METHOD FOR PRODUCING CATALYST FOR HYDROCARBON OIL HYDROGENATION AND METHOD FOR HYDROCARBON OIL HYDROGENATION

Abstract

To provide a method for manufacturing a catalyst for hydrotreating a hydrocarbon oil having high hydrogenation activity per unit specific surface area and to provide a method for hydrotreating a hydrocarbon oil using the catalyst for hydrotreating a hydrocarbon oil manufactured by the manufacturing method.SOLUTION: There is provided a method for manufacturing a catalyst for hydrotreating a hydrocarbon oil wich comprises supporting at least one metal selected from Group 6 metals in the periodic table and Group 9 and Group 10 metals in the periodic table on a carrier obtained by subjecting a metal oxide to hydrothermal treatment.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a catalyst for hydrotreating hydrocarbon oils and a method for hydrotreating hydrocarbon oils. [Background technology]

[0002] The oil fractions obtained by distillation or cracking of crude oil generally contain sulfur compounds, and when these oils are used as fuel, sulfur oxides and the like are generated due to these sulfur compounds. Therefore, the process of producing petroleum products from crude oil includes a hydrotreating step to remove the sulfur compounds.

[0003] In the hydrotreating step, the feedstock oil derived from crude oil is hydrotreated by contacting the feedstock oil with a hydrotreating catalyst in the presence of hydrogen. As the hydrotreating catalyst, a catalyst in which a hydrogenation active metal such as molybdenum, nickel, or cobalt is supported on a metal oxide support is widely used.

[0004] To increase the efficiency of hydrotreating, it is desirable to improve the performance of hydrotreating catalysts. To improve the performance of hydrotreating catalysts, metal oxide supports and hydrogenation active metals are being investigated.

[0005] Regarding metal oxide supports, for example, Patent Document 1 discloses that coke deterioration of hydrotreating catalysts can be suppressed by incorporating zinc oxide into a metal oxide support.

[0006] In studies of hydrogenation-active metals, for example, Non-Patent Documents 1 and 2 suggest that hydrogenation-active metals in hydrotreating catalysts include hydrogenation-active metal species that are supported on a metal oxide support in tetrahedrally coordinated positions (hereinafter also referred to as "tetrahedrally coordinated hydrogenation-active metal species") and hydrogenation-active metal species that are supported on a metal oxide support in octahedral coordinated positions (hereinafter also referred to as "octahedral coordinated hydrogenation-active metal species"), and that the octahedral coordinated hydrogenation-active metal species have higher hydrogenation activity than the tetrahedrally coordinated hydrogenation-active metal species. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2015 / 046345 [Non-patent literature]

[0008] [Non-Patent Document 1] CTJ Mensch, et al., J. Phys. Chem., 92, 4961(1988) [Non-patent document 2] H. Topsoe, et al., Ind. Eng. Chem. Fundam., 25, 25(1986) Summary of the Invention [Problem to be solved by the invention]

[0009] Non-Patent Documents 1 and 2 suggest a qualitative relationship between the type of hydrogenation-active metal species and hydrogenation activity, but do not disclose any specific method for increasing the proportion of octahedral-coordinated hydrogenation-active metal species and improving the performance of hydrotreating catalysts.

[0010] In general, the larger the specific surface area of ​​a hydrotreating catalyst, the higher its hydrogenation activity tends to be. Therefore, when examining the relative merits of activity depending on the structure of the hydrogenation-active metal, such as the above-mentioned tetrahedrally coordinated hydrogenation-active metal species and octahedrally coordinated hydrogenation-active metal species, it is reasonable to evaluate the hydrogenation activity of the hydrotreating catalyst per unit specific surface area.

[0011] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a hydrocarbon oil hydrotreating catalyst having high hydrogenation activity per unit specific surface area, and a method for hydrotreating hydrocarbon oil using the hydrocarbon oil hydrotreating catalyst produced by the production method. [Means for solving the problem]

[0012] In order to solve the above problems, the present invention has the following aspects. [1] A method for producing a catalyst for hydrotreating hydrocarbon oils, comprising supporting 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 on a support obtained by subjecting a metal oxide to hydrothermal treatment. [2] The hydrothermal treatment is performed by subjecting the metal oxide to steam at a temperature of 200°C or higher and GHSV100h. -1 The method for producing a hydrocarbon oil hydrotreating catalyst according to [1], wherein the hydrothermal treatment is carried out under the above conditions. [3] A method for producing a catalyst for hydrotreating hydrocarbon oils according to [1] or [2], wherein the catalyst supports at least one metal selected from Group 6 metals of the periodic table in an amount of 5 to 35 mass % in terms of oxide, 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 18 mass % in terms of oxide, based on the catalyst. [4] Hydrogen partial pressure: 3-20 MPa, reaction temperature: 280-420°C, liquid hourly space velocity: 0.1-10 h -1 A method for hydrotreating a hydrocarbon oil, comprising contacting the hydrocarbon oil with a hydrotreating catalyst produced by the production method according to any one of [1] to [3]. [5] Hydrogen partial pressure: 3-20 MPa, reaction temperature: 280-420°C, liquid hourly space velocity: 0.1-10 h -1 A method for producing a hydrogenated hydrocarbon oil, comprising contacting a hydrocarbon oil with a hydrotreating catalyst produced by the production method according to any one of [1] to [3]. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a method for producing a hydrocarbon oil hydrotreating catalyst having high hydrogenation activity per unit specific surface area, and a method for hydrotreating hydrocarbon oil using the hydrocarbon oil hydrotreating catalyst produced by the production method. 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] <Method for producing a catalyst for hydrotreating hydrocarbon oil> The method for producing a hydrocarbon oil hydrotreating catalyst (hereinafter also simply referred to as "hydrotreating catalyst") of this embodiment includes supporting 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 on a support obtained by hydrothermal treatment of a metal oxide. 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."

