Hydrocarbon oil hydrotreating catalyst, method for producing hydrocarbon oil hydrotreating catalyst, and method for hydrotreating hydrocarbon oil

Abstract

The present invention pertains to a hydrogenation treatment catalyst which is for a hydrocarbon oil and in which at least one metal selected from among metals belonging to Group 6 in the periodic table and at least one metal selected from among metals belonging to Group 9 and Group 10 in the periodic table are carried on a zinc and titanium-containing alumina carrier containing zinc and titanium.

Description

[Technical Field]

[0001] The present invention relates to a catalyst for hydrotreating hydrocarbon oils, a method for producing a catalyst for hydrotreating hydrocarbon oils, and a method for hydrotreating hydrocarbon oils. This application claims priority based on US63 / 047,921 filed in the United States on July 3, 2020, and Japanese Patent Application No. 2020-130680 filed in Japan on July 31, 2020, the contents of which are incorporated herein by reference. [Background technology]

[0002] Due to the decline in demand for heavy oil, there is a demand for technology that can efficiently convert atmospheric distillation residue oil, which is the main heavy oil base material obtained by processing crude oil in an atmospheric distillation unit, and vacuum distillation residue oil, which is obtained by processing the atmospheric distillation residue oil in a vacuum distillation unit, into light oil with high added value.

[0003] A known technology for converting heavy oil base materials into light oil is a process in which atmospheric distillation residue or a mixture of atmospheric distillation residue and vacuum distillation residue is treated in a fluid catalytic cracking unit to produce middle distillates such as gasoline, kerosene, and diesel.

[0004] The sulfur content of the feedstock oil processed in the fluid catalytic cracking unit must be reduced to a certain level in order to meet the specifications for the target middle distillate and to protect the fluid catalytic cracking catalyst. Therefore, the atmospheric distillation residue oil and the mixed oil are hydrotreated using a hydrotreating catalyst before being processed in the fluid catalytic cracking unit.

[0005] Hydrotreating difficult-to-desulfurize atmospheric distillation residue or vacuum distillation residue requires severe processing conditions such as high temperature and high pressure, which causes the problem of easily degrading the hydrotreating catalyst and shortening its lifespan.

[0006] One of the known causes of degradation of hydrotreating catalysts is coke degradation due to carbon (coke) generated during cracking reactions. Coke accumulates on the hydrotreating catalyst, covering the active sites and / or blocking the pores of the hydrotreating catalyst, resulting in a decrease in catalytic activity. In particular, at the start of the reaction, there are many active sites (acid sites) with high cracking activity on the surface of the hydrotreating catalyst, which results in the generation of a large amount of coke and a significant decrease in catalytic activity.

[0007] When the catalytic activity of a hydrotreating catalyst decreases, it is necessary to increase the reaction temperature to maintain a certain level of hydrotreating performance. However, hydrotreating devices have a maximum operating temperature set according to their materials, structure, and the capacity of their peripheral equipment, and are constrained to operate at or below this maximum operating temperature. Therefore, when the maximum operating temperature is reached, the hydrotreating catalyst must be replaced with a new one, and the frequency of replacement of this hydrotreating catalyst essentially determines the life of the hydrotreating catalyst.

[0008] In view of this, there is a demand for a hydrotreating catalyst that is resistant to decline in activity and has a long life in the hydrotreating of difficult-to-desulfurize atmospheric distillation residue and vacuum distillation residue. Patent Document 1 discloses that coke deterioration of a hydrotreating catalyst can be suppressed by adding zinc oxide to the hydrotreating catalyst. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] International Publication No. 2015 / 046345 Summary of the Invention [Problem to be solved by the invention]

[0010] In recent years, there has been a demand for increasing the throughput of atmospheric distillation residue and vacuum distillation residue in order to convert more heavy oil base stocks into light oils. Increasing the throughput of atmospheric distillation residue and vacuum distillation residue requires more stringent processing conditions, which leads to more severe degradation of hydrotreating catalysts. Therefore, there is a demand for hydrotreating catalysts that are less susceptible to degradation in activity, but the catalyst life of the hydrotreating catalyst described in Patent Document 1 is insufficient.

[0011] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a hydrocarbon oil hydrotreating catalyst that is resistant to a decrease in hydrocarbon oil hydrogenation activity and has a longer life than conventional catalysts, a method for producing the hydrocarbon oil hydrotreating catalyst, and a hydrocarbon oil hydrotreating method that uses the hydrocarbon oil hydrotreating catalyst. [Means for solving the problem]

[0012] In order to solve the above problems, the present invention has the following aspects. [1-1] A catalyst for hydrotreating hydrocarbon oils, comprising a zinc-titanium-containing alumina carrier containing zinc and titanium, and carrying thereon at least one metal selected from Group 6 metals of the periodic table and at least one metal selected from Group 9 and Group 10 metals of the periodic table, wherein the zinc content is 0.8 to 10 mass% on an elemental basis based on the catalyst, the titanium content is 0.03 to 10 mass% on an elemental basis based on the catalyst, the at least one metal selected from Group 6 metals of the periodic table is 5 to 16 mass% on an elemental basis based on the catalyst, and the at least one metal selected from Group 9 and Group 10 metals of the periodic table is 1 to 5 mass% on an elemental basis based on the catalyst. [1] A hydrocarbon oil hydrotreating catalyst comprising a zinc-titanium-containing alumina carrier containing zinc and titanium, and carrying thereon at least one metal selected from Group 6 metals of the periodic table and at least one metal selected from Group 9 and Group 10 metals of the periodic table, wherein the zinc content is 0.8 to 10 mass% on an elemental basis based on the catalyst, the titanium content is 0.03 to 10 mass% on an elemental basis based on the catalyst, the at least one metal selected from Group 6 metals of the periodic table is 5 to 16 mass% on an elemental basis based on the catalyst, and the at least one metal selected from Group 9 and Group 10 metals is 1 to 5 mass% on an elemental basis based on the catalyst, and when the hydrotreating catalyst is analyzed using a transmission electron microscope with energy dispersive X-ray analysis, the average particle size of titanium-derived particles observed is 0.3 to 10 nm. [2] The catalyst for hydrotreating hydrocarbon oils according to [1-1] or [1], wherein the support is a zinc-titanium-phosphorus-containing alumina support further containing phosphorus, and the phosphorus content is 0.04 to 2 mass% in elemental terms based on the catalyst. [3] The hydrotreating catalyst for hydrocarbon oils according to [1-1], [1], or [2], wherein the average particle size of zinc-derived particles observed when the hydrotreating catalyst is analyzed using a transmission electron microscope with energy dispersive X-ray analysis is 0.3 to 10 nm. [4-1] A method for producing a catalyst for hydrotreating hydrocarbon oils, comprising supporting, on a zinc-titanium-containing alumina support containing 1 to 14 mass% zinc, calculated as an element, and 0.1 to 13 mass% titanium, calculated as an element, based on the support, at least one metal selected from Group 6 metals of the periodic table in an amount of 5 to 16 mass% elemental based on the catalyst, and at least one metal selected from Group 9 and Group 10 metals of the periodic table in an amount of 1 to 5 mass% elemental based on the catalyst. [4] A method for producing a hydrocarbon oil hydrotreating catalyst, comprising supporting at least one metal selected from Group 6 metals of the periodic table in an amount of 5 to 16 mass %, in elemental terms, based on the catalyst, and at least one metal selected from Group 9 and Group 10 metals of the periodic table in an amount of 1 to 5 mass %, in elemental terms, based on the catalyst, on a zinc-titanium-containing alumina support containing 1 to 14 mass % zinc, in elemental terms, based on the support, and 0.1 to 13 mass % titanium, in elemental terms, based on the support, wherein the hydrotreating catalyst is analyzed using a transmission electron microscope with energy dispersive X-ray analysis, and the average particle size of titanium-derived particles observed is 0.3 to 10 nm. [5] The method for producing a hydrocarbon oil hydrotreating catalyst according to [4-1] or [4], wherein the support is a zinc-titanium-phosphorus-containing alumina support further containing 0.04 to 3 mass % of phosphorus in elemental terms based on the support. [6] The method for producing a hydrotreating catalyst according to [4-1], [4], or [5], wherein the average particle size of zinc-derived particles observed when the hydrotreating catalyst is analyzed using a transmission electron microscope with energy dispersive X-ray analysis is 0.3 to 10 nm. [7] Hydrogen partial pressure: 3-20 MPa, reaction temperature: 280-450°C, liquid hourly space velocity: 0.01-5 hr -1 [1-1], [1] to [3], and a method for producing hydrogenated hydrocarbon oil, comprising contacting a hydrocarbon oil with the catalyst for hydrotreating a hydrocarbon oil according to any one of [1] to [3] and hydrotreating the hydrocarbon oil. [8] Hydrogen partial pressure: 3-20 MPa, reaction temperature: 280-450°C, liquid hourly space velocity: 0.01-5 h -1 [1-1], [1] to [3], and a method for hydrotreating a hydrocarbon oil, comprising contacting the hydrocarbon oil with the catalyst for hydrotreating a hydrocarbon oil according to any one of [1-1] and [1] to [3]. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a hydrocarbon oil hydrotreating catalyst that is less likely to decrease in hydrocarbon oil hydrogenation activity and has a longer life than conventional catalysts. It is also possible to provide a method for producing the hydrocarbon oil hydrotreating catalyst and a hydrocarbon oil hydrotreating method that uses the hydrocarbon oil hydrotreating catalyst. DETAILED DESCRIPTION OF THE INVENTION

[0014] The following describes in detail the embodiments of the present invention. However, the following description is an example of an embodiment of the present invention, and the present invention is not limited to these contents and can be modified and implemented within the scope of its gist.

[0015] <Hydrocarbon oil hydrotreating catalyst> The hydrocarbon oil hydrotreating catalyst of this embodiment (hereinafter also simply referred to as "hydrotreating catalyst") contains alumina, zinc, titanium, at least one metal selected from Group 6 metals of the periodic table, and at least one metal selected from Group 9 and Group 10 metals of the periodic table.

[0016] The hydrotreating catalyst is a hydrocarbon oil hydrotreating catalyst comprising a zinc-titanium-containing alumina carrier containing zinc and titanium, and carrying at least one metal selected from Group 6 metals of the periodic table and at least one metal selected from Groups 9 and 10 metals of the periodic table. The zinc content is 0.8 to 10 mass% in elemental terms based on the catalyst, the titanium content is 0.03 to 10 mass% in elemental terms based on the catalyst, the at least one metal selected from Group 6 metals of the periodic table is 5 to 16 mass% in elemental terms based on the catalyst, and the at least one metal selected from Groups 9 and 10 metals of the periodic table is 1 to 5 mass% in elemental terms based on the catalyst. When the hydrotreating catalyst is analyzed using a transmission electron microscope with energy dispersive X-ray analysis, the average particle size of titanium-derived particles observed is preferably 0.3 to 10 nm.

