Hydrotreatment catalyst for hydrocarbon oil and method for producing same

Abstract

[Problem] To provide a hydrotreatment catalyst for hydrocarbon oils that has improved hydrodesulfurization activity, hydrodemetallization ability, and silicon trap ability. [Solution] A hydrotreatment catalyst for hydrocarbon oils that includes an inorganic oxide carrier and an active metal component supported on the inorganic oxide carrier. The active metal component includes a first metal that is at least one from among molybdenum and tungsten, and a second metal that is at least one from among cobalt and nickel. The following requirements (1) to (3) are satisfied in the log differential pore volume distribution measured by the mercury intrusion technique. Requirement (1): dV / d(logD) is at an absolute maximum in the range of pore diameter 5-30 nm. Requirement (2): dV / d(logD) is at a local maximum in the range of pore diameter 2-50 μm. Requirement (3): The ratio of the pore volume in the range of pore diameter 2-50 μm to the total pore volume is 3% or more.

Description

Hydrocarbon oil hydrotreating catalyst and method for producing same

[0001] The present invention relates to a hydrotreating catalyst for removing sulfur, metals, and silicon from hydrocarbon oils in the presence of hydrogen, and a method for producing the same.

[0002] Hydrogenation of hydrocarbon oils involves a catalytic reaction under high temperature and pressure. However, the economic viability of the process can be improved by lowering the reaction temperature and pressure, so high catalytic activity is desirable.

[0003] Hydrotreating catalysts are prepared by impregnating a support made of an inorganic oxide such as alumina with an impregnation solution containing active metals such as molybdenum and cobalt or nickel, followed by drying and calcination. In the hydrotreating of hydrocarbon oils, the supported metals of the catalyst are sulfurized with a sulfur compound and reacted with the hydrocarbon oil at high temperatures to simultaneously hydrogenate and remove sulfur and metals. Silicon, contained in antifoaming agents used in processes from crude oil extraction to the hydrotreating process, also deposits on the catalyst surface and deactivates the catalyst during the hydrotreating process, so it must be removed.

[0004] To date, various studies have been conducted on the shape and pore structure of hydrotreating catalysts in order to improve their performance (see, for example, Patent Document 1). In addition, a paper in Non-Patent Document 1 entitled "Hydrodesulfurization Activity of Catalysts with Non-Cylindrical Shape" states that hydrodesulfurization activity is closely correlated with the catalyst surface area, and that improving the geometric surface ratio by examining the size and shape of the catalyst is effective in improving activity.

[0005] Another method that is thought to improve the geometric surface ratio, different from the consideration of shape and size, is the generation of micropores on the order of micrometers. As a method for this, several reports have been made on adding organic particles (various starch granules, polyethylene glycol) that are removed during the calcination process in catalyst preparation to the catalyst support substrate (for example, Patent Documents 2 and 3).

[0006] JP-T-2004-537406 A JP-A-2001-270782 JP-A-2020-078794

[0007] J. Japan Petrol.Inst., Vol.23, No.4, 1980, p268-273.

[0008] Conventional hydrotreating catalysts have room for further improvement in terms of hydrodesulfurization activity, hydrodemetalization ability, and silicon trapping ability. Therefore, an object of the present invention is to provide a catalyst with improved performance in these areas in the hydrotreating of hydrocarbon oils.

[0009] The present inventors have conducted extensive research and found that the above-mentioned problems can be solved by controlling the macropore structure of a molded catalyst support, and have completed the present invention. The present invention relates to, for example, the following [1] to [9].

[0010] [1] A catalyst for hydrotreating hydrocarbon oils, comprising an inorganic oxide support and an active metal component supported on the inorganic oxide support, wherein the active metal component comprises a first metal which is at least one of molybdenum and tungsten, and a second metal which is at least one of cobalt and nickel, and wherein the following requirements (1) to (3) are satisfied in the log differential pore volume distribution measured by mercury intrusion porosimetry. Requirement (1): dV / d (log D) is maximized in the pore diameter range of 5-30 nm. Requirement (2): dV / d (log D) is locally maximized in the pore diameter range of 2-50 μm. Requirement (3): The ratio of the pore volume in the pore diameter range of 2-50 μm to the total pore volume is 3% or more.

[0011] [2] The catalyst for hydrotreating hydrocarbon oils according to [1] above, wherein the inorganic oxide support comprises an inorganic oxide matrix and inorganic fibers.

[0012] [3] The catalyst for hydrotreating hydrocarbon oils according to [2], wherein the content of the inorganic fibers in the inorganic oxide support is 0.2 to 10 mass %.

[0013] [4] The catalyst for hydrotreating hydrocarbon oils according to [2] or [3], wherein the inorganic oxide matrix comprises an oxide or composite oxide of aluminum, silicon, titanium, boron, zirconium, cerium, or phosphorus.

[0014] [5] The surface of the inorganic oxide support has 3 cracks (hereinafter also referred to as "crevasses") having a maximum width of 2 μm or more and a length of 100 μm or more per mm. 2 The hydrocarbon oil hydrotreating catalyst according to any one of [1] to [4] above,

[0015] [6] An inorganic oxide support and an active metal component supported on the inorganic oxide support, wherein the active metal component includes a first metal which is at least one of molybdenum and tungsten, and a second metal which is at least one of cobalt and nickel, and the surface of the inorganic oxide support has 3 crevices per mm with a maximum width of 2 μm or more and a length of 100 μm or more. 2 A catalyst for hydrotreating hydrocarbon oils, which has the above-mentioned properties and satisfies the following requirement (1) in the log differential pore volume distribution measured by mercury intrusion porosimetry: Requirement (1): dV / d (logD) is maximum in the pore diameter range of 5-30 nm.

[0016] [7] A method for producing a catalyst for hydrotreating a hydrocarbon oil, comprising: (1) a step of mixing an inorganic oxide or a precursor of the inorganic oxide with inorganic fibers to prepare a carrier raw material mixture; (2) a step of obtaining a molded product from the carrier raw material mixture by extrusion molding; (3) a step of drying and calcining the molded product to obtain an inorganic oxide carrier; (4) a step of preparing an impregnation liquid containing a raw material for a first metal component which is at least one of molybdenum and tungsten, a raw material for a second metal component which is at least one of cobalt and nickel, and a solvent, and bringing the impregnation liquid into contact with the inorganic oxide carrier to obtain a supported material; and (5) a step of heat-treating the supported material to obtain a hydrotreating catalyst.

