A hydrogenation catalyst, its preparation method and application

Abstract

This invention provides a hydrogenation catalyst, its preparation method, and its application. The hydrogenation catalyst comprises an organic treatment agent and an oil-soluble catalyst dispersed in the organic treatment agent. The oil-soluble catalyst contains an active metal central atom or ion and an organic ligand coordinated to the active metal central atom or ion. In the hydrogenation catalyst, the molar ratio between the active metal and the organic ligand is 1:(0.5-3.5), and the mass ratio between the active metal and the organic treatment agent is 1:(0.1-10). The initial boiling point of the organic treatment agent is higher than the boiling point of the organic ligand. The hydrogenation catalyst of this invention exhibits high thermal stability and, when used for oil hydrogenation, can achieve higher residue cracking rates, lower condensation rates, and higher distillate oil yields.

Description

Technical Field

[0001] This invention belongs to the field of petrochemicals, specifically relating to a hydrogenation catalyst, its preparation method, and its application. Background Technology

[0002] With the decline in light oil yield and the increasing demand for light oil, efficient oil processing, especially the efficient conversion of high-sulfur, high-nitrogen inferior heavy oil into light oil and gas, is an effective way to solve the current problems of tight domestic energy supply and demand and high dependence on foreign crude oil.

[0003] Oil-soluble unsupported catalysts used in slurry bed residue oil processing possess high dispersibility, nanoscale size, and high hydrogenation activity. They can overcome steric hindrance, efficiently convert asphaltene, and avoid problems such as short operating cycles caused by coking and scaling. Therefore, they are considered an effective way to hydrotreat feedstock oils. However, current synthetic oil-soluble catalysts still contain a certain amount of organic ligand compounds. For example, in the preparation of synthetic oil-soluble highly dispersed Mo-based catalysts, in order to ensure that more metal is converted into the catalyst product (metal conversion rate >95%), an excess of organic coordination reagents is usually used in the preparation process. Therefore, the catalyst product usually contains a large amount of organic ligand compounds. At the same time, the catalyst product is in a liquid state and is easily oxidized and deteriorated by air, which is not conducive to storage and transportation. Therefore, how to treat and recover the solvent in the oil-soluble catalyst to obtain the ideal treated product is a problem that needs to be solved.

[0004] Chinese patent application 201810186262.X discloses a method for treating oil-soluble catalysts. This method involves reacting the oil-soluble catalyst with an aniline compound at 30-300℃ for 0.5-5 hours until the reaction is complete; then drying under vacuum at 30-80℃ until completely dried, and finally cooling to room temperature to obtain an oil-soluble hydrogenation catalyst. Chinese patent ZL201911047233.6 provides a method for preparing and applying a heavy oil hydrocracking molybdenum-nickel catalyst. This method involves dissolving and dispersing a hexavalent molybdenum source compound in a solvent, adding an inorganic acid catalyst, reacting it with a small-molecule organic acid, and then adding a large-molecule organic acid or ester. The reaction product is separated to remove the solvent phase, the oil phase is washed with water, and light components are removed by vacuum distillation to obtain an organic molybdenum salt. An organic nickel salt is then prepared using a similar method. Finally, the organic molybdenum salt and the organic nickel salt are mixed in a specific ratio to obtain the heavy oil hydrocracking molybdenum-nickel catalyst.

[0005] Chinese patent application 202210674912.1 discloses a method for preparing an organic acid molybdenum oil-soluble catalyst for slurry bed hydrogenation. The method uses a long-chain organic acid as an organic ligand and a molybdenum source as its catalytically active metal. The method involves allowing the prepared product to stand for a predetermined time and then cooling it to room temperature. After that, a predetermined volume ratio of toluene or xylene is added to the cooled oil phase for washing, followed by rotary evaporation to remove the solvent. After drying, the organic acid molybdenum oil-soluble catalyst is obtained.