[0017] In this specification, "Group 6 metals of the periodic table" (hereinafter sometimes referred to as "Group 6 metals") means Group 6 metals in the long-form periodic table, and "Group 9 and Group 10 metals of the periodic table" (hereinafter sometimes referred to as "Group 9 and Group 10 metals") means Group 9 and Group 10 metals in the long-form periodic table. Group 6 metals and Group 9 and 10 metals are also collectively referred to as "hydrogenation active components." In this specification, the term "content ratio in elemental terms on a catalyst basis" refers to the ratio of the mass of a specific element to the total mass of the hydrotreating catalyst.

[0018] As the alumina in the hydrotreating catalyst, various aluminas can be used, such as α-alumina, β-alumina, γ-alumina, δ-alumina, etc. Alumina that is porous and has a high specific surface area is preferred, and among these, γ-alumina is more preferred. The purity of the alumina is preferably 98% by mass or more, more preferably 99% by mass or more. Impurities in the alumina include SO4 2- , Cl - , Fe2O3, Na2O, etc. It is preferable that the amount of these impurities is as small as possible. The total content of impurities relative to the total mass of alumina is preferably 2 mass% or less, more preferably 1 mass% or less. In terms of each component, the total mass of alumina is preferably 0.01 mass% or less, and more preferably 0.1 mass% or less. 2- is 1.5 mass% or less, Cl - , Fe2O3, and Na2O are each preferably 0.1 mass % or less.

[0019] The alumina in the hydrotreating catalyst may be a composite alumina obtained by compositely combining at least one oxide selected from zeolite, silica, and zirconia. Composite alumina refers to a mixture of alumina and the oxide, or a composite oxide of alumina and the oxide. The alumina content relative to the total mass of the composite alumina is preferably 92 to 99.9 mass%, more preferably 95 to 98 mass%. The combined content of at least one oxide selected from zeolite, silica, and zirconia relative to the total mass of the composite alumina is preferably 0.1 to 8 mass%, more preferably 2 to 5 mass%. The zeolite, silica, and zirconia used as the composite components may be those generally used as carrier components for this type of catalyst.

[0020] The content of alumina (including composite alumina) in the hydrotreating catalyst is preferably 55 to 90 mass%, more preferably 65 to 80 mass%, and even more preferably 65 to 75 mass%, based on the catalyst. The content of alumina in the hydrotreating catalyst can be determined by calculating the difference between the total mass of the hydrotreating catalyst and the oxide-equivalent mass of each component (zinc, titanium, phosphorus, boron, Group 6 metal, and Group 9 and Group 10 metal) in the hydrotreating catalyst. The oxide-equivalent mass of each component can be determined by measuring the elemental mass of each component in the hydrotreating catalyst using the measurement method described below, and converting zinc to ZnO, titanium to TiO, phosphorus to P, boron to B, O, the Group 6 metal to a hexavalent oxide (MoO when the Group 6 metal is Mo), and the Group 9 and Group 10 metal to a divalent oxide (NiO when the Group 10 metal is Ni).

[0021] The form of zinc in the hydrotreating catalyst may be elemental zinc or a zinc compound. The hydrotreating catalyst may contain either elemental zinc or a zinc compound, or both. Examples of zinc compounds in the hydrotreating catalyst include zinc oxide, zinc nitrate, zinc sulfate, zinc carbonate, zinc phosphate, zinc aluminate, zinc titanate, and zinc molybdate, with zinc oxide and zinc aluminate being preferred. In addition to the above compounds, examples of zinc compounds in the hydrotreating catalyst include composite oxides and composite sulfides of zinc and at least one metal selected from the group consisting of titanium, phosphorus, boron, Group 6 metals, and Group 9 and Group 10 metals contained in the hydrotreating catalyst. The zinc compound in the hydrotreating catalyst may be of one type or two or more types.

[0022] The zinc content in the hydrotreating catalyst is 0.8 to 10 mass%, preferably 2 to 5 mass%, and more preferably 2.5 to 4 mass%, calculated as the element based on the catalyst. When the zinc content is equal to or greater than the lower limit of the above range, the neutralization effect of acid sites on the surface of the hydrotreating catalyst, which serve as active sites for coke formation, is improved, thereby suppressing coke formation. Furthermore, hydrogen molecules dissociate on the zinc surface to generate active hydrogen species, thereby improving the hydrogenation activity of the hydrotreating active component for coke and coke precursors. When the zinc content is equal to or less than the upper limit of the above range, the pore volume and specific surface area of ​​the hydrotreating catalyst are less likely to decrease, the Group 6 metal is sufficiently dispersed, and the sulfidity of the Group 9 and Group 10 metals is less likely to decrease. In this specification, the content ratio of the zinc and other elements in the hydrotreating catalyst and the support can be measured by inductively coupled plasma atomic emission spectrometry.

[0023] The average particle size of zinc-derived particles observed when the hydrotreating catalyst is analyzed with a transmission electron microscope using energy dispersive X-ray analysis (hereinafter also referred to as "TEM-EDS") is preferably 0.3 to 10 nm, more preferably 0.3 to 5 nm, and even more preferably 0.3 to 2 nm. When the average particle size of zinc-derived particles is within this range, a sufficient number of acid sites can be neutralized and a sufficient amount of active hydrogen species can be generated without causing a significant decrease in the pore volume or specific surface area of ​​the hydrotreating catalyst. In this specification, "particles derived from elemental zinc" refers to particles containing elemental zinc as a main component, as confirmed by a transmission electron microscope equipped with an energy dispersive X-ray spectrometer (hereinafter also referred to as "TEM-EDS"). Hereinafter, "particles derived from elemental titanium" and "particles derived from elemental phosphorus" similarly refer to particles containing elemental titanium and elemental phosphorus as main components, respectively, as confirmed by TEM-EDS. The measurement conditions for TEM-EDS can be those described in the Examples below. Particles containing zinc as the main component can be identified by the energy level (keV) of characteristic X-rays emitted from the sample: 8.630. Particles containing titanium as the main component can be identified by the energy level (keV) of 4.508 of the characteristic X-rays emitted from the sample. Particles containing phosphorus as the main component can be identified by the energy level (keV) of 2.013 of the characteristic X-rays emitted from the sample. The particle size of particles derived from elemental zinc in a hydrotreating catalyst means the maximum distance between two parallel lines sandwiching a planar image of particles derived from elemental zinc observed by TEM-EDS. The average particle size of particles derived from elemental zinc in a hydrotreating catalyst means the average particle size of 10 randomly selected particles derived from elemental zinc.

[0024] The shape of the particles derived from elemental zinc in the hydrotreating catalyst is not particularly limited, but is preferably approximately circular. In this specification, the particle shape is said to be approximately circular when the maximum distance (L max ) to the minimum distance (L min ) ratio is 0.8 to 1.

[0025] The form of titanium in the hydrotreating catalyst may be titanium alone or a titanium compound. The hydrotreating catalyst may contain either titanium alone or a titanium compound, or both. Examples of titanium compounds in the hydrotreating catalyst include titanium oxide, aluminum titanate, zinc titanate, and nickel titanate, with titanium oxide, zinc titanate, and nickel titanate being preferred. In addition to the above compounds, examples of titanium compounds in the hydrotreating catalyst include composite oxides and composite sulfides of titanium and at least one metal selected from the group consisting of zinc, phosphorus, boron, Group 6 metals, and Group 9 and Group 10 metals contained in the hydrotreating catalyst. The hydrotreating catalyst may contain one type of titanium compound or two or more types of titanium compounds.

[0026] The titanium content in the hydrotreating catalyst is 0.03 to 10 mass%, preferably 2 to 8 mass%, and more preferably 4 to 7.5 mass%, calculated as the element based on the catalyst. When the titanium content is equal to or greater than the lower limit of the above range, the interaction between the hydrogenation active component and alumina is weakened, enhancing the activity of the hydrogenation active component. It also enhances the efficiency with which active hydrogen species generated by zinc migrate across the catalyst surface to the hydrogenation active component. When the titanium content is equal to or less than the upper limit of the above range, the dispersibility of titanium is improved, and the particle size of particles derived from titanium observed when the hydrotreating catalyst is analyzed by TEM-EDS is below a certain size, making it easier to achieve the above effects.

[0027] The average particle size of the particles derived from titanium element observed when the hydrotreating catalyst is analyzed by TEM-EDS is preferably 0.3 to 10 nm, more preferably 0.3 to 5 nm, and even more preferably 0.3 to 2 nm. When the average particle size of the particles derived from titanium element is within this range, the above-mentioned effects can be easily obtained without causing a significant decrease in the pore volume or specific surface area of ​​the hydrotreating catalyst. The particle size of titanium-derived particles in a hydrotreating catalyst refers to the maximum distance between two parallel lines sandwiching a planar image of the titanium-derived particles observed by TEM-EDS. The average particle size of titanium-derived particles in a hydrotreating catalyst refers to the average particle size of 10 randomly selected titanium-derived particles. The shape of the titanium-derived particles in a hydrotreating catalyst is not particularly limited, but is preferably approximately circular.

[0028] The molar ratio of titanium to zinc (titanium element / zinc element) in the hydrotreating catalyst is preferably 0.1 to 12, more preferably 0.4 to 8, and even more preferably 2 to 4. When the molar ratio is within the above range, active hydrogen species generated by zinc can be efficiently transferred to the catalyst surface.

[0029] The ratio of the average particle size of particles derived from titanium to the average particle size of particles derived from zinc in the hydrotreating catalyst (average particle size of particles derived from titanium / average particle size of particles derived from zinc) is preferably 0.1 to 5, more preferably 0.4 to 3, and even more preferably 0.7 to 1. When the average particle size ratio is within the above range, activity reduction due to sintering of the particles derived from zinc and titanium is less likely to occur, and reduction in the transfer efficiency of active hydrogen species can be suppressed.

[0030] Examples of Group 6 metals include molybdenum, tungsten, and chromium, and among these, molybdenum is preferred because of its high hydrogenation activity per unit mass. The form of the Group 6 metal in the hydrotreating catalyst may be a simple Group 6 metal or a Group 6 metal compound. The hydrotreating catalyst may contain either a simple Group 6 metal or a Group 6 metal compound, or both. The Group 6 metal compound in the hydrotreating catalyst is preferably a molybdenum compound, and examples thereof include molybdenum trioxide, molybdophosphoric acid, ammonium molybdate, molybdenum sulfide, aluminum molybdate, nickel molybdate, zinc molybdate, and molybdic acid, with molybdophosphoric acid, molybdenum trioxide, nickel molybdate, and zinc molybdate being preferred. In addition to the above compounds, examples of the Group 6 metal compound in the hydrotreating catalyst include composite oxides and composite sulfides of a Group 6 metal and at least one metal selected from the group consisting of zinc, titanium, phosphorus, boron, and Group 9 and Group 10 metals contained in the hydrotreating catalyst. The hydrotreating catalyst may contain one or more types of Group 6 metal compounds.

[0031] The content of the Group 6 metal in the hydrotreating catalyst is 5 to 16 mass%, preferably 6 to 13 mass%, more preferably 6 to 10 mass%, and even more preferably 7 to 10 mass%, based on the catalyst in terms of element. When the content of the Group 6 metal is equal to or greater than the lower limit of the above range, it is sufficient to exhibit the effects attributable to the Group 6 metal. When the content of the Group 6 metal is equal to or less than the upper limit of the above range, the Group 6 metal is less likely to aggregate and is sufficiently dispersed. In other words, the amount of the Group 6 metal that can be efficiently dispersed is not exceeded, and the catalyst surface area is not significantly reduced, thereby improving catalytic activity.

