Carrier for a catalyst for hydrotreating hydrocarbon oils, method for producing a catalyst for hydrotreating hydrocarbon oils, method for producing a catalyst for hydrotreating hydrocarbon oils, and method for hydrotreating hydrocarbon oils

Abstract

To provide: a carrier for a catalyst for hydrotreating a hydrocarbon oil which has higher hydrogenation activity than a conventional catalyst and a long service life; a method manufacturing a carrier for the catalyst for hydrotreating a hydrocarbon oil; a method for manufacturing a catalyst for hydrotreating a hydrocarbon oil; and a method for hydrotreating a hydrocarbon oil.SOLUTION: There is provided a carrier for a catalyst for hydrotreating a hydrocarbon oil in which an organic acid is supported on a metal oxide containing alumina, wherein the organic acid has one carboxy group and has a solubility in 100 g water at 20°C of less than 0.015 g.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Each oil fraction obtained by distillation or cracking of crude oil generally contains sulfur compounds, and when these oils are used as fuel, sulfur oxides and the like caused by these sulfur compounds are generated. Therefore, the process for producing petroleum products from crude oil includes a hydrotreating process for removing 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] In order to increase the efficiency of hydrotreating, it is desirable to improve the performance of hydrotreating catalysts. To this end, metal oxide supports and hydrogenation active metals have been investigated.

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

[0006] [Patent Document 1] International Publication No. 2015 / 046345 Summary of the Invention [Problem to be solved by the invention]

[0007] The hydrotreating catalyst described in Patent Document 1 is a hydrotreating catalyst for heavy hydrocarbon oils such as atmospheric distillation residual oil, vacuum distillation residual oil, etc. Heavy hydrocarbon oils are more difficult to desulfurize than light hydrocarbon oils, and therefore require severe hydrotreating conditions such as high temperature and high pressure, which causes problems such as the hydrotreating catalyst being easily deteriorated and the catalyst life being shortened. Therefore, there is a need to further improve the hydrogenation activity and catalyst life of the hydrotreating catalyst described in Patent Document 1.

[0008] The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a carrier for a hydrocarbon oil hydrotreating catalyst which has higher hydrogenation activity and a longer life than conventional catalysts, a method for producing the carrier for a hydrocarbon oil hydrotreating catalyst, a method for producing a hydrocarbon oil hydrotreating catalyst, and a method for hydrotreating a hydrocarbon oil. [Means for solving the problem]

[0009] In order to solve the above problems, the present invention has the following aspects. [1] A catalyst carrier for hydrotreating hydrocarbon oils, comprising an organic acid supported on a metal oxide containing alumina, the organic acid having one or more carboxy groups and a solubility of less than 0.015 g in 100 g of water at 20°C. [2] The support for a catalyst for hydrotreating a hydrocarbon oil according to [1], wherein the organic acid has 12 to 26 carbon atoms. [3] The support for a catalyst for hydrotreating a hydrocarbon oil according to [1] or [2], wherein the organic acid is an organic acid having one carboxy group. [4] A method for producing a catalyst support for hydrotreating a hydrocarbon oil according to any one of [1] to [3], comprising supporting the organic acid on a metal oxide containing alumina. [5] A method for producing a catalyst for hydrotreating a hydrocarbon oil, comprising supporting at least one metal selected from Group 6 metals of the periodic table in an amount of 0.5 to 25 mass%, calculated as an oxide, based on the catalyst, and at least one metal selected from Groups 9 and 10 metals of the periodic table in an amount of 0.5 to 15 mass%, calculated as an oxide, based on the catalyst, on the hydrotreating catalyst support according to any one of [1] to [3], and then calcining the support at 300° C. or higher. [6] Hydrogen partial pressure: 3-20MPa, reaction temperature: 280-420℃, liquid hourly space velocity: 0.1-10hr -1 A method for hydrotreating a hydrocarbon oil, comprising contacting the hydrocarbon oil with a hydrotreating catalyst produced by the production method according to [5]. [7] Hydrogen partial pressure: 3-20MPa, reaction temperature: 280-420℃, liquid hourly space velocity: 0.1-10hr -1 A method for producing hydrogenated hydrocarbon oil, comprising contacting a hydrocarbon oil with a hydrotreating catalyst produced by the production method according to [5]. Effect of the Invention

[0010] According to the present invention, it is possible to provide a carrier for a hydrocarbon oil hydrotreating catalyst which has higher hydrogenation activity and a longer life than conventional catalysts, a method for producing the carrier for a hydrocarbon oil hydrotreating catalyst, a method for producing a hydrocarbon oil hydrotreating catalyst, and a method for hydrotreating a hydrocarbon oil. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] 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.

[0012] <Catalyst carrier for hydrotreating hydrocarbon oil> The carrier for a hydrotreating catalyst for hydrocarbon oils (hereinafter, simply referred to as the "carrier") of this embodiment is a carrier in which an organic acid is supported on a metal oxide containing alumina. The organic acid has one or more carboxy groups and has a solubility of less than 0.015 g in 100 g of water at 20°C.

[0013] <Metal oxide> The metal oxide in this embodiment includes alumina. The metal oxide may include a metal oxide other than alumina. As the metal oxide other than alumina, any metal oxide that can be contained in the carrier of the hydrotreating catalyst for hydrocarbon oil in this field can be used, and examples thereof include zeolite, silica, zirconia, titania, boria, phosphorus oxide, zinc oxide, etc., with phosphorus oxide, zinc oxide, titania, and boria being preferred, and phosphorus oxide and zinc oxide being particularly preferred. Note that boron and silicon are elements that are generally considered to be semimetallic, but are treated as metals in this specification.

[0014] The metal oxide other than alumina may be a mixture with alumina, or may form a composite oxide with alumina. The metal oxide other than alumina may be one type or two or more types. When there are two or more types of metal oxides, the metal oxide may be a mixture of alumina and these two or more types of metal oxides, or these two or more types of metal oxides may form a composite oxide.

[0015] When the metal oxide contains a metal oxide other than alumina, the preferred range of the content of each metal oxide is as follows. The content of alumina relative to the total mass of the metal oxides is preferably from 80 to 99.9 mass %, more preferably from 82.5 to 99.8 mass %, and further preferably from 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 %, and 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 %, and 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 %, and 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 %, and 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 %, and 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 %, and more preferably 0.01 to 5 mass %.