[0016] <Carrier> The support used in the method for producing a hydrotreating catalyst of this embodiment is a support obtained by subjecting a metal oxide to hydrothermal treatment. The metal oxide and hydrothermal treatment will be described below.

[0017] (metal oxides) As the metal oxide, any metal oxide usable as a support for a hydrocarbon oil hydrotreating catalyst in this field can be used, and examples thereof include alumina, zeolite, silica, zirconia, titania, boria, phosphorus oxide, zinc oxide, etc., with alumina, phosphorus oxide, zinc oxide, titania, and boria being preferred, and alumina being particularly preferred. Note that boron and silicon are elements generally considered to be semimetals, but are treated as metals in this specification.

[0018] The metal oxide may be one kind or two or more kinds. When two or more kinds of metal oxides are used, the metal oxide may be a mixture of these two or more kinds of metal oxides, or a composite oxide of these two or more kinds of metal oxides.

[0019] When a plurality of metal oxides are contained, the preferred ranges of the content ratio of each metal oxide are as follows. When the metal oxide contains alumina, the content of alumina relative to the total mass of the metal oxide is preferably 80 to 99.9 mass %, more preferably 82.5 to 99.8 mass %, and even more preferably 85 to 99.6 mass %. When the metal oxide contains phosphorus oxide, the content of phosphorus oxide relative to the total mass of the metal oxide is preferably 0.01 to 10 mass %, more preferably 0.01 to 5 mass %. When the metal oxide contains zinc oxide, the content of zinc oxide relative to the total mass of the metal oxide is preferably 0.01 to 15 mass %, more preferably 0.01 to 10 mass %. When the metal oxide contains silica, the content of silica relative to the total mass of the metal oxide is preferably 0.01 to 18 mass %, more preferably 0.01 to 15 mass %. When the metal oxide contains titania, the content of titania relative to the total mass of the metal oxide is preferably 0.01 to 20 mass %, more preferably 0.01 to 17.5 mass %. When the metal oxide contains boria, the content of boria relative to the total mass of the metal oxide is preferably 0.01 to 20 mass %, more preferably 0.01 to 15 mass %. When the metal oxide contains zeolite, the content of the zeolite relative to the total mass of the metal oxide is preferably 0.01 to 10 mass %, more preferably 0.01 to 5 mass %. In one aspect of the present invention, the metal oxide preferably does not include zeolite.

[0020] The content ratio of each metal oxide in the metal oxides can be determined by measuring the mass of each metal oxide converted into element, and dividing the converted value by the total mass of the metal oxides: Al2O3 for alumina, P2O5 for phosphorus oxide, ZnO for zinc oxide, SiO2 for silica, TiO2 for titania, and B2O3 for boria. In this specification, the mass of the metal oxide, the support, and the hydrotreating catalyst in terms of element can be measured by inductively coupled plasma atomic emission spectrometry.

[0021] The support of this embodiment is obtained by subjecting metal oxides to hydrothermal treatment, but the content ratio of each metal oxide before and after the hydrothermal treatment remains substantially unchanged. "Substantially unchanged" means that the ratio of (content ratio of each metal oxide after hydrothermal treatment) / (content ratio of each metal oxide before hydrothermal treatment) falls within the range of 0.98 to 1.02.

[0022] As the alumina, various types of alumina such as α-alumina, β-alumina, γ-alumina, and δ-alumina can be used, but alumina that is porous and has a large 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., but it is preferable that the amount of these impurities is as small as possible, and the total amount of impurities is preferably 2 mass% or less, and more preferably 1 mass% or less. 2- is 1.5 mass% or less, Cl - , Fe2O3, and Na2O are each preferably 0.1 mass % or less.

[0023] (Physical properties of metal oxides) The physical properties of the metal oxide can be adjusted appropriately depending on the conditions of the hydrothermal treatment described below and the physical properties of the target support. The specific surface area of ​​the metal oxide of this embodiment is 200 to 400 m as measured by the nitrogen adsorption method (BET method). 2 / g is preferred, and 250 to 350m 2 / g is more preferred. The average pore size in the pore distribution of the metal oxide of this embodiment measured by mercury intrusion porosimetry is preferably 5 to 12 nm, more preferably 6 to 10 nm. The pore volume of the metal oxide of this embodiment is preferably 0.4 to 0.9 mL / g, more preferably 0.5 to 0.8 mL / g, as measured by mercury intrusion porosimetry.

