JP2006035052A - Catalyst for hydro-desulfurizing petroleum hydrocarbon and hydro-desulfurizing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydro-desulfurization catalyst which can achieve such an extremely high degree of desulfurization that sulfur content is ≤10 mass ppm and has high nitrogen resistance to a nitrogen compound being a substance hindering a desulfurization reaction. <P>SOLUTION: This catalyst for hydro-desulfurizing a petroleum hydrocarbon is characterized in that at least one metal selected from metals of group 8 in the periodic table and at least one metal selected from metals of group 6A in the periodic table as active metals are contained in the scope of 0.055-0.150 in the mole ratio of [group 8 metal oxide]/[group 6A metal oxide] in an inorganic porous carrier containing alumina and phosphorus, and the content of the group 6A metal is 30-40 mass% to the weight of the catalyst in oxide conversion. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hydrodesulfurization catalyst and hydrodesulfurization method for petroleum hydrocarbons. Specifically, the present invention relates to a method for desulfurizing petroleum hydrocarbons using a specific catalyst and under specific reaction conditions when desulfurizing petroleum hydrocarbons containing sulfur.

  In recent years, awareness of environmental problems and air pollution is increasing, and the sulfur content in transportation fuel oil has attracted particular attention. In particular, exhaust gas discharged from diesel vehicles using light oil as fuel contains fine particles called particulates in addition to chemical substances such as SOx and NOx, and there is concern about damage to health. For this reason, it has been proposed to install a particulate removal filter such as DPF or a device having a particulate combustion removal function at the rear stage of the engine as a measure for removing particulates, and application to diesel engine vehicles is being studied. Further, for NOx, a reduction removal catalyst or the like is being developed. However, these devices and catalysts cause poisoning and deterioration due to SOx generated by changing the sulfur content in the fuel oil. In diesel vehicles such as transport trucks, which have a longer mileage than gasoline vehicles, deterioration of these exhaust gas cleaning devices and catalysts is a more serious problem. In order to solve such problems, it is strongly desired to reduce the sulfur content in light oil as much as possible. At this time, the light oil used as diesel fuel is also mixed with a fraction that is classified into kerosene fraction as the boiling range in order to maintain the product properties optimally. In order to lower the sulfur content, it is necessary to reduce the sulfur content in both the kerosene fraction and the light oil fraction. Furthermore, generation of harmful sulfur oxides or the like can be reduced when used as a heating appliance fuel such as a stove.

  Since petroleum hydrocarbon fractions other than residual oil obtained by crude oil distillation or heavy oil cracking reaction contain sulfur content of about 0.1 to 3% by mass, usually after hydrodesulfurization treatment Used as fuel substrate. The main sulfur compounds present in these petroleum hydrocarbon fractions are thiophene, benzothiophene, dibenzothiophene and their derivatives, but the desulfurization depth of each fraction such as kerosene and light oil in petroleum hydrocarbons is low. As desulfurization proceeds to a low sulfur region as the progress proceeds, the reactivity tends to be poor. That is, the sulfur compound remaining in the fractions with the progress of hydrodesulfurization is poor in reactivity, and desulfurization is difficult to proceed unless the conditions are more severe. For example, benzothiophenes for kerosene fractions and alkyl-substituted dibenzothiophenes having a plurality of methyl groups represented by 4,6-dimethyldibenzothiophene as substituents for gas oil fractions are particularly poor in reactivity and sulfur content. This is an obstacle to proceeding with desulfurization to a lower sulfur region such as 10 ppm by mass.

  In the hydrodesulfurization reaction of petroleum hydrocarbons, it is known that there is a reaction mechanism that directly extracts sulfur atoms from sulfur compounds and a reaction mechanism that involves a reaction in which an aromatic ring adjacent to the sulfur atom is hydrogenated. . In particular, when desulfurizing a compound having poor desulfurization reactivity, a route via the latter aromatic ring hydrogenation is considered necessary. Furthermore, not only a hydrogenation reaction but also a decomposition reaction that can efficiently cleave a sulfur-carbon bond is strongly required.