[0006] However, the hydrogenation activity of existing oil-soluble catalysts still needs to be improved when used for hydrotreating. Summary of the Invention

[0007] The purpose of this invention is to improve the hydrogenation activity of oil-soluble catalysts.

[0008] To achieve the above objectives, a first aspect of the present invention provides a hydrogenation catalyst, comprising an organic treatment agent and an oil-soluble catalyst dispersed in the organic treatment agent; wherein the oil-soluble catalyst comprises an active metal central atom or central ion and an organic ligand coordinated with the active metal central atom or central ion; the active metal is selected from one or more of Group VB, Group VIB, Group VIII, and Group IB metals having hydrogenation properties; the organic ligand comprises a hydrocarbon moiety and a coordinating group moiety, wherein the coordinating group is a -C(=O)-O group and forms a coordinate bond with the metal central atom or central ion through an oxygen atom; in the hydrogenation catalyst, the molar ratio between the active metal and the organic ligand is 1:(0.5-3.5), and the mass ratio between the active metal and the organic treatment agent is 1:(0.1-10); the initial boiling point of the organic treatment agent is higher than the boiling point of the organic ligand.

[0009] Optionally, preferably, in the hydrogenation catalyst, the molar ratio between the active metal and the organic ligand is 1:(1.5-2.5), and the mass ratio between the active metal and the organic treatment agent is 1:(0.5-5).

[0010] Optionally, the oil-soluble catalyst has the schematic composition shown in general formula (I):

[0011] MO a [R(COO) x ] b (I),

[0012] Where M represents metal, and R(COO) xThe symbol represents an organic ligand, R represents a hydrocarbon group in the organic ligand, COO represents a coordinating group in the organic ligand, x represents the number of coordinating groups in the organic ligand, a represents the molar ratio of non-coordinated oxygen atoms connected to metal M to metal M, and b represents the molar ratio of the organic ligand to metal M. Wherein: R is a C3-C19 hydrocarbon group, preferably selected from C5-C11 normal or isoalkyl, C5-C12 cycloalkyl, and C6-C12 aryl; x is 1, 2, or 3, preferably 1 or 2; a is a positive number from 0 to 5, preferably a positive number from 1 to 3; and the infrared spectrum of the oil-soluble catalyst is in the range of 700-1000 cm⁻¹. -1 1350-1450cm -1 and 1500-1610cm -1 It has a characteristic peak at the location.

[0013] Optionally, the group VB, group VIB, group VIII, and group IB metals with hydrogenation properties are selected from V, Cr, Mo, W, Fe, Co, Ru, Ni, Cu, and Zn, preferably from V, Mo, W, Fe, Co, Ni, Cu, and Zn, and more preferably from Mo, Ni, and Co; the organic ligand is derived from C4-C20 organic carboxylic acids and / or the anhydrides of C4-C20 organic carboxylic acids, wherein the organic carboxylic acid is preferably selected from one or more of C4-C20 normal or isomeric alkyl carboxylic acids, C6-C20 cycloalkane carboxylic acids containing saturated carbocyclic rings, and C7-C20 aromatic carboxylic acids containing aromatic rings, and more preferably from one or more of C4-C12 normal or isomeric alkyl carboxylic acids, C6-C13 cycloalkane carboxylic acids containing saturated carbocyclic rings, and C7-C13 aromatic carboxylic acids containing aromatic rings.

[0014] Optionally, the initial boiling point of the organic treatment agent is 10-150°C higher than the boiling point of the organic ligand; the organic treatment agent is selected from one or more of the following: alkanes with C>17, monocyclic aromatic hydrocarbons with side chains C>14, aromatic hydrocarbons with not less than 2 aromatic rings, dodecylbenzene sulfonic acid, oleic acid, oleylamine, stearic acid, hexadecyltrimethylammonium bromide, ethylenediaminetetraacetic acid, diesel oil, paraffin wax, ceresin wax, oil slurry, residual oil, asphalt, and coal tar.