[0017] [8] The method for producing a hydrocarbon oil hydrotreating catalyst according to [7] above, wherein in the step (3), drying and calcination are carried out at 50 to 800°C.

[0018] [9] The method for producing a catalyst for hydrotreating a hydrocarbon oil according to [7] or [8], wherein in the step (5), the heat treatment is carried out at 50 to 800°C.

[0019] The hydrocarbon oil hydrotreating catalyst of the present invention has excellent hydrodesulfurization activity, hydrodemetalization ability, and silicon trapping ability. Furthermore, according to the method for producing a hydrocarbon oil hydrotreating catalyst of the present invention, a hydrocarbon oil hydrotreating catalyst having excellent hydrodesulfurization activity, hydrodemetalization ability, and silicon trapping ability can be produced.

[0020] Pore ​​size distributions of the catalysts of Example 1 and Comparative Example 1 measured by mercury porosimetry. Enlarged views of the pore size distributions of the catalysts of Example 1 and Comparative Example 1 measured by mercury porosimetry. Micrographs of the catalyst of Example 1.

[0021] The present invention will be described in further detail below. [Catalyst for Hydrogenation of Hydrocarbon Oils] The catalyst for hydrotreating hydrocarbon oils according to the present invention (hereinafter also referred to simply as "hydrogenation catalyst") comprises an inorganic oxide support and an active metal component supported on the inorganic oxide support, and is characterized in that the pore size distribution measured by mercury intrusion porosimetry satisfies the following requirements (1) to (3).

[0022] <Inorganic Oxide Support> Examples of inorganic oxides constituting the support include oxides or composite oxides of aluminum, silicon, titanium, boron, zirconium, cerium, or phosphorus, and specific examples include alumina, silica, titania, boria, zirconia, ceria, phosphate, silica-alumina, alumina-titania, alumina-zirconia, alumina-boria, phosphate-alumina, silica-alumina-boria, phosphate-alumina-boria, phosphate-alumina-silica, silica-alumina-titania, and silica-alumina-zirconia, with alumina or composite oxides of aluminum and other elements containing alumina as the main component being preferred. These may be used alone or in combination of two or more.

[0023] The inorganic oxide support contains a matrix component made of the inorganic oxide and inorganic fibers, for example, when produced by the production method described below. The content of the inorganic fibers in the inorganic oxide support is preferably 0.2 to 10 mass %, more preferably 0.5 to 5 mass %.

[0024] Preferred embodiments of the inorganic fibers will be described in detail in the description of the method for producing a hydrotreating catalyst below. <Active Metal Component> An active metal component is supported on an inorganic composite oxide support. The active metal component contains, as active metal species, a first metal which is at least one of molybdenum and tungsten, and a second metal which is at least one of cobalt and nickel. Therefore, for example, an active metal component containing molybdenum as the first metal and cobalt as the second metal is supported on the support. Examples of the active metal component include oxides containing the first metal and the second metal.

[0025] The first metal may be molybdenum, tungsten, or both molybdenum and tungsten, preferably molybdenum. The content (supported amount) of the first metal component in the catalyst of the present invention can be appropriately changed depending on the properties of the feed oil to be treated, and is, for example, 10 to 30 mass %, preferably 15 to 22 mass %, calculated as oxide (i.e., MoO3, WO3).

[0026] When the content of the first metal is equal to or greater than the lower limit, the catalyst of the present invention exhibits good desulfurization activity. When the content of the first metal is equal to or less than the upper limit, aggregation of the first metal is prevented, and good dispersibility is obtained.

[0027] The second metal may be cobalt, nickel, or both cobalt and nickel. The content (supported amount) of the second metal component in the catalyst of the present invention can be appropriately changed depending on the properties of the feed oil to be treated, and is, for example, 2.0 to 10.0 mass%, preferably 2.0 to 8.0 mass%, calculated as oxide (i.e., CoO, NiO).

[0028] The second metal acts as a promoter for the first metal. When the content of the second metal is equal to or greater than the lower limit, the first metal and the second metal, which are active metal species, can maintain an appropriate structure.

[0029] <Optional Components> In addition to the components described above, the hydrotreating catalyst of the present invention may contain carbon, phosphorus, boron, and the like derived from an organic acid that may be used in the production process.

[0030] (Hydrotreatment Catalyst) The hydrotreatment catalyst of the present invention comprises an inorganic oxide support and an active metal component supported on the inorganic oxide support, and satisfies the following requirements (1) to (3) in the log differential pore volume distribution measured by mercury porosimetry (mercury contact angle: 130°, surface tension: 480 dyn / cm). Requirement (1): dV / d (log D) is maximized in the pore diameter range of 5-30 nm. Requirement (2): dV / d (log D) is maximized in the pore diameter range of 2-50 μm (2000-50,000 nm). Requirement (3): The ratio of the pore volume in the pore diameter range of 2-50 μm (2000-50,000 nm) to the total pore volume is 3% or more.

[0031] Requirement (1) indicates that the hydrotreating catalyst of the present invention has mesopores similar to those of general hydrotreating catalysts. Requirement (2) indicates that the hydrotreating catalyst of the present invention has characteristic crevices on its surface, as shown in FIG. 3. If a peak (maximum point) of dV / d (log D) exists in the pore diameter range of 2 μm (2000 nm) or more, the hydrotreating catalyst has excellent hydrodesulfurization activity, hydrodemetalization ability, and silicon trapping ability. Furthermore, if a peak (maximum point) of dV / d (log D) exists in the pore diameter range of 50 μm (50,000 nm) or less, the hydrotreating catalyst has high strength. The value of this peak (maximum point) is, for example, 0.02 cc / g or more.