[0024] (Metal oxide manufacturing method) The metal oxide of this embodiment can be produced by a method known in the art. An example of a method for producing a metal oxide containing alumina as a main component will be described below. The method for producing a metal oxide containing alumina as a main component of this embodiment includes, for example, an alumina gel preparation step for preparing an alumina gel, a kneading step for kneading the alumina gel to obtain a kneaded mixture, a molding step for molding the kneaded mixture to obtain a molded product, and a firing step for drying and firing the molded product to obtain a metal oxide as a fired product. The alumina gel preparation step, kneading step, molding step, and firing step are preferably performed in the above-mentioned order. However, the firing step may be performed between the alumina gel preparation step and the kneading step, or between the kneading step and the molding step.

[0025] When the metal oxide containing alumina as a main component contains the above-mentioned zeolite, silica, zirconia, titania, boria, phosphorus oxide, zinc oxide, etc., the metal oxide or a raw material compound thereof (hereinafter also referred to as "metal oxide raw material") may be added to any of the alumina gel (including the alumina gel during kneading), the kneaded product, and the molded product. Among these, it is preferable to add the metal oxide raw material to the alumina gel during the kneading step and then perform the kneading step.

[0026] 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 %.

[0027] 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.

[0028] The resulting alumina gel was then added to the filtrate with SO4 2- , Na + After washing until no trace of fluorine is detected, the alumina gel is mixed with pure water to form a uniform slurry, and the resulting alumina gel slurry is dehydrated until the water content is 60 to 90 mass % to obtain a cake.

[0029] 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).

[0030] By dehydrating the alumina gel slurry using a filter press, the surface condition of the obtained 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, or may be carried out after both steps. In particular, it is more preferable to carry out the dehydration step after the alumina gel preparation step and before the kneading step.

[0031] 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.

[0032] When the above-mentioned metal oxide raw material is added to the alumina gel, the alumina gel is prepared by the above-mentioned method, and the obtained alumina gel is aged, washed, dehydrated and dried, and the water content is adjusted, after which the metal oxide raw material can be added to the alumina gel. The metal oxide raw material can be added to the alumina gel by a coprecipitation method, a kneading method, or the like.

[0033] When adding a metal oxide raw material to an alumina gel by a kneading method, the metal oxide raw material is added to the alumina gel obtained in the alumina gel preparation step, and kneading is performed. Specifically, the metal oxide raw material heated to 15 to 90°C is 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 performed after kneading and stirring the alumina gel and the metal oxide raw material. The metal oxide raw material may be added as a solid or liquid, or as a liquid obtained by dissolving or suspending the metal oxide raw material in a solvent.

[0034] As the metal oxide raw material, raw materials known in the art can be used.

[0035] When producing a metal oxide containing zinc oxide, the zinc oxide raw material to be added can be zinc itself or various zinc compounds, 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.

[0036] When the zinc oxide raw material is a solid such as zinc oxide, it is preferable to add the zinc oxide raw material to the aluminum gel together with an acid such as nitric acid and then carry out the kneading step.When the zinc oxide 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 oxide 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.

[0037] When producing a metal oxide containing phosphorus oxide, the phosphorus oxide raw material to be added can be simple phosphorus or various compounds, such as orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, and aluminum phosphate, with orthophosphoric acid being preferred.

[0038] The kneaded product thus obtained is 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 of the firing can be appropriately set as needed, but for example, the firing temperature to obtain 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.

[0039] (Hydrothermal treatment) The hydrothermal treatment of this embodiment is a treatment in which the metal oxide is brought into contact with water vapor. Hereinafter, a treatment in which water vapor is brought into contact with the metal oxide in the calcined form described above will be described. However, the object to be contacted with water vapor may also be the calcined powder obtained by calcining the alumina gel obtained in the alumina gel preparation step or the kneaded product obtained in the kneading step by the method described in the calcination step. In this case, the calcined powder after the hydrothermal treatment can be molded or otherwise formed by the method described above to produce a carrier. The hydrothermal treatment method is not particularly limited as long as the effects of the present invention can be obtained, but for example, the treatment can be carried out by filling a treatment device with the metal oxide and circulating water vapor. The metal oxide filled in the treatment device may be in a fixed bed, a fluidized bed, or a moving bed. Among these, a fixed bed is preferred.

[0040] The gas hourly space velocity (GHSV) of water vapor relative to the metal oxide is 100h -1 It is preferable that the temperature is at least 120 h. -1 It is preferable that the temperature is at least 150 h. -1 When the GHSV of water vapor relative to the metal oxide is equal to or greater than the lower limit, the hydrogenation activity per unit specific surface area of ​​the finally obtained hydrotreating catalyst is improved. The upper limit of the GHSV is not particularly limited as long as the effects of the present invention can be obtained. For example, -1 Less than 500h is fine. -1 Less than 250h is fine. -1 The following is also acceptable. The lower limit and upper limit can be combined in any way. GHSV can be calculated from the volume of the metal oxide packed in the treatment device and the standard state equivalent water vapor flow rate (e.g., NmL / h). For example, if the treatment device is cylindrical, the volume of the metal oxide is calculated as (the inner diameter of the treatment device / 2) 2 ×π×metal oxide layer height.