[0032] Examples of Group 9 and Group 10 metals include nickel and cobalt, and among these, nickel is preferred because it has high hydrogenation ability and low catalyst preparation costs. The hydrotreating catalyst may contain only a Group 9 metal, only a Group 10 metal, or both a Group 9 metal and a Group 10 metal. The forms of the Group 9 and Group 10 metals in the hydrotreating catalyst include simple metals and compounds of metals of Group 9 and Group 10. The hydrotreating catalyst may contain only one of simple metals of Group 9 and Group 10 and compounds of metals of Group 9 and Group 10, or may contain both. Examples of the Group 9 and Group 10 metal compounds in the hydrotreating catalyst include nickel oxides, carbonates, nitrates, sulfates, phosphates, aluminates, titanates, and molybdates, with phosphates, titanates, and molybdates being preferred. In addition to the above compounds, examples of the Group 9 and Group 10 metal compounds in the hydrotreating catalyst include composite oxides and composite sulfides of Group 9 and Group 10 metals and at least one selected from the group consisting of zinc, titanium, phosphorus, boron, and Group 6 metals contained in the hydrotreating catalyst. The hydrotreating catalyst may contain only one type of Group 9 and Group 10 metal compound, or two or more types.

[0033] The content of Group 9 and Group 10 metals in the hydrotreating catalyst is 1 to 5 mass%, preferably 2 to 4 mass%, and more preferably 2.5 to 3.5 mass%, calculated as the element based on the catalyst. When the content of Group 9 and Group 10 metals is equal to or greater than the lower limit of the above range, sufficient active sites attributable to the Group 9 and Group 10 metals are obtained. When the content of Group 9 and Group 10 metals is equal to or less than the upper limit of the above range, the Group 9 and Group 10 metals are less likely to aggregate, improving dispersibility. For example, when nickel is used as the Group 9 and Group 10 metal, the catalytic activity is improved because inactive precursors, such as NiO species (which exist as NiS species after catalyst sulfurization or during hydrotreating) and Ni spinel species incorporated into the support lattice, are less likely to be generated.

[0034] The hydrotreating catalyst of this embodiment preferably further contains either or both of phosphorus and boron. Specifically, the support of the hydrotreating catalyst is preferably a zinc-titanium-(phosphorus and / or boron)-containing alumina support containing zinc, titanium, and either or both of phosphorus and boron.

[0035] The form of phosphorus in the hydrotreating catalyst may be elemental phosphorus or a phosphorus compound. The hydrotreating catalyst may contain either elemental phosphorus or a phosphorus compound, or both. Examples of phosphorus compounds in the hydrotreating catalyst include phosphorus oxide, molybdophosphate, ammonium phosphate, aluminum phosphate, zinc phosphate, titanium phosphate, and nickel phosphate, with phosphorus oxide, molybdophosphate, and nickel phosphate being preferred. In addition to the above compounds, examples of phosphorus compounds in the hydrotreating catalyst include composite oxides and composite sulfides of phosphorus and at least one metal selected from the group consisting of zinc, titanium, boron, Group 6 metals, and Group 9 and Group 10 metals contained in the hydrotreating catalyst. The hydrotreating catalyst may contain one kind of phosphorus compound or two or more kinds of phosphorus compounds.

[0036] The phosphorus content in the hydrotreating catalyst is preferably 0.04 to 2 mass%, more preferably 0.2 to 1 mass%, and even more preferably 0.3 to 0.8 mass%, calculated as the element based on the catalyst. When the phosphorus content is equal to or greater than the lower limit of the above range, the sulfidity of the Group 6 metal can be sufficiently improved. Furthermore, a decrease in the activity of the hydrogenation active component is suppressed. When the phosphorus content is equal to or less than the upper limit of the above range, a decrease in pore volume and specific surface area is unlikely to occur, the Group 6 metal is sufficiently dispersed, and the sulfidity of the Group 9 and Group 10 metals is unlikely to decrease.

[0037] The average particle size of particles derived from elemental phosphorus observed when the hydrotreating catalyst is analyzed by TEM-EDS is preferably 0.3 to 10 nm, more preferably 0.3 to 5 nm, and even more preferably 0.3 to 2 nm. The particle size of the phosphorus-derived particles in the hydrotreating catalyst refers to the maximum distance between two parallel lines sandwiching a planar image of the phosphorus-derived particles observed by TEM-EDS. The average particle size of the phosphorus-derived particles in the hydrotreating catalyst refers to the average particle size of 10 randomly selected phosphorus-derived particles. The shape of the phosphorus-derived particles in the hydrotreating catalyst is not particularly limited, but is preferably approximately circular.

[0038] When the hydrotreating catalyst contains phosphorus, the molar ratio of titanium to phosphorus in the hydrotreating catalyst (titanium element / phosphorus element) is preferably 0.5 to 15, more preferably 1 to 13, and even more preferably 5 to 11. When the molar ratio is within the above range, deterioration of the hydrotreating active sites can be suppressed without causing a significant decrease in pore volume or specific surface area.

[0039] When the hydrotreating catalyst contains phosphorus, the molar ratio of zinc to phosphorus in the hydrotreating catalyst (elemental zinc / elemental phosphorus) is preferably 0.1 to 6, more preferably 1 to 5, and even more preferably 2 to 4. When the molar ratio is within the above range, it is possible to suppress the production of zinc phosphate, which has low hydrogen dissociation activity, during catalyst calcination.

[0040] The ratio of the average particle size of titanium-derived particles to the average particle size of phosphorus-derived particles in the hydrotreating catalyst (average particle size of titanium-derived particles / average particle size of phosphorus-derived particles) is preferably 0.1 to 5, more preferably 0.4 to 3, and even more preferably 0.8 to 1.6. When the average particle size ratio is within the above range, activity reduction due to sintering of the phosphorus-derived particles and titanium-derived particles is unlikely to occur, and reduction in the transfer efficiency of active hydrogen species can be suppressed.

[0041] The ratio of the average particle size of zinc-derived particles to the average particle size of phosphorus-derived particles in the hydrotreating catalyst (average particle size of zinc-derived particles / average particle size of phosphorus-derived particles) is preferably 0.1 to 5, more preferably 0.4 to 3, and even more preferably 0.8 to 1.6. When the average particle size ratio is within the above range, the generation of zinc phosphate due to sintering can be suppressed.

[0042] The form of boron in the hydrotreating catalyst may be boron alone or a boron compound. The hydrotreating catalyst may contain either boron alone or a boron compound, or both. Examples of the boron compound in the hydrotreating catalyst include boron oxide, ammonium borate, sodium borate, lithium borate, aluminum borate, zinc borate, and nickel borate, with boron oxide and nickel borate being preferred. In addition to the above compounds, examples of the boron compound in the hydrotreating catalyst include composite oxides of boron and at least one selected from the group consisting of zinc, titanium, phosphorus, Group 6 metals, and Group 9 and Group 10 metals contained in the hydrotreating catalyst. The hydrotreating catalyst may contain one kind of boron compound or two or more kinds of boron compounds.

[0043] The boron content in the hydrotreating catalyst is preferably 0.1 to 5 mass%, more preferably 0.2 to 4 mass%, and even more preferably 0.4 to 2 mass%, calculated as an element based on the catalyst. When the boron content is equal to or greater than the lower limit of the above range, the interaction between the hydrotreating active component and alumina is weakened, enhancing the activity of the hydrotreating active component. Furthermore, a decrease in the activity of the hydrotreating catalyst is suppressed. When the boron content is equal to or less than the upper limit of the above range, a decrease in pore volume and specific surface area is unlikely to occur, and the hydrotreating active component and the like are sufficiently dispersed.

[0044] When the hydrotreating catalyst contains boron, the molar ratio of titanium to boron in the hydrotreating catalyst (titanium element / boron element) is preferably 0.01 to 10, more preferably 0.1 to 5, and even more preferably 0.2 to 1. When the molar ratio is within the above range, titanium is less likely to aggregate.

[0045] When the hydrotreating catalyst contains boron, the molar ratio of zinc to boron in the hydrotreating catalyst (elemental zinc / elemental boron) is preferably 0.01 to 5, more preferably 0.1 to 2, even more preferably 0.1 to 1, and still more preferably 0.2 to 1. When the molar ratio is within the above range, boron is sufficiently dispersed.

[0046] When the hydrotreating catalyst contains boron and phosphorus, the molar ratio of phosphorus to boron in the hydrotreating catalyst (elemental phosphorus / elemental boron) is preferably 0.01 to 10, more preferably 0.01 to 1, and even more preferably 0.1 to 0.5.

[0047] The specific surface area of ​​the hydrotreating catalyst is 150 to 300 m as measured by the BET method. 2 / g is preferred, and 190 to 250m 2 / g is more preferable. When the specific surface area is equal to or greater than the lower limit of the above range, the hydrogenation active component is sufficiently dispersed, resulting in high hydrogenation activity. When the specific surface area is equal to or less than the upper limit of the above range, the hydrotreating catalyst has a sufficiently large pore diameter. As a result, sulfur compounds are sufficiently diffused into the catalyst pores, resulting in high hydrogenation activity. In other words, when the specific surface area is within the above range, it is possible to improve both the dispersibility of the hydrogenation active component and the diffusibility of sulfur compounds into the catalyst pores during hydrotreating.

[0048] The average pore diameter of the hydrotreating catalyst in the pore distribution measured by mercury intrusion porosimetry is preferably 5 to 20 nm, more preferably 7 to 11 nm. When the average pore diameter is within this range, the catalyst has a sufficient surface area within the pores (i.e., the effective surface area of ​​the catalyst), while enhancing the diffusibility of sulfur compounds into the catalyst pores, thereby further improving the hydrogenation activity.

[0049] The pore volume of the hydrotreating catalyst, as measured by mercury intrusion porosimetry, is preferably 0.45 to 0.8 mL / g, more preferably 0.45 to 0.7 mL / g. When the pore volume is equal to or greater than the lower limit of the above range, sulfur compounds are sufficiently diffused within the catalyst pores during hydrotreating, improving the hydrogenation activity. When the pore volume is equal to or less than the upper limit of the above range, the specific surface area of ​​the catalyst can be prevented from becoming extremely small. When the pore volume is within the above range, both the dispersibility of the hydrotreating active component and the diffusibility of sulfur compounds into the catalyst pores during hydrotreating can be improved.

[0050] In order to increase the effective number of pores that satisfy the above-mentioned average pore diameter and pore volume, the pore size distribution of the hydrotreating catalyst of this embodiment is such that the ratio of the volume of pores having pore diameters within ±1.5 nm of the average pore diameter to the total pore volume is preferably 65% ​​or more, more preferably 70% or more.

[0051] Furthermore, the distribution state of zinc, titanium, phosphorus, boron, and the hydrogenation active component in the hydrotreating catalyst of this embodiment is preferably a uniform type in which these components are uniformly distributed in the catalyst.