[0032] Furthermore, requirement (3) indicates that the volume of the pores due to the crevices accounts for a certain proportion of the pore volume of the entire hydrotreating catalyst. Because the hydrotreating catalyst of the present invention has the crevices specified by requirements (2) and (3), the catalyst volume-to-surface ratio is dramatically improved compared to prior art, and catalytic performance correlated with the catalyst surface, such as hydrodesulfurization activity, demetalization ability, and silicon trapping ability, is improved.

[0033] Furthermore, the presence of numerous crevices in the catalyst is expected to improve the catalyst volume-surface ratio significantly more than by changing the size or shape of the molded body, and it is expected that the diffusion of reaction oil into the inside of the catalyst will be better than in catalysts with macropores formed by adding organic additives.

[0034] The surface of the inorganic oxide support (when the support is produced by extrusion molding, the surface facing the direction perpendicular to the extrusion direction) preferably has 3 crevices per mm with a maximum width of 2 μm or more and a length of 100 μm or more. 2 More preferably, the number of crevasses is 5 / mm, with a maximum width of 10 μm or more and a length of 100 μm or more. 2 or more (the upper limit is, for example, 50 pieces / mm 2 These values ​​can be measured based on SEM images of the hydrotreating catalyst.

[0035] The crushing strength of the hydrotreating catalyst of the present invention, measured by the method described below, is usually 5 N / mm or more, preferably 8 N / mm or more, and more preferably 10 N / mm or more. When the crushing strength is in this range, the catalyst can be prevented from breaking when packed, which can cause drift or pressure loss during the reaction.

[0036] <Method for measuring crushing strength> As a pretreatment, a sample (hydrotreating catalyst) was calcined at 500°C for 1 hour and then cooled to room temperature in a desiccator. From these, 40 or more samples with a length of 4 mm or more were compressed using a Kiya hardness tester (compressor 3.18 mm), and the applied pressure at which the sample was crushed was determined, and the crushing strength was calculated using the following formula.

[0037] Crushing strength (N / mm) = (S × 9.807 (m / s 2)) / (L×n) (S represents the total pressure load (kg), L represents the diameter of the compressor (3.18 mm), and n represents the number of measurements.) Another embodiment of the hydrotreating catalyst of the present invention comprises an inorganic oxide support and an active metal component supported on the inorganic oxide support, wherein the active metal component comprises a first metal which is at least one of molybdenum and tungsten, and a second metal which is at least one of cobalt and nickel, and the inorganic oxide support has a surface on which 3 crevices / mm2 each having a maximum width of 2 μm or more and a length of 100 μm or more are formed. 2 The present invention provides a hydrocarbon oil hydrotreating catalyst that satisfies the above requirement (1) in the Log differential pore volume distribution measured by mercury intrusion porosimetry.

[0038] The details of the inorganic oxide support, the active metal component, and the crevices are as described above. [Method for producing a catalyst for hydrotreating hydrocarbon oils] The method for producing a catalyst for hydrotreating hydrocarbon oils of the present invention is characterized by comprising: (1) a step of mixing an inorganic oxide or a precursor of the inorganic oxide with inorganic fibers to prepare a carrier raw material mixture, (2) a step of extruding the carrier raw material mixture to obtain a molded product, (3) a step of drying and calcining the molded product to obtain an inorganic oxide support, (4) a step of preparing an impregnation solution containing a raw material for a first metal component which is at least one of molybdenum and tungsten, a raw material for a second metal component which is at least one of cobalt and nickel, and a solvent, and bringing the impregnation solution into contact with the inorganic oxide support to obtain a supported product, and (5) a step of heat-treating the supported product to obtain a hydrotreating catalyst.

[0039] Each step will be described below. <Step (1)> Step (1) is a step of mixing an inorganic oxide or its precursor with inorganic fibers to prepare a carrier raw material mixture.

[0040] Inorganic oxide precursors can be produced by conventional methods. An example is given below. First, an aqueous solution of a basic metal salt and an aqueous solution of an acidic metal salt are mixed to obtain a slurry of an inorganic oxide precursor (hydrate). Examples of suitable basic aluminum salts include sodium aluminate and potassium aluminate. Examples of suitable acidic aluminum salts include aluminum sulfate, aluminum chloride, and aluminum nitrate. When preparing a composite oxide precursor, silica sources include alkali silicate solutions such as sodium silicate aqueous solutions and sodium silicate hydrogels. Phosphate sources include phosphite ions, and phosphoric acid compounds that generate phosphate ions in water, such as ammonium phosphate, potassium phosphate, sodium phosphate, phosphoric acid, and phosphorous acid, can be used. Examples of titanate mineral salts include titanium tetrachloride, titanium trichloride, titanium sulfate, titanyl sulfate, and titanium nitrate. Titanium sulfate and titanyl sulfate are particularly preferred due to their low cost.

[0041] The slurry is then dehydrated and washed with warm water, for example, a 0.3% by mass aqueous ammonia solution. Ion-exchanged water is then added to the washed cake-like slurry to form a slurry, which is then subjected to an aging step. In the aging step, for example, an organic acid aqueous solution, ammonia water, or the like is added to the resulting slurry to adjust the pH to, for example, 9.5 to 10.5, and the slurry is heated and aged with stirring in an aging tank equipped with a reflux condenser at 30°C or higher, preferably 80 to 100°C, for, for example, 1 to 20 hours, preferably 2 to 15 hours.

[0042] The aged product obtained in the aging step is placed in a steam-jacketed twin-arm kneader and heated and kneaded to obtain an inorganic oxide precursor. Examples of the inorganic fiber include glass fiber, silica fiber, alumina fiber, alumina-silica fiber, rock wool, and carbon fiber.

[0043] The inorganic fibers preferably have an average diameter of 0.1 to 20 μm, more preferably 5 to 10 μm. If the average diameter is equal to or greater than the lower limit, crevices can be formed on the catalyst support surface, while if the average diameter is equal to or less than the upper limit, extrusion molding can be easily performed.

[0044] The average length of the inorganic fibers is preferably 0.1 mm or more, more preferably 0.5 mm or more, and the upper limit may be, for example, 5 mm. When the average length is equal to or greater than the lower limit, the inorganic fibers can be oriented substantially in the extrusion direction during extrusion molding.

[0045] These average diameter and average length can be determined, for example, by measuring the diameter and length of 100 inorganic fibers randomly selected on an SEM image and calculating the arithmetic mean value.

