JP2007308567A - Hydrogenation purification method and environmental low load type gasoline base material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogenation purification method by which a hydrogenation-purified oil having a sufficiently reduced oxygen content, a sufficiently reduced sulfur content, and a sufficiently small normal paraffin content can be obtained, when a treating oil containing oxygen-containing hydrocarbon compounds and sulfur-containing compounds is used, and to provide an environmental low load type gasoline base material obtained by the hydrogenation purification method. <P>SOLUTION: This hydrogenation purification method is characterized by contacting the treating oil containing the oxygen-containing hydrocarbon compounds and the sulfur-containing compounds with a catalyst comprising a carrier containing metallosilicate and one or more elements of the group 6A and the group 8 in the periodic table carried on the carrier in hydrogen to obtain the hydrogenation purified oil sulfur-containing compounds. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a hydrorefining method, and more particularly, to a hydrotreating method for oil to be treated containing fat and oil components derived from animal and vegetable oils.

  Attention has been focused on the effective use of biomass energy as a measure to prevent global warming. Among biomass energy, biomass energy derived from plants can effectively use hydrocarbons converted from carbon dioxide by photosynthesis during the growth of plants, so it does not lead to an increase in carbon dioxide in the atmosphere from the viewpoint of life cycle, so-called, It has the property of being carbon neutral.

Various uses of such biomass energy have been studied in the field of transportation fuel. For example, if a fuel derived from animal and vegetable oils can be used as gasoline fuel, it is expected to play an effective role in reducing carbon dioxide emissions due to the high penetration rate of gasoline engines. Fatty acid methyl ester oil is known as a fuel using animal and vegetable oils. Fatty acid methyl ester oil is produced by transesterifying with methanol with an alkali or the like for a triglyceride structure which is a general structure of animal and vegetable oils. However, in the process for producing fatty acid methyl ester oil, as described in Patent Document 1 below, it is necessary to treat glycerin produced as a by-product, and cost and energy are required for washing the produced oil. It has been pointed out.
JP 2005-154647 A

  In addition to the above problems, there are the following problems in order to use oil and fat components derived from animal and vegetable oils and fuels produced from these components. That is, since the oil and fat component derived from animal and vegetable oils generally has an oxygen atom in the molecule, there is a concern that the oxygen content may adversely affect the engine material, and that the oxygen content is removed to an extremely low concentration. Is difficult. In addition, when using a mixture of oil and fat components derived from animal and vegetable oils and petroleum hydrocarbon fractions, in the conventional technology, the oxygen content in the oil and fat components and the sulfur content in the petroleum hydrocarbon fractions are used. Both cannot be reduced sufficiently. Furthermore, when used as a fuel substrate, it is desirable that the normal paraffin content is low and the isoparaffin content is high. For example, in the case of automobile gasoline, the octane number becomes insufficient when the normal paraffin content increases.

  Therefore, in the present invention, when an oil to be treated containing an oxygen-containing hydrocarbon compound and a sulfur-containing hydrocarbon compound is used, both the oxygen content and the sulfur content are sufficiently reduced and the normal paraffin content is sufficient. It is an object of the present invention to provide a hydrorefining method capable of obtaining a small amount of hydrorefined oil and an environmentally low-load gasoline base material obtained by using such a hydrorefining method.

  In order to solve the above-mentioned problems, the present invention provides an oil to be treated containing an oxygen-containing hydrocarbon compound and a sulfur-containing hydrocarbon compound in the presence of hydrogen, a carrier containing a crystalline metallosilicate, and a carrier. The hydrorefining method is characterized in that a hydrorefined oil is obtained by contacting a catalyst containing one or more metals selected from Group 6A and Group 8 elements of the periodic table.

  According to the hydrorefining method of the present invention, by bringing the oil to be treated containing the oxygen-containing hydrocarbon compound into contact with the specific catalyst, both the oxygen content and the sulfur content are sufficiently reduced and normal. A hydrorefined oil having a sufficiently low paraffin content can be obtained very effectively economically.

