire catalyst is preferably 2 to 90% by mass, more preferably 5 to 85% by mass, and even more preferably 10 to 80% by mass. preferable. When the content is less than 2% by mass, hydrodeoxygenation activity and hydroisomerization activity as a catalyst are not sufficient, and when the initial content exceeds 90% by mass, catalyst moldability is not easy, There is a risk of hindrance to industrial production.

  In the catalyst used for the hydrocracking B of the present invention, the porous inorganic oxide as a support carries one or more metals selected from Group 8 elements of the periodic table. Furthermore, it is preferable to use one or more metals selected from Co, Mo and Ni as active metals, and it is more preferable to combine two or more metals. Suitable combinations include Co—Mo, Ni—Mo, and Ni—Co—Mo. When one or more metals selected from Co, Mo, and Ni are used as the active metal, the total content of the active metal based on the catalyst mass is preferably 15 to 35 mass%, more preferably 17 to 30 mass%. preferable. When the total supported amount of the metal is less than 15% by mass, the active sites are decreased and sufficient activity tends not to be obtained. On the other hand, if it exceeds 35% by mass, the metal is not effectively dispersed and sufficient activity tends not to be obtained.

  The method for supporting these active metals on a carrier is not particularly limited, and a known method applied when producing an ordinary catalyst can be used. Usually, a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed. In addition, 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 carrier is measured in advance and impregnated with a metal salt solution having the same volume. The impregnation method is not particularly limited, and it can be impregnated by an appropriate method according to the amount of metal supported and the physical properties of the catalyst carrier.

When combining a plurality of catalysts having different support components, for example, the content of the crystalline metallosilicate is 2 in the subsequent stage of the catalyst having a crystalline metallosilicate content of 5% by mass or less based on the total mass of the support. What is necessary is just to use the catalyst which exists in the range of -90 mass%.
Furthermore, in addition to hydrocracking catalysts, guard catalysts and demetals are used to trap the scale that flows in along with the oil to be treated as needed and to support the hydrocracking catalyst at the separation part of the catalyst bed. Catalysts and inert packing may be used. In addition, these can be used individually or in combination.

In the hydrocracking B of the present invention, the conditions for contacting the oil to be treated and the catalyst in the presence of hydrogen are as follows: hydrogen pressure: 2 to 13 MPa, liquid space velocity (LHSV): 0.1 to 3.0 h ^{− 1} , preferably a hydrogen oil ratio (hydrogen / oil ratio) of 150 to 1500 NL / L, a hydrogen pressure of 2 to 10 MPa, a liquid space velocity of 0.2 to 2.0 h ⁻¹ , and a hydrogen oil ratio of 200 to 1200 NL / L. More preferably, the hydrogen pressure is 2 to 6 MPa, the space velocity is 0.3 to 1.5 h ⁻¹ , and the hydrogen oil ratio is 250 to 1000 NL / L. These conditions are factors that influence the reaction activity. For example, when the hydrogen pressure and the hydrogen oil ratio are less than the above lower limit values, the reactivity tends to decrease or the activity rapidly decreases. is there. On the other hand, when the hydrogen pressure and the hydrogen oil ratio exceed the above upper limit values, there is a tendency that excessive equipment investment such as a compressor is required. Further, the lower the liquid space velocity tends to be advantageous for the reaction, but if the liquid space velocity is less than the above lower limit value, there is a tendency that an extremely large internal volume reactor is required and excessive equipment investment is required, When the liquid space velocity exceeds the above upper limit, the reaction tends not to proceed sufficiently.

  In the hydrocracking B of the present invention, a fixed bed system can be adopted as the reactor type. That is, hydrogen can adopt either a countercurrent or a parallel flow type with respect to the oil to be treated. Moreover, it is good also as a form which combined the countercurrent and the parallel flow using several reactors. As a general format, it is a down flow, and a gas-liquid twin parallel flow format can be adopted. Moreover, the reactor may be used alone or in combination, and a structure in which one reactor is divided into a plurality of catalyst beds may be adopted.

  In the hydrocracking B of the present invention, the hydrocracked oil hydrocracked in the reactor is fractionated into a hydrocracked oil containing a predetermined fraction through a gas-liquid separation process, a rectification process, and the like. . For example, it is fractionated into gas, naphtha fraction, kerosene fraction, light oil fraction and residual fraction. In addition, water, carbon monoxide, carbon dioxide, hydrogen sulfide, etc. may be generated due to the reaction of oxygen and sulfur contained in the oil to be treated. A gas-liquid separation facility or other by-product gas removal device may be installed in the recovery process.

In the hydrocracking B of the present invention, the hydrogen gas is generally introduced from the inlet of the first reactor along with the oil to be treated before or after passing through the heating furnace. Hydrogen gas may be introduced from between the catalyst beds or between a plurality of reactors for the purpose of controlling the temperature in the reactor and maintaining the hydrogen pressure throughout the reactor. The hydrogen thus introduced is generally called quench hydrogen. The ratio of quench hydrogen to hydrogen gas introduced along with the oil to be treated is preferably 10 to 60% by volume, and more preferably 15 to 50% by volume. If the rate of quench hydrogen is less than 10% by volume, the reaction at the subsequent reaction site tends not to proceed sufficiently. If the rate of quench hydrogen exceeds 60% by volume, the reaction proceeds sufficiently near the reactor inlet. There is a tendency not to.
The kerosene fraction and / or light oil fraction and / or residue obtained by the hydrocracking B of the present invention may be recycled by mixing the entire amount or a part thereof with the oil to be treated. Thereby, the yield of a gasoline fraction can be raised more.