[0016] The content ratio of each metal oxide in the metal oxides can be determined by measuring the mass of each metal oxide in elemental terms and dividing the converted value by the total mass of the metal oxides: alumina: Al2O3, phosphorus oxide: P2O5, zinc oxide: ZnO, silica: SiO2, titania: TiO2, boria: B2O3, and zirconia: ZrO2. In this specification, the masses of the metal oxides, the support, the metal oxides, the metals of Group 6 of the periodic table, and the metals of Groups 9 and 10 of the periodic table contained in the hydrotreating catalyst in terms of elements can be measured by inductively coupled plasma atomic emission spectrometry.

[0017] As the alumina, various types of alumina such as α-alumina, β-alumina, γ-alumina, δ-alumina, etc. 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 contained in an amount of 0.1 mass % or less.

[0018] <Organic acid> The organic acid of this embodiment has one or more carboxy groups and has a solubility in 100 g of water at 20° C. of less than 0.015 g. The organic acid supported on the metal oxide containing alumina may be one type or two or more types.

[0019] The number of carboxy groups in the organic acid is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. When the number of carboxy groups is equal to or less than the upper limit, the acid sites of the catalyst are selectively covered, improving the dispersibility of the active metal.

[0020] The solubility of the organic acid in 100 g of water at 20° C. is preferably 0.01 g or less, more preferably 0.005 g or less, and even more preferably 0.001 g or less (insoluble). When the solubility of the organic acid in 100 g of water at 20° C. is less than (equal to) the upper limit, the hydrogenation activity of the resulting hydrotreating catalyst is improved, and the catalyst life is improved.

[0021] The solubility of an organic acid in 100 g of water at 20° C. can be measured, for example, according to JIS K 8001: 2017. In addition, when the solubility of an organic acid in 100 g of water at 20° C. is known, for example, the value listed in the Kanagawa Prefecture Chemical Substance Safety Information System (KIS-NET) can be used.

[0022] As long as the solubility in 100 g of water at 20° C. is less than 0.015 g, the basic skeleton structure of the organic acid other than the carboxy group is not particularly limited, but for example, a hydrocarbon structure consisting only of carbon and hydrogen is preferred. That is, the organic acid is preferably an organic acid in which one or more hydrogen atoms in a hydrocarbon compound consisting of only carbon and hydrogen are substituted with a carboxy group.

[0023] Examples of such a hydrocarbon compound include saturated hydrocarbon compounds and unsaturated hydrocarbon compounds. The hydrocarbon compound may be a hydrocarbon compound consisting of only a chain structure, a hydrocarbon compound consisting of only a cyclic structure, or a hydrocarbon compound having both a chain structure and a cyclic structure. The chain structure may be a straight chain structure or a branched structure.

[0024] An example of a saturated hydrocarbon compound consisting of only a chain structure is an alkane, and an example of a saturated hydrocarbon compound consisting of only a cyclic structure is a cycloalkane. An example of a saturated hydrocarbon compound having both a chain structure and a cyclic structure is a saturated hydrocarbon compound in which one or more hydrogen atoms in a cycloalkane are substituted with an alkyl group.

[0025] Examples of unsaturated hydrocarbon compounds consisting of only chain structures include unsaturated hydrocarbon compounds in which one or more carbon-carbon single bonds of alkenes, alkynes, and alkanes are replaced with double bonds or triple bonds. Examples of unsaturated hydrocarbon compounds consisting of only cyclic structures include unsaturated hydrocarbon compounds in which one or more carbon-carbon single bonds of aromatic hydrocarbon compounds, cycloalkenes, and cycloalkanes are replaced with double bonds. Examples of unsaturated hydrocarbon compounds having both chain structures and cyclic structures include unsaturated hydrocarbon compounds in which one or more hydrogen atoms in aromatic hydrocarbon compounds, cycloalkenes, or unsaturated hydrocarbon compounds in which one or more carbon-carbon single bonds of cycloalkanes are replaced with double bonds are replaced with alkyl groups, alkenyl groups, or alkynyl groups.

[0026] Among the above, the saturated hydrocarbon compound is preferably an alkane, more preferably a linear alkane.The unsaturated hydrocarbon compound is preferably an alkene or an alkane in which two or more carbon-carbon single bonds are replaced with double bonds, and more preferably a linear alkene or an alkane in which two or more carbon-carbon single bonds are replaced with double bonds.

[0027] That is, the organic acid is preferably an organic acid in which one or more hydrogen atoms in an alkane are substituted with a carboxy group, and more preferably an organic acid in which one or more hydrogen atoms in a straight-chain alkane are substituted with a carboxy group. Furthermore, the organic acid is preferably an organic acid in which one or more hydrogen atoms in an alkene or an unsaturated hydrocarbon compound in which two or more carbon-carbon single bonds in an alkane are replaced with double bonds, and more preferably an organic acid in which one or more hydrogen atoms in a straight-chain alkene or an unsaturated hydrocarbon compound in which two or more carbon-carbon single bonds in a straight-chain alkane are replaced with double bonds, are replaced with a carboxy group.

[0028] The carbon number of the organic acid is preferably 12 to 26, more preferably 14 to 26, and even more preferably 14 to 22. When the carbon number is equal to or more than the lower limit, the hydrogenation activity of the resulting hydrotreating catalyst is improved, and the catalyst life is improved. When the carbon number is equal to or less than the upper limit, the organic acid is easily dissolved in a solvent such as alcohol, which makes it easy to prepare an impregnation solution used when supporting the organic acid on a carrier, and makes it easy to produce a catalyst, which is advantageous for industrial use.

[0029] Preferred organic acids having 12 to 26 carbon atoms in which one or more hydrogen atoms in a straight-chain alkane have been substituted with a carboxy group include dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid (arachidic acid), henicosanoic acid (henicosylic acid), docosanoic acid (behenic acid), tricosanoic acid, tetracosanoic acid (lignoceric acid), pentacosanoic acid, and hexacosanoic acid.

[0030] As the organic acid having 12 to 26 carbon atoms in which one or more hydrogen atoms in a linear alkene are substituted with a carboxy group, dodecenoic acid, tridecenoic acid, tetradecenoic acid (myristoleic acid), pentadecenoic acid, hexadecenoic acid (palmitoleic acid), heptadecenoic acid, octadecenoic acid (oleic acid), icosenoic acid (eicosenoic acid), docosenoic acid, tricosenoic acid, tetracosenoic acid, pentacosenoic acid, and hexacosenoic acid are preferred. The organic acids include both cis and trans isomers.

