JP2007308564A - Hydrorefining method - Google Patents

Abstract

To provide a hydrorefining method capable of obtaining a hydrorefined oil having a sufficiently reduced oxygen content when an oil to be treated containing an oxygen-containing hydrocarbon compound is used.
The hydrorefining method of the present invention comprises an oil to be treated containing an oxygen-containing hydrocarbon compound in the presence of hydrogen, and two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium. And a catalyst containing one or more metals selected from Group 8 elements of the periodic table supported on the porous inorganic oxide, and a hydrogen pressure of 2 to 13 MPa The liquid space velocity is 0.1 to 3.0 h ⁻¹ , the hydrogen oil ratio is 150 to 1500 NL / L, and the reaction temperature is 150 to 380 ° C.
[Selection figure] None

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 a diesel fuel, it is expected to play an effective role in reducing carbon dioxide emissions due to a synergistic effect with the high energy efficiency of a diesel engine. Fatty acid methyl ester oil is known as a diesel 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.

  Therefore, the present invention provides a hydrorefining method capable of obtaining a hydrorefined oil having a sufficiently reduced oxygen content when an oil to be treated containing an oxygen-containing hydrocarbon compound is used. Objective.

In order to solve the above problems, the present invention comprises an oil to be treated containing an oxygen-containing hydrocarbon compound in the presence of hydrogen, and two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium. A porous inorganic oxide comprising and a catalyst containing one or more metals selected from Group 8 elements supported on the porous inorganic oxide, a hydrogen pressure of 2 to 13 MPa, There is provided a hydrorefining method characterized by contacting under the conditions of a liquid space velocity of 0.1 to 3.0 h ⁻¹ , a hydrogen oil ratio of 150 to 1500 NL / L, and a reaction temperature of 150 to 380 ° C.

  According to the hydrorefining method of the present invention, hydrogenation in which the oxygen content is sufficiently reduced by contacting an oil to be treated containing an oxygen-containing hydrocarbon compound with the specific catalyst under the specific conditions. Refined oil can be obtained very effectively economically.

  In the hydrorefining method of this invention, it is preferable that content of oxygen content is 0.1-15 mass% on the basis of the whole quantity of to-be-processed oil. Moreover, when the to-be-processed oil contains a sulfur content, it is preferable that the content is 50 mass ppm or less. 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. Therefore, according to the present invention, it is possible to obtain a hydrorefined oil in which both the oxygen content and the sulfur content are sufficiently reduced by using the oil to be treated containing the oxygen-containing hydrocarbon compound and the sulfur-containing hydrocarbon compound. Is possible.

  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.

  From the viewpoint of further improving the deoxygenation activity of the catalyst used in the hydrorefining method of the present invention, the metal supported on the catalyst is one or more selected from Pd, Pt, Rh, Ir, Au and Ni. It is preferable that it is an element of these.

  Furthermore, in the present invention, from the viewpoint of maintaining a high catalyst activity for a sufficiently long time, the carbon monoxide adsorption amount per 1 g of the catalyst in which the metal supported on the catalyst is in a reduced state is 0.003 to 0.05 mmol. It is preferable that

  According to the present invention, hydrotreating capable of obtaining a hydrorefined oil having a sufficiently reduced oxygen content economically and effectively when an oil to be treated containing an oxygen-containing hydrocarbon compound is used. A method 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 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 oil to be treated may contain a petroleum hydrocarbon fraction, and can be obtained by a fraction obtained by distillation of crude oil or a reaction such as hydrodesulfurization, hydrocracking, fluid catalytic cracking, catalytic reforming. A fraction may be included. The mixing amount of these fractions can be arbitrarily set as long as the oxygen content and sulfur content contained in the oil to be treated satisfy a predetermined concentration range. Furthermore, these fractions may be mixed together with the above-mentioned chemical-derived compounds and synthetic oils obtained via the Fischer-Tropsch reaction.

  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.