[0041] The hydrothermal treatment may contain gases other than water vapor, and examples of such gases include inert gases such as helium, nitrogen, and argon, air, etc. When the hydrothermal treatment contains gases other than water vapor, the ratio of the water vapor to the gas other than water vapor is not particularly limited as long as the GHSV of the water vapor relative to the metal oxide is equal to or greater than the lower limit, but for example, the ratio of the flow rate of water vapor to the total flow rate (100%) of the water vapor and the gas other than water vapor is preferably 10% or more, more preferably 50% or more.

[0042] The temperature of the hydrothermal treatment is preferably 200° C. or higher, more preferably 300° C. or higher, and even more preferably 350° C. or higher. When the temperature of the hydrothermal treatment is equal to or higher than the lower limit, the hydrogenation activity per unit specific surface area of ​​the finally obtained hydrotreatment catalyst is improved. The temperature of the hydrothermal treatment is preferably 800° C. or less, more preferably 600° C. or less, even more preferably 500° C. or less, and particularly preferably 450° C. or less. When the temperature of the hydrothermal treatment is the above upper limit or less, a decrease in the specific surface area of ​​the obtained support (and catalyst) is suppressed. The lower limit and upper limit can be combined in any way.

[0043] The hydrothermal treatment time can be adjusted appropriately depending on the GHSV of the steam and the temperature of the hydrothermal treatment. The hydrothermal treatment time is, for example, preferably 1 hour or more, more preferably 2 hours or more, and even more preferably 4 hours or more. If the hydrothermal treatment time is equal to or greater than the lower limit, the hydrogenation activity per unit specific surface area of ​​the finally obtained hydrotreatment catalyst is improved. The upper limit of the steam treatment time is not particularly limited as long as the effects of the present invention can be obtained, but it may be, for example, 10 hours or less, or 8 hours or less. The lower limit and upper limit can be combined in any way.

[0044] The pressure during the hydrothermal treatment is not particularly limited as long as the effects of the present invention can be obtained, but may be 0.1 to 2 MPa or 0.1 to 1 MPa.

[0045] (Carrier properties) The specific surface area of ​​the carrier of this embodiment is 100 to 400 m as measured by the nitrogen adsorption method (BET method). 2 / g is preferred, and 150 to 400m 2 / g is more preferable, and 200 to 350m 2 / g is more preferable, and 240 to 350m 2 / g is particularly preferred, and when the specific surface area is at least 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 not more 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.

[0046] The average pore diameter of the support of this embodiment in the pore distribution measured by mercury intrusion porosimetry is preferably 5 to 15 nm, more preferably 6 to 14 nm. When the average pore diameter is within this range, the support has a sufficient inner pore surface area, and the sulfur compound diffuses sufficiently into the catalyst pores, resulting in high hydrogenation activity.

[0047] 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.

[0048] <Supporting process> The supporting step of this embodiment includes supporting 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.

[0049] 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.

[0050] Examples of metals in Groups 9 and 10 include nickel and cobalt, and among these, nickel is preferred because it has a high hydrogenation ability and low catalyst preparation costs.

[0051] In the hydrotreating catalyst of this embodiment, examples of the Group 6 metal raw material to be supported on the support include molybdenum compounds, tungsten compounds, and chromium compounds, with molybdenum compounds being preferred. The Group 6 metal raw material may be one type or two or more types.

[0052] Examples of the molybdenum compound include molybdenum trioxide, molybdophosphoric acid, ammonium molybdate, and molybdic acid, with molybdophosphoric acid, molybdenum trioxide, and ammonium molybdate being preferred. The molybdenum compound may be of one type or of two or more types.

[0053] Examples of tungsten compounds include tungstic acid, ammonium metatungstate, ammonium paratungstate, tungsten trioxide, and phosphotungstic acid, with tungstic acid, ammonium metatungstate, and ammonium paratungstate being preferred. The tungsten compound may be one type or two or more types.

[0054] Examples of chromium compounds include chromium oxide, chromium acetate, chromium sulfate, chromium phosphate, chromic acid, dichromic acid, and neutral red, with chromic acid being preferred. The chromium compound may be of one type or of two or more types.

[0055] In the hydrotreating catalyst of this embodiment, the Group 9 and Group 10 metal raw material to be supported on the support is preferably a nickel compound or a cobalt compound. Examples of nickel compounds include nickel oxide, nickel carbonate, nickel acetate, nickel nitrate, nickel sulfate, and nickel chloride, with nickel nitrate and nickel carbonate being preferred. Examples of the cobalt compound include cobalt carbonate, cobalt acetate, cobalt nitrate, cobalt sulfate, and cobalt chloride, with cobalt carbonate and cobalt acetate being preferred, and cobalt carbonate being more preferred.