[0046] The inorganic fibers are used in an amount such that the amount in the obtained inorganic oxide support is, for example, 0.2 to 10 mass %, preferably 0.5 to 5 mass %. If the amount of inorganic fibers is equal to or greater than the lower limit, crevices can be formed on the catalyst support surface, while if the amount of inorganic fibers is equal to or less than the upper limit, extrusion molding can be easily performed and a catalyst with high strength can be obtained.

[0047] In step (1), the inorganic oxide or the inorganic oxide precursor (preferably the inorganic oxide precursor) is mixed with the inorganic fibers to obtain a carrier raw material mixture. For the mixing, a conventionally known apparatus, for example, a steam-jacketed twin-arm kneader, can be used.

[0048] <Step (2)> Step (2) is a step of obtaining a molded product by extrusion molding from the carrier raw material mixture obtained in step (1).

[0049] The extrusion molding can be carried out by a conventionally known method, except that the carrier raw material mixture obtained in step (1) is used as the raw material. The preferred conditions for the extrusion molding are as follows.

[0050] By extruding the carrier raw material mixture containing inorganic fibers, a molded body is obtained in which the inorganic fibers are oriented approximately in the extrusion direction, and by drying this in the next step (3), a large number of crevices are formed on the surface of the molded body in a direction approximately perpendicular to the extrusion direction.

[0051] The shape of the molded body may be a shape commonly used for hydrotreating catalysts, such as a cylinder, a trilobe, or a quadrilobe. The size of the molded body may be a general size of a molded body used in producing a hydrotreating catalyst. For example, a cylindrical molded body has a diameter of, for example, 1 mm to 10 mm and a length of, for example, 2 mm to 50 mm.

[0052] <Step (3)> Step (3) is a step of drying and calcining the molded product obtained in step (2) to obtain an inorganic oxide support.

[0053] The drying and calcination are usually carried out at 50 to 800° C. More specifically, the molded product is dried by heat treatment in an air atmosphere, for example, at 50 to 200° C., preferably 75 to 150° C., for example, for 0.5 to 24 hours, preferably 6 to 18 hours, and then calcined by heat treatment, for example, at 350 to 800° C., preferably 400 to 600° C., for example, for 0.5 to 10 hours, preferably 2 to 5 hours, to obtain an inorganic oxide support.

[0054] <Step (4)> Step (4) is a step of preparing an impregnation liquid containing a raw material for a first metal component, a raw material for a second metal component, and a solvent, and bringing the impregnation liquid into contact with the inorganic oxide support obtained in step (3) to obtain a supported material.

[0055] The details of the first metal component and the second metal component are as described above. Examples of preferred raw materials for the first metal component include molybdenum trioxide, ammonium molybdate, ammonium metatungstate, ammonium paratungstate, and tungsten trioxide. Examples of preferred raw materials for the second metal component include nickel nitrate, nickel carbonate, cobalt nitrate, and cobalt carbonate.

[0056] The solvent is usually water. The impregnation solution may further contain a phosphorus component. Preferred examples of the phosphorus component include orthophosphoric acid (hereinafter simply referred to as "phosphoric acid"), ammonium dihydrogen phosphate, diammonium hydrogen phosphate, trimetaphosphoric acid, pyrophosphoric acid, and tripolyphosphoric acid.

[0057] The concentration of phosphorus in the impregnation solution is preferably 0.5 to 5.0 mass% in terms of oxide (PO). The impregnation solution may further contain an organic acid. Examples of organic acids include citric acid, malic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), and diethylenetriaminepentaacetic acid (DTPA).

[0058] In addition to the organic acid, an organic additive may be used. Examples of the organic additive include sugars (monosaccharides, disaccharides, polysaccharides, etc.). Specifically, for example, glucose (C6H 12 O6), fructose (C6H 12 O6), maltose (C 12 H 22 O 11 ), lactose (C 12 H 22 O 11 ), sucrose (C 12 H 22 O 11 ) etc. may be added.

[0059] The impregnation solution can be prepared by mixing the components in a conventional manner. The prepared impregnation solution is brought into contact with an inorganic oxide support to impregnate the inorganic oxide support, thereby obtaining an inorganic oxide support impregnated with the impregnation solution (hereinafter also referred to as a "supported material").

[0060] The amounts of each component contained in the impregnation solution may be appropriately set so as to obtain a hydrotreating catalyst having a desired composition. <Step (5)> Step (5) is a step of heat-treating the supported material obtained in step (4) to obtain a hydrotreating catalyst.

[0061] This heat treatment is usually carried out at 50 to 800° C. More specifically, the support is dried by heat treatment in an air atmosphere, for example, at 50 to 200° C., preferably 75 to 150° C., for example, for 0.5 to 24 hours, preferably 0.5 to 4.0 hours, and then calcined by heat treatment, for example, at 350 to 800° C., preferably 400 to 600° C., for example, for 0.5 to 5.0 hours, preferably 0.5 to 2.0 hours, to obtain the hydrotreating catalyst of the present invention in which the active metal component is supported on the inorganic oxide support.

[0062] [Hydrotreatment of Hydrocarbon Oils] By contacting light or heavy hydrocarbon oils with hydrogen in the presence of the hydrocarbon oil hydrotreatment catalyst of the present invention under a high-temperature, high-pressure atmosphere, reactions such as desulfurization, denitrification, demetalization, and hydrocracking can be promoted. When the hydrotreatment catalyst is packed into the reactor, a guard catalyst, trapping agent, or the like may be installed at the inlet of the reactor to remove impurities or catalyst poisons.

[0063] Examples of light oils include naphtha, kerosene, light gas oil (LGO), heavy gas oil (HGO), and vacuum gas oil (VGO), and examples of heavy oils include atmospheric residue (AR) and vacuum residue (VR).

[0064] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. [Measurement Methods] Various measurements were carried out as follows.