  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 50 mass ppm or less, more preferably 20 mass ppm or less, still more preferably 10 mass ppm or less, based on the total amount of the oil to be treated. 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 hydrorefined oil tends to increase. When used as a fuel for a diesel engine or the like, there is a concern about an adverse effect on the engine exhaust gas purification device. 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 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 porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium, and magnesium, and the porous inorganic oxide are supported. In addition, a catalyst containing one or more metals selected from Group 8 elements of the periodic table is used.

  As the catalyst carrier used in the present invention, a porous inorganic oxide comprising two or more selected from aluminum, silicon, zirconium, boron, titanium and magnesium as described above is used. The porous inorganic oxide is preferably at least two selected from aluminum, silicon, zirconium, boron, titanium and magnesium from the viewpoint that the deoxygenation activity and desulfurization activity can be further improved. Aluminum and other elements And an inorganic oxide (a composite oxide of aluminum oxide and another oxide) is more preferable.

  The method for introducing silicon, zirconium, boron, titanium and magnesium, which are carrier constituent elements other than aluminum, is not particularly limited, and a solution containing these elements may be used as a raw material. For example, for silicon, silicon, water glass, silica sol, etc., for boron, boric acid, etc., for phosphorus, phosphoric acid and alkali metal salts of phosphoric acid, etc., for titanium, titanium sulfide, titanium tetrachloride and various alkoxide salts, etc. As for zirconium, zirconium sulfate and various alkoxide salts can be used.

  It is preferable to add the raw materials for the carrier constituents other than the above-described aluminum oxide in the step prior to the firing of the carrier. For example, after adding the said raw material previously to aluminum aqueous solution, the aluminum hydroxide gel containing these structural components may be prepared, and the said raw material may be added with respect to the prepared aluminum hydroxide gel. Alternatively, the above raw materials may be added in a step of adding water or an acidic aqueous solution to a commercially available aluminum oxide intermediate or boehmite powder and kneading them, but it is more preferable to coexist at the stage of preparing aluminum hydroxide gel. Although the mechanism of the effect of the carrier constituents other than aluminum oxide has not necessarily been elucidated, it is presumed that it forms a complex oxide state with aluminum, which increases the surface area of the carrier and the interaction with the active metal. It is considered that the activity is affected by producing the action.

  The porous inorganic oxide as a carrier carries one or more metals selected from Group 8 elements of the periodic table. Among these metals, it is preferable to use one or more metals selected from Pd, Pt, Rh, Ir, Au, and Ni, and it is more preferable to use a combination of two or more. 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, Pd—Pt—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 still more preferable. In hydrorefining, these metals are used after being converted to a reduced state.

  The total supported amount of the active metal based on the catalyst mass is preferably 0.1 to 2% by mass, more preferably 0.2 to 1.5% by mass, and further 0.5 to 1.3% by mass as the metal. 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.

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

  When a plurality of catalysts having different support components are combined, for example, the content of aluminum oxide is included in the subsequent stage of the catalyst having an aluminum oxide content of 50% by mass or more and less than 97% by mass based on the total mass of the support. A catalyst having an amount in the range of 1 to 30% by mass may be used.

  When the active metal of the catalyst used in the present invention is in a reduced state, the carbon monoxide adsorption amount per 1 g of the catalyst is preferably 0.003 to 0.05 mmol, and is preferably 0.005 to 0.04 mmol. It is more preferable, and it is still more preferable that it is 0.009-0.03 mmol. When the adsorption amount is less than 0.003 mmol, the metal is in an aggregated state, and the active sites tend to decrease. On the other hand, when the adsorption amount exceeds 0.05 mmol, the activity decrease tends to be promoted as the reaction time elapses. For the measurement of the carbon monoxide adsorption amount, a general measurement method used for a catalyst supporting a reduced metal can be applied. Specifically, after reducing a certain amount of catalyst at a temperature of 350 ° C. in a hydrogen stream, the catalyst can be cooled to 50 ° C. and obtained by a pulse method or a constant volume method.