[0031] Preferred organic acids having 12 to 26 carbon atoms in an unsaturated hydrocarbon compound in which two or more carbon-carbon single bonds of a straight-chain alkane have been replaced with double bonds and one or more hydrogen atoms have been replaced with a carboxy group include hexadecadienoic acid, hexadecatrienoic acid, hexadecatetraenoic acid, heptadecadienoic acid, octadecadienoic acid (linoleic acid), octadecatrienoic acid (α-linolenic acid, γ-linolenic acid), octadecatetraenoic acid, icosadienoic acid (eicosadienoic acid), icosatrienoic acid (eicosatrienoic acid), icosatetraenoic acid (eicosatetraenoic acid, arachidonic acid), icosapentaenoic acid (eicosapentaenoic acid), henicosapentaenoic acid, docosadienoic acid, docosatetraenoic acid, docosapentaenoic acid, and docosahexaenoic acid.

[0032] The amount of the organic acid supported is preferably 0.2 to 25% by mass or more, more preferably 0.5 to 20% by mass, and even more preferably 1 to 5% by mass, based on the total mass of the support. When the amount of the organic acid supported is equal to or more than the lower limit, the strong acid sites on the catalyst surface are preferentially covered, contributing to improved dispersibility of the active metal. When the amount of the organic acid supported is equal to or less than the upper limit, the hydrophilicity of the catalyst support is not inhibited, and therefore the dispersion of the metal is not adversely affected. The amount of organic acid carried can be measured by a total organic carbon (TOC) meter.

[0033] (Carrier properties) The specific surface area of ​​the carrier of this embodiment is 200 to 400 m as measured by the nitrogen adsorption method (BET method). 2 / g, and 250 to 360m 2 / g is more preferable. When the specific surface area is equal to or greater than the lower limit of the above range, the periodic table group 6 metals, periodic table group 9 metals, and periodic table group 10 metals are sufficiently dispersed, resulting in high hydrogenation activity. When the specific surface area is equal to or less than the upper limit of the above range, the support has a sufficiently large pore diameter, so that the pore diameter of the hydrotreating catalyst is also sufficiently large. Therefore, the diffusion of sulfur compounds into the catalyst pores is sufficient, resulting in high hydrogenation activity. That is, when the specific surface area is within the above range, the dispersibility of the periodic table group 6 metals, periodic table group 9 metals, and periodic table group 10 metals is good, and a hydrotreating catalyst having a sufficiently large pore diameter is obtained.

[0034] The average pore diameter of the support of this embodiment in the pore distribution measured by mercury intrusion porosimetry is preferably 4 to 12 nm, more preferably 6 to 10 nm. When the average pore diameter is within the above range, the support has a sufficient inner pore surface area, and the diffusion of sulfur compounds into the catalyst pores is sufficient, resulting in high hydrogenation activity.

[0035] The pore volume of the carrier of this embodiment is preferably 0.5 to 0.9 mL / g, more preferably 0.55 to 0.85 mL / g, as measured by mercury intrusion porosimetry. When the pore volume is equal to or greater than the lower limit of the range, the amount of solvent that enters the pores is sufficient when the catalyst is prepared by a normal impregnation method. When the amount of solvent is sufficient, the raw material compounds of metals in Group 6 of the periodic table, metals in Groups 9 and 10 of the periodic table are well dissolved in the solvent, the dispersibility of metals in Groups 6 of the periodic table, metals in Groups 9 and 10 of the periodic table is improved, and a hydrotreating catalyst with high hydrogenation activity can be obtained. In order to increase the solubility of raw material compounds of metals in Groups 6 of the periodic table, metals in Groups 9 and 10 of the periodic table, there is a method of adding a large amount of acid such as nitric acid, but if too much acid is added, the surface area of ​​the carrier is reduced, which is the main cause of the 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 metals of Group 6, Group 9, and Group 10 of the periodic table. That is, when the pore volume is within the above range, the specific surface area is sufficient and a sufficient amount of solvent can enter the pore volume, so that the solubility and dispersibility of the raw material compounds of the metals of Group 6, Group 9, and Group 10 of the periodic table are both good, and the hydrogenation activity is further improved.

[0036] <<Method for producing a carrier for a catalyst for hydrotreating hydrocarbon oil>> The method for producing a hydrotreating catalyst support of the present embodiment is a method for producing a hydrotreating catalyst support for hydrocarbon oils, comprising a step of supporting the organic acid on a metal oxide containing alumina.

[0037] <Metal oxide manufacturing method> The metal oxide of the present 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 the present embodiment includes, for example, an alumina gel preparation step of preparing an alumina gel, a kneading step of kneading the alumina gel to obtain a kneaded product, a molding step of molding the kneaded product to obtain a molded product, and a firing step of drying and firing the molded product to obtain the metal oxide as a fired product.

[0038] When the metal oxide mainly composed of alumina 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 them, it is preferable to add the metal oxide raw material to the alumina gel during the kneading process and then perform the kneading process.

[0039] Any alumina raw material can be used as long as it contains aluminum, but aluminum salts such as aluminum sulfate, aluminum nitrate, etc. are preferred. These alumina raw materials are usually provided as aqueous solutions, and although there are no particular limitations on their concentration, they are preferably 2 to 50 mass %, more preferably 5 to 40 mass %.

[0040] For example, the alumina gel is prepared by mixing an aqueous solution of sulfuric acid, sodium aluminate, and aluminum hydroxide in a stirring vessel to prepare a slurry. The resulting slurry is subjected to removal of water using a rotary cylindrical continuous vacuum filter and washed with pure water to obtain the alumina gel.

[0041] The resulting alumina gel was then added to the filtrate with SO4 2- , Na + After washing until no more can be detected, the alumina gel is mixed with pure water to obtain a uniform slurry, and the resulting alumina gel slurry is dehydrated until the water content is 60 to 90% by mass to obtain a cake.

[0042] The alumina gel slurry is preferably dehydrated using a press filter. A press filter is a device that filters a slurry by applying compressed air or pump pressure, and is also generally called a filter press. There are plate-frame type and concave-plate type presses. In a plate-frame type filter press, filter plates and filter frames are alternately clamped between end plates, and the slurry is pressed into the filter frames to filter. The filter plates have grooves that serve as filtrate flow paths, 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).

[0043] By dehydrating the alumina gel slurry with a press filter, the surface condition of the obtained carrier can be improved, and the sulfidity of the hydrogenation active component can be improved. The dehydration step with the press filter is preferably carried out after at least one of the alumina gel preparation step and the kneading step, and may be carried out after both steps. Among them, it is more preferable to carry out the dehydration step after the alumina gel preparation step and before the kneading step.

[0044] In addition to the above-mentioned 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 with a precipitating agent such as hexamethylenetetramine or calcium carbonate. The amount of the neutralizing agent 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 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.