  Conventionally, as a hydrodesulfurization catalyst in petroleum refining, the active metal species and the amount and ratio of the metal have been optimized within the range conceivable in the past. Under such circumstances, the catalyst containing active metals such as cobalt-molybdenum and nickel-molybdenum is vigorously optimized. In hydrodesulfurization catalysts using these metals as active metals, cobalt / molybdenum or nickel / molybdenum are used. It has been said that there is an optimum point with the highest desulfurization activity in the molar ratio of molybdenum in the range of 0.3 to 1 (see, for example, Non-Patent Document 1 and Non-Patent Document 2). However, as a result of various studies by the inventors, in order to reach a very high desulfurization depth of 10 ppm by mass or less, such a conventional hydrotreating catalyst having a metal ratio has sufficient desulfurization activity. It was found that could not be demonstrated. This strongly suggests that a function different from the catalytic activity function required at the conventional desulfurization level as described above is necessary.

As a method of achieving a high desulfurization activity, a method of increasing the number of active sites by increasing the amount of active metal supported can be considered. However, even when a porous support mainly composed of alumina and having a high surface area is used, active metal is supported. There is a limit to the amount, and if it is excessively supported, the active metal aggregates and the activity is reduced. Furthermore, there is a technical limit that the active metal is excessively supported and the pores of the catalyst are blocked, so that sufficient activity cannot be exhibited, or the decrease in activity becomes significant.
By the way, in general, petroleum hydrocarbon fractions other than residual oil obtained by distillation of crude oil or heavy oil decomposition reaction contain nitrogen in addition to sulfur. Nitrogen is present as an organic nitrogen compound, and is said to contain, for example, amine, pyridine, pyrrole, indole, quinoline, carbazole, and derivatives thereof. Such nitrogen compounds are known to adsorb to the catalyst and inhibit the activity (see, for example, Non-Patent Document 3), and depending on the crude oil type and the refining process, hydrocarbons containing a large amount of nitrogen compounds are treated. In some cases, as long as the prior art is used, the presence of nitrogen compounds has been regarded as one of the major obstacles in promoting desulfurization.

Henrik Topsoe et al., “Industrial & Engineering Chemistry Fundamentals” (USA), American Chemical Society, 1986, Vol. 25, p. 25-36 Emmanuel Lecrenay, Shinya Sakanishi, Isao Mochida, “Catalysis Today” (Netherlands), Elsevier, 1997, Vol. 39, p. 13-20 Edward Furimsky, Franklin E. Massoth, “Catalysis Today” (Netherlands), Elsevier, 1999, Vol. 52, p. 381-495

  An object of the present invention is to provide a catalyst and a hydrodesulfurization method which have a very high desulfurization activity and can achieve a very high desulfurization depth of 10 ppm by mass or less. Furthermore, the present invention provides a catalyst that is not easily affected by inhibition of desulfurization reaction of nitrogen compounds.

  As a result of intensive studies on such problems, the inventors have completed the present invention. That is, the present invention relates to an inorganic porous carrier containing alumina and phosphorus, and at least one metal selected from Group 8A metals and Periodic Table Group 8A metals as active metals. Is contained in a molar ratio of [Group 8 metal oxide] / [Group 6A metal oxide] in the range of 0.105 to 0.265, and the Group 6A metal content is oxidized. The present invention relates to a hydrodesulfurization catalyst for petroleum hydrocarbons, characterized in that it is in the range of 20 to 30% by mass in terms of catalyst.

  The present invention also relates to a hydrodesulfurization method for petroleum hydrocarbons, characterized in that petroleum hydrocarbons are hydrodesulfurized using the hydrodesulfurization catalyst.

  The present invention is described in detail below.