  Furthermore, in addition to the above catalyst (hydrorefining catalyst), for the purpose of trapping the scale component that flows along with the oil to be treated, if necessary, or supporting the hydrorefining catalyst at the separation part of the catalyst bed. A guard catalyst, a metal removal catalyst, or an 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, the hydrogen pressure is 2.5 to 10 MPa, the liquid space velocity is 0.5 to 2.0 h ⁻¹ , and the hydrogen oil ratio is 380 to 1200 NL / L, more preferably the hydrogen pressure is 3 to 8 MPa, and the liquid space velocity is 0.8 to It is 1.8h < ^-1 >, hydrogen oil ratio 350-1000NL / 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, the temperature conditions at the time of making a to-be-processed oil and a catalyst contact in presence of hydrogen are 150-380 degreeC. The temperature is preferably 170 to 360 ° C, more preferably 220 to 350 ° C. If the temperature is less than 150 ° C, the deoxygenation activity tends to be insufficient. On the other hand, if it exceeds 380 ° C, the oil to be treated is excessively decomposed, and a fraction useful for the production of liquid fuel (for example, , The yield of the boiling point temperature in the range of 250 to 350 ° C.) tends to decrease.

  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. Hydrogen can be produced by reforming a part of the light hydrocarbon fraction produced in a steam reformer. The hydrogen produced in this way has a characteristic of carbon neutral because the raw material used for steam reforming is a biomass-derived hydrocarbon, and can reduce the burden on the environment. 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.

  When the hydrorefined oil produced according to the present invention is used as a light oil fraction base, it contains a fraction having a boiling point of at least 260 to 300 ° C., a sulfur content of 10 mass ppm or less, and oxygen The content of min is preferably 0.5% by mass or less, more preferably the content of sulfur is 7% by mass or less, and the content of oxygen is 0.3% by mass or less. More preferably, the content is 3 mass ppm or less and the oxygen content is 0.2 mass% or less. When the sulfur content and the oxygen content exceed the above upper limit values, there is a risk of affecting the filter and catalyst used in the exhaust gas treatment device of the diesel engine, and further the engine and other materials.

  The hydrorefined oil produced by the present invention can be suitably used particularly as a diesel light oil or heavy oil base material. 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.

  The residual fraction obtained by the hydrorefining method of the present invention has a sulfur content of 0.1% by mass or less, an oxygen content of 1% by mass or less, and is used as a low sulfur heavy substrate. Can be used. The residual fraction is suitable as a feedstock for catalytic cracking. Thus, a gasoline base material and other fuel oil base materials with little sulfur content can be manufactured by using the residue fraction of a low sulfur level for a catalytic cracking apparatus. Further, the residual fraction can be used as a feedstock for hydrocracking. By providing such a residual fraction to a hydrocracking apparatus, it is possible to improve the cracking activity and to improve the quality of each product oil fraction.

  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>
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. The obtained kneaded material was extruded into a 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.

  50 g of the obtained shaped carrier was put into an eggplant-shaped flask, and impregnated with metal using 35 ml of a mixed aqueous solution of tetraammineplatinum (II) chloride and tetraamminepalladium (II) chloride while degassing with a rotary evaporator. The impregnated sample was dried at 110 ° C. and then calcined at 350 ° C. to obtain Catalyst A. The supported amounts of platinum and palladium in the catalyst A were 0.5% by mass and 0.7% by mass, respectively, based on the catalyst mass. Table 1 shows the physical properties of the prepared catalyst A.

<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 reflux condenser, 150 ml of distilled water and 10 g of a 27% ammonia aqueous 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 material was extruded into a 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.

  50 g of the obtained shaped carrier was put into an eggplant-shaped flask, and impregnated with metal using 35 ml of a mixed aqueous solution of dinitroammineplatinum (II) and dinitroamminepalladium (II) while degassing with a rotary evaporator. The impregnated sample was dried at 110 ° C. and then calcined at 350 ° C. to obtain Catalyst B. The supported amounts of platinum and palladium in the catalyst B were 0.5 mass% and 0.7 mass%, respectively, based on the catalyst mass. The physical properties of the prepared catalyst B are shown in Table 1.