[0052] The content of components other than alumina (including composite alumina), zinc, titanium, phosphorus, boron, Group 6 metals, and Group 9 and 10 metals in the hydrotreating catalyst is preferably as low as possible, and the content of these components relative to the total mass of the hydrotreating catalyst is preferably 2 mass% or less, more preferably 1 mass% or less. The content of these components is preferably 2 mass% or less, more preferably 1 mass% or less, based on the total mass of the hydrotreating catalyst. 2- , Cl - , Fe2O3, Na2O, etc. In one aspect of the present invention, the hydrotreating catalyst is preferably substantially free of carbon, which means that the carbon content relative to the total mass of the hydrotreating catalyst is 0.3 mass% or less.

[0053] <Method of manufacturing hydrotreating catalyst> The method for producing a hydrocarbon oil hydrotreating catalyst of this embodiment includes supporting, on a zinc-titanium-containing alumina support containing 1 to 14 mass% zinc, calculated as elemental, and 0.1 to 13 mass% titanium, calculated as elemental, based on the support, at least one metal selected from Group 6 metals of the periodic table in an amount of 5 to 16 mass% elemental, based on the catalyst, and at least one metal selected from Groups 9 and 10 metals of the periodic table in an amount of 1 to 5 mass% elemental, based on the catalyst. When the hydrotreating catalyst is analyzed by TEM-EDS, the average particle size of particles derived from elemental titanium observed is preferably 0.3 to 10 nm. The support used in the method for producing a hydrocarbon oil hydrotreating catalyst of this embodiment is preferably a zinc-titanium-(phosphorus and / or boron)-containing alumina support further containing, in elemental terms, 0.04 to 3 mass% of phosphorus based on the support, and / or further containing, in elemental terms, 0.1 to 3 mass% of boron based on the support.

[0054] (Method for producing zinc-titanium (phosphorus and / or boron)-containing alumina support) The method for producing a zinc-titanium (and phosphorus and / or boron)-containing alumina support of this embodiment includes, for example, an alumina gel preparation step of preparing an alumina gel, a kneading step of kneading the alumina gel to obtain a kneaded mixture, a molding step of molding the kneaded mixture to obtain a molded product, and a firing step of drying and firing the molded product to obtain a fired product. The method further comprises a step of adding a zinc raw material and a titanium raw material to the alumina gel, the kneaded product, the formed product, or the sintered body during each of the steps or after the sintering step so that the sintered body contains 1 to 14 mass % of zinc, calculated as an element, based on the carrier, and 0.1 to 13 mass % of titanium, calculated as an element, based on the carrier. Furthermore, it is preferable to have a step of adding a phosphorus raw material to the alumina gel, the kneaded product, the molded product, or the sintered body during each of the steps or after the sintering step so that the sintered body contains phosphorus in an amount of 0.04 to 3 mass % in elemental terms based on the carrier. Furthermore, it is preferable to have a step of adding a boron raw material to the alumina gel, the kneaded product, the molded product, or the sintered body during each of the steps or after the sintering step so that the sintered body contains 0.1 to 8 mass % of boron in elemental terms based on the carrier.

[0055] Any alumina raw material can be used as long as it contains aluminum, but aluminum salts such as aluminum sulfate, aluminum nitrate, etc. These alumina raw materials are usually provided as aqueous solutions, and although there are no particular limitations on their concentration, it is preferably 2 to 50 mass %, more preferably 5 to 40 mass %, based on the total mass of the aqueous solution.

[0056] To prepare alumina gel, for example, an aqueous solution of sulfuric acid, sodium aluminate, and aluminum hydroxide are mixed in a stirring vessel to prepare a slurry. The resulting slurry is then subjected to a rotary cylindrical continuous vacuum filter to remove water and washed with pure water to obtain alumina gel.

[0057] The resulting alumina gel was then added to the filtrate with SO4 2- , Na +After washing until no trace of alumina can be detected, the alumina gel is mixed with pure water to form a uniform slurry. The resulting alumina gel slurry is dehydrated until the water content relative to the total mass of the slurry is 60 to 90 mass % to obtain a cake.

[0058] The alumina gel slurry is preferably dehydrated using a filter press. A filter press is a device that filters a slurry by applying compressed air or pump pressure, and is also commonly called a filter press. Filter presses are divided into plate and frame types and concave plate types. In a plate and frame type filter press, filter plates and filter frames are alternately clamped between end plates, and the slurry is filtered by being forced into the filter frames. The filter plates have grooves that serve as filtrate flow channels, and filter cloth is stretched over the filter frames. On the other hand, in a concave plate type filter press, filter cloth and concave plate type filter plates are alternately arranged and clamped between the end plates to form a filter chamber (Reference: Chemical Engineering Handbook, p. 715).

[0059] By dehydrating the alumina gel slurry using a filter press, the surface condition of the resulting alumina-containing carrier can be improved, and the sulfidity of the hydrogenation active component can be increased. The dehydration step using a filter press is preferably carried out after at least one of the alumina gel preparation step and the kneading step, and may be carried out after both steps. Of these, it is more preferable to carry out the dehydration step after the alumina gel preparation step and before the kneading step.

[0060] In addition to the above-described method, other methods for preparing alumina gel include a method of neutralizing an aqueous solution containing an alumina raw material with a neutralizing agent such as sodium aluminate, aluminic acid, or ammonia, and a method of mixing the aqueous solution with a precipitating agent such as hexanemethylenetetramine or calcium carbonate. The amount of the neutralizing agent used is not particularly limited, but is preferably 30 to 70 mass % based on the total amount of the aqueous solution containing the alumina raw material and the neutralizing agent.The amount of the precipitating agent used is not particularly limited, but is preferably 30 to 70 mass % based on the total amount of the aqueous solution containing the alumina raw material and the precipitating agent.

[0061] When alumina is to be composited with an oxide such as zeolite to form composite alumina, the process may be carried out after preparing an alumina gel by the above-described method and subjecting the obtained alumina gel to aging, washing, dehydration, drying, and moisture adjustment. As a composite method, alumina can be composited with an oxide such as zeolite by a coprecipitation method, a kneading method, or the like. The composite alumina gel is then subjected to aging, washing, dehydration, drying, and moisture adjustment. It is also preferable to use a press filter for dehydration in the final dehydration step before molding the composite alumina gel.

[0062] When the zinc source, titanium source, phosphorus source, and boron source are solid, it is preferable to add these sources to the alumina gel before carrying out the kneading step. When the zinc raw material, the titanium raw material, the phosphorus raw material, and the boron raw material are dissolved in a liquid or a solvent, it is preferable to add these raw materials to the alumina gel before carrying out the kneading step, add these raw materials to the kneaded product before carrying out the molding step, add these raw materials to the molded product before drying and firing, or add these raw materials to the fired product, and it is more preferable to add these raw materials to the fired product.

[0063] As the zinc raw material to be added to the alumina of the hydrotreating catalyst of this embodiment, zinc itself or various zinc compounds can be used, and examples thereof include zinc oxide, zinc nitrate, zinc sulfate, zinc carbonate, zinc chloride, zinc acetate, zinc hydroxide, zinc oxalate, zinc phosphate, zinc aluminate, zinc titanate, and zinc molybdate. Of these, zinc oxide, zinc nitrate, zinc sulfate, and zinc aluminate are preferred, and zinc nitrate, zinc oxide, and zinc aluminate are particularly preferred.

[0064] When the zinc raw material is a solid such as zinc oxide, it is preferable to add the zinc raw material to the aluminum gel together with an acid such as nitric acid and then carry out the kneading step.When the zinc raw material is a solid, its average particle size is preferably 0.01 to 5 μm, more preferably 0.01 to 2 μm, and even more preferably 0.01 to 1 μm. The average particle size of the zinc raw material is the volume average of the particle size distribution obtained by measurement using a laser diffraction scattering method in accordance with JIS R1629.

[0065] When the zinc raw material is a liquid or a solution dissolved in a solvent (such as an aqueous zinc nitrate solution), it is preferable to add the liquid or solution to the fired body.

[0066] The content of zinc in the support is preferably 1 to 14 mass %, more preferably 3 to 7 mass %, and even more preferably 3 to 5 mass %, calculated as the element, based on the support.

[0067] The average particle size of the zinc-derived particles in the hydrotreating catalyst and the support is preferably 0.3 to 10 nm, more preferably 0.3 to 5 nm, and even more preferably 0.3 to 2 nm. The average particle size of the zinc-derived particles in the support can be determined in the same manner as the average particle size of the zinc-derived particles in the hydrotreating catalyst described above.

[0068] As the titanium raw material to be added to the alumina of the hydrotreating catalyst of this embodiment, titanium itself or various titanium compounds can be used. As the titanium compound, a titanium compound that is soluble in a solvent is preferred, and a water-soluble titanium compound that is soluble in water is more preferred.

[0069] The water-soluble titanium compound is preferably a compound that is resistant to hydrolysis, such as at least one water-soluble titanium compound selected from the group consisting of (i) peroxotitanium compounds, (ii) peroxotitanium compounds, (iii) oxotitanium compounds, and (iv) hydroxy(hydroxycarboxylato)titanium compounds. Aqueous solutions of these water-soluble titanium compounds are resistant to hydrolysis and stable, allowing the titanium compound to be highly dispersed and uniformly supported on alumina.

[0070] (i) Peroxotitanium compounds The peroxotitanium compound has the general formula A 1 x1 [Ti(O2) y1 B 1 z1In the general formula, A is a water-soluble titanium compound represented by the formula: 1 is a cation, B 1 represents a hydroxycarboxylic acid, and x1, y1, and z1 each independently represent an integer of 1 to 4. The cation is preferably a cation that does not contain a metal element, and is more preferably an ammonium ion. The hydroxycarboxylic acid can be a hydroxycarboxylic acid known in the art, and citric acid, malic acid, lactic acid, or tartaric acid is preferred. The peroxotitanic acid can be produced by known production methods such as those disclosed in JP-A No. 2002-1115 or JP-A No. 2000-159786.

[0071] (ii) Peroxotitanium Peroxotitanium is a compound of the general formula A 2 x2 [Ti(O2) y2 In the general formula, A is a water-soluble titanium compound represented by the formula: 2 represents a cation, and x2 and y2 each independently represent an integer of 1 to 4. The cation is preferably a cation that does not contain a metal element, and is more preferably an ammonium ion. The peroxotitanium can be produced by adding an alkali compound and hydrogen peroxide to a titanium source and dissolving the titanium source in a pH range of 7 to 14.

[0072] The titanium source preferably does not substantially contain metals other than titanium and anions such as chloride ions and sulfate ions. Examples of such titanium sources include titanium hydroxide, titanium hydrous oxide, titanium oxide, and titanium metal. From the viewpoint of ease of dissolution, the titanium source is preferably in powder form. Here, titanium hydroxide is a compound represented by orthotitanic acid (TiO2·nH2O, n=approximately 2), and is either a gel obtained by a commonly known method, i.e., by neutralizing an aqueous solution of titanium tetrachloride or titanyl sulfate with an alkali at room temperature followed by thorough washing, or a solid obtained by further drying, with a water content of 2% by mass or more. Titanium hydroxide is preferably used in which substantially no anions, such as chloride ions, sulfate ions, or nitrate ions, are detected. "Substantially no anions are detected" means that the anion content is 10% by mass or less, preferably 5% by mass or less, and more preferably 2% by mass or less, based on TiO2.