  The catalyst in the present invention uses an inorganic porous material containing alumina and phosphorus as a carrier. The content of alumina is preferably 80% by mass or more, more preferably 85% by mass or more, and further preferably 90% by mass or more with respect to the support. Alumina is a porous carrier particularly suitable for providing a pore volume suitable for diffusing hydrocarbon molecules having a boiling point of 230 to 380 ° C., and is sufficient when the content of alumina is less than 80% by mass. It is difficult to obtain a large support pore volume.

  The content of phosphorus contained in the inorganic porous carrier is preferably 0.5 to 10% by mass, more preferably 1 to 9% by mass, more preferably 2 to 6% by mass in terms of oxide. More preferably, it is mass%. If the phosphorus content is less than 0.5% by mass in terms of oxide, sufficient desulfurization activity cannot be exhibited. On the other hand, if it exceeds 10% by mass, the acidity of the carrier is increased, and hydrocarbon decomposition occurs. There is a risk of a decrease in yield and a decrease in activity due to coke formation accompanying decomposition.

  The carrier preferably contains at least one selected from Si, Ti, Zr, Mg, Ca and B as a component other than alumina and phosphorus in the range of 1 to 10% by mass in terms of oxide. . The content is more preferably 1.2 to 9% by mass, and further preferably 1.5 to 8% by mass. As these elements, Si, Ti, Zr, and B are preferable, Si, Ti, and B are more preferable, and Si is particularly preferable. Moreover, these elements can also be used in combination. When these elements are used in combination, a combination of Si-Ti, Si-Zr, Si-B, and Ti-B is preferable, Si-Ti, Si-B, and Ti-B are more preferable, and Si-Ti Si-B is more preferable. Although the mechanism of the effect of these elements has not been elucidated, it forms a complex oxide state with alumina, works synergistically with the effect of the supported active metal, and the carbon and nitrogen atoms of sulfur and nitrogen compounds It is thought that it promotes the cleavage of the bond between or between the sulfur atoms, and the desulfurization activity and nitrogen resistance are improved. When the content of these elements is less than 1% by mass in terms of oxide, the desulfurization activity and nitrogen resistance are reduced. When the content exceeds 10% by mass, the acidity of the carrier becomes strong, and decomposition and the like. There are concerns about undesirable side reactions.

  The method for preparing alumina as the main component of the carrier is not particularly limited. For example, it can be obtained via an alumina intermediate obtained from a method of neutralizing or hydrolyzing aluminum salt and aluminate, or a method of hydrolyzing aluminum amalgam or aluminum alcoholate. Moreover, you may use a commercially available alumina intermediate body and boehmite powder.

  There is no particular limitation on the method for incorporating phosphorus into the carrier. Usually, a method in which phosphoric acid or an alkali salt of phosphoric acid is added during the preparation of alumina is preferably employed. For example, it may be added to an aluminum aqueous solution in advance and then an aluminum hydroxide gel containing phosphorus, may be added to a prepared aluminum hydroxide gel, or water or an acidic aqueous solution may be added to a commercially available alumina intermediate or boehmite powder. It may be added to the kneading step. It is preferable that phosphorus is already contained in the step of preparing the aluminum hydroxide gel. Phosphorus is present in the support in the form of an oxide.

  There is no particular limitation on the method of incorporating an element selected from Si, Ti, Zr, Mg, Ca and B into the support. For example, there is a method of adding oxides, hydroxides, nitrates, sulfates or other salt compounds of these elements in a solid or solution state at any stage of preparing alumina. Alternatively, only alumina may be once fired and then impregnated and supported in a solution state. Preferably, it is added at any stage before firing the alumina. These elements are present in the support in the form of oxides.