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. Thereafter, the reduction treatment of the catalyst was performed for 6 hours under the conditions of an average catalyst layer temperature (reaction temperature) of 320 ° C., a hydrogen partial pressure of 5 MPa, and a hydrogen gas amount of 83 ml / min.

After reducing the catalyst, hydrorefining was performed using palm oil (ratio of the compound having a triglyceride structure in the oxygen-containing hydrocarbon compound: 98 mol%) as the oil to be treated. The 15 ° C. density of the oil to be treated was 0.916 g / ml, and the oxygen content was 11.4% by mass. The hydrorefining conditions were such that the reaction temperature of the first and second reaction tubes was 250 ° C., the pressure was 5.5 MPa, and the liquid space velocity was 0.8 h ⁻¹ . The volume ratio of hydrogen gas introduced between the first reaction pipe and the second reaction pipe (quenched hydrogen ratio) is 20% by volume of the total introduced hydrogen, and the hydrogen / oil ratio obtained from the total hydrogen introduced is 600 NL / L. The obtained results are shown in Table 2.

(Example 2)
A mixed oil obtained by mixing 70 parts by volume of the same palm oil and 30 parts by volume of petroleum-based desulfurized light oil used in Example 1 was used as the oil to be treated, and the reaction temperature of the first and second reaction tubes was 260 ° C. Except that, hydrorefining was performed in the same manner as in Example 1. The petroleum-based desulfurized light oil has a 15 ° C. density of 0.838 g / ml, a sulfur content of 15 ppm by mass, and an initial boiling point and an end point of 211 ° C. and 365 ° C., respectively. The density of the oil to be treated is 0.893 g / ml, the oxygen content is 8.2 mass%, and the sulfur content is 4.2 mass ppm.

(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. The obtained results are shown in Table 2.

(Comparative Example 2)
Hydrorefining was carried out in the same manner as in Example 1 except that the reaction temperature of the first and second reaction tubes was 120 ° C. during the hydrorefining. The obtained results are shown in Table 2.

(Comparative Example 3)
Hydrorefining was performed in the same manner as in Example 1 except that the reaction temperature of the first and second reaction tubes was set to 400 ° C. during hydrorefining. The obtained results are shown in Table 2.

(Comparative Example 4)
The hydrorefining was performed in the same manner as in Example 2 except that the catalyst B was used instead of the catalyst A. The obtained results are shown in Table 2.

Claims (6)

In the presence of hydrogen,
An oil to be treated containing an oxygen-containing hydrocarbon compound;
From a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and an element belonging to Group 8 of the periodic table carried on the porous inorganic oxide A catalyst containing one or more selected metals,
A hydrorefining method comprising contacting under conditions of a hydrogen pressure of 2 to 13 MPa, a liquid space velocity of 0.1 to 3.0 h ⁻¹ , a hydrogen oil ratio of 150 to 1500 NL / L, and a reaction temperature of 150 to 380 ° C.   The oxygen content is 0.1 to 15% by mass and the sulfur content is 50 mass ppm or less, based on the total amount of the oil to be treated, according to claim 1. Hydrorefining method.   The hydrorefining method according to claim 1 or 2, 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 3, wherein the proportion of the compound having a triglyceride structure in the oxygen-containing hydrocarbon compound is 90 mol% or more.   The metal supported on the catalyst is one or more elements selected from Pd, Pt, Rh, Ir, Au, and Ni, according to any one of claims 1 to 4. Hydrorefining method.   The hydrogenation according to any one of claims 1 to 5, wherein the amount of carbon monoxide adsorbed per 1 g of the catalyst in which the metal is in a reduced state is 0.003 to 0.05 mmol. Purification method.