[0045] 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 resulting alumina gel is aged, washed, dehydrated and dried, and its moisture 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.

[0046] When the metal oxide raw material is added to the alumina gel by the 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 the moisture-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 product. 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 may be added as a liquid in which the metal oxide raw material is dissolved or suspended in a solvent.

[0047] As the metal oxide raw material, raw materials known in the art can be used.

[0048] When producing a metal oxide containing zinc oxide, the zinc oxide raw material to be added may be zinc itself or various zinc compounds. Examples include zinc oxide, zinc nitrate, zinc sulfate, zinc carbonate, zinc chloride, zinc acetate, zinc hydroxide, zinc oxalate, zinc phosphate, zinc aluminate, zinc titanate, zinc molybdate, and the like. Of these, zinc oxide, zinc nitrate, zinc sulfate, and zinc aluminate are preferred, and zinc nitrate, zinc oxide, and zinc aluminate are particularly preferred.

[0049] 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 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.

[0050] When producing a metal oxide containing phosphorus oxide, the phosphorus oxide raw material to be added may 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.

[0051] The kneaded product thus obtained is molded, dried, and fired to obtain a fired product. The kneaded product can be molded 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 necessary, but for example, the firing temperature for obtaining γ-alumina is preferably 450°C or more, more preferably 480 to 600°C. The firing time is preferably 2 hours or more, more preferably 3 to 12 hours.

[0052] <Organic acid support> The organic acid can be supported on the metal oxide containing alumina by a method known in the art. One example of such a supporting method is an impregnation method in which the metal oxide containing alumina is impregnated with the organic acid. The impregnation method will be described below.

[0053] Examples of the impregnation method include an evaporation to dryness method in which a metal oxide is immersed in an impregnation liquid in excess of the total pore volume of the metal oxide and then the solvent is completely dried to support an organic acid, an equilibrium adsorption method in which a metal oxide is immersed in an impregnation liquid in excess of the total pore volume of the metal oxide and then a catalyst carrying an organic acid is obtained by solid-liquid separation such as filtration, and a pore filling method in which a metal oxide is impregnated with an impregnation liquid in an amount approximately equal to the total pore volume of the metal oxide and then the solvent is completely dried to support an organic acid. The method for impregnating a metal oxide containing alumina with two or more organic acids 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.

[0054] The impregnation solution can be prepared by dissolving an organic acid in an organic solvent. The organic solvent is not particularly limited as long as it can dissolve the organic acid and can be removed by evaporation in the drying step described below. Examples of the organic solvent include isopropyl alcohol, ethanol, butanol, pentanol, and octanol.

[0055] The impregnation method can provide an impregnated body in which a metal oxide is impregnated with an impregnation liquid containing an organic acid and an organic solvent. It is preferable to remove the solvent from the impregnated body by drying. The drying can be performed by a method known in the art, and the drying temperature, drying time, drying pressure, and drying atmosphere can be appropriately adjusted depending on the boiling points of the solvent and organic acid to be removed, etc.

[0056] For example, the drying temperature may be from 20 to less than 300°C, from 20 to 200°C, or from 20 to 150°C. The drying time may be 1 to 24 hours, 1 to 8 hours, or 1 to 3 hours. The drying atmosphere may be a nitrogen atmosphere, an air atmosphere, or the like, and the drying pressure may be normal pressure or reduced pressure.

[0057] <Method for producing a catalyst for hydrotreating hydrocarbon oil> The method for producing a hydrocarbon oil hydrotreating catalyst of this embodiment includes supporting, on the support, at least one metal selected from Group 6 metals of the periodic table in an amount of 0.5 to 25 mass %, calculated as an oxide, based on the catalyst, and at least one metal selected from Groups 9 and 10 metals of the periodic table in an amount of 0.5 to 15 mass %, calculated as an oxide, based on the catalyst, and then calcining the support at 300°C or higher. In this specification, "metals of Group 6 of the periodic table" (hereinafter sometimes referred to as "Group 6 metals") means metals of Group 6 in the long-form periodic table, and "metals of Groups 9 and 10 of the periodic table" (hereinafter sometimes referred to as "Groups 9 and 10 metals") means metals of Groups 9 and 10 in the long-form periodic table. Group 6 metals and Group 9 and Group 10 metals are collectively referred to as "hydrogenation active components."

[0058] 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.

[0059] Examples of Group 9 and Group 10 metals include nickel and cobalt, and among these, nickel is preferred because it has high hydrogenation ability and low catalyst preparation costs.

[0060] In the method for producing the 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 source may be one type or two or more types.

[0061] 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.

[0062] Examples of the tungsten compound 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 of one type or of two or more types.

[0063] Examples of chromium compounds include chromium oxide, chromium acetate, chromium sulfate, chromium phosphate, chromic acid, dichromate, and neutral red, with chromic acid being preferred. The chromium compound may be of one type or of two or more types.

[0064] In the method for producing a 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 the nickel compound 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.

[0065] The amount of the Group 6 metal supported is 0.5 to 25 mass% in terms of oxide based on the catalyst, preferably 2.5 to 25 mass%, more preferably 8 to 20 mass%, and even more preferably 10 to 16 mass%. When the amount of the Group 6 metal supported is equal to or more than the lower limit of the above range, it is sufficient to exhibit 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 that can be efficiently dispersed is not exceeded, and the catalyst surface area is not significantly reduced, so that the catalytic activity can be improved.

[0066] The amount of the metals of Groups 9 and 10 supported is 0.5 to 15 mass% based on the catalyst in terms of oxide, preferably 0.5 to 10 mass%, more preferably 1 to 8 mass%, and even more preferably 1 to 6 mass%. When the amount of the metals of Groups 9 and 10 supported is equal to or greater than the lower limit of the above range, the active sites belonging to the metals of Groups 9 and 10 are sufficiently obtained. When the amount of the metals of Groups 9 and 10 supported is equal to or less than the upper limit of the above range, the metals of Groups 9 and 10 are less likely to aggregate, and the dispersibility is improved. For example, when nickel is used as the metal of Groups 9 and 10, NiO species (which exist as NiS species after catalyst sulfurization or during hydrogenation treatment) that are inactive precursors, and Ni spinel species incorporated into the lattice of the support are less likely to be generated, and therefore the catalytic activity is improved.

[0067] The supported amounts of the Group 6 metal and the Group 9 and Group 10 metals on a catalyst basis, calculated as oxides, can be determined by measuring the masses of the Group 6 metal and the Group 9 and Group 10 metals in elemental terms, and dividing the values ​​converted into 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.