  In the hydrorefining method of the present invention, the content of oxygen in the fraction having a boiling range of 80 to 135 ° C. of the resulting hydrorefined oil is 0.2% by mass or less and the content of normal paraffin is 30% by mass or less. It is preferable to bring the oil to be treated and the catalyst into contact with each other under the following conditions. By hydrotreating the oil to be treated so as to satisfy such conditions, a hydrorefined oil containing a higher content of components useful as a gasoline base can be obtained. In this case, an environmentally low-load gasoline base material in which both the oxygen content and the sulfur content are sufficiently reduced and the normal paraffin content is sufficiently low can be obtained very effectively economically.

  In the hydrorefining method of the present invention, the oxygen content is 0.1 to 15% by mass and the sulfur content is 1 mass ppm to 1% by mass based on the total amount of the oil to be treated. It is preferable. When the oxygen content and sulfur content of the oil to be treated are within the above ranges, stable deoxygenation activity can be maintained over a long period of time.

  Moreover, in the hydrorefining method of this invention, it is preferable that an oxygen-containing hydrocarbon compound is an oil-fat component originating in animal and vegetable oil from the point of effective utilization of biomass energy.

  Moreover, since the energy required for processing raw materials can be reduced, the proportion of the compound having a triglyceride structure in the oxygen-containing hydrocarbon compound is preferably 90 mol% or more.

  In the hydrorefining method of the present invention, the catalyst preferably contains at least one metal selected from Group 6A elements of the periodic table.

  In the hydrorefining method of the present invention, it is preferable that the crystalline metallosilicate contained in the catalyst has a faujasite structure.

  Furthermore, it is preferable that the crystalline metallosilicate is a super-stabilized Y-type zeolite having a silica to alumina molar ratio (silica / alumina) in the range of 10 to 100. When such a molar ratio is less than 10, coke formation tends to be promoted and a significant decrease in activity tends to be caused. When the molar ratio exceeds 100, hydrocracking activity becomes insufficient and useful as a fuel substrate. The component yield tends to decrease.

  The present invention also includes an environmentally low-load gasoline group characterized by including a fraction having a boiling point in the range of 25 to 220 ° C. among the hydrorefined oil obtained by the hydrorefining method of the present invention. Providing materials. According to the environmentally low load gasoline base material of the present invention, it is possible to effectively reduce the emission amount of carbon dioxide.

  According to the present invention, when an oil to be treated containing an oxygen-containing hydrocarbon compound and a sulfur-containing hydrocarbon compound is used, both the oxygen content and the sulfur content are sufficiently reduced and the normal paraffin content is sufficient. Provided is a hydrorefining method capable of economically and extremely effectively obtaining a small amount of hydrorefined oil. Moreover, according to this invention, the environmental low load type gasoline base material which can implement | achieve the reduction of the discharge | emission amount of a carbon dioxide effectively is provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

  In the present invention, an oil to be treated containing an oxygen-containing hydrocarbon compound and a sulfur-containing hydrocarbon compound is used. As the oxygen-containing hydrocarbon compound, oil and fat components derived from animal and vegetable oils are suitable. Here, the fats and oils component in the present invention includes natural and artificially produced and manufactured animal and vegetable oils and fats and / or animal and vegetable oil components and / or components produced and produced from these fats and oils and the performance of these fat and oil products. Components added for the purpose of maintaining and improving the above are included.

  Examples of the oil and fat component derived from animal and vegetable oils include beef tallow, rapeseed oil, soybean oil, and palm oil. In the present invention, any fats and oils derived from animal and vegetable oils may be used, and waste oil after using these fats and oils may be used. However, vegetable oils and fats are preferable from the viewpoint of carbon neutral, and rapeseed oil, soybean oil, and palm oil are more preferable from the viewpoint of the number of fatty acid alkyl chain carbons and their reactivity. In addition, you may use said fats and oils individually by 1 type or in mixture of 2 or more types.

  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 present invention, the proportion of the compound having a triglyceride structure in the oxygenated hydrocarbon compound 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 may contain, as an oxygen-containing hydrocarbon compound, a compound derived from a chemical such as a plastic or a solvent, in addition to the oil and fat component derived from the above-mentioned animal and vegetable oils, and consists of carbon monoxide and hydrogen. A synthetic oil obtained via a Fischer-Tropsch reaction using synthesis gas as a raw material may be contained.