  In the present invention, the distillation temperature range obtained by treating the oil to be treated containing biomass by hydrocracking such as hydrocracking A of the present invention or hydrocracking B of the present invention is 25 ° C to 220 ° C. It is preferable that the oxygen content of the base material consisting of all or a part of this fraction is 0.2% by mass or less and the normal paraffin content is 30% by mass or less. Of these, the normal paraffin content is more preferably 25% by mass or less. In the product oil obtained by hydrocracking such as hydrocracking A of the present invention or hydrocracking B of the present invention, the remaining oxygen content is mainly composed of one or more functional groups of hydroxyl group, aldehyde group, carboxyl group. Although it exists in a state, when oxygen content exceeds 0.2 mass%, there exists a possibility that the aldehyde density | concentration in exhaust gas at the time of using corrosivity and the gasoline of this invention may become high. When the normal paraffin content exceeds 30% by mass, there is a concern that the octane number as a gasoline base material is lowered. The composition of normal paraffin or the like can be determined by measuring in accordance with JIS K 2536-2 “Petroleum products—component test method—how to obtain full analysis by gas chromatograph”.

The gasoline of the present invention is a base material consisting of all or a part of a fraction having a distillation temperature range of 25 ° C to 220 ° C obtained by treating the oil to be treated containing biomass by hydrocracking (hereinafter referred to as this). The hydrocracking substrate of the invention).
Examples of the fraction range include a light fraction of 25 ° C to 70 ° C, an intermediate fraction of 70 ° C to 160 ° C, and a heavy fraction of 160 ° C to 220 ° C. In addition, the remainder obtained by removing a part of the fraction range from the 25 ° C. to 220 ° C. fraction can be used as the base material.
From the viewpoint of octane number, a light fraction is preferable, specifically, a fraction of 150 ° C. or lower is preferable, a fraction of 120 ° C. or lower is more preferable, and a fraction of 100 ° C. or lower is more preferable.

  In the gasoline of the present invention, when the hydrocracking base material of the present invention is blended, the base material can be subjected to a treatment such as desulfurization as necessary. The treatment such as desulfurization may be performed for the entire fraction of the base material to be blended or a part of the fraction. Moreover, the hydrocracking base material of the present invention can be treated with a catalytic reformer and blended with the gasoline of the present invention as a gasoline base having a higher octane number.

  In the gasoline of the present invention, the content of the hydrocracking base material of the present invention is preferably 3% by volume or more with respect to the total amount of gasoline, from the viewpoint that it contains a large amount of biomass-derived base material. The above is more preferable. On the other hand, from the viewpoint of fuel efficiency, the content of the base material is preferably 30% by volume or less, more preferably 25% by volume or less, and further preferably 20% by volume or less.

The gasoline of the present invention is not particularly limited to the base material to be blended except for the hydrocracking base material of the present invention, and one or more gasoline base materials that can be produced by any conventionally known method. Can also be blended.
Specifically, for example, a straight-run propane fraction centered on propane obtained from a crude oil distillation apparatus, a naphtha reformer, an alkylation apparatus, etc., a straight-run butane fraction centered on butane, and desulfurizing them. Straight-run desulfurized propane fraction obtained by treatment, straight-run desulfurized butane fraction, cracked propane fraction centered on propane / propylene obtained from catalytic cracker etc., cracked system centered on butane / butene Butane fraction, naphtha fraction obtained by atmospheric distillation of crude oil (hole range naphtha), naphtha light fraction, naphtha heavy fraction, desulfurization whole range naphtha, desulfurized whole range naphtha, light naphtha Desulfurized light naphtha, desulfurized heavy naphtha obtained by desulfurizing heavy naphtha, isomerized gasoline obtained by converting light naphtha into isoparaffin using an isomerizer, isobutane, etc. Alkylate obtained by addition (alkylation) of lower olefin to hydrogen, reformed gasoline obtained by catalytic reforming method, raffinate which is a residue extracted from aromatics from reformed gasoline, lightness of reformed gasoline Light reformed gasoline that is a fraction, medium reformed gasoline that is a medium fraction of reformed gasoline, medium heavy reformed gasoline that is a medium heavy fraction of reformed gasoline, and heavy fraction of reformed gasoline Heavy reformed gasoline, a mixture of two or more of each reformed gasoline, catalytic cracked gasoline obtained by catalytic cracking (hole range cracked gasoline), light cracked gasoline that is a light fraction of catalytic cracked gasoline, contact Heavy cracked gasoline, which is a heavy fraction of cracked gasoline, hydrocracked gasoline obtained by hydrocracking method, polymerized gasoline obtained by polymerization of olefin, propylene or Olefin fraction obtained by dimerization of butene, paraffin fraction obtained by hydrogenation of olefin fraction obtained by dimerization of propylene or butene, denormalized paraffin oil, aromatic hydrocarbon compound (toluene, carbon number 8 Of GTL (Gas to Liquids) obtained by FT (Fischer-Tropsch) synthesis after decomposition of natural gas, etc. into carbon monoxide and hydrogen Examples of the base material include fractions.
The blending amounts of these base materials are arbitrary as long as the gasoline of the present invention is adjusted so as to have a necessary property range, but typical examples of the blending ranges of base materials are shown below.
(1) Reformed gasoline: 0 to 80% by volume
(2) Cracked gasoline: 0-60% by volume
(3) Alkylate: 0 to 40% by volume
(4) Isomerized gasoline: 0-30% by volume