[0065] <Method for measuring the silica content of the catalyst> The catalyst was calcined at 500°C for 1 hour and then allowed to cool in a desiccator. 3 g of the resulting sample was placed in a 30 ml zirconia bowl with a lid, heated (200°C, 20 minutes), and calcined (700°C, 5 minutes). After that, 2 g of Na2O2 and 1 g of NaOH were added and melted for 15 minutes. Further, 25 ml of H2SO4 and 200 ml of water were added and dissolved, and the mixture was diluted with pure water to 500 ml to obtain a sample. The silicon content of the resulting sample was measured in terms of oxide (SiO2) using an ICP apparatus (Shimadzu Corporation, ICPS-8100, analysis software ICPS-8000).

[0066] <Method for measuring silica content in spent catalyst> For Si trap evaluation, the catalyst after operation was removed, washed, and calcined. The catalyst after calcination was calcined at 500 ° C for 1 hour and then allowed to cool in a desiccator. 3 g of the resulting sample was collected in a 30 ml lidded zirconia bowl, heat-treated (200 ° C, 20 minutes), and calcined (700 ° C, 5 minutes). After that, 2 g of Na2O2 and 1 g of NaOH were added and melted for 15 minutes. Further, 25 ml of H2SO4 and 200 ml of water were added and dissolved, and the mixture was diluted with pure water to 500 ml to prepare a sample. The silicon content of the resulting sample was measured in terms of oxide (SiO2) using an ICP apparatus (Shimadzu Corporation, ICPS-8100, analysis software ICPS-8000).

[0067] <Measurement of Pore Distribution> The pore distribution of the catalysts produced in the examples and comparative examples was measured by mercury intrusion porosimetry.

[0068] [Production of Hydrotreating Catalyst] (Preparation of Carrier) <Preparation of Carrier A (Al Carrier)> Step (a) 9.09 kg of a sodium aluminate aqueous solution having a 22% by mass calculated as Al2O3 concentration was placed in a 100 L (liter) steam-jacketed tank and diluted with ion-exchanged water to 40.00 kg. Next, 230.8 g of a sodium gluconate aqueous solution having a 26% by mass concentration was added to this solution, and the mixture was heated to 60°C with stirring to obtain a 5% by mass sodium aluminate / sodium gluconate mixed solution. Separately, 14.29 kg of an aluminum sulfate aqueous solution having a 7% by mass concentration calculated as Al2O3 was diluted with 25.71 kg of ion-exchanged water at room temperature and then heated to 60°C to prepare a diluted aluminum sulfate aqueous solution. Next, the diluted aluminum sulfate aqueous solution was added to the 5% by weight sodium aluminate-sodium gluconate mixed solution at a constant rate over 10 minutes while stirring to prepare an alumina hydrate slurry with an AlO concentration of 3.8% by weight. The pH of the slurry was 7.2. The alumina hydrate slurry was then aged at 60°C for 60 minutes while stirring.

[0069] Step (b) Next, the aged alumina hydrate slurry was dehydrated and then washed with 1.5 L of an aqueous ammonia solution having a concentration of 0.3 mass %.

[0070] Step (c) The cake-like slurry after washing was diluted with ion-exchanged water to a concentration of 10% by mass in terms of AlO to form a slurry, and then ammonia water having a concentration of 15% by mass was added to adjust the pH to 10.2, and the slurry was aged at 95°C for 10 hours while stirring.

[0071] Step (d): The slurry after aging was dehydrated and heated while kneading in a steam-jacketed twin-arm kneader to concentrate it to an alumina concentration of 20% or more. 0.30 kg of a 10% by mass solution of malic acid was added to the concentrate, and then further heated to concentrate and knead it to a predetermined moisture content.

[0072] Step (e) The kneaded product was then molded into a cylindrical shape with a diameter of 1.6 mm using a screw extruder.

[0073] Step (f) The molded product was then dried at 110°C for 12 hours and then calcined at 500°C for 3 hours to obtain Carrier A. After drying in step (f), no crevices corresponding to requirements (2) and (3) were observed on the surface of the molded product.

[0074] <Preparation of Carrier B (Al Carrier GF)> Steps (a) to (d) for preparing Carrier A were carried out. 60 g of glass fiber (chopped strand, product name: CS 3DE-704S, manufactured by Nitto Boseki Co., Ltd.) was added to the kneaded product obtained in step (d), and the mixture was further kneaded for 5 minutes. The kneaded product was then molded into a cylindrical shape with a diameter of 1.6 mm using a screw extruder. Carrier B was then obtained using the same procedure as in step (f) for preparing Carrier A. After drying in step (f), numerous crevices corresponding to requirements (2) and (3) were confirmed on the surface of the molded product in a direction approximately perpendicular to the extrusion direction.

[0075] Preparation of Support C (Al / P Support) Step (a) 7.23 kg of a sodium aluminate aqueous solution (equivalent to a 22% by mass AlO concentration) was placed in a 100 L (liter) steam-jacketed tank and diluted with 39.8 kg of ion-exchanged water. 4.5 kg of a sodium phosphate solution (equivalent to a 2.5% by mass PO concentration) was added with stirring, and the mixture was heated to 60°C with stirring to prepare a basic aluminum salt mixed aqueous solution. 11.37 kg of an aluminum sulfate aqueous solution (equivalent to a 7% by mass AlO concentration) was diluted with 20.46 kg of ion-exchanged water and then heated to 60°C to prepare a diluted aluminum sulfate aqueous solution.

[0076] Next, while stirring the basic aluminum salt mixed aqueous solution in the tank, the diluted aluminum sulfate aqueous solution was added at a constant rate over 10 minutes using a roller pump to prepare hydrate slurry A containing phosphorus and alumina. This hydrate slurry A was then aged at 60°C for 60 minutes while stirring.

[0077] Step (b) Next, the aged alumina hydrate slurry was dehydrated and then washed with 120 L of an aqueous ammonia solution having a concentration of 0.3 mass %.

[0078] Step (c) The cake-like slurry after washing was diluted with ion-exchanged water to a concentration of 10% by mass in terms of AlO to form a slurry, and then 0.50 kg of a 10% by mass aqueous solution of citric acid was added, followed by adding a 15% by mass aqueous ammonia solution to adjust the pH to 10.3, and the mixture was aged at 95°C for 10 hours while stirring.

[0079] Step (d) After the aging, the slurry was dehydrated and heated while being kneaded in a steam-jacketed twin-arm kneader to concentrate and knead the slurry to a predetermined water content.