  The oxygen content contained in the oil to be treated is preferably 0.1 to 15% by mass, more preferably 1 to 15% by mass, still more preferably 3 to 14% by mass, particularly preferably based on the total amount of the oil to be treated. Is 5 to 13% by 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.

  In the present invention, the oil to be treated may contain a sulfur-containing hydrocarbon compound. Although it does not restrict | limit especially as a sulfur-containing hydrocarbon compound, Specifically, sulfide, disulfide, polysulfide, thiol, thiophene, benzothiophene, dibenzothiophene, these derivatives, etc. are 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 is preferably 1 mass ppm to 1 mass%, more preferably 15 mass ppm to 0.5 mass%, still more preferably 30 mass ppm to 30 mass ppm, based on the total amount of the oil to be treated. 0.1% by 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, when the sulfur content exceeds 1% by mass, the sulfur content contained in the hydrorefined oil tends to increase, and when used as a fuel for diesel engines, the engine exhaust gas purification device is adversely affected. Concerned. 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 used in 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 hydrorefining method of the present invention, a catalyst containing a crystalline metallosilicate and a catalyst containing one or more metals selected from Group 6A and Group 8 elements of the periodic table supported on the carrier are provided. Used.

  As the catalyst carrier used in the present invention, a porous inorganic oxide containing a crystalline metallosilicate is used. The crystalline metallosilicate preferably has a structure represented by each code of FAU, AEL, MFI, MMW, TON, MTW, * BEA, MOR among structures defined by the International Zeolite Society. FAU, * BEA, MOR And those having a structure represented by each code of MFI are more preferable. In the present invention, it is even more preferable that the crystalline metallosilicate has a structure represented by FAU also called a faujasite type. The crystalline metallosilicate is particularly preferably Y-type that has undergone ultrastabilization treatment. The ultra-stabilization treatment refers to a hydrothermal treatment and / or a washing treatment with an acidic aqueous solution. By such an operation, for example, when the structure contains aluminum, the content thereof is adjusted, and the pore diameter is 2 to 50 nm. A pore volume derived from the defined mesopores can be imparted.

  The crystalline metallosilicate contained in the catalyst carrier is preferably a crystalline aluminosilicate composed of three elements of aluminum, silicon and oxygen. A so-called zeolite containing silica and alumina can be used as the crystalline aluminosilicate. Preferable examples include Y-type zeolite, ultra-stabilized Y-type zeolite (USY-type zeolite), β-type zeolite, mordenite, ZSM-5, etc. Among them, USY zeolite is particularly preferable. In the present invention, one type of crystalline aluminosilicate may be used alone, or two or more types may be used in combination.

  When the crystalline metallosilicate includes silica and alumina, the molar ratio of silica to alumina (silica / alumina) is preferably in the range of 10 to 100. When such a molar ratio is less than 10, coke formation tends to be promoted and a significant decrease in activity tends to be caused. When the molar ratio exceeds 100, hydrocracking activity becomes insufficient and useful as a fuel substrate. The component yield tends to decrease. In the present invention, it is particularly preferable that the catalyst carrier contains, as a crystalline metallosilicate, a super-stabilized Y-type zeolite in which the molar ratio of silica to alumina (silica / alumina) is in the range of 10 to 100.

  The method for synthesizing the crystalline metallosilicate used in the present invention is not particularly limited, and a generally known method can be used. For example, a crystalline metallosilicate can be synthesized by heating a constituent raw material in the presence of a structure indicator if necessary. Examples of the constituent raw material include silicon-containing compounds such as sodium silicate, colloidal silica and alkoxide silicate, and aluminum-containing compounds such as aluminum hydroxide and sodium aluminate. Examples of the structure directing agent include amine compounds such as tetrapropylammonium salt.