[0015] A second aspect of the present invention provides a method for preparing a hydrogenation catalyst, the method comprising: mixing a metal-organic acid complex and an organic treatment agent to obtain a mixture; heating the mixture to remove some of the organic ligands in the metal-organic acid complex and retaining the organic treatment agent to obtain a residual material; wherein the metal-organic acid complex comprises an active metal central atom or central ion and an organic ligand coordinated to the active metal central atom or central ion; wherein the active metal is selected from one or more of Group VB, Group VIB, Group VIII, and Group IB metals having hydrogenation properties; wherein the organic ligand comprises a hydrocarbon moiety and a coordinating group moiety, wherein the coordinating group is a -C(=O)-O group and forms a coordinate bond with the metal central atom or central ion through an oxygen atom; wherein the molar ratio between the active metal and the organic ligand in the metal-organic acid complex is 1:(1-10).

[0016] Optionally, the mass ratio of the active metal in the organometallic acid complex to the organic treatment agent is 1:(0.1-10), preferably 1:(0.5-5).

[0017] Optionally, the heat treatment is performed at a temperature of 200-450°C for a duration of 0.5-8 hours.

[0018] Optionally, the organometallic acid complex has the illustrative composition shown in general formula (I):

[0019] MO a [R(COO) x ] b (I),

[0020] Where M represents metal, and R(COO) x The symbol represents an organic ligand, R represents a hydrocarbon group in the organic ligand, COO represents a coordinating group in the organic ligand, x represents the number of coordinating groups in the organic ligand, a represents the molar ratio of noncoordinated oxygen atoms bonded to metal M to metal M, and b represents the molar ratio of the organic ligand to metal M. Wherein: R is a C3-C19 hydrocarbon group, preferably selected from C5-C11 normal or isomeric alkyl groups, C5-C12 cycloalkyl groups, and C6-C12 aryl groups; x is 1, 2, or 3, preferably 1 or 2; a is a positive number from 0 to 5, preferably a positive number from 1 to 3; the infrared spectrum of the metal-organic acid complex is in the range of 700-1000 cm⁻¹. -1 1350-1450cm -1 and 1500-1610cm -1 It has a characteristic peak at the location.

[0021] Optionally, the group VB, group VIB, group VIII, and group IB metals with hydrogenation properties are selected from V, Cr, Mo, W, Fe, Co, Ru, Ni, Cu, and Zn, preferably from V, Mo, W, Fe, Co, Ni, Cu, and Zn, and more preferably from Mo, Ni, and Co; the organic ligand is derived from C4-C20 organic carboxylic acids and / or the anhydrides of C4-C20 organic carboxylic acids, wherein the organic carboxylic acid is preferably selected from one of C4-C20 n- or iso-alkyl carboxylic acids, C6-C20 cycloalkane carboxylic acids containing saturated carbocyclic rings, and C7-C20 aromatic carboxylic acids containing aromatic rings. Or several, preferably selected from one or more of the following: C4-C12 normal or isomeric alkyl carboxylic acids, C6-C13 cycloalkanic carboxylic acids containing saturated carbon rings, and C7-C13 aromatic carboxylic acids containing aromatic rings; the organic treatment agent is selected from one or more of the following: alkanes with C>17, monocyclic aromatic hydrocarbons with side chains C>14, aromatic hydrocarbons with not less than 2 aromatic rings, dodecylbenzenesulfonic acid, oleic acid, oleylamine, stearic acid, hexadecyltrimethylammonium bromide, ethylenediaminetetraacetic acid, diesel oil, paraffin wax, ceresin wax, slurry oil, residual oil, asphalt, and coal tar; in the metal-organic acid complex, the molar ratio between the active metal and the organic ligand is 1:(1-10).