[0080] Step (e) The kneaded product was then molded into a cylindrical shape with a diameter of 1.6 mm using a screw extruder.

[0081] Step (f) The molded product was then dried at 110° C. for 12 hours and then calcined at 500° C. for 3 hours to obtain Support C. After drying in step (f), no crevices corresponding to requirements (2) and (3) were observed on the surface of the molded product.

[0082] <Preparation of Carrier D (Al / P Carrier GF)> Steps (a) to (d) for preparing Carrier C were carried out. 60 g of glass fiber (chopped strand, product name: CS 3DE-704S, manufactured by Nitto Boseki Co., Ltd.) was added to the kneaded product obtained in step (d), and the mixture was further kneaded for 5 minutes. The kneaded product was then molded into a cylindrical shape with a diameter of 1.6 mm using a screw extruder. Carrier D was then obtained using the same procedure as in step (f) for preparing Carrier C. After drying in step (f), numerous crevices corresponding to requirements (2) and (3) were confirmed on the surface of the molded product in a direction approximately perpendicular to the extrusion direction.

[0083] <Preparation of Support E (Al / P Support SiFiber)> Steps (a) to (d) for preparing Support C were carried out. 30 g of quartz wool (coarse grade, manufactured by Tosoh Corporation) was added to the kneaded product obtained in step (d), and the mixture was further kneaded for 5 minutes. The kneaded product was then molded into a cylindrical shape with a diameter of 1.6 mm using a screw extruder. Support E was then obtained using the same procedure as in step (f) for preparing Support C. After drying in step (f), numerous crevices corresponding to requirements (2) and (3) were confirmed on the surface of the molded product in a direction approximately perpendicular to the extrusion direction.

[0084] (Preparation of Impregnation Solution) <Preparation of Impregnation Solution a> 205 g of molybdenum trioxide, 63.0 g of cobalt carbonate, and 23.3 g of nickel carbonate were suspended in 700 ml of ion-exchanged water, and 41.6 g of 85% phosphoric acid was slowly added. This suspension was heated at 90°C for 1 hour using an appropriate reflux device so as not to reduce the volume of the solution, after which 77 g of citric acid was added and stirred for 5 minutes. The solution was then allowed to cool and filtered, yielding 780 ml of impregnation solution a. The same procedure was repeated multiple times to prepare multiple impregnation solutions a.

[0085] <Preparation of Impregnation Solution b> 116 g of molybdenum trioxide and 42.3 g of nickel carbonate were suspended in 700 ml of ion-exchanged water, and 41.6 g of 85% phosphoric acid was slowly added. This suspension was heated at 90°C for 1 hour using an appropriate reflux device so as not to reduce the volume of the liquid, and then allowed to cool. The solution was filtered to obtain 760 ml of impregnation solution b. The same procedure was repeated multiple times to prepare multiple impregnation solutions b.

[0086] <Preparation of Impregnation Solution c> 115 g of molybdenum trioxide and 65.7 g of nickel carbonate were suspended in 700 ml of ion-exchanged water, and 41.6 g of 85% phosphoric acid was slowly added. This suspension was heated at 90°C for 1 hour using an appropriate reflux device so as not to reduce the volume of the liquid. After allowing to cool, the solution was filtered to obtain 770 ml of impregnation solution c. The same procedure was repeated multiple times to prepare multiple impregnation solutions c.

[0087] (Catalyst Preparation) Example 1 Preparation of Hydrotreating Catalyst (Al Carrier GF) 780 ml of the impregnation solution a was sprayed onto 1,000 g of the carrier B to impregnate it, and then the carrier was dried at 100°C for 1 hour and calcined at 500°C for 1 hour to obtain a hydrotreating catalyst (hereinafter also simply referred to as "catalyst"; the same applies to the following examples).

[0088] Example 2 Preparation of Hydrotreating Catalyst (Al / P Support GF) 780 ml of the impregnation solution a was sprayed onto 1,000 g of the support D to impregnate it, and then the resultant was dried at 100°C for 1 hour and calcined at 500°C for 1 hour to obtain a hydrotreating catalyst.

[0089] Example 3 Preparation of Hydrotreating Catalyst (Al / P Support SiFiber) 780 ml of impregnation solution a was sprayed onto 1,000 g of support E to impregnate it, and then the resultant was dried at 100°C for 1 hour and calcined at 500°C for 1 hour to obtain a hydrotreating catalyst.

[0090] Example 4 Preparation of Hydrotreating Catalyst (Al Support GF) 760 ml of impregnation solution b was sprayed onto 1,000 g of support B to impregnate it, and then the resultant was dried at 100°C for 1 hour and calcined at 500°C for 1 hour to obtain a hydrotreating catalyst.

[0091] Example 5 Preparation of Hydrotreating Catalyst (Al / P Support GF) 760 ml of the impregnation solution b was sprayed onto 1,000 g of the support D to impregnate it, and then the support was dried at 100°C for 1 hour and calcined at 500°C for 1 hour to obtain a hydrotreating catalyst.

[0092] Example 6 Preparation of Hydrotreating Catalyst (Al / P Support SiFiber) 760 ml of impregnation solution b was sprayed onto 1000 g of support E to impregnate it, and then the resultant was dried at 100°C for 1 hour and calcined at 500°C for 1 hour to obtain a hydrotreating catalyst.

[0093] Example 7 Preparation of Hydrotreating Catalyst (Al Support GF) 770 ml of the impregnation solution c was sprayed onto 1,000 g of the support B to impregnate it, and then the resultant was dried at 100°C for 1 hour and calcined at 500°C for 1 hour to obtain a hydrotreating catalyst.

[0094] Example 8 Preparation of Hydrotreating Catalyst (Al / P Support GF) 770 ml of the impregnation solution c was sprayed onto 1,000 g of the support D to impregnate it, and then the resultant was dried at 100°C for 1 hour and calcined at 500°C for 1 hour to obtain a hydrotreating catalyst.

[0095] Example 9 Preparation of Hydrotreating Catalyst (Al / P Support SiFiber) 770 ml of impregnation solution c was sprayed onto 1000 g of support E to impregnate it, and then the resultant was dried at 100°C for 1 hour and calcined at 500°C for 1 hour to obtain a hydrotreating catalyst.