[0073] On the other hand, titanium hydrous oxide is a compound represented by metatitanic acid (TiO2·nH2O, n=1 or so). It is a gel obtained by thermally hydrolyzing a titanium sulfate solution in a process substantially equivalent to or using the sulfuric acid method for producing titanium oxide, followed by thorough washing with water or aqueous ammonia, or a solid obtained by further drying. It has a moisture content of 2% by mass or more. The moisture content is preferably 5% by mass or more, and more preferably 10% by mass or more. Titanium hydrous oxides with a sulfate ion content of 5% by mass or less, preferably 2% by mass or less, based on TiO2, are preferred. If the sulfate ion content in titanium hydrous oxide is 5% by mass or less, this is preferred because when the resulting peroxotitanium is added to the alumina of a hydrotreating catalyst, the sulfur content as an impurity in the final hydrotreating catalyst is reduced. Titanium hydroxide and titanium hydrous oxide may be used as a slurry, or may be dried. There are no particular restrictions on the drying conditions, but it is preferable to dry them under general conditions, i.e., under atmospheric pressure or reduced pressure at a temperature of 150°C or less. The TiO2 content is determined by calcining at 550°C for 2 hours, removing moisture, and then weighing. It is generally believed that there is no difference between titanium hydroxide and titanium hydrate as chemical species, and that the only difference is the degree of aggregation of the fine particles produced, and the above n values ​​are merely guide values.

[0074] A titanium source such as titanium hydroxide, titanium hydrous oxide, or titanium metal is dispersed in a predetermined amount of water to form a slurry. Next, this slurry is maintained at a pH of 7 to 14, preferably 8 to 13, in the presence of an alkali compound and hydrogen peroxide to dissolve the titanium source. The pH can be adjusted by the amount of alkali compound added. When the pH is equal to or higher than the lower limit of the aforementioned range, the dissolution of the titanium source proceeds favorably, while when the pH is equal to or lower than the upper limit of the aforementioned range, the decomposition reaction of hydrogen peroxide is suppressed. The dissolution temperature of the titanium source is not particularly limited, but is preferably 5 to 80°C, more preferably 10 to 70°C. When the dissolution temperature is equal to or higher than the lower limit of the above range, the dissolution of the titanium source proceeds favorably. When the dissolution temperature is equal to or lower than the upper limit of the above range, the decomposition reaction of hydrogen peroxide is suppressed.

[0075] Alkali metals, alkaline earth metals, rare earth metals, etc. can also be used as alkaline compounds, and aqueous solutions of alkali metal salts, alkaline earth metal salts, and rare earth metal salts of peroxotitanium can be prepared. However, since it is generally preferable that the aqueous peroxotitanium solution does not contain any metals other than titanium, ammonia (water) is usually used as the alkaline compound.

[0076] The amount of alkali compound added is preferably 1.5 to 20 moles per mole of TiO2. The amount of hydrogen peroxide added is preferably 1 to 20 moles per mole of TiO2. When the amounts of alkali compound and hydrogen peroxide added are equal to or greater than the lower limit of the above range, dissolution of the titanium source proceeds smoothly. The order of addition of the alkali compound and aqueous hydrogen peroxide is not particularly limited, and they may be added in any order as long as the pH is set within the above range. However, from the viewpoint of suppressing the decomposition reaction of hydrogen peroxide, it is preferable to add the aqueous hydrogen peroxide little by little after adding the alkali compound. The aqueous peroxotitanium solution thus produced can be diluted before use, if necessary.

[0077] (iii) Oxotitanium compounds Oxotitanium compounds are compounds of the general formula A 3 x3[Ti(O) y3 B 3 z3 In the general formula, A is a water-soluble titanium compound represented by the formula: 3 is a cation, B 3 represents a hydroxycarboxylic acid, x3 is 0.4 to 4, and y3 and z3 each independently are 0.2 to 2. The cation is preferably a cation that does not contain a metal element, and is more preferably an ammonium ion. The hydroxycarboxylic acid can be a hydroxycarboxylic acid known in the art, and citric acid, malic acid, lactic acid, or tartaric acid is preferred. The oxotitanium compound can be produced by known production methods such as those disclosed in JP-A-2004-74148.

[0078] (iv) Hydroxy(hydroxycarboxylato)titanium compounds Hydroxy(hydroxycarboxylato)titanium compounds are compounds having the general formula [Ti(OH) x4 (B 4 ) y4 In the general formula, B is a water-soluble titanium compound represented by the formula: 4 represents a hydroxycarboxylic acid, and x4 and y4 each independently represent 1 to 4. As the hydroxycarboxylic acid, a hydroxycarboxylic acid known in the art can be used, and citric acid, malic acid, lactic acid, and tartaric acid are preferred. The hydroxy(hydroxycarboxylato)titanium compound can be produced by the known production method disclosed in JP-A No. 2000-256376 or JP-A No. 2000-351787. Commercially available products include dihydroxybis(lactato)titanium monoammonium salt.

[0079] It is preferable to add an aqueous solution of a water-soluble titanium compound, prepared by dissolving a water-soluble titanium compound in water, to the fired body.

[0080] The content of titanium in the support is preferably 0.1 to 13 mass %, more preferably 3 to 10 mass %, and even more preferably 5 to 9 mass %, calculated as the element, based on the support.

[0081] The average particle size of the particles derived from titanium element in the hydrotreating catalyst and the support is preferably 0.3 to 10 nm, more preferably 0.3 to 5 nm, and even more preferably 0.3 to 2 nm. The average particle size of the particles derived from titanium element in the support can be determined in the same manner as the average particle size of the particles derived from titanium element in the hydrotreating catalyst described above.

[0082] As the phosphorus source to be added to the alumina of the hydrotreating catalyst of this embodiment, simple phosphorus or various compounds can be used, and examples thereof include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, and aluminum phosphate, with orthophosphoric acid being preferred.

[0083] It is preferable to carry out the kneading step by adding a phosphorus raw material to the aluminum gel.

[0084] The phosphorus content in the support is preferably 0.04 to 3 mass %, more preferably 0.2 to 2 mass %, and even more preferably 0.4 to 1 mass %, calculated as the element, based on the support.

[0085] The average particle size of the particles derived from phosphorus in the hydrotreating catalyst and the support is preferably 0.3 to 10 nm, more preferably 0.3 to 5 nm, and even more preferably 0.3 to 2 nm. The average particle size of the particles derived from phosphorus in the support can be determined in the same manner as the average particle size of the particles derived from phosphorus in the hydrotreating catalyst described above.

[0086] As the boron source to be added to the alumina of the hydrotreating catalyst of this embodiment, boron itself or various compounds can be used, and examples thereof include boric acid, boron oxide, ammonium borate, sodium borate, lithium borate, aluminum borate, zinc borate, and nickel borate, with boric acid being preferred.

[0087] It is preferable to add an aqueous solution of a boron source, in which a boron source is dissolved in water, to the fired body.

[0088] The content of boron in the support is preferably 0.1 to 8 mass %, more preferably 0.3 to 5 mass %, and even more preferably 0.5 to 2 mass %, calculated as the element, based on the support.

[0089] When the kneading step is carried out after adding the raw materials to the alumina gel, the raw materials are added to the alumina gel obtained in the alumina gel preparation step, and kneading is carried out. Specifically, the raw materials heated to 15 to 90°C are added to a water-adjusted alumina gel heated to 50 to 90°C. Then, the mixture is kneaded and stirred using a heated kneader or the like to obtain a kneaded mixture. As described above, dehydration using a press filter may be carried out after kneading and stirring the alumina gel and the raw materials. As described above, the raw materials may be added as solids or liquids, or as liquids dissolved or suspended in a solvent.

[0090] The kneaded product thus obtained is then molded, dried, and fired to obtain a fired body. The molding of the kneaded product can be carried out by various molding methods such as extrusion molding and pressure molding. The drying temperature of the molded product thus obtained is preferably 15 to 150°C, more preferably 80 to 120°C. The drying time is preferably 30 minutes or more. The firing temperature can be appropriately set as needed, but for example, the firing temperature for obtaining γ-alumina is preferably 450°C or higher, more preferably 480 to 600°C. The firing time is preferably 2 hours or more, more preferably 3 to 12 hours.

[0091] When adding the raw materials to the sintered body, known methods such as impregnation, coprecipitation, deposition, and ion exchange may be used. Examples of impregnation methods include an evaporation-to-dryness method in which the sintered body is immersed in an impregnation solution in excess of the total pore volume of the sintered body and then the solvent is completely dried to support the raw materials; an equilibrium adsorption method in which the sintered body is immersed in an impregnation solution in excess of the total pore volume of the sintered body and then subjected to solid-liquid separation such as filtration to obtain an impregnated body carrying the raw materials; and a pore filling method in which the sintered body is impregnated with an impregnation solution in an amount approximately equal to the total pore volume of the sintered body and then the solvent is completely dried to support the raw materials. The method for impregnating the sintered body with the raw materials may be a batch impregnation method in which each of the raw materials is simultaneously impregnated, or a sequential impregnation method in which each of the raw materials is individually impregnated.

[0092] When the raw materials are supported by the impregnation method, the moisture is generally removed to a certain extent (so that the LOI (loss on ignition) is 50% or less) in a nitrogen stream, air stream, or vacuum at room temperature to 80°C, and the resulting material is dried in an air stream at 80 to 150°C for 10 minutes to 10 hours in a drying furnace.Then, the material is calcined in an air stream at 300 to 700°C, more preferably 500 to 650°C, for 10 minutes to 10 hours, more preferably 3 to 6 hours.

[0093] The specific surface area of ​​the carrier of this embodiment is 200 to 400 m as measured by the nitrogen adsorption method (BET method). 2 / g is preferred, and 250 to 360m 2 / g is more preferable. When the specific surface area is equal to or greater than the lower limit of the above range, the hydrogenation active component is sufficiently dispersed, resulting in high hydrogenation activity. When the specific surface area is equal to or less than the upper limit of the above range, the support has a sufficiently large pore diameter, resulting in a sufficiently large pore diameter of the hydrotreating catalyst. As a result, sulfur compounds are sufficiently diffused into the catalyst pores, resulting in high hydrogenation activity. In other words, when the specific surface area is within the above range, the hydrotreating catalyst has good dispersibility of the hydrogenation active component and a sufficiently large pore diameter.

[0094] The average pore diameter of the support of this embodiment in the pore distribution measured by mercury intrusion porosimetry is preferably 4 to 12 nm, more preferably 6 to 8 nm. When the average pore diameter is within this range, the support has a sufficient inner pore surface area, and sulfur compounds diffuse sufficiently into the catalyst pores, resulting in high hydrogenation activity.