  In the present invention, as the active metal supported on the carrier, at least one metal selected from Group 8 metal of the periodic table and at least one metal selected from Group 6A metal of the periodic table are used. The Group 8 metal includes Co and Ni, and the Group 6A metal includes Mo and W. As the combination of the Group 8 metal and the Group 6A metal, Co—Mo, Ni—Mo, Co—W, Ni—W, Co—Ni—Mo, and Co—Ni—W are preferable, and Co—Mo or Ni— A combination of Mo is particularly preferred. The content of the Group 6A metal is preferably in the range of 20 to 30% by mass of the catalyst weight in terms of oxide, more preferably in the range of 21 to 26% by mass, and even more preferably 22 to 25% by mass. Range. When it is less than 20% by mass, there are few active sites and sufficient desulfurization activity and nitrogen resistance cannot be exhibited. When the amount is more than 30% by mass, metal agglomeration occurs, and the desulfurization activity may be lowered.

  The supporting ratio of the Group 8 metal to the Group 6A metal needs to be in the range of 0.105 to 0.265 in terms of a [Group 8 metal oxide] / [Group 6A metal oxide] molar ratio. is there. Preferably it is 0.110-0.260, More preferably, it is 0.115-0.250, More preferably, it is 0.140-0.245. When the molar ratio is less than 0.105, the cocatalyst effect of the Group 8 metal cannot be sufficiently exerted and the desulfurization activity is lowered. Further, when the molar ratio is larger than 0.265, sufficient hydrogenation activity cannot be exhibited, and the inhibitory effect on the activity by the nitrogen compound is increased, and the desulfurization activity and nitrogen resistance may be reduced. There is.

  The total content of the Group 8 metal and the Group 6A metal is preferably 22% by mass or more, more preferably 23% by mass or more, and further preferably 25% by mass or more based on the catalyst weight in terms of oxide. When the amount is less than 22% by mass, there is a concern that sufficient desulfurization activity cannot be exhibited because there are few active metals.

  Moreover, it is preferable that phosphorus is carried with the active metal as an active ingredient. The amount of phosphorus supported on the carrier is preferably in the range of 0.105 to 0.255, more preferably 0.120 to 0.005 in terms of a molar ratio of [phosphorus pentoxide] / [Group 6A metal oxide]. 240, most preferably 0.125 to 0.205. If the molar ratio is less than 0.105, the effect of phosphorus cannot be sufficiently exerted, and if it is greater than 0.255, the acidity of the catalyst becomes strong and the decomposition reaction or coke formation reaction may be promoted. is there.

  The method for supporting the group 8 metal and the group 6A metal, which are active metal components, on the carrier is not particularly limited, and a known method applied when producing an ordinary hydrodesulfurization catalyst can be used. For example, a method of impregnating a support with a solution containing a salt of an active metal is preferably employed. Further, an equilibrium adsorption method, a pore-filling method, an incident-wetness method, and the like are also preferably employed. For example, the pore-filling method is a method in which the pore volume of the support is measured in advance and impregnated with the same volume of the metal salt solution, but the impregnation method is not particularly limited, and the amount of metal supported Depending on the physical properties of the carrier and the carrier, it can be impregnated by an appropriate method.

  The method for supporting phosphorus on the carrier is not particularly limited, and it may be supported in the aqueous solution containing the Group 8 metal and the Group 6A metal described above, or sequentially before or after the metal is supported. You may carry. Further, the method described above such as the equilibrium adsorption method is preferably employed as the method for supporting.