[0056] The amount of the Group 6 metal supported is preferably 5 to 35 mass % of the catalyst in terms of oxide, more preferably 7 to 30 mass %, even more preferably 8 to 25 mass %, particularly preferably 10 to 20 mass %, and most preferably 10 to 18 mass %. When the amount of the Group 6 metal supported is equal to or greater than the lower limit of the above range, it is sufficient to realize the effects attributable to the Group 6 metal. When the amount of the Group 6 metal supported 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 supported does not exceed the amount that can be efficiently dispersed, and the catalyst surface area does not decrease significantly, thereby improving catalytic activity.

[0057] The amount of the Group 9 and 10 metals supported is preferably 1 to 18 mass %, more preferably 2 to 15 mass %, even more preferably 2.5 to 10 mass %, particularly preferably 3 to 6 mass %, and most preferably 3.5 to 5 mass % based on the catalyst in terms of oxide. When the amount of the Group 9 and 10 metals supported is equal to or greater than the lower limit of the above range, sufficient active sites attributable to the Group 9 and 10 metals are obtained. When the amount of the Group 9 and 10 metals supported is equal to or less than the upper limit of the above range, the Group 9 and 10 metals are less likely to aggregate, improving dispersibility. For example, when nickel is used as the Group 9 and 10 metal, the catalytic activity is improved because inactive precursors, such as NiO species (which exist as NiS species after catalyst sulfidation or during hydrogenation treatment) and Ni spinel species incorporated into the support lattice, are less likely to be generated.

[0058] The supported amounts of the Group 6 metals and the Group 9 and Group 10 metals, calculated as oxides based on the catalyst, can be determined by measuring the masses of the Group 6 metals and the Group 9 and Group 10 metals calculated as elements, and dividing the values ​​calculated as hexavalent oxides for the Group 6 metals and divalent oxides for the Group 9 and Group 10 metals by the total mass of the hydrotreating catalyst.

[0059] Methods for supporting a Group 6 metal source and Group 9 and Group 10 metal sources (hereinafter also referred to as "hydrogenation active component source") on a 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 a 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 a 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 a 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 a support with the hydrogenation active component source may be a batch impregnation method in which each of these components is simultaneously impregnated, or a sequential impregnation method in which each component is individually impregnated.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] The ratio of the mass of phosphorus contained in 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 degradation.

[0064] When a molybdenum compound is used as the Group 6 metal raw material, the ratio of the mass of phosphorus contained in 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 contained in 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 naturally integrated with the Group 9 and Group 10 metal compounds in the hydrotreating catalyst.

[0065] 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. Subsequently, calcination may be performed 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. Alternatively, calcination may not be performed.

[0066] <Hydrotreatment catalyst> The hydrotreating catalyst produced by the method for producing a hydrocarbon oil hydrotreating catalyst of this embodiment includes a support obtained by subjecting a metal oxide to hydrothermal treatment, 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. That is, the hydrotreating catalyst is a hydrocarbon oil hydrotreating catalyst in which 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 are supported on a support obtained by hydrothermal treatment of a metal oxide.

[0067] Examples of the Group 6 metal contained in the hydrotreating catalyst of this embodiment include the Group 6 metal raw material, the oxide produced by the calcination (specific example: molybdenum trioxide), and a composite oxide of a Group 6 metal and at least one element selected from the group consisting of aluminum, zinc, phosphorus, Group 9 metals, and Group 10 metals.

[0068] Examples of Group 9 and Group 10 metals contained in the hydrotreating catalyst of this embodiment include the Group 9 and Group 10 metal raw materials, oxides produced by the calcination (specific example: nickel oxide), and composite oxides of Group 9 and Group 10 metals and at least one element selected from the group consisting of aluminum, zinc, phosphorus, and Group 6 metals.

[0069] The content of the Group 6 metal and the content of the Group 9 and Group 10 metals contained in the hydrotreating catalyst are as described above. Similarly, the content of each metal oxide contained in the hydrotreating catalyst is appropriately determined from the composition of the metal oxide and the content of the Group 6 metal and the content of the Group 9 and Group 10 metals.

[0070] The phosphorus content in the hydrotreating catalyst is preferably 0.1 to 6 mass% and more preferably 0.5 to 3 mass% in terms of oxide based on the catalyst. When the phosphorus content is equal to or greater than the lower limit, the sulfidity of the Group 6 metal can be sufficiently improved. Furthermore, a decrease in the activity of the hydrotreating catalyst is suppressed. When the phosphorus content is equal to or less than the upper limit, a decrease in pore volume and specific surface area is unlikely to occur, and the Group 6 metal is sufficiently dispersed, thereby fully achieving the effect of adding phosphorus.

[0071] The zinc content in the hydrotreating catalyst is preferably 0.01 to 14.5 mass% and more preferably 0.01 to 9.5 mass% in terms of oxide, based on the catalyst. When the zinc content is equal to or greater than the lower limit, the sulfidity of the Group 6 metal can be sufficiently improved. Furthermore, a decrease in the activity of the hydrotreating catalyst is suppressed. When the zinc content is equal to or less than the upper limit, 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.