[0095] The pore volume of the carrier of this embodiment, as measured by mercury intrusion porosimetry, is preferably 0.5 to 0.9 mL / g, more preferably 0.55 to 0.8 mL / g. When the pore volume is equal to or greater than the lower limit of the above range, a sufficient amount of solvent can penetrate into the pores when preparing a catalyst by a conventional impregnation method. A sufficient amount of solvent allows the hydrogenation active component to dissolve well in the solvent, improving the dispersibility of the hydrogenation active component and resulting in a highly active catalyst. One method for increasing the solubility of the hydrogenation active component is to add a large amount of acid such as nitric acid, but adding too much acid reduces the surface area of ​​the carrier, which is the main cause of a decrease in hydrogenation activity. When the pore volume is equal to or less than the upper limit of the above range, the specific surface area is sufficiently large, improving the dispersibility of the hydrogenation active component. That is, when the pore volume is within the above range, the carrier has a sufficient specific surface area and a sufficient amount of solvent can penetrate into the pore volume, resulting in both good solubility and dispersibility of the hydrogenation active component and further improving hydrogenation activity.

[0096] (Supporting of hydrogenation active components) On the zinc-titanium (phosphorus and / or boron)-containing alumina support thus obtained, at least one metal selected from Group 6 metals of the periodic table is supported in an amount of 5 to 16 mass % in elemental terms based on the catalyst, and metals of Groups 9 and 10 of the periodic table are supported in an amount of 1 to 5 mass % in elemental terms based on the catalyst.

[0097] In the hydrotreating catalyst of this embodiment, the Group 6 metal raw material supported on the support is preferably a molybdenum compound, and examples thereof include molybdenum trioxide, molybdophosphoric acid, ammonium molybdate, and molybdic acid, with molybdophosphoric acid, molybdenum trioxide, and ammonium molybdate being preferred.

[0098] In the hydrotreating catalyst of this embodiment, examples of the Group 9 and Group 10 metal raw material to be supported on the support include nickel oxide, nickel carbonate, nickel acetate, nickel nitrate, nickel sulfate, and nickel chloride, with nickel nitrate and nickel carbonate being preferred.

[0099] Methods for supporting the Group 6 metal source and the Group 9 and Group 10 metal sources (hereinafter also referred to as "hydrogenation active component source") on the support may be known methods such as impregnation, coprecipitation, kneading, deposition, and ion exchange. Examples of impregnation methods include an evaporation-to-dryness method in which the support is immersed in an impregnation solution in excess of the total pore volume of the support and then the solvent is completely dried to support the hydrogenation active component source; an equilibrium adsorption method in which the support is immersed in an impregnation solution in excess of the total pore volume of the support and then subjected to solid-liquid separation such as filtration to obtain a catalyst supporting the hydrogenation active component source; and a pore-filling method in which the support is impregnated with an impregnation solution in an amount approximately equal to the total pore volume of the support and then the solvent is completely dried to support the hydrogenation active component source. The method for impregnating the support with the hydrogenation active component source may be a batch impregnation method in which each component is simultaneously impregnated, or a sequential impregnation method in which each component is individually impregnated.

[0100] Specific methods for supporting the hydrogenation active component raw material on the carrier include the following methods. First, an impregnation solution containing the hydrogenation active ingredient raw materials is prepared. During preparation, in order to promote dissolution of these hydrogenation active ingredient raw materials, heating (30 to 100°C) or addition of an acid (nitric acid, phosphoric acid, organic acid (citric acid, acetic acid, malic acid, tartaric acid, etc.)) may be performed. That is, in this embodiment, when the hydrogenation active ingredient raw materials are supported on the support, phosphorus may be separately supported in addition to the phosphorus contained in the support.

[0101] Examples of phosphorus compounds that may be added separately when supporting the hydrogenation active component raw material, etc., on the support include phosphorus-containing hydrogenation active component raw materials such as molybdophosphoric acid, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid, with orthophosphoric acid being preferred. If phosphorus is separately supported when supporting the hydrogenation active component raw material on the support, the dispersibility of the hydrogenation active component in the resulting hydrotreating catalyst can be improved.

[0102] Next, the prepared impregnation solution is gradually added to the carrier so as to be uniform, and the carrier is impregnated. The impregnation time is preferably 1 minute to 5 hours, more preferably 5 minutes to 3 hours. The impregnation temperature is preferably 5 to 100°C, more preferably 10 to 80°C. The impregnation atmosphere is not particularly limited, but air, nitrogen, and vacuum are each suitable.

[0103] The ratio of the mass of phosphorus kneaded into the support in terms of oxide to the mass of the Group 6 metal raw material in terms of oxide is preferably 0.01 to 1.5. Within this range, the surface area and pore volume of the catalyst are not reduced, and a decrease in catalytic activity is suppressed. Furthermore, the amount of acid is not increased, and carbon deposition can be prevented, thereby suppressing activity deterioration.

[0104] When a molybdenum compound is used as the Group 6 metal raw material, the ratio of the mass of phosphorus kneaded with the support in terms of oxide to the mass of molybdenum compound in terms of oxide is preferably 0.01 to 1.5, more preferably 0.05 to 1.0. When the ratio of the mass of phosphorus kneaded with the support in terms of oxide to the mass of molybdenum compound in terms of oxide is within the above range, the molybdenum can be thoroughly integrated with the Group 9 and Group 10 metal compounds in the hydrotreating catalyst.

[0105] In the method for producing a hydrotreating catalyst of this embodiment, after loading the hydrogenation active component raw material and the like, the impregnated body is first dehydrated to a certain extent (so that the LOI (loss on ignition) is 50% or less) at 15 to 80°C in a nitrogen stream, an air stream, or in a vacuum. The impregnated body is then dried in a drying furnace in an air stream at 80 to 150°C for 10 minutes to 10 hours. The impregnated body is then calcined in a calcining furnace in an air stream. The calcination temperature is preferably 300 to 700°C, more preferably 500 to 650°C. The calcination time is preferably 10 minutes to 10 hours, more preferably 3 hours or longer.

[0106] <Method for producing hydrogenated hydrocarbon oil (hydrogenation treatment method for hydrocarbon oil)> The method for producing hydrogenated hydrocarbon oil of this embodiment is carried out under the conditions of a hydrogen partial pressure of 3 to 20 MPa, a reaction temperature of 280 to 450°C, and a liquid hourly space velocity of 0.01 to 5 h -1 The method for producing hydrogenated hydrocarbon oil comprises contacting a hydrocarbon oil with the hydrocarbon oil hydrotreating catalyst of the present invention to hydrotreat the hydrocarbon oil. The method for hydrotreating hydrocarbon oil of this embodiment is carried out under a hydrogen partial pressure of 3 to 20 MPa, a reaction temperature of 280 to 450°C, and a liquid hourly space velocity of 0.01 to 5 h -1 The present invention provides a method for hydrotreating hydrocarbon oils, which comprises contacting hydrocarbon oils with the above-described catalyst for hydrotreating hydrocarbon oils of the present invention.

[0107] The hydrogen partial pressure is preferably 3 to 20 MPa, more preferably 5 to 17.5 MPa, and even more preferably 7 to 15 MPa. When the hydrogen partial pressure is equal to or higher than the lower limit of the above range, the hydrogenation reaction tends to proceed.

[0108] The reaction temperature is preferably 280 to 450°C, more preferably 290 to 430°C, and even more preferably 300 to 420°C. When the reaction temperature is equal to or higher than the lower limit of the above range, the catalytic activity can be fully exerted. When the reaction temperature is equal to or lower than the upper limit of the above range, the thermal cracking of the hydrocarbon oil proceeds appropriately, while catalyst deterioration is unlikely to occur. The reaction temperature means the average temperature of the catalyst layer.

[0109] Liquid hourly space velocity is 0.01 to 5 h -1is preferable, and 0.05 to 4 hours -1 More preferably, 0.1 to 3 hours -1 When the liquid hourly space velocity is equal to or higher than the lower limit of the above range, productivity is improved, and when the liquid hourly space velocity is equal to or lower than the upper limit of the above range, the ability to remove sulfur components is improved.

[0110] Hydrogen / hydrocarbon oil ratio: 400~3000Nm 3 / kL is preferred, and 450 to 2500Nm 3 / kL is more preferable, and 500 to 2000Nm 3 / kL is more preferred.

[0111] Examples of hydrocarbon oils to be subjected to the method for producing hydrogenated hydrocarbon oils (hydrocarbon oil hydrotreating method) of this embodiment include atmospheric distillation residual oil obtained by atmospheric distillation of crude oil in an atmospheric distillation unit, vacuum distillation residual oil obtained by further vacuum distillation of the atmospheric distillation residual oil in a vacuum distillation unit, vacuum distillation light oil, heavy extracts which are particularly heavy oils among the oils extracted and removed by solvent extraction of lubricating base oils such as hydrocracked heavy oil, fluid catalytic cracking residual oil, and de-gravelized oil.

[0112] The density of the hydrocarbon oil used in the method for producing hydrogenated hydrocarbon oil (hydrogenation treatment method for hydrocarbon oil) of this embodiment is 0.8 to 1.15 g / cm 3 is preferred, and 0.82 to 1.1 g / cm 3 More preferably, 0.84 to 1.06 g / cm 3 The sulfur content is preferably 2 to 7 mass%, more preferably 1.5 to 6.5 mass%, and even more preferably 0.8 to 6 mass%. The nickel content is preferably 200 mass ppm or less, the vanadium content is preferably 400 mass ppm or less, and the asphaltene content is preferably 15 mass% or less.

[0113] The density of the hydrogenated hydrocarbon oil produced by the method for producing hydrogenated hydrocarbon oil (hydrogenation treatment method for hydrocarbon oil) of this embodiment is 0.7 to 1.05 g / cm 3 is preferred, and 0.75 to 1.0 g / cm 3 More preferably, 0.77 to 0.95 g / cm3 The sulfur content is preferably 0.01 to 0.8 mass%, more preferably 0.05 to 0.6 mass%, and even more preferably 0.1 to 0.5 mass%. The nickel content is preferably 50 ppm by mass or less, the vanadium content is preferably 100 ppm by mass or less, and the asphaltene content is preferably 5% by mass or less.

[0114] The hydrotreating catalyst of this embodiment may be activated by sulfiding in a reactor before use (i.e., before carrying out the hydrotreating method of this embodiment). This sulfiding is generally carried out at 200 to 400°C, preferably 250 to 350°C, in a hydrogen atmosphere at atmospheric or higher hydrogen partial pressure, by flowing a petroleum distillate containing sulfur compounds, to which a sulfiding agent such as dimethyl disulfide or carbon disulfide has been added, or hydrogen sulfide, through the hydrotreating catalyst.

[0115] By hydrotreating hydrocarbon oils using the hydrotreating catalyst of this embodiment, the hydrotreating proceeds sufficiently and it becomes possible to reduce the sulfur compounds in the hydrocarbon oils over a long period of time.