  In the hydrodesulfurization catalyst of the present invention, the average pore radius of the catalyst determined by the BET method using nitrogen is preferably in the range of 30 to 45 mm, more preferably in the range of 32 to 40 mm. If it is less than 30 mm, the reaction molecules do not diffuse sufficiently in the pores and the activity becomes low, which is not preferable. On the other hand, if it is larger than 45 mm, the surface area of the catalyst becomes small and sufficient desulfurization activity cannot be exhibited, which is not preferable. The pore volume occupied by the pore radius of 30 mm or less of the catalyst is preferably in the range of 13 to 33% of the total pore volume, more preferably in the range of 15 to 30%, and further preferably in the range of 25 to 30. % Range. The ease of diffusion of reaction molecules in pores having a pore radius of 30 mm or less is inferior to pores larger than this, but the contribution to the desulfurization reaction cannot be ignored. If it is less than 13%, the effective catalyst surface area decreases. There is a concern that the activity will decrease. On the other hand, if it is larger than 33%, there is a concern that the activity may decrease due to the influence of diffusion. The pore volume occupied by the pore radius of 45 mm or more of the catalyst is preferably in the range of 5 to 20%, more preferably in the range of 8 to 15%, and further preferably in the range of 12 to 15%. . The pores in this region are considered to be important pores that influence the degree of arrival of the reactive molecules at the reaction active point, and if it is less than 5%, there is a concern that the diffusion of the reactive molecules is not sufficient and the activity is lowered. is there. However, when the amount is more than 20%, the surface area of the catalyst itself is decreased, and there is a concern that the activity is lowered.

  Petroleum hydrocarbons used in the present invention include a crude oil atmospheric distillation apparatus, a vacuum distillation apparatus, thermal cracking, catalytic cracking, hydrotreating and the like containing a fraction having a boiling point range of 140 to 550 ° C. of 80% by volume or more. And a fraction produced in the oil refining process. Furthermore, a petroleum hydrocarbon fraction containing 70 vol% or more of a boiling point range of 240 to 380 ° C. which is a light oil fraction, or a 70 wt% or more fraction of a boiling point range of 140 to 240 ° C. which is a kerosene fraction. It is preferably a petroleum hydrocarbon fraction containing, and even more preferably a petroleum hydrocarbon fraction containing 70 vol% or more of a fraction having a boiling range of 240 to 380 ° C. that is a light oil fraction. Petroleum hydrocarbons can include fractions obtained by distillation of crude oil, as well as fractions obtained by thermal cracking and catalytic cracking reactions. Preferably, 50% by volume or more of gas oil fractions are straight-run. Light oil, more preferably 70% by volume. Pyrolysis gas oil and catalytic cracking gas oil contain more olefins and aromatics than straight-run gas oil, and when the proportion of these fractions increases, the reactivity tends to deteriorate and the hue of the product oil tends to deteriorate. . Further, 50% by volume or more in the kerosene fraction is preferably straight-run kerosene for the same reason, more preferably 70% by volume.

  The hydrodesulfurization catalyst of the present invention is suitable for desulfurization from sulfur molecules having a structure such as thiophenes, benzothiophenes, and dibenzothiophenes, and in particular, 80% by volume of a gas oil fraction having a boiling point of 240 to 380 ° C. Although it is suitable for the petroleum-based hydrocarbons contained above, it can also be used favorably for petroleum-based hydrocarbons containing 80% by volume or more of a fraction having a boiling range of 140 to 240 ° C. as a kerosene fraction. In addition, about the value of the distillation property shown here, it is a value measured based on the method as described in JISK2254 "petroleum product-evaporation test method".

  In the present invention, the sulfur concentration can be reduced to 10 mass ppm or less, preferably 7 mass ppm or less by hydrodesulfurizing such a petroleum hydrocarbon using the specific catalyst of the present invention. .

  Among petroleum-based hydrocarbons in the present invention, for petroleum-based hydrocarbons containing 80 vol% or more of a boiling point of 240 to 380 ° C., which is a light oil fraction, in the case where nitrogen content is 100 ppm or more, The effect of nitrogen resistance can be further exerted, and the effect becomes remarkable when it is preferably 120 mass ppm or more, more preferably 150 mass ppm or more, and further preferably 200 mass ppm or more.

  In addition, petroleum petroleum hydrocarbons containing 80 vol% or more of a boiling point range of 140 to 240 ° C. as a kerosene fraction exhibit more sulfur resistance when nitrogen content is 4 ppm by mass or more. Preferably, the effect becomes remarkable at 6 mass ppm or more, more preferably 8 mass ppm or more, and further preferably 10 mass ppm or more.