[0068] The method for supporting the Group 6 metal raw material and the Group 9 and Group 10 metal raw materials (hereinafter also referred to as "hydrogenation active component raw material") on the carrier may be a known method such as an impregnation method, a coprecipitation method, a kneading method, a deposition method, an ion exchange method, etc. Examples of the impregnation method include an evaporation to dryness method in which the carrier is immersed in an impregnation solution that is excessive with respect to the total pore volume of the carrier, and then the solvent is completely dried to support the hydrogenation active component raw material, an equilibrium adsorption method in which the carrier is immersed in an impregnation solution that is excessive with respect to the total pore volume of the carrier, and then a catalyst on which the hydrogenation active component raw material is supported is obtained by solid-liquid separation such as filtration, and a pore filling method in which the carrier is impregnated with an impregnation solution in an amount approximately equal to the total pore volume of the carrier, and then the solvent is completely dried to support the hydrogenation active component raw material. The method for impregnating the carrier with the hydrogenation active component raw material may be a batch impregnation method in which each of these components is simultaneously impregnated, or a sequential impregnation method in which each of these components is individually impregnated.

[0069] Specific methods (impregnation 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 material is prepared. The impregnation solution can be prepared by dissolving the hydrogenation active ingredient raw material in water. 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, in addition to the phosphorus contained in the carrier, phosphorus may be separately supported when the hydrogenation active ingredient raw material, etc. are supported on the carrier.

[0070] Examples of phosphorus compounds that are added separately when the hydrogenation active component raw material is supported 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 the hydrogenation active component raw material is supported on the support, the dispersibility of the hydrogenation active component in the resulting hydrotreating catalyst can be improved.

[0071] 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.

[0072] 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, not only is the surface area and pore volume of the resulting hydrotreating catalyst not reduced and a decrease in hydrogenation activity suppressed, but carbon deposition can be prevented without an increase in the amount of acid, thereby suppressing activity deterioration.

[0073] 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 the 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 the molybdenum compound in terms of oxide is within the above range, the Group 9 and Group 10 metal compounds and molybdenum in the obtained hydrotreatment catalyst can be naturally integrated.

[0074] After loading the hydrogenation active component raw material, the impregnated body is preferably subjected to a nitrogen stream, an air stream, or a vacuum at 15 to 80° C. to remove moisture to a certain extent (so that LOI (loss on ignition) is 50% or less), followed by drying in an air stream at 80 to 150° C. for 10 minutes to 10 hours in a drying furnace.

[0075] Subsequently, the impregnated body or the dried impregnated body is calcined at 300° C. or higher. The calcination temperature is preferably 300 to 700° C., more preferably 400 to 600° C., and particularly preferably 450 to 550° C. The calcination time is preferably 1 to 24 hours, and more preferably 1 to 8 hours. The calcination atmosphere may be an oxygen-containing atmosphere, and is preferably an air atmosphere.

[0076] <Hydrotreatment catalyst> The hydrotreating catalyst produced by the method for producing a hydrocarbon oil hydrotreating catalyst of this embodiment contains a metal oxide containing alumina, 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 hydrotreating catalyst for hydrocarbon oils 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 metal oxide containing alumina.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] Hydrotreating catalysts are produced by calcining at 300°C or higher, and organic acids are removed by evaporation, decomposition, and combustion. Therefore, organic acids are not contained in the hydrotreating catalyst, or even if they are contained, they are present in extremely small amounts.

[0081] The hydrotreating catalyst may contain an oxide other than alumina, Group 6 metals, Group 9 metals, and Group 10 metals. Examples of the oxide include zeolite, silica, zirconia, titania, boria, phosphorus oxide, and zinc oxide, with phosphorus oxide, zinc oxide, titania, and boria being preferred, and phosphorus oxide and zinc oxide being particularly preferred.

[0082] When the hydrotreating catalyst contains phosphorus oxide, the content of phosphorus oxide relative to the total mass of the hydrotreating catalyst is preferably 0.01 to 9.5 mass %, and more preferably 0.01 to 4.7 mass %. When the hydrotreating catalyst contains zinc oxide, the content of zinc oxide relative to the total mass of the hydrotreating catalyst is preferably 0.01 to 14.5 mass %, and more preferably 0.01 to 9.5 mass %. When the hydrotreating catalyst contains silica, the content of silica relative to the total mass of the hydrotreating catalyst is preferably from 0.01 to 17 mass %, and more preferably from 0.01 to 14 mass %. When the hydrotreating catalyst contains titania, the content of titania relative to the total mass of the hydrotreating catalyst is preferably 0.01 to 19 mass %, and more preferably 0.01 to 16.5 mass %. When the hydrotreating catalyst contains boria, the content of boria relative to the total mass of the hydrotreating catalyst is preferably 0.01 to 19 mass %, and more preferably 0.01 to 14.5 mass %.

[0083] The total content of at least one oxide selected from zeolite, silica, boria, phosphorus oxide, titania, zinc oxide, and zirconia relative to the total mass of the hydrotreating catalyst is preferably 0.01 to 18 mass%, more preferably 0.01 to 15 mass%, and still more preferably 0.01 to 10 mass%. As the zeolite, silica, boria, phosphorus oxide, titania, zinc oxide, and zirconia, those generally used as carrier components for this type of catalyst can be used.

[0084] The specific surface area of ​​the hydrotreating catalyst is 100 to 300 m, as measured by the BET method. 2 / g, and 150 to 250m 2 / g is more preferable. When the specific surface area is equal to or greater than the lower limit of the above range, the hydrogenation active component is sufficiently dispersed, resulting in high hydrogenation activity. When the specific surface area is equal to or less than the upper limit of the above range, the hydrotreating catalyst has a sufficiently large pore diameter. Therefore, the 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 the sulfur compounds into the catalyst pores during hydrotreating.

[0085] The average pore diameter in the pore distribution of the hydrotreating catalyst measured by mercury intrusion porosimetry is preferably 6 to 11 nm, more preferably 7 to 10.5 nm. When the average pore diameter is within the above range, the catalyst has a sufficient inner pore surface area (i.e., the effective surface area of ​​the catalyst) while increasing the diffusibility of sulfur compounds into the catalyst pores, and the hydrotreating activity can be further improved.

[0086] The pore volume of the hydrotreating catalyst is preferably 0.35 to 0.80 mL / g, more preferably 0.35 to 0.70 mL / g, as measured by mercury intrusion porosimetry. When the pore volume is equal to or greater than the lower limit of the above range, the diffusion of sulfur compounds in the catalyst pores during hydrotreating is sufficient, 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 diffusion of sulfur compounds into the catalyst pores during hydrotreating can be improved.