[0022] A third aspect of the present invention provides a method for hydrotreating oil products, the method comprising: contacting an oil product feedstock with a hydrotreating catalyst described in the first or second aspect of the present invention under hydrotreating reaction conditions; wherein the oil product feedstock is selected from at least one of benzene, alkylbenzene, naphthalene, alkylnaphthalene, anthracene, alkylanthracene, crude oil, gasoline, diesel, wax oil, slurry oil, residual oil, coal tar, and biomass oil.

[0023] Optionally, the conditions for the hydrogenation reaction include: based on the weight of the oil feedstock and calculated in metals, the amount of the hydrogenation catalyst is 50-10000 μg / g, preferably 50-3000 μg / g; the initial hydrogen pressure is 1-20 MPa, preferably 3-15 MPa; the reaction temperature is 300-500℃, preferably 350-450℃; and the liquid hourly space velocity is 0.05-5.0 h⁻¹. -1 Preferably, it is 0.05-1.0h. -1 The hydrogen-to-oil volume ratio is 100-3000, preferably 200-2000.

[0024] Through the above technical solution, the present invention improves the hydrogenation activity of oil-soluble catalysts. When the hydrogenation catalyst of the present invention is used for oil hydrogenation, the hydrogenation catalyst is fully dispersed in the feedstock, which can achieve higher residue cracking rate, lower condensation rate and higher distillate oil yield.

[0025] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

[0026] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the following detailed description to explain the invention, but do not constitute a limitation thereof. In the drawings:

[0027] Figure 1 This is a thermogravimetric (TGA) diagram of the molybdenum organic acid complex used in Example 1 of this invention.

[0028] Figure 2 This is the thermogravimetric analysis (TGA) chart of the product obtained in Embodiment 1 of the present invention.

[0029] Figure 3 This is the infrared spectrum of the product obtained in Embodiment 1 of the present invention.

[0030] Figure 4 This is the infrared spectrum of the product obtained in Embodiment 2 of the present invention. Detailed Implementation

[0031] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0032] The inventors discovered that existing oil-soluble catalysts have low hydrogenation activity, possibly because they are prone to agglomeration under heating conditions and have low thermal stability. However, by replacing a portion of the organic ligands in the oil-soluble catalyst with an organic treatment agent, the agglomeration of the oil-soluble catalyst under heating conditions is reduced, and the thermal stability and hydrogenation activity are improved.

[0033] A first aspect of the present invention provides a hydrogenation catalyst, comprising an organic treatment agent and an oil-soluble catalyst dispersed in the organic treatment agent; wherein the oil-soluble catalyst comprises an active metal central atom or central ion and an organic ligand coordinated to the active metal central atom or central ion; the active metal is selected from one or more of Group VB, Group VIB, Group VIII and Group IB metals having hydrogenation properties; the organic ligand comprises a hydrocarbon moiety and a coordinating group moiety, wherein the coordinating group is a -C(=O)-O group and forms a coordinate bond with the metal central atom or central ion through an oxygen atom; in the hydrogenation catalyst, the molar ratio between the active metal and the organic ligand is 1:(0.5-3.5), and the mass ratio between the active metal and the organic treatment agent is 1:(0.1-10); the initial boiling point of the organic treatment agent is higher than the boiling point of the organic ligand.

[0034] Through the above technical solution, the oil-soluble catalyst in the hydrogenation catalyst of the present invention is dispersed in the organic treatment agent. The initial boiling point of the organic treatment agent is higher than the boiling point of the organic ligand, thereby improving the oxidation resistance of the hydrogenation catalyst. At the same time, the agglomeration phenomenon of the hydrogenation catalyst of the present invention is reduced under heating conditions, thereby improving the thermal stability of the hydrogenation catalyst.

[0035] Preferably, in the hydrogenation catalyst, the molar ratio between the active metal and the organic ligand is 1:(1.5-2.5), and the mass ratio between the active metal and the organic treatment agent is 1:(0.5-5).