  In the present invention, the sulfur content (sulfur content) is based on the total amount of petroleum hydrocarbons measured according to the method described in JIS K 2541 “Sulfur Content Test Method” or ASTM-D5453. It means the mass content of sulfur. The nitrogen content is the mass content of nitrogen based on the total amount of petroleum hydrocarbons measured in accordance with JIS K2609 “Method for testing nitrogen content” or ASTM-D4629, D-5762. Means.

  The kerosene fraction is used by mixing a predetermined amount with the diesel oil fraction in order to adjust the properties as diesel fuel such as fluidity in cold regions. For this reason, in the present invention, preferably, such a kerosene fraction is hydrodesulfurized using a specific catalyst so as to reduce the sulfur concentration to 10 ppm by mass or less. Can be demonstrated. Furthermore, when used as a heating appliance fuel such as a stove, the use of kerosene having a sulfur content concentration of 10 mass ppm or less can be expected to significantly reduce the generation of harmful sulfur oxides.

In the present invention, hydrodesulfurization treatment of petroleum hydrocarbons is performed using the above-described catalyst.
As hydrodesulfurization reaction conditions in the present invention, LHSV is preferably 0.3~5.0h ^-1, more preferably at 0.35~4.0h ^-1, more preferably 0.4～3.5H ^-1 is there. When LHSV is lower than 0.3 h ⁻¹ , the volume of the reaction tower for obtaining a certain oil flow rate becomes extremely large, and therefore a huge capital investment such as installation of a reaction tower may be required. On the other hand, when LHSV is larger than 5.0 h ⁻¹ , the contact time between the catalyst and the oil is shortened, so that the desulfurization reaction does not proceed sufficiently and the desulfurization effect may not be exhibited.

  The hydrogen partial pressure is preferably 3 to 8 MPa, more preferably 3.5 to 7 MPa, and still more preferably 4 to 6.5 MPa. When the hydrogen partial pressure is lower than 3 MPa, there is a concern that the effect of desulfurization cannot be exhibited. When the hydrogen partial pressure is higher than 8 MPa, there is a possibility that a large capital investment such as a review of the compressor and the equipment strength may be required. .

  The reaction temperature is preferably 280 to 380 ° C. When the reaction temperature is lower than 280 ° C., a sufficient desulfurization reaction rate or aromatic hydrogenation reaction rate may not be obtained. Moreover, when higher than 380 degreeC, since there exists a possibility of causing the fall of the target fraction yield by the deterioration of the hue of a product oil, or decomposition | disassembly, it is unpreferable.

  The hydrogen / oil ratio is preferably 50 to 500 NL / L. The hydrogen / oil ratio indicates the ratio of the hydrogen gas flow rate to the feed oil flow rate. The higher the hydrogen / oil ratio is, the more hydrogen supply into the system becomes, and the faster the substances that poison the catalytic active sites such as hydrogen sulfide. Since it can be removed out of the system, the reactivity tends to be improved. However, when it exceeds 500 NL / L, the reactivity is improved, but the effect is gradually reduced. Moreover, there is a risk that a large capital investment such as a compressor may be required. On the other hand, when it is less than 50 NL / L, the reactivity is lowered, and the desulfurization / dearomatic reaction may not be sufficiently progressed.

  In an actual commercial apparatus, the catalyst is pre-sulfided after the reaction tower is filled with the catalyst. The conditions for the preliminary sulfidation are not particularly limited, but in general, the catalyst is packed in an active metal such as cobalt, nickel, and molybdenum into the reaction tower, and sulfur or dimethyl contained in the petroleum hydrocarbon fraction. A method is used in which a petroleum hydrocarbon fraction alone or a fraction to which a sulfurizing agent is added is passed through a sulfurizing agent such as disulfide and the active metal is brought into a sulfide state by giving a temperature of 200 ° C. or higher. .