  The catalyst used in the present invention may contain components other than the crystalline metallosilicate. Examples of constituents other than the crystalline metallosilicate include inorganic oxides containing an element selected from aluminum, silicon, zirconium, boron, titanium, and magnesium. These inorganic oxides can function as a bonding agent when forming a crystalline metallosilicate, and can also function as an active component that promotes hydrodeoxygenation and hydroisomerization. From the viewpoint of more reliably obtaining these functions, the inorganic oxide preferably contains two or more elements selected from aluminum, silicon, zirconium, boron, titanium, and magnesium.

  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. When the content is less than 2% by mass, the hydrodeoxygenation activity and hydroisomerization activity of the catalyst tend to be insufficient. When the content exceeds 90% by mass, catalyst molding is performed. Therefore, it becomes difficult to industrially produce the catalyst.

  The porous inorganic oxide as the catalyst carrier supports one or more metals selected from Group 6A and Group 8 elements of the periodic table. Among these metals, it is preferable that one or more metals selected from Co, Mo, and Ni are supported, and it is more preferable that two or more metals of Co, Mo, and Ni are supported in combination. Suitable combinations include Co—Mo, Ni—Mo, and Ni—Co—Mo. Thus, it is preferable that at least one metal selected from Group 6A elements of the periodic table is supported on the porous inorganic oxide. In hydrorefining, it is preferable to convert these metals into a sulfide state.

  When one or more kinds of metals selected from Co, Mo and Ni are supported, the content of active metals based on the mass of the catalyst is such that the total of these metals is in the range of 15 to 35% by mass. Preferably, it is in the range of 17 to 30% by mass. When the total content of the metals is less than 15% by mass, the active sites tend to decrease and sufficient activity cannot 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. In addition, about the content of Co, Mo, and Ni, the value in oxide conversion is employ | adopted.

  The method for incorporating these active metals into the catalyst is not particularly limited, and a known method applied when producing an ordinary desulfurization 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.

  In the present invention, the number of hydrorefining catalysts to be used is not particularly limited. For example, one type of catalyst may be used alone, or a plurality of catalysts having different active metal species and carrier components may be used. In the case of combining a plurality of catalysts having different support components, for example, the content of the crystalline metallosilicate is the latter stage of the catalyst in which the content of the crystalline metallosilicate is 5% by mass or less based on the total mass of the support. What is necessary is just to use the catalyst in the range of 2-90 mass%.

  In addition to hydrorefining catalysts, guard catalysts and demetals are used to trap the scale that flows in along with the oil to be treated, if necessary, and to support the hydrorefining 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.

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 , hydrogen oil ratio (hydrogen / oil Ratio) 150-1500 NL / L, preferably hydrogen pressure 2-10 MPa, liquid space velocity 0.2-2.0 h ⁻¹ , hydrogen oil ratio 200-1200 NL / L, more preferably hydrogen pressure 2 More preferably, it is -6MPa, space velocity 0.3-1.5h- ¹ , and hydrogen oil ratio 250-1000NL / 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. Moreover, 250-550 degreeC is preferable for reaction temperature, 280-480 degreeC is more preferable, and 300-460 degreeC is still more preferable.

  As the type of the reactor, a fixed bed system can be adopted. 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.

  The hydrorefined oil hydrorefined in the reactor is fractionated into a hydrorefined oil containing a predetermined fraction through a gas-liquid separation process, a rectification process, and the like. For example, it is fractionated into a light oil fraction and a residual fraction. Furthermore, the gas, naphtha fraction, and kerosene fraction may be fractionated as necessary. 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 general, hydrogen gas is introduced from the inlet of the first reactor along with the oil to be treated before or after passing through the heating furnace, but separately from this, the temperature in the reactor is controlled. In order to maintain the hydrogen pressure throughout the reactor, hydrogen gas may be introduced between the catalyst beds or between a plurality of reactors. 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 volumes, the reaction at the subsequent reaction site tends not to proceed sufficiently. If the rate of quench hydrogen exceeds 60% by volume, the reaction near the reactor inlet does not proceed sufficiently. Tend.