Moreover, the gasoline of the present invention may contain an oxygen-containing compound.
Examples of the oxygen-containing compound include alcohols having 2 to 4 carbon atoms and ethers having 4 to 8 carbon atoms. Specific examples of oxygen-containing compounds include ethanol, methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), and tert-amyl ethyl ether. it can. Of these, ethanol, MTBE, and ETBE are preferable. From the viewpoint of suppressing carbon dioxide emission, ethanol derived from biomass and ETBE produced using biomass-derived ethanol as a raw material can be particularly preferably used. Methanol is not detected when tested in accordance with JIS K 2536 “Petroleum product-component test method” (0.5% by volume) because it is corrosive and may increase the concentration of aldehyde in the exhaust gas. It is preferable that
The oxygen-containing compound content in the gasoline of the present invention is preferably 3.8% by mass or less in terms of oxygen atom from the viewpoint of compatibility with automobile fuel system members and suppression of increase in NOx in exhaust gas. 3.5 mass% or less, more preferably 2.7 mass% or less, and most preferably 1.3 mass% or less.

The research octane number (RON) of the gasoline of the present invention is 96. In order to maximize the knocking resistance, acceleration and driving performance when the gasoline of the present invention is mainly used in premium gasoline specification vehicles. 0 or more is necessary, more preferably 98.0 or more, still more preferably 99.5 or more, and most preferably 100.0 or more. Further, from the viewpoint of preventing deterioration of anti-knocking performance at high speed, the motor method octane number (MON) of the gasoline of the present invention is preferably 85.0 or more, and more preferably 87.0 or more.
The research method octane number (RON) and the motor method octane number (MON) as used herein mean the research method octane number and the motor method octane number measured by JIS K 2280 “Testing method for octane number and cetane number”.

The sulfur content of the gasoline of the present invention needs to be 10 mass ppm or less, preferably 8 mass ppm or less, more preferably 5 mass ppm or less. If the sulfur content exceeds 10 ppm by mass, the performance of the exhaust gas purification catalyst may be adversely affected, the concentration of NOx, CO, and HC in the exhaust gas may increase, and the amount of benzene emitted may increase. This is not preferable.
The sulfur content here means a value measured according to JIS K 2541 “Crude oil and petroleum products—Sulfur content test method”.

  It is necessary for the gasoline of the present invention to be unleaded. The term “lead-free” as used herein means that an alkyl lead compound such as tetraethyl lead is not substantially added. Even when a very small amount of lead compound is contained, the content is JIS K 2255 “in gasoline. It means that it is not more than the application category lower limit value (0.001 g / l) of “lead content test method”.

The distillation initial boiling point (IBP) of the gasoline of the present invention is preferably 20 ° C. or higher, more preferably 23 ° C. or higher. When IBP is less than 20 ° C., hydrocarbons in the exhaust gas may increase. On the other hand, IBP is preferably 37 ° C. or lower, more preferably 35 ° C. or lower. When IBP exceeds 37 ° C., low temperature drivability may be reduced.
The 10% distillation temperature (T10) of the gasoline of the present invention is preferably 35 ° C. or higher, more preferably 40 ° C. or higher. When T10 is less than 35 ° C., hydrocarbons in the exhaust gas may increase, and high temperature operability may decrease due to vapor lock. On the other hand, T10 is preferably 70 ° C. or lower, more preferably 60 ° C. or lower. When T10 exceeds 70 ° C, the low temperature startability may be reduced.

The 30% distillation temperature (T30) of the gasoline of the present invention is preferably 55 ° C or higher, more preferably 60 ° C or higher. If T30 is less than 55 ° C., fuel consumption may be deteriorated. On the other hand, T30 is preferably 77 ° C or lower, more preferably 75 ° C or lower, and further preferably 70 ° C or lower. When T30 exceeds 77 ° C, the medium / low temperature drivability may be lowered.
The 50% distillation temperature (T50) of the gasoline of the present invention is preferably 75 ° C. or higher, more preferably 80 ° C. or higher, from the viewpoint of preventing deterioration of fuel consumption. On the other hand, from the viewpoint of preventing deterioration in normal temperature drivability, T50 is preferably 110 ° C. or lower, more preferably 105 ° C. or lower, and further preferably 100 ° C. or lower.

The 70% distillation temperature (T70) of the gasoline of the present invention is preferably 95 ° C. or higher. When T70 is less than 95 ° C., fuel consumption may be deteriorated. On the other hand, T70 is preferably 135 ° C. or lower, more preferably 130 ° C. or lower. When T70 exceeds 135 ° C., the medium / low temperature operability during cold operation may decrease, and there may be an increase in hydrocarbons in exhaust gas, an increase in intake valve deposits, and an increase in combustion chamber deposits. .
The 90% distillation temperature (T90) of the gasoline of the present invention is preferably 115 ° C or higher, more preferably 120 ° C or higher. When T90 is less than 115 ° C., fuel consumption may be deteriorated. On the other hand, T90 is preferable from the viewpoint of preventing deterioration of low temperature and normal temperature drivability during cold operation, increase in dilution of engine oil with gasoline, increase in hydrocarbon exhaust gas, deterioration of engine oil and generation of sludge. Is 180 ° C. or lower, more preferably 175 ° C. or lower, more preferably 170 ° C. or lower, and even more preferably 165 ° C. or lower.