[0072] The specific surface area of ​​the hydrotreating catalyst is 100 to 300 m as measured by the BET method. 2 / g, and 120 to 300m 2 / g, and more preferably 150 to 280m 2 / g, and more preferably 200 to 280m 2 / g is particularly preferred. 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.

[0073] The average pore diameter of the hydrotreating catalyst in the pore distribution measured by mercury intrusion porosimetry is preferably 7 to 18 nm, more preferably 7 to 12 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.

[0074] The pore volume of the hydrotreating catalyst, as measured by mercury intrusion porosimetry, is preferably 0.4 to 0.8 mL / g, more preferably 0.45 to 0.8 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.

[0075] In order to increase the effective number of pores that satisfy the above-mentioned average pore diameter and pore volume, the pore diameter 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.

[0076] Furthermore, the distribution state of the hydrogenation active components in the hydrotreating catalyst of this embodiment is preferably a uniform type in which these components are uniformly distributed in the catalyst.

[0077] <Mechanism of action> In the method for producing a hydrocarbon oil hydrotreating catalyst of this embodiment, a carrier obtained by subjecting a metal oxide to hydrothermal treatment is used. It is believed that this hydrothermal treatment causes metal (aluminum, when the metal oxide is alumina) to be desorbed from the crystal structure of the metal oxide, generating Lewis acid sites at the desorbed sites. It is believed that hydrogenation-active metals (particularly Group 9 and 10 metals) are tetrahedrally coordinated to hydroxyl groups in the metal oxide and octahedrally coordinated to Lewis acid sites. It is believed that the proportion of octahedrally coordinated hydrogenation-active metals increases in proportion to the number of Lewis acid sites generated by hydrothermal treatment. During sulfurization, octahedrally coordinated Group 9 and 10 metals create a Ni-Mo-S phase (desulfurization active site) in highly active, e.g., NiMo-based catalysts, resulting in improved hydrogenation activity. While the present specification has primarily described carriers obtained by subjecting alumina-based metal oxides to hydrothermal treatment, it is believed that similar effects can be obtained with any metal oxide that generates Lewis acid sites upon hydrothermal treatment, similar to alumina.

[0078] <Method for Hydrocarbon Oil Hydrogenation> 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 420°C, and a liquid hourly space velocity of 0.1 to 10 h -1 The present invention relates to a method for hydrotreating hydrocarbon oils, which comprises contacting the hydrocarbon oil with the hydrotreating catalyst produced by the production method of the present invention. In addition, according to the method for hydrotreating hydrocarbon oil, the hydrogen partial pressure is 3 to 20 MPa, the reaction temperature is 280 to 420°C, and the liquid hourly space velocity is 0.1 to 10 h -1 The present invention also provides a method for producing hydrogenated hydrocarbon oils, which comprises contacting a hydrocarbon oil with the hydrotreating catalyst produced by the production method of the present invention.

[0079] The hydrogen partial pressure is preferably 3 to 20 MPa, more preferably 4 to 17.5 MPa, and even more preferably 5 to 15 MPa. When the hydrogen partial pressure is equal to or higher than the lower limit of the above range, the hydrotreatment tends to proceed easily.

[0080] The reaction temperature is preferably 280 to 420°C, more preferably 300 to 410°C, and even more preferably 320 to 400°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.

[0081] Liquid hourly space velocity is 0.1 to 10 h -1 It is preferable that the time is 0.1 to 5 hours. -1 It is more preferable that the time is 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 sulfur removal ability is improved.

[0082] Hydrogen / hydrocarbon oil ratio is 50 to 3000 Nm 3 / kL is preferred, and 100 to 2500 Nm 3 / kL is more preferable, and 200 to 2000Nm 3 / kL is more preferred.

[0083] Examples of hydrocarbon oils that can be subjected to the hydrocarbon oil hydrotreating method of this embodiment include atmospheric distillation light oil, atmospheric distillation kerosene, atmospheric distillation heavy oil, 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, vacuum distillation heavy oil, hydrocracked heavy oil, etc. Heavy extracts, which are particularly heavy oil components among the oil components extracted and removed by solvent extraction of lubricating base oils, fluid catalytic cracking residual oil, fluid catalytic cracking light oil, thermal cracking heavy oil, thermal cracking light oil, and de-sludge oil.

[0084] The density of the hydrocarbon oil to be subjected to the hydrotreating method of the present embodiment is 0.78 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 3The sulfur content is preferably 0.05 to 7 mass%, more preferably 0.5 to 6.5 mass%, and even more preferably 0.8 to 6 mass%. When the hydrocarbon oil is residual oil, 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.

[0085] The density of the hydrogenated hydrocarbon oil produced by the hydrocarbon oil hydrotreating method 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 / cm 3 The sulfur content is preferably 0.001 to 0.8% by mass, more preferably 0.01 to 0.6% by mass, and even more preferably 0.05 to 0.5% by mass. When the hydrocarbon oil is residual oil, 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.