[0036] The oil-soluble catalyst has the schematic composition shown in general formula (I):

[0037] MO a [R(COO) x ] b (I),

[0038] Where M represents metal, and R(COO) x The symbol represents an organic ligand, R represents a hydrocarbon group in the organic ligand, COO represents a coordinating group in the organic ligand, x represents the number of coordinating groups in the organic ligand, a represents the molar ratio of non-coordinated oxygen atoms connected to metal M to metal M, and b represents the molar ratio of the organic ligand to metal M. Wherein: R is a C3-C19 hydrocarbon group, preferably selected from C5-C11 normal or isoalkyl, C5-C12 cycloalkyl, and C6-C12 aryl; x is 1, 2, or 3, preferably 1 or 2; a is a positive number from 0 to 5, preferably a positive number from 1 to 3; and the infrared spectrum of the oil-soluble catalyst is in the range of 700-1000 cm⁻¹. -1 1350-1450cm -1 and 1500-1610cm -1 It has a characteristic peak at the location.

[0039] In this invention, "C3-C19 hydrocarbon group" refers to a hydrocarbon group having 3-19 carbon atoms. The hydrocarbon group can be a saturated or unsaturated straight-chain, branched, or carbon ring hydrocarbon group, including but not limited to C3-C19 normal alkyl, C3-C19 isoalkyl, C5-C19 cycloalkyl, and C6-C19 aryl.

[0040] In this invention, "C5-C11 n-alkyl" refers to a straight-chain alkyl group having 5-11 carbon atoms, such as n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and n-undecyl.

[0041] In this invention, "C5-C11 isoalkyl" refers to a branched alkyl group having 5-11 carbon atoms, such as isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, and isoundecyl.

[0042] In this invention, "C5-C12 cycloalkyl group" refers to a saturated hydrocarbon group containing a saturated carbon ring with 5-12 carbon atoms, such as cyclopentyl, cyclohexyl, methylcyclohexyl, decahydronaphthyl, methyldecahydronaphthyl, ethyldecahydronaphthyl, etc.

[0043] In this invention, "C6-C12 aryl" refers to a group containing an aromatic ring having 6-12 carbon atoms, such as phenyl, naphthyl, anthracene, p-tolyl, benzyl, methylnaphthyl, etc.

[0044] According to the present invention, the C3-C19 hydrocarbon group, C5-C11 normal alkyl group, C5-C11 isoalkyl group, C5-C12 cycloalkyl group and C6-C12 aryl group may be optionally substituted, for example, they may be unsubstituted, or they may be substituted by one or more groups selected from halogen, nitro, sulfonic acid group and the like.

[0045] The group VB, group VIB, group VIII, and group IB metals with hydrogenation properties are selected from V, Cr, Mo, W, Fe, Co, Ru, Ni, Cu, and Zn, preferably from V, Mo, W, Fe, Co, Ni, Cu, and Zn, and more preferably from Mo, Ni, and Co; the organic ligand is derived from C4-C20 organic carboxylic acids and / or the anhydrides of C4-C20 organic carboxylic acids, wherein the organic carboxylic acid is preferably selected from one or more of C4-C20 normal or isomeric alkyl carboxylic acids, C6-C20 cycloalkane carboxylic acids containing saturated carbocyclic rings, and C7-C20 aromatic carboxylic acids containing aromatic rings, and more preferably from one or more of C4-C12 normal or isomeric alkyl carboxylic acids, C6-C13 cycloalkane carboxylic acids containing saturated carbocyclic rings, and C7-C13 aromatic carboxylic acids containing aromatic rings.

[0046] According to the present invention, C4-C20 organic carboxylic acids refer to monocarboxylic acids having 4-20 carbon atoms. The organic carboxylic acids may be saturated or unsaturated straight-chain, branched, or monocarboxylic acids having carbon rings, including but not limited to C4-C20 n-alkyl carboxylic acids, C4-C20 isoalkyl carboxylic acids, C6-C20 cycloalkane carboxylic acids containing saturated carbon rings, and C7-C20 aromatic carboxylic acids containing aromatic rings.