The distillation end point (EP) of the gasoline of the present invention is preferably 150 ° C. or higher. EP is preferably 220 ° C. or lower, more preferably 215 ° C. or lower, further preferably 200 ° C. or lower, and even more preferably 195 ° C. or lower. If EP exceeds 220 ° C., intake valve deposits and combustion chamber deposits may increase, and spark plug smoldering may occur.
Here, IBP, T10, T30, T50, T70, T90, and EP mean values (° C.) measured by JIS K 2254 “Petroleum products—distillation test method”.

  The lead vapor pressure (RVP) of the gasoline of the present invention is preferably adjusted according to the season and region in which the gasoline is used. Specifically, for warm seasons and regions, 44 to 72 kPa is preferable, 44 to 65 kPa is more preferable, 50 to 65 kPa is further preferable, and 55 to 65 kPa is most preferable. On the other hand, for cold seasons and regions, 60 to 93 kPa is preferable, 65 to 93 kPa is more preferable, 70 to 93 kPa is further preferable, and 70 to 88 kPa is most preferable. If the RVP is high, there may be a problem in drivability due to vapor lock or the like, and if the RVP is low, the startability in the cold state may be deteriorated. The vapor pressure (RVP) here refers to a value (kPa) measured by JIS K 2258 “Crude oil and fuel oil vapor pressure test method (Lead method)”.

Density at 15 ℃ gasoline of the present invention, from the viewpoint of suppressing deterioration of the fuel economy, preferably 0.700 g / cm ³ or more, more preferably 0.710 g / cm ³ or more, 0.720 g / cm ³ or more and more Preferably, 0.730 g / cm ³ or more is most preferable. On the other hand, density at 15 ℃, from the viewpoint of preventing the smoldering acceleration of deterioration or plug, preferably 0.783g / cm ³ or less, more preferably 0.770 g / cm ³ or less, 0.760 g / cm ³ or less Is more preferable.
Here, the density at 15 ° C. means a value (g / cm ³ ) measured according to JIS K 2249 “Density test method and density / mass / capacity conversion table for crude oil and petroleum products”.

The oxidation stability of the gasoline of the present invention is preferably 240 minutes or more, more preferably 480 minutes or more, and further preferably 1440 minutes or more, from the viewpoint of suppressing the formation of gum during storage. .
The oxidation stability here means a value (minutes) measured by JIS K 2287 “Gasoline oxidation stability test method (induction period method)”.

The gasoline of the present invention preferably has a copper plate corrosion (50 ° C., 3 h) of 1 or less, more preferably 1a. If the copper plate corrosion exceeds 1, the fuel system conduit may corrode.
The copper plate corrosion here means a value measured according to JIS K 2513 “Petroleum products—copper plate corrosion test method” (test temperature 50 ° C., test time 3 hours).

The actual washing amount of the gasoline of the present invention is preferably 5 mg / 100 ml or less, more preferably 3 mg / 100 ml or less, and even more preferably 1 mg / 100 ml or less. Moreover, it is preferable that the amount of unwashed actual gum of the gasoline of the present invention is 20 mg / 100 ml or less. When the unwashed actual gum amount and the washed actual gum amount exceed the above values, there is a concern that precipitates are generated in the fuel introduction system or the suction valve is stuck.
As used herein, the amount of washed actual gum and the amount of unwashed actual gum mean values (mg / 100 ml) measured according to JIS K 2261 “Petroleum products—automobile gasoline and aviation fuel oil—existing gum test method—injection evaporation method”. To do.

The benzene content in the gasoline of the present invention is preferably 1% by volume or less, and more preferably 0.5% by volume or less. If the benzene content exceeds 1% by volume, the concentration of benzene in the exhaust gas may increase.
The benzene content here means the benzene content (volume%) measured according to JIS K 2536 “Petroleum products—component test method—aromatic test method by gas chromatography”.

The aromatic content in the gasoline of the present invention is preferably 45% by volume or less, more preferably 42% by volume or less, and still more preferably 40% by volume or less. If the aromatic content exceeds 45% by volume, intake valve deposits and combustion chamber deposits may increase, and spark plug smoldering may occur. In addition, the concentration of benzene in the exhaust gas may increase. On the other hand, the aromatic content is preferably 20% by volume or more, and more preferably 25% by volume or more. If the aromatic content is less than 20% by volume, the fuel efficiency may deteriorate.
The aromatic content here means the aromatic content (volume%) in gasoline measured by JIS K 2536 “Petroleum products—component test method—fluorescent indicator adsorption method”.

The olefin content in the gasoline of the present invention is preferably 35% by volume or less, and more preferably 25% by volume or less. When the olefin content exceeds 35% by volume, there is a possibility that the oxidation stability of gasoline is deteriorated and the intake valve deposit is increased.
The olefin content here means the olefin content (volume%) in gasoline measured by JIS K 2536 “Petroleum products—component test method—fluorescent indicator adsorption method”.

The amount of kerosene mixed in the gasoline of the present invention is preferably 4% by volume or less. If the amount of kerosene mixed exceeds 4% by volume, the startability of the engine may deteriorate.
Here, the amount of kerosene mixed is determined by the content of normal paraffin hydrocarbons having 13 and 14 carbon atoms on the basis of the total amount of gasoline, and the converted value of kerosene obtained according to the provisions of JIS K 2536 “Petroleum products-component test method” Is 4% by volume or less.