[0086] The hydrotreating catalyst of this embodiment is generally activated by sulfiding in a reactor before use (i.e., prior to carrying out the hydrotreating method of this embodiment). This sulfiding is generally carried out at 200 to 400°C, preferably 250 to 350°C, under a hydrogen atmosphere at atmospheric or higher hydrogen partial pressure, using a petroleum distillate containing sulfur compounds to which a sulfiding agent such as dimethyl disulfide or carbon disulfide has been added, or hydrogen sulfide.

[0087] 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.

[0088] 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 is formed in a reactor, a feedstock is introduced into this reactor, and the hydrogenation reaction is carried out under the conditions described above. Most commonly, a fixed-bed catalyst layer is formed in the reactor, and the feedstock is introduced into the upper part of the reactor, passes from the top to the bottom of the fixed bed, and the product is discharged from the bottom of the reactor, or conversely, the feedstock is introduced into the lower part of the reactor, passes from the bottom to the top of the fixed bed, and the product is discharged from the top of the reactor.

[0089] 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.

[0090] The hydrotreating method of this embodiment may be a hydrotreating method in which the catalyst 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, and each catalyst is 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 and second-stage catalysts. The first-stage catalyst can be a known first-stage catalyst in the field. Examples of such first-stage catalysts include the first-stage catalysts described in JP 2010-248476 A, WO 2015 / 053087 A, WO 2015 / 046316 A, and WO 2015 / 046323 A. Examples of the middle stage catalyst include those described in WO 2015 / 046323 and WO 2015 / 053087. Examples of the second stage catalyst include those described in JP 2010-248476 A, WO 2015 / 053087 and WO 2015 / 046323.

[0091] 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%. Loading ratios of the first-stage catalyst, middle-stage catalyst, and second-stage catalyst within the above ranges are suitable for maintaining catalyst life, desulfurization activity, and demetallization activity. [Example]

[0092] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. 2 and3 is a reference example.

[0093] <Physical and chemical properties of catalyst and carrier> [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).

[0094] (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. Pore ​​volume is the total volume of mercury that has entered the pores per gram of catalyst or support. 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.

[0095] (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 x 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 or carrier) 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.

[0096] [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 catalyst and the support 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.

[0097] (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.

[0098] <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 hydrotreating 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 hydrotreating was carried out under the following conditions. The mixed fluid of product oil and gas was discharged from the bottom of the reactor, and the product oil was separated in a gas-liquid separator. Note that the liquid hourly space velocity (LHSV) below is the LHSV of the mixed oil relative to the total catalyst layer of the demetallization catalyst and the hydrotreating catalyst from each Example or Comparative Example.

[0099] 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.

[0100] Reaction conditions: Pressure (hydrogen partial pressure): 10.3 MPa Liquid space velocity: 0.253hr -1 Hydrogen / oil ratio: 876.2Nm 3 / kL Reaction temperature: 380℃

[0101] Feedstock properties: Oil type: Mixture of atmospheric distillation residue and vacuum distillation residue (derived from Middle Eastern crude oil) Density (15℃); 0.991g / cm 3 Sulfur content: 3.31% by mass Vanadium: 22 ppm by mass Nickel: 34 ppm by mass Asphaltene content: 4.21 mass%

[0102] 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.

[0103] [Manufacturing Example 1] (1) Production of metal oxides 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 vigorously stirred with a stirring blade for 5 minutes. Then, 3.9 L of sodium aluminate with an alumina concentration of 70 g / L was added to the stirring vessel to prepare aluminum hydroxide, which was stirred with a stirring blade for 24 hours. The resulting slurry was placed in a filter and filtered to remove water. Next, the resulting gel was dissolved in pure water and added to the filtrate with SO4 2- , Na + The gel was washed until no more traces of cellulose were detected. The washed gel was then mixed with pure water to form a uniform slurry, which was then placed in a compression filter. The slurry was sandwiched between filter plates via a filter cloth, and the filter plates were squeezed to remove water. Filtration was interrupted when the moisture content of the resulting cake reached 80% by mass. This cake was placed in a heated kneader (set temperature 80°C) and thoroughly kneaded to homogenize. After that, phosphoric acid and zinc oxide particles (particle diameter 0.8 μm) were added to obtain the composition of Carrier D listed in Table 1, and further kneaded to homogenize. The kneaded cake was placed in an extruder and extruded into a four-leaf shape with a major axis of 1.3 mm and a minor axis of 1.1 mm. This extruded product was dried and then calcined at 600°C for 4 hours to obtain a metal oxide containing alumina as the main component, phosphorus oxide, and zinc oxide. The resulting metal oxide had a phosphorus content of 1.2% by mass (oxide equivalent) based on the carrier, a zinc content of 4.0% by mass (oxide equivalent) based on the carrier, a pore volume of 0.71 mL / g, and a specific surface area of ​​290 m. 2 / g and the average pore diameter was 7.7 nm.