[0116] To carry out the hydrotreating method of this embodiment on a commercial scale, a fixed-bed, moving-bed, or fluidized-bed catalyst layer of the hydrotreating catalyst of this embodiment may be formed in a reactor, a feedstock oil may be introduced into this reactor, and hydrotreating may be carried out under the conditions described above. Most commonly, a fixed-bed catalyst layer is formed in the reactor, and the feedstock oil is introduced into the upper part of the reactor, passed from top to bottom through the fixed bed, and the product discharged from the bottom of the reactor; alternatively, the feedstock oil is introduced into the lower part of the reactor, passed from bottom to top through the fixed bed, and the product discharged from the top of the reactor.

[0117] The hydrotreating method of this embodiment may be a single-stage hydrotreating method in which the hydrotreating catalyst of this embodiment is packed into a single reactor, or may be a multi-stage continuous hydrotreating method in which the hydrotreating catalyst of this embodiment is packed into several reactors.

[0118] The hydrotreating method of this embodiment may be a hydrotreating method in which the reaction mixture is contacted with three types of catalysts (first-stage catalyst, middle-stage catalyst, and second-stage catalyst). Hydrotreating methods using these three types of catalysts are preferably used for heavy hydrocarbon oils such as atmospheric distillation residue and vacuum distillation residue, with each catalyst primarily required to have different performance characteristics. The first-stage catalyst is primarily required to have metal resistance and demetalization activity to protect the middle and subsequent catalysts. The middle-stage catalyst is primarily required to have a balanced combination of metal resistance and demetalization activity, as well as desulfurization performance. The second-stage catalyst is primarily required to have desulfurization performance. In such a reaction system, it is preferable to use the hydrotreating catalyst of the present invention described above as the middle-stage catalyst. A known first-stage catalyst in the field can be used as the first-stage catalyst. Examples of such first-stage catalysts include the first-stage catalysts described in JP 2010-248476 A, WO 2015 / 053087 A, and WO 2015 / 046323 A. As the second-stage catalyst, a second-stage catalyst known in the art can be used. Examples of such second-stage catalysts include the second-stage catalysts described in JP 2010-248476 A, WO 2015 / 053087 A, and WO 2015 / 046323 A.

[0119] In the hydrotreating method of this embodiment, the loading ratio of the first-stage catalyst is preferably 10 to 50% of the total catalyst volume, and more preferably 15 to 40%. The loading ratio of the middle-stage catalyst is preferably 10 to 50% of the total catalyst volume, and more preferably 15 to 40%. The loading ratio of the second-stage catalyst is preferably 20 to 70% of the total catalyst volume, and more preferably 30 to 65%. The sum of the loading ratios of the first-stage catalyst, the middle-stage catalyst, and the second-stage catalyst may be 100%. Loading ratios of the first-stage catalyst, the middle-stage catalyst, and the second-stage catalyst within the above ranges are advantageous for maintaining catalyst life, desulfurization activity, and demetallization activity. [Example]

[0120] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. Examples 1, 2, and 5 are reference examples.

[0121] <Physical and chemical properties of the catalyst> [1] Analysis of physical properties (specific surface area, pore volume, average pore diameter, pore distribution, and average particle diameter) (a) Measurement method and equipment used: The specific surface area was measured by the BET method using nitrogen adsorption. The nitrogen adsorption device used was a surface area measuring device (BELSORP-mini II) manufactured by Microtrack BEL Co., Ltd. The pore volume, average pore diameter, and pore distribution were measured by mercury intrusion porosimetry using a porosimeter (AutoPore IV, manufactured by Micromeritics). The particle sizes of zinc-derived particles, titanium-derived particles, and phosphorus-derived particles in the hydrotreating catalyst were measured as the maximum distance between two parallel lines sandwiching a planar image of each particle observed with a transmission electron microscope (TEM-EDS, JEM-ARM200F NEOARM: manufactured by JEOL Ltd.) using energy dispersive X-ray analysis. The particle sizes of 10 randomly selected particles for each particle were measured, and the average was taken as the average particle size. The measurement conditions were as follows: Acceleration voltage: 200.00kV ·Measurement magnification: 500,000 to 3 million times EDS energy range: 0~40keV

[0122] (b) Mercury porosimetry measurement principle: Mercury intrusion porosimetry is based on the law of capillary action. In the case of mercury and a cylindrical pore, this law is expressed as follows: The volume of mercury that penetrates into the pore is measured as a function of the applied pressure P. The surface tension of the mercury in the catalyst pore is set to 484 dyne / cm, and the contact angle is set to 130°. D=-(1 / P)4γcosθ In the formula, D is the pore diameter, P is the applied pressure, γ is the surface tension, and θ is the contact angle. The pore volume is the total volume of mercury that has entered the pores per gram of catalyst. The average pore diameter is the average value of D calculated as a function of P. The pore size distribution is the calculated distribution of D as a function of P.

[0123] (c) Measurement procedure: (1) Turn on the vacuum heating degassing device and set the temperature at 400°C and the vacuum level at 5 x 10 -2 Check that the temperature is below Torr. (2) Place the empty sample burette in a vacuum heating degasser. (3) Vacuum level is 5×10 -2 After confirming that the pressure has dropped to Torr or less, the sample burette is removed from the vacuum heating degasser with its cock closed, and after cooling, its weight is measured. (4) Place the sample (catalyst) in the sample buret. (5) Place the sample burette in a vacuum heating degasser until the vacuum reaches 5 x 10 -2 Torr or less and maintain the pressure for at least one hour. (6) Remove the sample burette containing the sample from the vacuum heating degasser, cool it, and then measure its weight to determine the sample weight. (7) Place the sample in the AutoPore IV cell. (8) Measured using AutoPore IV.

[0124] [2] Analysis of chemical composition It was confirmed by the following method that the content ratio of each element in the hydrotreating catalyst and in the carrier was the same as that based on the amount of the raw material charged. (a) Analytical methods and equipment used: Elemental analysis of the carrier and catalyst was carried out using an inductively coupled plasma emission spectrometer (iCAP 6000: manufactured by Thermo Scientific). The elemental quantification was carried out by the absolute calibration curve method.

[0125] (b) Measurement procedure: (1) 0.05 g of catalyst or carrier, 1 mL of hydrochloric acid (50% by mass), one drop of hydrofluoric acid, and 1 mL of pure water were placed in a Uniseal and heated to dissolve. (2) After dissolution, the solution was transferred to a polypropylene measuring flask (50 mL), and pure water was added to the flask to make a total volume of 50 mL. (3) This solution was measured using the inductively coupled plasma emission spectrometer.

[0126] <Hydroprocessing of hydrocarbon oils> A mixed oil of atmospheric distillation residue and vacuum distillation residue having the following properties was hydrotreated in the following manner. First, a demetallization catalyst (a hydrodemetallization catalyst comprising nickel and molybdenum supported on a zinc-containing alumina carrier) was used as the upstream catalyst, and a hydrotreatment catalyst from each Example or Comparative Example was used as the downstream catalyst, packed into a high-pressure flow reactor in a volume ratio of 15:85 to form a fixed-bed catalyst layer, and pretreatment was carried out under the following conditions. Next, a mixed fluid of feedstock oil and hydrogen-containing gas was introduced from the top of the reactor, and the hydrotreatment reaction was allowed to proceed under the following conditions. The mixed fluid of the product oil and gas was discharged from the bottom of the reactor, and the product oil was separated in a gas-liquid separator.

[0127] Catalyst pretreatment conditions: drying at 120°C for 3 hours under normal pressure. The catalyst was pre-sulfided using vacuum diesel fuel at a hydrogen partial pressure of 10.3 MPa and 370°C for 12 hours, after which the feedstock oil for activity evaluation was used.

[0128] Reaction conditions: Pressure (hydrogen partial pressure): 10.3 MPa Liquid space velocity: 0.253hr -1 Hydrogen / oil ratio: 876.2 Nm 3 / kL Reaction temperature: 380℃

[0129] Feedstock properties: Oil type: Mixture of atmospheric distillation residue and vacuum distillation residue (derived from Middle Eastern crude oil) Density (15℃); 0.9906g / cm 3 Sulfur content: 3.56% by mass Vanadium: 19.8 ppm by mass Nickel: 36.2 ppm by mass Asphaltene content: 4.21 mass%

[0130] The catalytic activity was analyzed by the following method: The reactor was operated under the above conditions, and the product oil was sampled every other day from the start of operation, and the desulfurization reaction rate constant was calculated using the following formula. Desulfurization reaction rate constant (Ks) = [1 / Sp-1 / Sf] × (LHSV) In the above formula, Sf represents the sulfur content in the feed oil, Sp represents the sulfur content in the product oil, and LHSV represents the liquid hourly space velocity. The reaction rate constant (Ks) is a constant in the reaction rate equation that obtains a second-order reaction order with respect to the reduction in the sulfur content (Sp) of the product oil. A higher reaction rate constant indicates higher catalytic activity.

[0131] [Manufacturing Example 1] 1.5 L of a 12% by mass aqueous solution of sulfuric acid was added to 100 L of pure water in a stirring vessel, heated to 95°C, and then vigorously stirred with a stirring blade for 5 minutes. 3.9 L of sodium aluminate with an alumina concentration of 70 g / L was added to prepare aluminum hydroxide, which was then stirred with a stirring blade for 24 hours. The resulting slurry was placed in a filter and filtered to remove water. The resulting gel was then dissolved in pure water and spun to form a filtrate containing SO4 2- , Na + The gel was washed until no trace of cellulose was detected. The washed gel was then turbidified with pure water to form a uniform slurry, which was then placed in a press filter. The slurry was sandwiched between filter plates via a filter cloth, and the filter plates were squeezed to dehydrate. Filtration was discontinued when the moisture content of the cake reached 80% by mass. The cake was placed in a heated kneader (set temperature 80°C) and thoroughly kneaded to homogenize. Phosphoric acid and zinc oxide particles were then added to form the composition of Carrier A listed in Table 1, and further kneaded to homogenize. The average particle diameter of the zinc oxide particles was 0.8 μm. The average particle diameter of the zinc oxide particles was the volume average of the particle size distribution measured by a laser diffraction scattering method in accordance with JIS R1629. The kneaded cake was placed in an extruder and extruded into a four-lobe shape with a major axis of 1.3 mm and a minor axis of 1.1 mm. The molded product was dried and then calcined at 600°C for 4 hours to obtain a phosphorus- and zinc-containing alumina support precursor.

[0132] 5.7 g of titanium metal powder, 80 mL of 30% hydrogen peroxide, and 20 mL of 30% ammonia water were mixed in a beaker and dissolved while cooling in a water bath, yielding a transparent yellow titanium peroxy solution. 27.4 g of citric acid was then added to the resulting solution and completely dissolved. This solution was heated at 50-80°C for 3 hours to remove unreacted hydrogen peroxide and ammonia, yielding 50 mL of a water-soluble titanium compound (titanium peroxycitric acid compound) aqueous solution. In a recovery flask, the aqueous solution of the water-soluble titanium compound was impregnated into a phosphorus- and zinc-containing alumina support precursor so as to obtain the composition of support A shown in Table 1. The impregnated body was dried and then calcined at 500°C for 4 hours in an air atmosphere to obtain zinc-titanium-phosphorus-containing alumina support A. The content ratio of each component in carrier A, calculated as an element, is shown in Table 1 (hereinafter, the same applies to carriers B to I).