2 mass ppm or less is preferable and, as for content of manganese in the gasoline of this invention, 1 mass ppm or less is more preferable. The content of iron in the gasoline of the present invention is preferably 2 ppm by mass or less, and more preferably 1 ppm by mass or less. The content of sodium in the gasoline of the present invention is preferably 2 ppm by mass or less, and more preferably 1 ppm by mass or less. The potassium content in the gasoline of the present invention is preferably 2 ppm by mass or less, and more preferably 1 ppm by mass or less. The phosphorus content in the gasoline of the present invention is preferably 2 ppm by mass or less, more preferably 1 ppm by mass or less, and even more preferably 0.2 ppm by mass or less. If the contents of manganese, iron, sodium, potassium, and phosphorus exceed the above values, the efficiency of the exhaust gas purification system will increase due to an increase in the amount accumulated on the exhaust gas purification catalyst, deterioration of the catalyst carrier, deterioration of the air-fuel ratio sensor, etc. May decrease.
The manganese, iron, and sodium contents here are “combustion ashing-inductively coupled plasma emission method”, the potassium content is “combustion ashing-atomic absorption method”, and the phosphorus content is ASTM D3231 “Standard Test Method”. for Phosphorus in Gasoline ”.

Hereinafter, measurement methods of “combustion ashing-inductively coupled plasma emission method” and “combustion ashing-atomic absorption method” will be described in detail.
(1) Collect 20 g of a sample in a platinum dish.
(2) In order to suppress the volatilization of the component elements, 0.4 g of powdered sulfur is added, and the volatile matter is removed on a sand bath at 150 ° C. for 1 hour.
(3) Burn the residue.
(4) Ash in an electric furnace at 500 ° C. for 2 to 3 hours.
(5) Dissolve in 2 to 3 mL of concentrated sulfuric acid and adjust to a volume of 20 mL.
(6) Manganese, iron, and sodium contents were measured using an inductively coupled plasma emission spectrometer (ICPS-8000, manufactured by Shimadzu Corporation), and phosphorus contents were measured using an atomic absorption photometer (made by Hitachi, Ltd., Z6100). analyse.

  The gasoline of the present invention preferably contains an antioxidant and a metal deactivator for storage stability. Specifically, examples of the antioxidant include phenylenediamines such as N, N′-diisopropyl-p-phenylenediamine and N, N′-diisobutyl-p-phenylenediamine, and 2,6-di-t-butyl. Known compounds can be used as alkylphenol-based antioxidants such as hindered phenols represented by -4-methylphenol, and N, N'-disalicylidene-1,2 is used as a metal deactivator. -Known compounds can be used as metal deactivators such as amine carbonyl condensation compounds such as diaminopropane.

  There are no particular restrictions on the amount of antioxidant or metal deactivator added, but the aforementioned oxidation stability is a preferred value, and the amount of unwashed real gum in the gasoline composition after addition including other additives is It is preferable to set the above-mentioned preferable value. Specifically, the antioxidant is preferably 5 to 100 mg / l, more preferably 10 to 50 mg / l. Moreover, 0.5-10 mg / l is preferable and, as for a metal deactivator, 1-5 mg / l is more preferable.

The gasoline of the present invention preferably contains a cleaning dispersant in order to prevent deposits such as intake valves from depositing. As the cleaning dispersant, compounds known as gasoline cleaning dispersants such as succinimide, polyalkylamine, and polyetheramine can be used. Among these, those having no residue when pyrolysis is performed at 300 ° C. in air are desirable. More preferably, polyisobutenylamine and / or polyetheramine is used.
The content of the cleaning dispersant is preferably 25 to 1000 mg per liter of gasoline of the present invention, more preferably 50 to 500 mg from the viewpoint of preventing intake valve deposits and further reducing combustion chamber deposits, ˜300 mg is most preferred. In the cleaning dispersant, an active ingredient that contributes to cleanliness may be diluted with an appropriate solvent. In such a case, the above-mentioned addition amount means an addition amount as an active ingredient.

  The gasoline of the present invention preferably contains a friction modifier in order to improve lubricity. Examples of the main friction modifier include, for example, alcohol; alcohol compound having 1 to 30 carbon atoms having 1 to 4 hydroxyl groups; carboxylic acid; hydroxyl group which is a reaction product of monocarboxylic acid and glycol or trihydric alcohol Containing ester; ester of polycarboxylic acid and polyhydric alcohol; and> NR (R is a hydrocarbon group having 5 to 40 carbon atoms), showing at least one nitrogen having one or more substituents Examples include esters of polyhydric alcohols in combination with compounds; amide compounds of carboxylic acids and alcohol amines, and the like. These can be used alone or as a mixture. Among these, a hydroxyl group-containing ester which is a reaction product of a monocarboxylic acid having 10 to 25 carbon atoms and glycol or a trihydric alcohol and / or an amide compound of a carboxylic acid having 5 to 25 carbon atoms and an alcohol amine are included. More preferably, an amide compound of a monocarboxylic acid having 10 to 25 carbon atoms and glycerin ester and / or a monocarboxylic acid having 5 to 25 carbon atoms and diethanolamine is more preferable.

The addition amount of the friction modifier is not particularly limited, but it may be added together with other additives so that the unwashed actual gum amount of the gasoline composition after the addition satisfies the above-mentioned preferable range. In addition, from the viewpoint that sufficient fuel economy and output improvement effect can be exhibited, while improvement of the effect cannot be expected even if more is added, preferably 10 to 300 mg, more preferably 30 per liter of gasoline of the present invention. It is good to add so that it may become a content rate of -250 mg.
In addition, since a product marketed as a friction modifier is sometimes diluted with an appropriate solvent for an active ingredient that contributes to wear resistance, such a commercial product is added to the gasoline of the present invention. Means the addition amount as an active ingredient.