[0087] In order to increase the effective number of pores that satisfy the above-mentioned average pore diameter and pore volume, the pore size distribution of the hydrotreating catalyst of this embodiment is such that the ratio of the volume of pores having pore diameters of the average pore diameter ±1.5 nm to the total pore volume is preferably 65% ​​or more, and more preferably 70% or more.

[0088] 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.

[0089] <Mechanism of action> The hydrotreating catalyst carrier of this embodiment contains alumina and an organic acid. When a hydrotreating active component is supported on a carrier containing alumina, it is considered that the hydrotreating active component (particularly a Group 6 metal) is likely to aggregate at the strong acid sites on the alumina. In the hydrotreating catalyst of this embodiment, it is considered that the number of strong acid sites on the alumina is reduced by covering the strong acid sites on the alumina with an organic acid containing a carboxy group. Therefore, when the hydrotreating active component is supported, the aggregation of the hydrotreating active component is suppressed and the hydrotreating active component is supported in a highly dispersed manner, which is considered to improve the hydrotreating activity and improve the catalyst life. In addition, the mechanism by which an organic acid having one or more carboxy groups and a solubility in 100 g of water at 20° C. of less than 0.015 g effectively covers the strong acid sites on the alumina is considered to be as follows. When an organic acid having one or more carboxy groups and a solubility of 0.015 g or more in 100 g of water at 20° C. is used, the organic acid is likely to be liberated from the carrier when an aqueous solution containing a hydrogenation active component (raw material) is supported on the carrier, and the coating effect is likely to be impaired. In addition, when an alcohol is used as an organic solvent for the impregnation liquid when an organic acid having one or more carboxy groups and a solubility of 0.015 g or more in 100 g of water at 20° C. is used, the alcohol and the organic acid react to easily form an ester. This ester is less polar than the organic acid (carboxylic acid), and therefore cannot be selectively adsorbed to the acid sites on the alumina, and the coating effect is likely to be impaired. Therefore, when an organic acid having one or more carboxy groups and a solubility of less than 0.015 g in 100 g of water at 20°C is used, it is considered that the hydrogenation active component (raw material) can be supported without losing the effect of covering the strong acid sites on the alumina by the organic acid when the hydrogenation active component (raw material) is added.

[0090] <Method for hydrotreating hydrocarbon oil> The hydrotreating method for 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 -1The present invention relates to a method for hydrotreating a hydrocarbon oil, comprising 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 hr -1 The present invention also provides a method for producing hydrogenated hydrocarbon oil, which comprises contacting a hydrocarbon oil with the hydrotreating catalyst produced by the production method of the present invention.

[0091] 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.

[0092] 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.

[0093] Liquid hourly space velocity is 0.1 to 10 h -1 It is preferable that the time is 0.1 to 5 hours. -1 More preferably, 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, the 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.

[0094] Hydrogen / hydrocarbon oil ratio is 50~3000Nm 3 / kL is preferred, and 100 to 2500 Nm 3 / kL is more preferable, and 200 to 2000 Nm 3 / kL is more preferred.

[0095] Examples of hydrocarbon oils to be subjected to the hydrotreating method of hydrocarbon oil 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., which are particularly heavy oils among the oils 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-graveled oil.

[0096] 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 preferably 0.82 to 1.1 g / cm 3 More preferably, 0.84 to 1.06 g / cm 3 The 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 a 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.

[0097] The density of the hydrogenated hydrocarbon oil produced by the hydrotreating method of the present embodiment is 0.7 to 1.05 g / cm 3 is preferable, 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 mass%, more preferably 0.01 to 0.6 mass%, and even more preferably 0.05 to 0.5 mass%. When the hydrocarbon oil is a 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 mass% or less.

[0098] The hydrotreating catalyst of this embodiment is generally activated by sulfurization in a reactor before use (i.e., prior to carrying out the hydrotreating method of this embodiment). This sulfurization is generally carried out at 200 to 400°C, preferably 250 to 350°C, under a hydrogen atmosphere with a hydrogen partial pressure of normal pressure or higher, using a petroleum distillate containing sulfur compounds to which a sulfurizing agent such as dimethyl disulfide or carbon disulfide has been added, or hydrogen sulfide.

[0099] By hydrotreating a hydrocarbon oil using the hydrotreating catalyst of this embodiment, the hydrotreating process proceeds sufficiently, and it becomes possible to reduce the amount of sulfur compounds in the hydrocarbon oil over a long period of time.

[0100] To carry out the hydrotreating method of this embodiment on a commercial scale, a fixed bed, moving bed, or fluidized bed type catalyst layer of the hydrotreating catalyst of this embodiment is formed in a reactor, a feed oil is introduced into this reactor, and a hydrotreating reaction is carried out under the above-mentioned conditions. Most commonly, a fixed bed type catalyst layer is formed in the reactor, the feed oil is introduced into the upper part of the reactor, the feed oil 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 feed oil is introduced into the lower part of the reactor, the feed oil passes from the bottom to the top of the fixed bed, and the product is discharged from the top of the reactor.

[0101] The hydrotreating method of the present embodiment may be a single-stage hydrotreating method in which the hydrotreating catalyst of the present embodiment is packed into a single reactor, or may be a multi-stage continuous hydrotreating method in which the hydrotreating catalyst of the present embodiment is packed into several reactors.

[0102] The hydrotreating method of this embodiment may be a hydrotreating method in which the catalyst is contacted with three types of catalysts (front-stage catalyst, middle-stage catalyst, and rear-stage catalyst). Such a hydrotreating method using three types of catalysts is preferably used for heavy hydrocarbon oils such as atmospheric distillation residual oil and vacuum distillation residual oil, and each catalyst is mainly required to have different performances. The front-stage catalyst is mainly required to have metal resistance performance and demetalization activity to protect the catalysts in the middle and subsequent stages. The middle-stage catalyst is required to have a good balance of metal resistance performance, demetalization activity, and desulfurization performance at the same time. The rear-stage catalyst is mainly required to have desulfurization performance. In such a reaction system, the hydrotreating catalyst of the present invention described above can be used as any of the front-stage catalyst, middle-stage catalyst, and rear-stage catalyst, and is preferably used as the middle-stage catalyst. As the first stage catalyst, a first stage catalyst known in the art can be used, and examples of such a first stage catalyst include those described in JP 2010-248476 A, WO 2015 / 053087 A, WO 2015 / 046316 A, and WO 2015 / 046323 A. As the middle stage catalyst, examples of the middle stage catalysts described in WO 2015 / 046323 A and WO 2015 / 053087 A. As the second stage catalyst, a second stage catalyst known in the art can be used, and examples of such a second stage catalyst include those described in JP 2010-248476 A, WO 2015 / 053087 A, and WO 2015 / 046323 A.