  Although the reaction mode of the reaction tower in hydrodesulfurization is not particularly limited, it can usually be selected from processes such as a fixed bed and a moving bed, but a fixed bed is preferred. Moreover, about the distribution | circulation method of raw material oil, any form of a down flow and an up flow can be employ | adopted.

  The ultra-low sulfur / low aromatic light oil produced when the hydrodesulfurization treatment of the present invention is performed on the light oil fraction may be used alone as diesel light oil. Components such as a base material can be mixed and used as diesel light oil. Moreover, the kerosene fraction produced | generated when the hydrodesulfurization process of this invention is performed about a kerosene fraction can be used as diesel light oil.

  The catalyst of the present invention has a very high desulfurization activity and can achieve a very high desulfurization depth of 10 ppm by mass or less. In addition, nitrogen compounds that are desulfurization reaction inhibitors also have high nitrogen resistance.

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

Example 1
18.0 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 the mixture was placed in a container kept at 65 ° C. A solution in which 6.0 g of phosphoric acid (concentration 85%) is added to 3000 g of an aluminum sulfate aqueous solution having a concentration of 2.5% by mass is prepared in a separate container kept at 65 ° C., and the aqueous solution containing sodium aluminate is added dropwise. did. 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 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 80 ° C. for 24 hours. The slurry was put into a kneading apparatus, 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 while degassing with a rotary evaporator, 17.3 g of molybdenum trioxide, 13.2 g of cobalt nitrate (II) hexahydrate, 3.9 g of phosphoric acid (concentration 85%) 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 physical properties of the prepared catalyst A are summarized in Table 1.

(Example 2)
50 g of the shaped carrier obtained in Example 1 was placed in an eggplant-shaped flask, and 17.0 g of molybdenum trioxide, 13.2 g of nickel (II) nitrate hexahydrate, phosphoric acid (concentration 85%) while degassing with a rotary evaporator. ) An impregnation solution containing 3.9 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 physical properties of the prepared catalyst B are summarized in Table 1.

Example 3
10.0 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. A solution obtained by adding 4.0 g of boric acid to 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 and phosphoric acid (concentration 85%) ) 50 ml of an aqueous solution containing 6.0 g was added dropwise at the same time. 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 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 80 ° C. for 24 hours. The slurry was put into a kneading apparatus, 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 while degassing with a rotary evaporator, 17.3 g of molybdenum trioxide, 13.2 g of cobalt nitrate (II) hexahydrate, 3.9 g of phosphoric acid (concentration 85%) 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 C. The physical properties of the prepared catalyst C are summarized in Table 1.

Example 4
The average catalyst layer temperature is 300 using straight-run gas oil (sulfur content 3% by mass) in which 20 ml of catalyst A is packed in a reaction tube having an inner diameter of 15 mm and dimethyl disulfide is added so that the sulfur concentration is 3% by mass. The catalyst was presulfided for 4 hours under the conditions of ° C., hydrogen partial pressure of 5 MPa, LHSV1 h ⁻¹ , hydrogen / oil ratio of 200 NL / L. After preliminary sulfidation, a raw oil A (10% distillation point 210 ° C., 90% distillation point 342 ° C., sulfur content 1.00% by mass, nitrogen content 90% by mass), which is a Middle Eastern straight-run gas oil, is reacted at a reaction temperature 340 Hydrodesulfurization was performed by passing oil under the conditions of ° C., pressure 5.0 MPa, LHSV ¹ h ⁻¹ , hydrogen / oil ratio 200 NL / L. Thereafter, feed oil B (10% distillation point 232 ° C., 90% distillation point 349 ° C., sulfur content 1.20 mass%, nitrogen content 210 mass ppm) was passed through to perform hydrodesulfurization, A comparison was made between the treated oil and the sulfur content of the product oil.
The same operation was performed for Catalyst B and Catalyst C, respectively. These results are summarized in Table 2.