Other fuel oil additives that can be added to the gasoline of the present invention include surface ignition preventives such as organophosphorus compounds, anti-icing agents such as polyhydric alcohols or ethers thereof, alkali metal salts or alkalis of organic acids. Auxiliary agents such as earth metal salts, higher alcohol sulfates, anionic surfactants, cationic surfactants, antistatic agents such as amphoteric surfactants, colorants such as azo dyes, organic carboxylic acids or their derivatives Rust inhibitors such as alkenyl succinic acid esters, draining agents such as sorbitan esters, discriminating agents such as kilyzanine and coumarin, and odorants such as natural essential oil synthetic fragrances.
One or two or more of these additives can be added, and the total addition amount is preferably 0.1% by mass or less based on the total amount of gasoline.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[Examples 1 to 4 and Comparative Examples 1 and 2]
As catalyst A for hydrocracking, a carrier in which crystalline metal silicate is composed of 55% by mass of ultrastable Y-type zeolite having a faujasite structure, 15.75% by mass of silica, and 29.25% by mass of alumina Then, a catalyst carrying 0.5% by mass and 0.7% by mass of platinum and palladium of Group 8 of the periodic table, respectively, was prepared. The silica / alumina ratio of the ultrastable Y-type zeolite was 33.
The oil to be treated for hydrocracking is palm oil, which is a vegetable oil of biomass. The triglyceride content is 98 mol%, the oxygen content is 11.4 mass%, and the sulfur content is less than 0.1 mass ppm. there were.
After the catalyst A is pre-reduced, hydrogen is brought into contact with palm oil to be treated under the conditions of a reaction temperature of 425 ° C., a hydrogen pressure of 5 MPa, a liquid space velocity of 0.4 h ⁻¹ , and a hydrogen oil ratio of 1010 NL / L. The biomass hydrocracking substrate A, which is a fraction at 35 ° C to 135 ° C, was obtained by distillation of the product oil. The biomass substrate A had an oxygen content of less than 0.1 mass%, a sulfur content of less than 0.1 mass ppm, and a normal paraffin content of 24.8 mass%.
5% by volume of biomass hydrocracking substrate A, light reformed gasoline (distillation range 27-128 ° C., density 0.690 g / cm ³ , aromatic content 23% by volume), medium heavy reformed gasoline (distilled) Min range 92-195 ° C., density 0.853 g / cm ³ , aromatic content 90% by volume), light catalytic cracking gasoline (distillation temperature 27-81 ° C., density 0.656 g / cm ³ , olefin content 47% by volume) , Heavy catalytic cracking gasoline (distillation range 75-198 ° C., density 0.764 g / cm ³ , olefin content 33% by volume), alkylate (distillation range 33-179 ° C., density 0.696 g / cm ³ , saturation 100% by volume), light naphtha (distillation range 28 to 105 ° C., density 0.637 g / cm ³ , saturation 99% by volume), gasoline base materials such as toluene, normal butane and antioxidants, metal deactivation Agent By compounding were prepared gasoline composition of Example 1.
5% by volume of biomass hydrocracking base material A and 7% by volume of ETBE produced using biomass-derived ethanol as a raw material, light reformed gasoline (distillation range 27-128 ° C., density 0.690 g / cm ³ , Aromatics 23% by volume), medium heavy reformed gasoline (distillation range 92-195 ° C., density 0.853 g / cm ³ , aromatics 90% by volume), light catalytic cracking gasoline (distillation temperature 27-81) ° C., a density 0.656 g / cm ^3, an olefin content 47% by volume), heavy catalytic cracked gasoline (a fraction range 75-198 ° C., density 0.764 g / cm ^3, an olefin content of 33 volume%), alkylate (distillate min range 33-179 ° C., a density 0.696 g / cm ^3, saturates 100 volume%), light naphtha (fraction range 28-105 ° C., a density 0.637 g / cm ^3, saturates 99% by volume), toluene , Gasoline components and antioxidants, such as normal butane, by blending a metal deactivator to prepare a gasoline composition of Example 2.

As catalyst B for hydrocracking, a carrier in which crystalline metal silicate is composed of 55% by mass of ultrastable Y-type zeolite having a faujasite type structure, 15.75% by mass of silica, and 29.25% by mass of alumina Then, a catalyst carrying 4.0% by mass of nickel of group 8 of the periodic table (as nickel oxide) and 16.0% by mass of molybten of group 6A of the periodic table (as molybdenum trioxide) was prepared. The silica / alumina ratio of the ultrastable Y-type zeolite was 30.
The oil to be treated for hydrocracking is palm oil, which is a vegetable oil of biomass (triglyceride content is 98 mol%, oxygen content is 11.4 mass%, sulfur content is less than 0.1 mass ppm) and dimethyl disulfide. Was added to adjust the sulfur content to 51 mass ppm.
After presulfiding the catalyst B, the above-mentioned dimethyl disulfide-added palm oil of the oil to be treated is obtained under the conditions of a reaction temperature of 425 ° C., a hydrogen pressure of 5 MPa, a liquid space velocity of 0.4 h ⁻¹ and a hydrogen oil ratio of 1010 NL / L Hydrocracking was performed by contacting, and a biomass hydrocracking base material B that was a fraction of 35 ° C to 135 ° C was obtained by distillation of the product oil. The biomass hydrocracking base material B had an oxygen content of less than 0.1 mass%, a sulfur content of 1.3 mass ppm, and a normal paraffin content of 24.3 mass%.