[0103] In the hydrotreating method of this embodiment, the packing ratio of the first stage catalyst is preferably 10 to 50% of the total catalyst volume, and more preferably 15 to 40%. The packing ratio of the middle stage catalyst is preferably 10 to 50% of the total catalyst volume, and more preferably 15 to 40%. The packing ratio of the second stage catalyst is preferably 20 to 70% of the total catalyst volume, and more preferably 30 to 65%. Packing 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 demetalization activity. EXAMPLES

[0104] 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.

[0105] <Physical properties of metal oxides and chemical properties of catalysts and supports> [1] Analysis of physical properties (specific surface area, pore volume, and average pore 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 and average pore diameter were measured by mercury intrusion porosimetry using a porosimeter (AutoPore IV) manufactured by Micromeritics.

[0106] (b) Measurement principle of mercury intrusion method: Mercury intrusion porosimetry is based on the law of capillarity. 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 484 dyne / cm, and the contact angle is 130°. D=-(1 / P)4γcosθ In the formula, D is the pore diameter, P is the applied pressure, γ is the surface tension, and θ is the contact angle. The pore volume is the total volume of mercury that enters the pores per gram of metal oxide. The average pore diameter is the average value of D calculated as a function of P. The pore distribution is the calculated distribution of D as a function of P.

[0107] (c) Measurement procedure: (1) Turn on the vacuum heating degassing device and set the temperature at 400°C and the vacuum level at 5×10 -2 Verify that the temperature is below Torr. (2) Place the empty sample burette in a vacuum heating degassing apparatus. (3) The vacuum level is 5×10 -2After confirming that the pressure has reached or below Torr, the sample burette is removed from the vacuum heating degassing apparatus with its cock closed, and after cooling, its weight is measured. (4) Place the sample (metal oxide) in the sample burette. (5) Place the sample burette containing the sample in a vacuum heating degassing apparatus until the vacuum level 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 degassing apparatus, cool it, and then measure its weight to determine the sample weight. (7) Place the sample in the AutoPore IV cell. (8) Measure using AutoPore IV.

[0108] [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 based on the amount of the raw material charged. (a) Analytical methods and equipment used: The 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 quantitative determination of elements was carried out by the absolute calibration curve method.

[0109] (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 dissolved by heating. (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.

[0110] <Hydroprocessing of Hydrocarbon Oil> In the following manner, a mixed oil of atmospheric distillation residual oil and vacuum distillation residual oil having the following properties was hydrotreated. First, a demetallization catalyst (hydrogenation demetallization catalyst in which nickel and molybdenum are supported on a zinc-containing alumina carrier) as a front-stage catalyst and a hydrotreatment catalyst of each Example or Comparative Example as a rear-stage catalyst were filled in a high-pressure flow reactor in a volume ratio of 15:85 to form a fixed-bed catalyst layer, and pretreatment was performed under the following conditions. Next, a mixed fluid of a feedstock oil and a hydrogen-containing gas was introduced from the top of the reactor, hydrotreatment was carried out under the following conditions, and a mixed fluid of the product oil and gas was discharged from the bottom of the reactor, and the product oil was separated in a gas-liquid separator. The following liquid hourly space velocity (LHSV) is the LHSV of the mixed oil relative to the total catalyst layer of the demetallization catalyst and the hydrotreatment catalyst of the Example or Comparative Example.

[0111] Catalyst pretreatment conditions: dried at 120°C for 3 hours under normal pressure. The catalyst was presulfurized with 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.

[0112] Reaction conditions: Pressure (hydrogen partial pressure): 10.3MPa Liquid space velocity: 0.253hr -1 Hydrogen / oil ratio: 0.8762Nm 3 / kL Sulfur content: 0.3% by mass Reaction temperature: set so that the sulfur content was 0.3% by mass

[0113] Feedstock properties: Oil type: A mixture of atmospheric distillation residue and vacuum distillation residue (derived from Middle Eastern crude oil) Density (15℃); 0.991g / cm 3 Sulfur content: 3.37% by mass Vanadium: 24.96 ppm by mass Nickel: 34.7 ppm by mass Asphaltene content: 4.17% by mass

[0114] [Production Example 1] (1) Production of metal oxides including alumina 1.5 L of 12% by mass sulfuric acid aqueous solution was added to 100 L of pure water in a stirring kettle, 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 kettle to prepare aluminum hydroxide, which was stirred with a stirring blade for 24 hours. The obtained slurry was put into a filter and filtered to remove water. Next, the obtained gel was dissolved in pure water and the filtrate was diluted with SO4 2- , Na + The gel was washed until no more was detectable. The washed gel was then mixed with pure water to make a uniform slurry, which was then fed into a compression filter. The slurry was sandwiched between filter plates via a filter cloth, and the plates were squeezed to remove water. The filtration was interrupted when the moisture content in the obtained cake reached 80% by mass. The cake was placed in a heated kneader (set temperature 80°C) and thoroughly kneaded to be homogeneous. After that, phosphoric acid and zinc oxide particles (average particle size: 0.8 μm) were added so as to obtain the composition of carrier D shown in Table 1, and further kneaded to be homogeneous. The cake obtained by kneading was placed in an extrusion molding machine and extruded into a four-leaf clover shape with a major axis of 1.3 mm and a minor axis of 1.1 mm. This molded product was dried and then fired at 600°C for 4 hours to obtain a metal oxide containing alumina as the main component, phosphorus oxide, and zinc oxide. The obtained metal oxide had phosphorus of 1.0% by mass on the basis of the metal oxide in terms of oxide, zinc of 4.0% by mass on the basis of the metal oxide in terms of oxide, a pore volume of 0.71 mL / g, and a specific surface area of ​​303 m 2 / g and the average pore diameter was 7.5 nm.

[0115] [Example 1] (1) Preparation of the carrier An impregnation solution for organic acid impregnation was prepared by dissolving 2.44 g of myristic acid in 65.24 g of isopropyl alcohol. 100 g of the metal oxide obtained in Production Example 1 was impregnated with the impregnation solution for organic acid impregnation so as to obtain the composition shown in Table 1, to obtain an impregnated body. The impregnated body was dried under reduced pressure at 50° C. in a nitrogen atmosphere, and then dried at 120° C. and a gauge pressure of about −0.1 MPa for 3 hours to obtain a carrier A. Myristic acid is a linear saturated fatty acid with 14 carbon atoms, and its solubility in 100 g of water at 20° C. is 0 g (insoluble). Table 1 shows the content of organic acid in carrier A based on the carrier, and the content of metal oxide in carrier A based on the carrier and calculated as oxide.