[0047] According to the present invention, the organic carboxylic acid is further preferably one or more selected from succinic acid, hexanoic acid, adipic acid, heptanoic acid, octanoic acid, nonanoic acid, ethylhexanoic acid, oleic acid, petroleum ether, salicylic acid, benzoic acid and phenylacetic acid.

[0048] In one specific embodiment of the present invention, the oil-soluble catalyst is a catalyst currently used in oil hydrogenation, which can be highly dispersed in the oil phase, such as oil-soluble molybdenum catalyst, oil-soluble molybdenum-cobalt catalyst, oil-soluble molybdenum-nickel catalyst, etc. In another specific embodiment of the present invention, the oil-soluble catalyst can be an oil-soluble catalyst such as nickel naphthenate, molybdenum carboxylate, or cobalt ketone.

[0049] The initial boiling point of the organic treatment agent is 10-150°C higher than the boiling point of the organic ligand; the organic treatment agent is selected from one or more of the following: alkanes with C>17, monocyclic aromatic hydrocarbons with side chains C>14, aromatic hydrocarbons with not less than 2 aromatic rings, dodecylbenzene sulfonic acid, oleic acid, oleylamine, stearic acid, hexadecyltrimethylammonium bromide, ethylenediaminetetraacetic acid, diesel oil, paraffin wax, ceresin wax, oil slurry, residual oil, asphalt, and coal tar.

[0050] In this invention, when the organic treatment agent is a pure substance, the initial boiling point of the organic treatment agent is the boiling point of the organic treatment agent; when the organic treatment agent is a mixture, the initial boiling point of the organic treatment agent is the temperature recorded when the first drop of condensate falls from the end of the condenser during distillation.

[0051] According to the present invention, alkanes with C>17 refer to n-alkanes or isoalkanes with more than 17 carbon atoms.

[0052] According to the present invention, monocyclic aromatic hydrocarbons with side chain C>14 refer to aromatic hydrocarbon compounds containing one benzene ring and having more than 14 carbon atoms on the side chain.

[0053] According to the present invention, aromatic hydrocarbons with at least two aromatic rings refer to aromatic hydrocarbon compounds containing at least two aromatic rings. Examples include biphenyl, parabens, tetrabenzene, diphenylmethane, and triphenylmethane.

[0054] A second aspect of the present invention provides a method for preparing a hydrogenation catalyst, the method comprising: mixing a metal-organic acid complex and an organic treatment agent to obtain a mixture; heating the mixture to remove some of the organic ligands in the metal-organic acid complex and retaining the organic treatment agent to obtain a residual material; wherein the metal-organic acid complex comprises an active metal central atom or central ion and an organic ligand coordinated to the active metal central atom or central ion; wherein the active metal is selected from one or more of Group VB, Group VIB, Group VIII, and Group IB metals having hydrogenation properties; wherein the organic ligand comprises a hydrocarbon moiety and a coordinating group moiety, wherein the coordinating group is a -C(=O)-O group and forms a coordinate bond with the metal central atom or central ion through an oxygen atom; wherein the molar ratio between the active metal and the organic ligand in the metal-organic acid complex is 1:(1-10).

[0055] According to the present invention, since the initial boiling point of the organic treatment agent is higher than the boiling point of the organic ligands in the organometallic acid complex, the organometallic acid complex rich in organic ligands, after heat treatment, removes some of the organic ligands while retaining the organic treatment agent. The organometallic acid complex is then dispersed in the organic treatment, thus exhibiting higher thermal stability, facilitating storage and transportation, and maintaining highly efficient catalytic activity. The remaining material obtained from the reaction is generally solid at room temperature and can be liquefied by heating or solvent dissolution.

[0056] The method for preparing the hydrogenation catalyst of the present invention uses only organometallic acid complexes and organic treatment agents as raw materials, requiring few raw materials, with a simple processing technology and low energy consumption. Furthermore, some of the organic ligands removed in the reaction can be recycled for the preparation of organometallic acid complexes, thereby reducing the cost of catalyst preparation.