5% by volume of biomass hydrocracking base material B, light reformed gasoline (distillation range 27-128 ° C., density 0.690 g / cm ³ , aromatic content 23% by volume), medium heavy reformed gasoline (distilled) Min range 92-195 ° C., density 0.853 g / cm ³ , aromatic content 90% by volume), light catalytic cracking gasoline (distillation temperature 27-81 ° C., density 0.656 g / cm ³ , olefin content 47% by volume) , Heavy catalytic cracking gasoline (distillation range 75-198 ° C., density 0.764 g / cm ³ , olefin content 33% by volume), alkylate (distillation range 33-179 ° C., density 0.696 g / cm ³ , saturation 100% by volume), light naphtha (distillation range 28 to 105 ° C., density 0.637 g / cm ³ , saturation 99% by volume), gasoline base materials such as toluene, normal butane and antioxidants, metal deactivation Agent By blending the detergent-dispersant, to prepare a gasoline composition of Example 3.
7% by volume of biomass hydrocracking substrate B, 3% by volume of biomass-derived ethanol, light reformed gasoline (distillation range 27-128 ° C., density 0.690 g / cm ³ , aromatic content 23% by volume ), Medium heavy reformed gasoline (distillation range 92-195 ° C., density 0.853 g / cm ³ , aromatic content 90% by volume), light catalytic cracking gasoline (distillation temperature 27-81 ° C., density 0.656 g) / Cm ³ , olefin content 47 vol%), heavy catalytic cracking gasoline (fraction range 75-198 ° C., density 0.764 g / cm ³ , olefin content 33 vol%), alkylate (fraction range 33-179 ° C. , density 0.696 g / cm ^3, saturates 100 volume%), light naphtha (fraction range twenty-eight to one hundred and five ° C., density 0.637 g / cm ^3, saturates 99% by volume), toluene, gasoline, such as normal butane Emission substrate and antioxidants, metal deactivators, detergent dispersant, by blending the friction modifier was prepared gasoline composition of Example 4.
40% by volume of biomass hydrocracking base material A, light reformed gasoline (distillation range 27-128 ° C., density 0.690 g / cm ³ , aromatic content 23% by volume), medium heavy reformed gasoline (fraction) Range 92-195 ° C., density 0.853 g / cm ³ , aromatic content 90% by volume), light catalytic cracking gasoline (distillation temperature 27-81 ° C., density 0.656 g / cm ³ , olefin content 47% by volume), Heavy catalytic cracking gasoline (distillation range 75-198 ° C., density 0.764 g / cm ³ , olefin content 33% by volume), alkylate (distillation range 33-179 ° C., density 0.696 g / cm ³ , saturation content 100 volume%), light naphtha (fraction range twenty-eight to one hundred and five ° C., density 0.637 g / cm ^3, saturates 99% by volume), toluene, gasoline components and antioxidants, such as normal butane, metal deactivators By compounding were prepared gasoline composition of Comparative Example 1.
Comparative Example 2 is a commercially available premium gasoline.

(Property measurement)
The properties of the gasoline compositions in Examples and Comparative Examples were measured by the following methods.
The research method octane number and the motor method octane number are values based on the research method octane number and the motor method octane number measured according to JIS K 2280 “Testing method for octane number and cetane number”.
The sulfur content was measured according to JIS K 2541 “Crude oil and petroleum products—sulfur content test method”.
The lead content was measured according to JIS K 2255 “Test method for lead content in gasoline”.
The distillation properties (IBP, T10, T30, T50, T70, T90, EP) were all measured according to JIS K 2254 “Petroleum products—Distillation test method—Atmospheric pressure method”.
The vapor pressure (@ 37.8 ° C.) was measured according to JIS K 2258 “Crude oil and fuel oil vapor pressure test method (Lead method)”.
The density (@ 15 ° C.) was measured according to JIS K 2249 “Crude oil and petroleum product density test method and density / mass / capacity conversion table”.
The oxidation stability was measured according to JIS K 2287 “Gasoline Oxidation Stability Test Method (Induction Period Method)”.
Copper plate corrosion was measured in accordance with JIS K 2513 “Petroleum products—Copper plate corrosion test method” (test temperature 50 ° C., test time 3 hours).
The unwashed actual gum amount and the washed actual gum amount were measured according to JIS K 2261 “Petroleum products—Automotive gasoline and aviation fuel oil—Real gum test method—Jet evaporation method”.
Benzene was measured according to JIS K 2536 “Petroleum products—component test method—aromatic test method using gas chromatography”.
The aromatic content and olefin content were measured according to JIS K 2536 “Petroleum products—component test method—fluorescent indicator adsorption method”.
The kerosene content was measured in accordance with the provisions of JIS K 2536 “Petroleum product-component test method”.
Manganese, iron and sodium contents are “combustion ashing-inductively coupled plasma emission method”, potassium content is “combustion ashing-atomic absorption method”, and phosphorus content is ASTM D3231 “Standard Test Method for Phosphorus in Measured by “Gasoline”.

(Biomass-derived base material content)
About the gasoline composition of an Example and a comparative example, content of the biomass origin base material and content of the vegetable oil origin base material of biomass were shown from the base-material mixture ratio.