  In the hydrorefining method of the present invention, the content of oxygen in the fraction having a boiling range of 80 to 135 ° C. of the resulting hydrorefined oil is 0.2% by mass or less and the content of normal paraffin is 30% by mass or less. It is preferable to hydrotreat the oil to be treated under such conditions. Furthermore, it is more preferable that the oil to be treated is hydrorefined under the condition that the content of oxygen in the fraction is 0.2% by mass or less and the content of normal paraffin is 25% by mass or less. In the hydrorefined oil obtained by the hydrorefining method of the present invention, the remaining oxygen content exists mainly in the state of any functional group of a hydroxyl group, an aldehyde group, a carboxyl group, or a plurality of these functional groups. Therefore, if the oxygen content in the fraction exceeds 0.2% by mass, there is a concern that the corrosiveness increases and the aldehyde concentration in the exhaust gas increases. In addition, when the content of normal paraffin in the fraction exceeds 30% by mass, the octane number as a gasoline base material is lowered, and there is a possibility of causing deterioration of anti-knocking performance at high speed when used for gasoline products. . By performing hydrorefining by preferably adjusting the reaction temperature and liquid space velocity among the conditions when contacting the oil to be treated and the catalyst so as to satisfy the conditions in the hydrorefined oil, A component useful as a gasoline base material can be obtained in high yield from the oil to be treated. In addition, normal paraffin content can be calculated | required by measuring according to JISK2536-2 "Petroleum products-component test method-how to obtain the total analysis by a gas chromatograph".

  When the hydrorefined oil produced by the present invention is used as a gasoline base, it preferably contains a fraction having a boiling point in the range of 25 to 220 ° C, more preferably in the range of 80 to 135 ° C. Thus, it is possible to obtain a high quality environmentally low load gasoline base material with good economic efficiency. Furthermore, from the viewpoint of suppressing adverse effects on the engine and other materials, the oxygen content in the fraction used as a gasoline base material is preferably 0.5% by mass or less, and 0.3% by mass or less. It is more preferable. Furthermore, it is preferable that the content of sulfur in the fraction is 20 ppm by mass or less. If the sulfur content exceeds the above upper limit, there is a risk of affecting the filter and catalyst used in the engine exhaust gas treatment device.

The gasoline fraction obtained by the present invention can also be used as a feedstock for a catalytic reformer. When the oil to be treated contains biomass, carbon dioxide emissions (LCA) estimated from the viewpoint of the life cycle in the production of hydrogen, gasoline engine fuel, and benzene, toluene and xylenes, which are basic raw materials for petrochemical products -CO ₂₎ can effectively impart the effect of reducing. That is, according to the present invention, hydrogen capable of sufficiently reducing LCA-CO ₂ , fuel for gasoline engines, and benzene, toluene and xylenes which are basic raw materials for petrochemical products can be obtained.

  Hydrogen can be produced by reforming a portion of the hydrorefined oil produced according to the present invention with a steam reformer or a catalytic reformer. When the oil to be treated contains biomass, the obtained hydrogen has the characteristic of being carbon neutral. Therefore, it is possible to reduce the environmental load in hydrogen production and / or gasoline base material production.

  Of the hydrorefined oil produced by the present invention, a kerosene fraction having a boiling point within the range of 220 to 350 ° C. can be suitably used particularly as a diesel light oil or heavy oil base material. When using the said fraction as diesel light oil, it is preferable that content of the sulfur content in this fraction is 10 mass ppm or less. When the sulfur content exceeds the above upper limit, there is a risk of affecting the filter and catalyst used in the exhaust gas treatment device of the diesel engine. The hydrorefined oil may be used alone as a diesel light oil or heavy oil base material, but can be used as a diesel light oil or a heavy base material mixed with components such as other base materials. As other base materials, a light oil fraction and / or kerosene fraction obtained in a general petroleum refining process and a residual fraction obtained by the hydrorefining method of the present invention can be mixed. Furthermore, a synthetic light oil or a kerosene obtained through a Fischer-Tropsch reaction or the like using so-called synthesis gas composed of hydrogen and carbon monoxide as a raw material can be mixed. These synthetic light oils and kerosene are characterized by containing almost no aromatic content, having a saturated hydrocarbon as a main component, and a high cetane number. In addition, a well-known method can be used as a manufacturing method of synthesis gas, and it is not specifically limited.