(Comparative Example 1)
50 g of the molded carrier obtained in Example 1 was placed in an eggplant-shaped flask and 16.1 g of molybdenum trioxide, 19.0 g of cobalt (II) nitrate hexahydrate, phosphoric acid (concentration 85%) while degassing with a rotary evaporator. An impregnation solution containing 1.9 g and malic acid 5.0 g 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 D. The physical properties of the prepared catalyst D are summarized in Table 1.

(Comparative Example 2)
10.0 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. An aqueous aluminum sulfate 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 was dropped. 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 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 80 ° C. for 24 hours. The slurry was put into a kneading apparatus, 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 placed in an eggplant-shaped flask and degassed with a rotary evaporator. 16.1 g of molybdenum trioxide, 19.0 g of cobalt nitrate (II) hexahydrate, 1.9 g of phosphoric acid (concentration 85%) And an impregnation solution containing 5.0 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 E. The physical properties of the prepared catalyst E are summarized in Table 1.

(Comparative Example 3)
For Catalyst D and Catalyst E, the same operations as in Example 4 were performed. These results are shown in Table 2.

Claims (11)

  At least one metal selected from Group 8A metal of the periodic table and at least one metal selected from Group 6A metal of the periodic table as the active metal is added to the inorganic porous carrier containing alumina and phosphorus [8th. Group metal oxide] / [Group 6A metal oxide] in a molar ratio of 0.105 to 0.265, and the content of Group 6A metal in the catalyst weight in terms of oxide A hydrodesulfurization catalyst for petroleum hydrocarbons, characterized by being in the range of 20 to 30% by mass.   The inorganic porous carrier further contains at least one selected from Si, Ti, Zr, Mg, Ca and B in the range of 1 to 10% by mass in terms of oxide. Hydrodesulfurization catalyst.   The Group 8 metal of the periodic table is cobalt and / or nickel, the Group 6A metal is molybdenum and / or tungsten, and the total content of these metals is 22% by mass with respect to the catalyst weight in terms of oxide. It is the above, The hydrodesulfurization catalyst of Claim 1 or 2 characterized by the above-mentioned.   4. Phosphorus is supported on the inorganic porous carrier in a molar ratio of [phosphorus pentoxide] / [Group 6A metal oxide] in the range of 0.105 to 0.255. The hydrodesulfurization catalyst according to any one of the above.   The average pore radius of the catalyst determined by the BET method using nitrogen is in the range of 30 to 45 mm, the pore volume occupied by the pore radius of 30 mm or less is 13 to 33% of the total pore volume, and the pore radius is 45 mm. The hydrodesulfurization catalyst according to any one of claims 1 to 4, wherein the pore volume occupied is 5 to 20%.   A hydrodesulfurization method for petroleum hydrocarbons, comprising hydrodesulfurizing petroleum hydrocarbons using the hydrodesulfurization catalyst according to any one of claims 1 to 5.   The hydrodesulfurization method according to claim 6, wherein the petroleum hydrocarbon is a petroleum hydrocarbon containing 80 vol% or more of a fraction having a boiling point of 230 to 380 ° C.   The hydrodesulfurization method according to claim 6 or 7, wherein the product oil obtained by the hydrodesulfurization treatment has a sulfur content of 10 ppm by mass or less and a nitrogen content of 3 ppm by mass or less.   The hydrodesulfurization method according to any one of claims 6 to 8, wherein the total aromatic content of the product oil obtained by the hydrodesulfurization treatment is 18% by volume or less.   The hydrodesulfurization method according to any one of claims 6 to 9, wherein the hue of the product oil obtained by the hydrodesulfurization treatment is 1.0 or less in terms of ASTM color. Hydrodesulfurization treatment of petroleum hydrocarbons under conditions of LHSV 0.3 to 5.0 h ⁻¹ , hydrogen pressure 3 to 8 MPa, reaction temperature 280 to 380 ° C., hydrogen / oil ratio 100 to 500 NL / L The hydrodesulfurization method according to claim 6, wherein the hydrodesulfurization method is performed.