(Acceleration performance evaluation)
The acceleration performance was evaluated using the following test vehicle on a chassis dynamometer maintained at an environmental temperature of 25 ° C. and an environmental humidity of 50%. In the test, after the test vehicle is sufficiently warmed up, the full acceleration from 50 km / h to 110 km / h is performed 10 times in the D range (OD is on), and it is necessary to reach 60 km to 100 km / h. The time was measured, and the average value of the seven required times excluding the first three times was defined as the acceleration time.
[Test vehicle]
Engine: Inline 4-cylinder (Premium gasoline specification, with charger)
Displacement: 1998cc
Injection system: Multi-point system Mission: Automatic transmission Exhaust gas purification system: Three-way catalyst, air-fuel ratio feedback control Complies with 2000 exhaust gas regulations

(Exhaust gas test)
In the exhaust gas test, the emissions of CO and NOx contained in the exhaust gas were measured using the above-described test vehicle in accordance with the technical guidelines of the gasoline automobile 10.15 mode exhaust gas measurement by the Ministry of Land, Infrastructure, Transport and Tourism.

(Fuel consumption test)
The fuel consumption test was measured using the above-described test vehicle according to the gasoline automobile 10.15 mode fuel consumption test method by the Ministry of Land, Infrastructure, Transport and Tourism.

As shown in Table 2, the gasoline of the present invention (Examples 1 to 4) is considered to contribute to diversification of fuel supply sources and suppression of increase in CO _{2 in} the life cycle by blending a biomass-derived base material. It can also be seen that good acceleration performance, low exhaust gas (CO, NOx) levels, and good fuel efficiency can be realized.

Claims (13)

An oil to be treated containing oil derived from plants or animals and a carrier containing at least one metal selected from the group consisting of Pd, Pt, Rh, Ir, Au and Ni and a crystalline metallosilicate Hydrocracking catalyst (A) or a carrier containing a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and Co supported on the carrier A hydrocracking catalyst (B) containing one or more metals selected from Mo, Ni, and hydrogen pressure in the presence of hydrogen, 2-13 MPa, liquid space velocity (LHSV) 0.1-3.0 h ^{− 1,} also all of the fraction of the hydrogen / distillation temperature range obtained by oil ratio is under conditions of 150 to 1500 NL / L and hydrocracking process 220 ° C. from 25 ° C. Ku production of RON of 96.0 or higher, sulfur content less unleaded gasoline composition 10 ppm by weight, characterized by containing a base material made of a part 3 volume% to 20 volume% or less Way . The method for producing an unleaded gasoline composition according to claim 1, wherein the catalyst support of the hydrocracking catalyst (B) contains the porous inorganic oxide and the crystalline metallosilicate . The crystalline metallosilicate contained in the catalyst carrier has a faujasite type structure, and the crystalline metallosilicate contained in the catalyst carrier is composed of silicon, aluminum, and oxygen, and SiO ₂ / Al ₂ contained in the structure method for producing the unleaded gasoline composition according to claim 1 or 2, characterized in that O ₃ molar ratio of ultrastable Y-type zeolite in the range of 10 to 100. Unleaded gasoline composition according to any one of claims 1-3 in which the content of oxygen content of the treated oil containing oil of vegetable or animal, wherein 0.1 to 15% by mass Rukoto Manufacturing method . The lead-free lead according to any one of claims 1 to 4, wherein the proportion of the compound having a triglyceride structure in oils and fats derived from plants or animals contained in the hydrocracked oil is 90 mol% or more. A method for producing a gasoline composition. The oil to be treated when hydrocracking using the hydrocracking catalyst (B) contains a sulfur-containing hydrocarbon compound, and the sulfur content of the oil to be treated is 1 mass ppm to 1 mass%. The method for producing an unleaded gasoline composition according to claim 1 . The oxygen content in the base material consisting of all or part of a fraction having a distillation temperature range of 25 ° C. to 220 ° C. obtained by treating the oil to be treated by hydrocracking is 0.2 mass. The method for producing an unleaded gasoline composition according to any one of claims 1 to 6 , wherein the normal paraffin content is 30% by mass or less. The unleaded gasoline composition has a 10% distillation temperature of 70 ° C. or less, a 50% distillation temperature of 75 ° C. or more and 110 ° C. or less, a 90% distillation temperature of 180 ° C. or less, a distillation end point or 220 ° C. or less, a vapor pressure (37. 8 ° C.) is 44 kPa or more and 93 kPa or less, density (15 ° C.) is 0.783 g / cm ³ or less, oxidation stability is 240 minutes or more, copper plate corrosion (50 ° C., 3 hours) is 1 or less, cleaning actual gum is 5 mg / The method for producing an unleaded gasoline composition according to any one of claims 1 to 7 , wherein 100ml or less, unwashed actual gum is 20mg / 100ml or less, and benzene content is 1% by volume or less. The method for producing an unleaded gasoline composition according to any one of claims 1 to 8 , wherein the unleaded gasoline composition has an aromatic content of 40% by volume or less and an olefin content of 35% by volume or less. . The lead-free gasoline composition has a manganese content of 2 mass ppm or less, an iron content of 2 mass ppm or less, a sodium content of 2 mass ppm or less, a potassium content of 2 mass ppm or less, and a phosphorus content. method for producing the unleaded gasoline composition according to any one of claims 1 to 9, characterized in that but more than 2 mass ppm. Antioxidant and a metal deactivator are added , The manufacturing method of the unleaded gasoline composition in any one of Claims 1-10 characterized by the above-mentioned. A method for producing an unleaded gasoline composition according to any one of claims 1 to 11 , wherein a cleaning dispersant is added . A method for producing an unleaded gasoline composition according to any one of claims 1 to 12 , wherein a friction modifier is added .