  Of the hydrorefined oil produced according to the present invention, the kerosene fraction and / or the residue may be mixed with the oil to be treated in whole or in part for recycling. Thereby, the yield of the fraction useful as a gasoline base material can be raised more.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

(Preparation of catalyst)
<Catalyst A>
After ultra-stabilizing a Y-type zeolite having a silica / alumina ratio (SiO ₂ / Al ₂ O ₃ ) of 5 by hydrothermal treatment in a saturated steam atmosphere at 780 ° C. for 1 hour using a steaming device Proton-type super-stabilized Y-type that is acid-treated with 1N nitric acid aqueous solution, has a lattice constant of 24.33Å determined by X-ray diffraction, and a ratio of silica to alumina (SiO ₂ / Al ₂ O ₃ ) of 30 210 g of zeolite was obtained.

  On the other hand, 185 g of water glass No. 3 was added to 3000 g of an aqueous sodium aluminate solution having a concentration of 5% by mass and placed in a container kept at 65 ° C. On the other hand, 3000 g of an aluminum sulfate aqueous solution having a concentration of 2.5% by mass was prepared in another container kept at 65 ° C., and the aqueous solution containing sodium aluminate described above was added dropwise thereto. The time when the pH of the mixed solution reached 7.0 was set as the end point, and the resulting slurry product was filtered through a filter to obtain a cake slurry.

  The cake-like slurry was transferred to a container equipped with a reflux condenser, 150 ml of distilled water and 10 g of 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 75 ° C. for 20 hours. The slurry was put in a kneading apparatus and heated to 80 ° C. or higher and kneaded while removing moisture to obtain a clay-like kneaded product. After adding 186 g of the ultra-stabilized Y-type zeolite obtained above to the kneaded product obtained and further kneading, this was extruded into the shape of a cylinder with a diameter of 1.5 mm by an extruder and dried at 110 ° C. for 1 hour, Firing was performed at 550 ° C. to obtain a shaped carrier.

  50 g of the obtained shaped carrier was placed in an eggplant-shaped flask and 10.0 g of molybdenum trioxide, 18.3 g of nickel (II) nitrate hexahydrate, 0.9 g of phosphoric acid (concentration 85%) while degassing with a rotary evaporator. And an impregnation solution containing 4.0 g of malic acid was poured into the flask. The impregnated sample was dried at 120 ° C. for 1 hour and then calcined at 550 ° C. to obtain Catalyst A. The supported amounts of nickel and molybdenum in catalyst A were 4.0% by mass (as nickel oxide) and 16.0% by mass (as molybdenum oxide), respectively, in terms of oxides, based on the total amount of the catalyst.

<Catalyst B>
A sodium aluminate aqueous solution having a concentration of 5% by mass was placed in a container kept at 65 ° C. On the other hand, 3000 g of a 2.5 mass% aluminum sulfate aqueous solution was prepared in another container kept at 65 ° C., and the above-mentioned sodium aluminate aqueous solution was added dropwise thereto. The end point was when the pH of the mixed solution reached 7.0, and the resulting slurry product was filtered through a filter to obtain a cake-like slurry.

  The cake-like slurry was transferred to a container equipped with a dry distillation cooler, 150 ml of distilled water and 10 g of a 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 75 ° C. for 20 hours. The slurry was put in a kneading apparatus and heated to 80 ° C. or higher and kneaded while removing moisture to obtain a clay-like kneaded product. The obtained kneaded product was extruded into the shape of a cylinder having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 550 ° C. to obtain a molded carrier.

  While putting 50 g of the obtained shaped carrier into an eggplant-shaped flask and degassing with a rotary evaporator, 10.0 g of molybdenum trioxide, 18.3 g of nickel (II) nitrate hexahydrate, and phosphoric acid (concentration 85%) 0. An impregnation solution containing 9 g and 4.0 g malic acid was poured into the flask. The impregnated sample was dried at 120 ° C. for 1 hour and then calcined at 550 ° C. to obtain catalyst B. The supported amounts of nickel and molybdenum in catalyst B were 4.0% by mass (as nickel oxide) and 16.0% by mass (as molybdenum oxide), respectively, based on the total amount of the catalyst.