[0104] [Example 1] (1) Carrier production (hydrothermal treatment) The metal oxide obtained in Production Example 1 was packed in a fixed-bed flow reactor, and nitrogen was supplied to the metal oxide at a GHSV of 180 h. -1 The temperature was raised to 400°C over 3 hours while circulating nitrogen. -1 The temperature was kept at 400°C and hydrothermal treatment was carried out for 6 hours. After 6 hours, nitrogen was used instead of water vapor, and the GHSV was 180h for the metal oxides. -1 The mixture was circulated at 100°C and allowed to cool to room temperature to obtain carrier A. The content ratio of each component in carrier A calculated as oxide, the specific surface area of ​​carrier A, the pore volume, the average pore diameter, and the ratio of the volume of pores having a pore diameter within ±1.5 nm of the average pore diameter to the total pore volume are shown in Table 1. Note that "pore distribution" in Table 1 means "the ratio of the volume of pores having a pore diameter within ±1.5 nm of the average pore diameter to the total pore volume" (hereinafter, this is also applied to carriers B to D).

[0105] (2) Production of hydrotreating catalysts 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 molybdenum-nickel aqueous solution was impregnated into carrier A to obtain the composition of catalyst A shown in Table 2. The impregnated material was dried and then calcined at 500°C for 4 hours in an air atmosphere to obtain catalyst A. Table 2 shows the catalyst-based oxide content of each component in catalyst A, as well as the specific surface area, pore volume, average pore diameter, and the ratio of the volume of pores with a pore diameter within ±1.5 nm of the average pore diameter to the total pore volume. Note that "pore distribution" in Table 2 refers to the ratio of the volume of pores with a pore diameter within ±1.5 nm of the average pore diameter to the total pore volume (hereinafter, this also applies to catalysts B to D). Using catalyst A, a mixed oil of atmospheric distillation residue and vacuum distillation residue was hydrotreated under the above-mentioned conditions. The results are shown in Table 3 (the results for catalysts B to D are also shown in the same way below). The specific activity in Table 3 refers to the value obtained by dividing the value of (reaction rate constant of catalyst A) / (specific surface area of ​​catalyst A) by the value of (reaction rate constant of catalyst D) / (specific surface area of ​​catalyst D) in Comparative Example 1 described below, and multiplying the result by 100. Similar calculations were also performed for catalysts B to D below.

[0106] [Example 2] (1) Carrier production (hydrothermal treatment) A carrier B was obtained in the same manner as in Example 1, except that the temperature of the hydrothermal treatment was set to 600°C.

[0107] (2) Production of hydrotreating catalysts Catalyst B was obtained in the same manner as in Example 1 except that carrier B was used instead of carrier A, and a hydrotreating reaction of a mixed oil of atmospheric distillation residue and vacuum distillation residue was carried out.

[0108] [Example 3] (1) Carrier production (hydrothermal treatment) A carrier C was obtained in the same manner as in Example 1, except that the temperature of the hydrothermal treatment was 800°C.

[0109] (2) Production of hydrotreating catalysts Catalyst C was obtained in the same manner as in Example 1 except that carrier C was used instead of carrier A, and a hydrotreating reaction of a mixed oil of atmospheric distillation residue and vacuum distillation residue was carried out.

[0110] [Comparative Example 1] (1) Production of hydrotreating catalysts The metal oxide obtained in Production Example 1 was used as carrier D. Except for using carrier D instead of carrier A, catalyst D was obtained in the same manner as in the examples, and a hydrotreating reaction of a mixed oil of atmospheric distillation residue oil and vacuum distillation residue oil was carried out.

[0111] [Table 1]

[0112] [Table 2]

[0113] [Table 3]

[0114] It was found that the catalysts of Examples 1 to 3 of the present invention had a higher reaction rate constant per unit specific surface area than the catalyst of Comparative Example 1, which used a carrier that had not been subjected to hydrothermal treatment. [Industrial Applicability]

[0115] 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 method for producing a catalyst for hydrotreating a hydrocarbon oil, comprising supporting, on a support obtained by subjecting a metal oxide to hydrothermal treatment, 5 to 35 mass % of molybdenum, calculated as oxide, based on the catalyst, and 1 to 18 mass % of either or both of nickel and cobalt, calculated as oxide, based on the catalyst, as a total amount of nickel and cobalt; the metal oxide contains alumina, and the content of alumina relative to the total mass of the metal oxide is 80 mass% or more; The hydrothermal treatment is a hydrothermal treatment in which the metal oxide is brought into contact with water vapor under conditions of a temperature of 200°C or higher and 500°C or lower and a GHSV of 100h -1 or higher and 1000h -1 or lower, The method for producing a catalyst for hydrotreating hydrocarbon oils, wherein the carrier has an average pore diameter of 5 to 9.4 nm.

2. Hydrogen partial pressure: 3 to 20 MPa, reaction temperature: 280 to 420°C, liquid hourly space velocity: 0.1 to 10 hr －１ A method for hydrotreating a hydrocarbon oil, comprising contacting the hydrotreating catalyst produced by the production method according to claim 1 with the hydrocarbon oil.

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