[0096] Comparative Example 1 Preparation of Hydrotreating Catalyst (Al Carrier) 780 ml of impregnation solution a was sprayed onto 1,000 g of carrier A to impregnate the carrier, followed by drying at 100°C for 1 hour and calcining at 500°C for 1 hour to obtain a hydrotreating catalyst (hereinafter also simply referred to as "catalyst"; the same applies to the following comparative examples).

[0097] Comparative Example 2 Preparation of Hydrotreating Catalyst (Al / P Support) 780 ml of impregnation solution a was sprayed onto 1,000 g of support C to impregnate it, and then the resultant was dried at 100°C for 1 hour and calcined at 500°C for 1 hour to obtain a hydrotreating catalyst.

[0098] Comparative Example 3 Preparation of Hydrotreating Catalyst (Al Carrier) 760 ml of impregnation solution b was sprayed onto 1,000 g of carrier A to impregnate it, and then the carrier was dried at 100°C for 1 hour and calcined at 500°C for 1 hour to obtain a hydrotreating catalyst.

[0099] Comparative Example 4 Preparation of Hydrotreating Catalyst (Al / P Support) 760 ml of impregnation solution b was sprayed onto 1,000 g of support C to impregnate it, and then the resultant was dried at 100°C for 1 hour and calcined at 500°C for 1 hour to obtain a hydrotreating catalyst.

[0100] Comparative Example 5 Preparation of Hydrotreating Catalyst (Al Carrier) 770 ml of impregnation solution c was sprayed onto 1,000 g of carrier A to impregnate the carrier, followed by drying at 100°C for 1 hour and calcining at 500°C for 1 hour to obtain a hydrotreating catalyst.

[0101] Comparative Example 6 Preparation of Hydrotreating Catalyst (Al / P Support) 770 ml of impregnation solution c was sprayed onto 1,000 g of support C to impregnate it, and then the resultant was dried at 100°C for 1 hour and calcined at 500°C for 1 hour to obtain a hydrotreating catalyst.

[0102] The results of pore distribution measurement for each catalyst obtained in the Examples and Comparative Examples (below, (a) to (c)) are shown in the table. (a) Pore diameter at which dV / d (log D) is maximum within the pore diameter range of 5-30 nm (b) Pore diameter at which dV / d (log D) is maximum within the pore diameter range of 2-50 μm (c) Ratio of pore volume within the pore diameter range of 2-50 μm to total pore volume

[0103] In Table 1, "◯" in the "glass fiber" column indicates that glass fiber was used as the raw material for the support.

[0104] Furthermore, a "○" in the "SiO2Fib" column indicates that quartz wool was used as the carrier raw material. As shown in Table 1, in the log differential pore volume distributions of the catalysts of Examples 1 to 9, a maximum point of dV / d (logD) was present in the pore diameter range of 5-30 nm, and a local maximum point of dV / d (logD) was also present in the pore diameter range of 2-50 μm (2000-50,000 nm). Furthermore, the pore volume in the pore diameter range of 2-50 μm (2000-50,000 nm) accounted for 3% or more of the total pore volume. Furthermore, as shown in the micrograph of the catalyst of Example 1 ( FIG. 3 ), numerous crevices running approximately perpendicular to the extrusion direction during molding were observed.

[0105] On the other hand, in the catalysts of Comparative Examples 1 to 6, in the log differential pore volume distribution, a maximum point of dV / d (logD) was present in the pore diameter range of 5-30 nm, but no maximum point was present in the pore diameter range of 2-50 μm (2000-50,000 nm). Furthermore, the pore volume in the pore diameter range of 2-50 μm (2000-50,000 nm) was less than 3% of the total pore volume. No crevices, as observed in the Examples, were observed on the surface of the support.

[0106] [Evaluation of catalytic performance] (1) Confirmation test for evaluating catalytic performance for vacuum gas oil treatment Each catalyst produced in the examples and comparative examples was packed into a fixed-bed reactor and subjected to a pre-sulfiding treatment to activate the catalyst by removing oxygen atoms contained in the catalyst. This treatment was carried out by flowing a liquid or gas containing sulfur compounds through a controlled reaction vessel at a temperature of 200°C to 400°C under a hydrogen pressure atmosphere of atmospheric pressure to 100 MPa.

[0107] Next, the catalyst was packed into a fixed-bed flow reactor, and vacuum gas oil (VGO) (density at 15°C: 0.9314 g / cm 3 The reaction conditions were a liquid hourly space velocity of 1.50 h -1 , hydrogen partial pressure 4.5 MPa, hydrogen-oil ratio 200 Nm 3 The temperature conditions were changed in the range of 350-380°C at 1000kJ / kl, and the temperature at which the sulfur content in the produced oil became 0.18% was determined.

[0108] (2) Confirmation test for evaluation as a silicon trapping agent Each catalyst was packed into a fixed-bed reactor and subjected to a preliminary sulfurization treatment to activate the catalyst by removing oxygen atoms contained in the catalyst. This treatment was carried out by flowing a liquid or gas containing sulfur compounds through a controlled reaction vessel at a temperature of 200 to 400°C under a hydrogen pressure of atmospheric pressure to 100 MPa.

[0109] The Si trapping ability was evaluated using the following method. (1) After a confirmation test to evaluate catalyst performance, operation was carried out at 360°C for one year. After operation was stopped, the catalyst was removed, dried overnight in a dryer at 110°C, and washed with toluene using a Soxhlet extractor. The washed catalyst was dried overnight in a dryer at 110°C and calcined at 500°C for 1 hour. The SiO2 concentration of the calcined catalyst was measured and compared.

[0110] (3) Confirmation Test for Evaluation as a Demetalization Catalyst A commercially available demetalization catalyst, a transition catalyst, and the hydrotreating catalyst produced in each Example or Comparative Example were packed into a fixed-bed flow reactor (catalyst packed volume: 350 ml) in the following order:

[0111] 35 ml of a commercially available demetallization catalyst CDS-RS110 (manufactured by JGC Catalysts and Chemicals Co., Ltd.) 35 ml of a commercially available demetallization catalyst CDS-RS210 (manufactured by JGC Catalysts and Chemicals Co., Ltd.) 70 ml of a commercially available transition catalyst CDS-RS420 (manufactured by JGC Catalysts and Chemicals Co., Ltd.) 210 ml of the hydrotreating catalyst produced in each Example or Comparative Example.