Example 1
A first reaction tube (inner diameter 20 mm) filled with catalyst A (50 ml) and a second reaction tube (inner diameter 20 mm) also filled with catalyst A (50 ml) were attached in series to a fixed bed flow reactor. Then, using straight-run gas oil to which dimethyl disulfide was added (sulfur content: 3% by mass), the catalyst layer average temperature was 300 ° C., the hydrogen partial pressure was 6 MPa, the liquid space velocity was 1 h ⁻¹ , and the hydrogen / oil ratio was 200 NL / L. The catalyst was presulfided for 4 hours.

After preliminary sulfidation of the catalyst, dimethyl sulfide is added to palm oil (ratio of compound having triglyceride structure in oxygen-containing hydrocarbon compound: 98 mol%) to adjust the sulfur content in the oil to be treated to 51 mass ppm. Hydrotreating was performed using the treated oil. In addition, 15 degreeC density of to-be-processed oil was 0.916 g / ml, and oxygen content was 11.4 mass%. The hydrorefining conditions were such that the reaction temperature of the first and second reaction tubes was 425 ° C., the pressure was 5 MPa, and the liquid space velocity was 0.4 h ⁻¹ . The volume ratio of hydrogen gas introduced between the first reaction pipe and the second reaction pipe (quenching hydrogen ratio) is 20% by volume of the total introduced hydrogen, and the hydrogen / oil ratio determined by the total introduced hydrogen is 1010 NL / L. About hydrorefined oil obtained by hydrorefining, oxygen content and sulfur content in hydrorefined oil, yield of each fraction, naphtha fraction having a boiling range of 80 to 135 ° C (hydrocarbon having 5 to 10 carbon atoms) The oxygen content, sulfur content and normal paraffin content in the fraction) were measured. The obtained results are shown in Table 1.

(Comparative Example 1)
The hydrorefining was performed in the same manner as in Example 1 except that the catalyst B was used instead of the catalyst A, and the reaction temperature of the first and second reaction tubes was changed to 430 ° C. during the hydrorefining. The obtained hydrorefined oil was measured in the same manner as in Example 1. The obtained results are shown in Table 1.

Claims (9)

In the presence of hydrogen,
Oil to be treated containing oxygen-containing hydrocarbon compound and sulfur-containing hydrocarbon compound;
A support containing a crystalline metallosilicate and a catalyst containing one or more metals selected from Group 6A and Group 8 elements of the periodic table supported on the support;
A hydrorefining method characterized in that hydrorefined oil is obtained by bringing into contact therewith.   The oil to be treated and the catalyst under the condition that the content of oxygen in the fraction of boiling point range of 80 to 135 ° C. of the hydrorefined oil is 0.2 mass% or less and the content of normal paraffin is 30 mass% or less. The hydrorefining method according to claim 1, wherein   The oxygen content is 0.1 to 15 mass% and the sulfur content is 1 mass ppm to 1 mass% based on the total amount of the oil to be treated. Or the hydrorefining method according to 2.   The hydrorefining method according to any one of claims 1 to 3, wherein the oxygen-containing hydrocarbon compound is an oil and fat component derived from animal and vegetable oils.   The hydrorefining method according to any one of claims 1 to 4, wherein the proportion of the compound having a triglyceride structure in the oxygen-containing hydrocarbon compound is 90 mol% or more.   The hydrotreating method according to any one of claims 1 to 5, wherein the catalyst contains at least one metal selected from Group 6A elements of the periodic table.   The hydrorefining method according to any one of claims 1 to 6, wherein the crystalline metallosilicate has a faujasite structure.   The crystalline metallosilicate is an ultra-stabilized Y-type zeolite having a silica to alumina molar ratio (silica / alumina) in the range of 10 to 100. The hydrorefining method according to any one of the above. The hydrorefined oil obtained by the hydrorefining method according to any one of claims 1 to 8 comprises a fraction having a boiling point in the range of 25 to 220 ° C. Environmentally low-load gasoline base material.