[0116] (2) Manufacture of hydrotreating catalysts A hydrogenation active component impregnation solution was prepared by dissolving 10.51 g of ammonium molybdate tetrahydrate, 13.77 g of citric acid monohydrate, and 11.12 g of nickel nitrate in 37.54 g of ion-exchanged water. The hydrogenation active component impregnation solution was impregnated into 61.43 g of carrier A so as to obtain the composition of catalyst A shown in Table 2, to obtain an impregnated body. The impregnated body was dried and then calcined at 500 ° C. for 4 hours in an air atmosphere to obtain a hydrotreating catalyst A. A hydrotreating reaction was carried out on a mixed oil of atmospheric distillation residue oil and vacuum distillation residue oil using the hydrogenation catalyst A. The results are shown in Table 3 (hereinafter, the results of catalysts B to F are also shown in the same manner).

[0117] [Example 2] (1) Preparation of the carrier Carrier B was obtained in the same manner as in Example 1, except that the composition of the impregnating solution for organic acid impregnation was changed so as to obtain the composition of carrier B shown in Table 1.

[0118] (2) Manufacture of hydrotreating catalysts Except for using carrier B instead of carrier A, the same procedure as in Example 1 was followed to obtain a hydrotreating catalyst B, and a hydrotreating reaction was carried out on a mixed oil of atmospheric distillation residue oil and vacuum distillation residue oil.

[0119] [Example 3] (1) Preparation of the carrier Carrier C was obtained in the same manner as in Example 1, except that the composition of the impregnating solution for organic acid impregnation was changed so as to obtain the composition of carrier C shown in Table 1.

[0120] (2) Manufacture of hydrotreating catalysts Except for using carrier C instead of carrier A, the same procedure as in Example 1 was followed to obtain hydrotreating catalyst C, and a hydrotreating reaction was carried out on a mixed oil of atmospheric distillation residue oil and vacuum distillation residue oil.

[0121] [Example 4] (1) Preparation of the carrier Carrier D was obtained in the same manner as in Example 1, except that the composition of the impregnating solution for organic acid impregnation was changed to the composition of carrier D shown in Table 1. Specifically, in the organic acid impregnating solution of Example 1, docosanoic acid was used instead of myristic acid, and its content was adjusted. Note that docosanoic acid is a linear saturated fatty acid having 22 carbon atoms, and its solubility in 100 g of water at 20°C is 0 g (insoluble).

[0122] (2) Manufacture of hydrotreating catalysts A hydrotreating catalyst D was obtained in the same manner as in Example 1 except that carrier D was used instead of carrier A, and a hydrotreating reaction of a mixed oil of atmospheric distillation residual oil and vacuum distillation residual oil was performed.

[0123] [Comparative Example 1] (1) Preparation of the carrier The metal oxide obtained in Production Example 1 was designated as Support E.

[0124] (2) Manufacture of hydrotreating catalysts A hydrotreating catalyst E was obtained in the same manner as in Example 1 except that carrier E was used instead of carrier A, and a hydrotreating reaction of a mixed oil of atmospheric distillation residue oil and vacuum distillation residue oil was carried out.

[0125] [Comparative Example 2] (1) Preparation of the carrier Carrier F was obtained in the same manner as in Example 1, except that the composition of the impregnating solution for organic acid impregnation was changed to the composition of carrier F shown in Table 1. Specifically, in the organic acid impregnating solution of Example 1, decanoic acid was used instead of myristic acid, and its content was adjusted. Decanoic acid is a linear saturated fatty acid having 10 carbon atoms, and its solubility in 100 g of water at 20°C is 0.015 g.

[0126] (2) Manufacture of hydrotreating catalysts Except for using carrier F instead of carrier A, the same procedure as in Example 1 was followed to obtain hydrotreating catalyst F, and a hydrotreating reaction was carried out on a mixed oil of atmospheric distillation residue and vacuum distillation residue.

[0127] [Table 1]

[0128] [Table 2]

[0129] [Table 3]

[0130] The catalyst of Comparative Example 2 required high temperature reaction throughout the reaction time, and had low hydrogenation activity. The catalysts of Examples 1 to 4 produced using the carrier of the present invention were capable of reaction at low temperature on the third day, when the reaction was stable, and had improved initial activity, compared with the catalyst of Comparative Example 1. Furthermore, all of the catalysts were capable of reaction at low temperature even after the seventh day, and were found to have high hydrogenation activity and long life. [Industrial Applicability]

[0131] INDUSTRIAL APPLICABILITY The catalyst for hydrotreating hydrocarbon oil according to the present invention is useful since it can be used to reduce the sulfur content in hydrocarbon oil.

Claims

1. A catalyst support for hydrotreating a hydrocarbon oil, comprising an organic acid supported on a metal oxide containing alumina, The organic acid has one or more carboxy groups and has a solubility in 100 g of water at 20° C. of less than 0.015 g.

2. 2. The carrier for a catalyst for hydrotreating a hydrocarbon oil according to claim 1, wherein the organic acid is an organic acid having 12 to 26 carbon atoms.

3. 3. The carrier for a catalyst for hydrotreating a hydrocarbon oil according to claim 1, wherein the organic acid is an organic acid having one carboxy group.

4. A method for producing a carrier for a hydrotreating catalyst for hydrocarbon oil according to any one of claims 1 to 3, comprising the steps of: A method for producing a carrier for a catalyst for hydrotreating a hydrocarbon oil, comprising supporting the organic acid on a metal oxide containing alumina.

5. A method for producing a catalyst for hydrotreating a hydrocarbon oil, comprising supporting, on the hydrotreating catalyst support according to any one of claims 1 to 3, at least one metal selected from Group 6 metals of the periodic table in an amount of 0.5 to 25 mass %, calculated as an oxide, based on the catalyst, and at least one metal selected from Groups 9 and 10 metals of the periodic table in an amount of 0.5 to 15 mass %, calculated as an oxide, based on the catalyst, and then calcining the support at 300°C or higher.

6. Hydrogen partial pressure: 3-20 MPa, reaction temperature: 280-420°C, liquid hourly space velocity: 0.1-10 hr －１ 6. A method for hydrotreating a hydrocarbon oil, comprising contacting the hydrocarbon oil with the hydrotreating catalyst produced by the production method according to claim 5 .

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