[0112] The packed catalyst was subjected to a preliminary sulfurization treatment in order to desorb oxygen atoms contained in the catalyst and activate it. This treatment was carried out by a conventional method, namely, by passing a liquid or gas containing a sulfur compound through a controlled reaction vessel at a temperature of 200 to 400°C under a hydrogen pressure of atmospheric pressure to 100 MPa.

[0113] Heavy oil (density at 15°C: 0.9750, sulfur content: 4.06 mass%, metal (Ni + V) content: 85.1 mass ppm, nitrogen content: 2075 mass ppm, asphaltene content: 4.2 mass%, residual carbon content: 10.7 mass%) was introduced into a fixed-bed flow reactor and hydrotreated. The reaction conditions were a hydrogen partial pressure of 13.5 MPa, a liquid hourly space velocity of 0.3 h -1 , hydrogen-oil ratio is 800Nm 3 The reaction temperature was 370° C. The metal content in the resulting oil was analyzed, and the demetalization rate was calculated by the following formula.

[0114] Demetalization rate = (metal concentration in feed oil - metal concentration in hydrotreated product oil / metal concentration in feed oil) x 100 The results of the above confirmation tests are shown in Tables 2, 3 and 4.

[0115]

[0116]

[0117] (Evaluation Results of Confirmation Tests) (1) Evaluation Results of Catalyst Performance for Vacuum Gas Oil Processing Example 1 and Comparative Example 1 used the same raw materials except for the presence or absence of inorganic fibers, and can serve as comparisons for verifying the effects of the present invention. The 0.18% ultimate temperature was 359.6°C in Example 1 and 363.4°C in Comparative Example 1, indicating a reaction temperature drop of 3.8°C, confirming the effects of the invention. Similarly, when Examples 2 and 3 were compared with Comparative Example 2, a reaction temperature drop of 3.9 to 4.9°C was observed, confirming the effects of the invention.

[0118] (2) Evaluation Results of Performance as a Silicon Trap Agent Example 4 and Comparative Example 3 used the same raw materials except for the presence or absence of inorganic fibers, and can serve as comparisons for verifying the effects of the present invention. The value obtained by subtracting the amount of catalyst SiO2 before evaluation from the amount of SiO2 in the spent was defined as the calculated deposited SiO2 value. The deposited SiO2 was 6.96% in Example 4 and 4.44% in Comparative Example 3, and a 141% improvement in silicon trapping ability was observed.

[0119] Examples 5 and 6 and Comparative Example 4 used the same raw materials except for the presence or absence of inorganic fibers. The deposited SiO2 was 6.57% in Example 5, 5.85% in Example 6, and 4.61% in Comparative Example 4. Example 5 showed a 141% improvement in silicon trapping ability compared to Comparative Example 4, and Example 6 showed a 127% improvement in silicon trapping ability compared to Comparative Example 4, confirming the effects of the invention. The improvement in silicon trapping ability was also observed when Example 1 was compared to Comparative Example 1, and when Examples 2 and 3 were compared to Comparative Example 2.

[0120] (3) Evaluation Results of Demetalization Catalysts The results in Table 4 show that the demetalization rates of the catalysts of Examples 7 to 9 are higher than those of the catalysts of Comparative Examples 5 and 6. The improvement in the demetalization rate was also confirmed by comparing Example 1 with Comparative Example 1, and by comparing Examples 2 and 3 with Comparative Example 2.

[0121] The hydrotreating catalyst of the present invention is extremely useful industrially because it can hydrotreat hydrocarbon oils to a high degree.

Claims

1. An inorganic oxide support and an active metal component supported on the inorganic oxide support, The active metal component includes at least one of molybdenum and tungsten, and at least one of cobalt and nickel; A catalyst for hydrotreating a hydrocarbon oil, which satisfies the following requirements (1) to (3) in a log differential pore volume distribution measured by mercury intrusion porosimetry: Requirement (1): dV / d (logD) is maximum within the pore diameter range of 5-30 nm. Requirement (2): dV / d (logD) is maximized in the pore diameter range of 2 to 50 μm. Requirement (3): The ratio of the volume of pores having diameters in the range of 2 to 50 μm to the total volume of pores is 3% or more.

2. The catalyst for hydrotreating a hydrocarbon oil according to claim 1 , wherein the inorganic oxide support comprises inorganic fibers.

3. An inorganic oxide support and an active metal component supported on the inorganic oxide support, The active metal component includes at least one of molybdenum and tungsten, and at least one of cobalt and nickel; The surface of the inorganic oxide support has 3 crevices per mm, each having a maximum width of 2 μm or more and a length of 100 μm or more. 2 There are more than The following requirement (1) is satisfied in the log differential pore volume distribution measured by mercury intrusion porosimetry: Hydroprocessing catalyst for hydrocarbon oils. Requirement (1): dV / d (logD) is maximized in the pore diameter range of 5 to 30 nm.

4. A method for producing a carrier raw material mixture, comprising: mixing an inorganic oxide or a precursor of the inorganic oxide with inorganic fibers; Obtaining a molded product from the carrier raw material mixture by extrusion molding; drying and calcining the molded product to obtain an inorganic oxide support; A step of preparing an impregnation liquid containing at least one of a source of molybdenum and tungsten, a source of at least one of a source of cobalt and nickel, and a solvent, and contacting the impregnation liquid with the inorganic oxide support to obtain a supported material; and a step of heat-treating the support to obtain a hydrotreating catalyst. The inorganic fibers have an average diameter of 0.1 to 20 μm, The average length of the inorganic fibers is 0.1 mm or more. A method for producing a catalyst for hydrotreating a hydrocarbon oil, comprising preparing the carrier raw material mixture using the inorganic fibers so that the amount of the inorganic fibers in the inorganic oxide carrier is 0.2 to 10 mass %.