[0133] [Manufacturing Example 2] A zinc-titanium-phosphorus-containing alumina carrier B was obtained in the same manner as in Production Example 1, except that the amounts of phosphoric acid, zinc oxide particles, and water-soluble titanium compound added were changed so as to obtain the composition of carrier B shown in Table 1.

[0134] [Manufacturing Example 3] A zinc-titanium-phosphorus-containing alumina carrier C was obtained in the same manner as in Production Example 1, except that the amounts of phosphoric acid, zinc oxide particles, and water-soluble titanium compound added were changed so as to obtain the composition of carrier C shown in Table 1.

[0135] [Manufacturing Example 4] A zinc-titanium-phosphorus-containing alumina carrier D was obtained in the same manner as in Production Example 1, except that the amounts of phosphoric acid, zinc oxide particles, and water-soluble titanium compound added were changed so as to obtain the composition of carrier D shown in Table 1.

[0136] [Manufacturing Example 5] A zinc-titanium-phosphorus-boron-containing alumina carrier E was obtained in the same manner as in Production Example 1, except that the amounts of phosphoric acid, zinc oxide particles, and water-soluble titanium compound added were adjusted to give the composition of carrier E shown in Table 1, and boric acid was added so as to give the composition of carrier E. A predetermined amount of boric acid was added to the aqueous solution of the water-soluble titanium compound and added simultaneously with the water-soluble titanium compound.

[0137] [Manufacturing Example 6] A zinc-phosphorus-containing alumina carrier F was obtained in the same manner as in Production Example 1, except that the amounts of phosphoric acid and zinc oxide particles added were adjusted to give the composition of carrier F shown in Table 1 and that the operations subsequent to the addition of the water-soluble titanium compound were not carried out.

[0138] [Manufacturing Example 7] Titanium-phosphorus-containing alumina carrier G was obtained in the same manner as in Production Example 1, except that the amounts of phosphoric acid and the water-soluble titanium compound added were adjusted to give the composition of carrier G shown in Table 1, and zinc oxide particles were not added.

[0139] [Manufacturing Example 8] Titanium-phosphorus-containing alumina carrier H was obtained in the same manner as in Production Example 1, except that a titanium ethanol solution prepared by dissolving tetrabutoxytitanium in ethanol was used instead of the water-soluble titanium compound, the amounts of phosphoric acid and titanium ethanol solution were adjusted to give the composition of carrier H shown in Table 1, and zinc oxide particles were not added.

[0140] [Manufacturing Example 9] Titanium-phosphorus-containing alumina carrier I was obtained in the same manner as in Production Example 1, except that a 30% aqueous titanium sulfate solution was used instead of the water-soluble titanium compound, the amounts of phosphoric acid and the 30% aqueous titanium sulfate solution were adjusted to give the composition of carrier I shown in Table 1, and zinc oxide particles were not added.

[0141] [Table 1]

[0142] [Example 1] A molybdenum-nickel aqueous solution was prepared by dissolving 10.77 g of ammonium molybdate tetrahydrate, 14.10 g of citric acid monohydrate, and 11.39 g of nickel nitrate in 37.2 g of ion-exchanged water. The zinc-titanium-phosphorus-containing alumina support A obtained in Production Example 1 was impregnated with the solution in a recovery flask to obtain the composition of catalyst A listed in Table 2. The impregnated body was then dried and calcined at 500°C for 4 hours in an air atmosphere to obtain catalyst A. Table 2 shows the catalyst-based, element-equivalent content, average particle size, specific surface area, pore volume, average pore diameter, and the ratio of the volume of pores with a diameter within ±1.5 nm of the average pore diameter to the total pore volume of catalyst A. Note that "pore distribution" in Table 2 refers to the ratio of the volume of pores with a diameter within ±1.5 nm of the average pore diameter to the total pore volume (hereinafter, this also applies to catalysts B to I). A hydrotreating reaction of a mixed oil of atmospheric distillation residue and vacuum distillation residue was carried out under the above-mentioned conditions using catalyst A. The results are shown in Table 3 (hereinafter, the results for catalysts B to I are also shown in the same manner). The specific activity in Table 3 is the specific activity when the desulfurization reaction rate constant when the hydrotreating reaction of the mixed oil was carried out using catalyst F (Comparative Example 1) was set to 100%.

[0143] [Example 2] Catalyst B was obtained in the same manner as in Example 1, except that the zinc-titanium-phosphorus-containing alumina support B obtained in Production Example 2 was used instead of the zinc-titanium-phosphorus-containing alumina support A, and a hydrotreating reaction of a mixed oil of atmospheric distillation residue and vacuum distillation residue was carried out.

[0144] [Example 3] Catalyst C was obtained in the same manner as in Example 1, except that the zinc-titanium-phosphorus-containing alumina support C obtained in Production Example 3 was used instead of the zinc-titanium-phosphorus-containing alumina support A, and a hydrotreating reaction of a mixed oil of atmospheric distillation residue and vacuum distillation residue was carried out.

[0145] [Example 4] Catalyst D was obtained in the same manner as in Example 1, except that the zinc-titanium-phosphorus-containing alumina carrier D obtained in Production Example 4 was used instead of the zinc-titanium-phosphorus-containing alumina carrier A, and a hydrotreating reaction of a mixed oil of atmospheric distillation residue and vacuum distillation residue was carried out.

[0146] [Example 5] Catalyst E was obtained in the same manner as in Example 1, except that the zinc-titanium-phosphorus-boron-containing alumina support E obtained in Production Example 5 was used instead of the zinc-titanium-phosphorus-boron-containing alumina support A, and a hydrotreating reaction of a mixed oil of atmospheric distillation residue and vacuum distillation residue was carried out.

[0147] [Comparative Example 1] Catalyst F was obtained in the same manner as in Example 1, except that the zinc-titanium-phosphorus-containing alumina support F obtained in Production Example 6 was used instead of the zinc-titanium-phosphorus-containing alumina support A, and a hydrotreating reaction of a mixed oil of atmospheric distillation residue and vacuum distillation residue was carried out.

[0148] Comparative Example 2 Catalyst G was obtained in the same manner as in Example 1, except that the titanium-phosphorus-containing alumina support G obtained in Production Example 7 was used instead of the zinc-titanium-phosphorus-containing alumina support A, and a hydrotreating reaction of a mixed oil of atmospheric distillation residue and vacuum distillation residue was carried out.

[0149] Comparative Example 3 Catalyst H was obtained in the same manner as in Example 1, except that the titanium-phosphorus-containing alumina support H obtained in Production Example 8 was used instead of the zinc-titanium-phosphorus-containing alumina support A, and a hydrotreating reaction of a mixed oil of atmospheric distillation residue and vacuum distillation residue was carried out.

[0150] Comparative Example 4 Catalyst I was obtained in the same manner as in Example 1, except that the titanium-phosphorus-containing alumina support I obtained in Production Example 9 was used instead of the zinc-titanium-phosphorus-containing alumina support A, and a hydrotreating reaction of a mixed oil of atmospheric distillation residue and vacuum distillation residue was carried out.

[0151] [Table 2]

[0152] [Table 3]

[0153] The catalysts of Examples 1 to 5 of the present invention were found to have higher specific activity after 7 days and less likely to decrease in hydrogenation activity than the catalysts of Comparative Example 1, which did not contain titanium, and Comparative Examples 2 to 4, which did not contain zinc. In particular, the effect of suppressing decrease in hydrogenation activity was remarkable in Examples 3 and 4, which contained 4.0 mass% or more of titanium, calculated as an element, based on the catalyst. [Industrial Applicability]

[0154] The hydrocarbon oil hydrotreating catalyst according to the present invention is useful because it can be used to reduce the sulfur content in hydrocarbon oil.

Claims

1. A hydrocarbon oil hydrotreating catalyst comprising a zinc-titanium-containing alumina carrier containing zinc and titanium, and carrying thereon at least one metal selected from Group 6 metals of the periodic table and at least one metal selected from Group 9 and Group 10 metals of the periodic table, a catalyst for hydrotreating a hydrocarbon oil, wherein the zinc content is 0.8 to 10 mass% in elemental terms based on the catalyst, the titanium content is 0.03 to 10 mass% in elemental terms based on the catalyst, the at least one metal selected from Group 6 metals of the periodic table is 5 to 16 mass% in elemental terms based on the catalyst, and the at least one metal selected from Group 9 and Group 10 metals of the periodic table is 1 to 5 mass% in elemental terms based on the catalyst, and the molar ratio of the titanium content to the zinc content is 2 to 12.

2. The hydrotreating catalyst for hydrocarbon oils according to claim 1, wherein the average particle size of particles derived from titanium element observed when the hydrotreating catalyst is analyzed with a transmission electron microscope using energy dispersive X-ray analysis is 0.3 to 10 nm.

3. the support is a zinc-titanium-phosphorus-containing alumina support further containing phosphorus, The catalyst for hydrotreating hydrocarbon oils according to claim 1 or 2, wherein the phosphorus content is 0.04 to 2 mass% in elemental terms based on the catalyst.

4. The hydrotreating catalyst for hydrocarbon oils according to any one of claims 1 to 3, wherein the average particle size of zinc-derived particles observed when the hydrotreating catalyst is analyzed with a transmission electron microscope using energy dispersive X-ray analysis is 0.3 to 10 nm.

5. A method for producing a hydrocarbon oil hydrotreating catalyst according to any one of claims 1 to 4, comprising: A method for producing a catalyst for hydrotreating hydrocarbon oils includes supporting, on a zinc / titanium-containing alumina support containing 1 to 14 mass % of zinc, calculated as an element, and 0.1 to 13 mass % of titanium, calculated as an element, based on the support, at least one metal selected from Group 6 metals of the periodic table in an amount of 5 to 16 mass % of the catalyst, calculated as an element, and at least one metal selected from Group 9 and Group 10 metals of the periodic table in an amount of 1 to 5 mass % of the catalyst, calculated as an element.

6. The method for producing a hydrocarbon oil hydrotreating catalyst according to claim 5, wherein the average particle size of particles derived from titanium element observed when the hydrotreating catalyst is analyzed with a transmission electron microscope using energy dispersive X-ray analysis is 0.3 to 10 nm.

7. 7. The method for producing a hydrocarbon oil hydrotreating catalyst according to claim 5, wherein the support is a zinc-titanium-phosphorus-containing alumina support further containing 0.04 to 3 mass% of phosphorus in elemental terms based on the support.

8. The method for producing a hydrotreating catalyst according to any one of claims 5 to 7, wherein the average particle size of zinc-derived particles observed when the hydrotreating catalyst is analyzed using a transmission electron microscope with energy dispersive X-ray analysis is 0.3 to 10 nm.

9. Hydrogen partial pressure: 3 to 20 MPa, reaction temperature: 280 to 450°C, liquid hourly space velocity: 0.01 to 5 hr －１ A method for hydrotreating a hydrocarbon oil, comprising contacting the hydrocarbon oil with the hydrocarbon oil hydrotreating catalyst according to any one of claims 1 to 4.

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