[0057] The method for preparing the hydrogenation catalyst described in this invention does not have strict requirements on the reaction pressure and reaction atmosphere. For example, the reaction pressure can be atmospheric pressure, and the reaction atmosphere can be air or an inert gas atmosphere. The method for removing some organic ligands in this invention is a conventional choice in the art and is not specifically required here; for example, distillation can be used.

[0058] The mass ratio of the active metal in the organometallic acid complex to the organic treatment agent is 1:(0.1-10), preferably 1:(0.5-5).

[0059] The heat treatment is performed at a temperature of 200-450℃ for 0.5-8 hours. Preferably, the heat treatment is performed at a temperature of 230-400℃ for 1-5 hours.

[0060] The metal-organic acid complex has the schematic composition shown in general formula (I):

[0061] MO a [R(COO) x ] b (I),

[0062] Where M represents metal, and R(COO) xThe symbol represents an organic ligand, R represents a hydrocarbon group in the organic ligand, COO represents a coordinating group in the organic ligand, x represents the number of coordinating groups in the organic ligand, a represents the molar ratio of noncoordinated oxygen atoms connected to metal M to metal M, and b represents the molar ratio of the organic ligand to metal M. Wherein: R is a C3-C19 hydrocarbon group, preferably selected from C5-C11 normal or isoalkyl, C5-C12 cycloalkyl, and C6-C12 aryl groups; x is 1, 2, or 3, preferably 1 or 2; a is a positive number from 0 to 5, preferably a positive number from 1 to 3; and the infrared spectrum of the metal-organic acid complex is in the range of 700-1000 cm⁻¹. -1 1350-1450cm -1 and 1500-1610cm -1 The position has a characteristic peak; the group VB, group VIB, group VIII, and group IB metals with hydrogenation properties are selected from V, Cr, Mo, W, Fe, Co, Ru, Ni, Cu, and Zn, preferably from V, Mo, W, Fe, Co, Ni, Cu, and Zn, and more preferably from Mo, Ni, and Co; the organic ligand is derived from C4-C20 organic carboxylic acids and / or the anhydrides of C4-C20 organic carboxylic acids, wherein the organic carboxylic acids are preferably selected from C4-C20 normal or isomeric alkyl carboxylic acids, C6-C20 cycloalkane carboxylic acids containing saturated carbocyclic rings, and C7-C20 aromatic carboxylic acids containing aromatic rings. One or more of the following are preferred: C4-C12 normal or isomeric alkyl carboxylic acids, C6-C13 cycloalkanic carboxylic acids containing saturated carbon rings, and C7-C13 aromatic carboxylic acids containing aromatic rings; the organic treatment agent is selected from one or more of C>17 alkanes, monocyclic aromatic hydrocarbons with side chains C>14, aromatic hydrocarbons with not less than 2 aromatic rings, dodecylbenzenesulfonic acid, oleic acid, oleylamine, stearic acid, hexadecyltrimethylammonium bromide, ethylenediaminetetraacetic acid, diesel oil, paraffin wax, ceresin wax, slurry oil, residual oil, asphalt, and coal tar; in the metal-organic acid complex, the molar ratio between the active metal and the organic ligand is 1:(1-10).

[0063] In one specific embodiment of the present invention, the method for preparing the hydrogenation catalyst includes: adding a metal-organic acid complex and an organic treatment agent into a reactor to obtain a mixture, wherein the mass ratio of the active metal in the metal-organic acid complex to the organic treatment agent is 1:(0.1-10). The mixture is stirred and heated to 200-450°C, held for 0.5-8 hours, and the gas produced by the reaction is separated by distillation. After the reaction is completed, the remaining material in the reactor is poured out, which is the hydrogenation catalyst.

[0064] A third aspect of the present invention provides a method for hydrotreating oil products, the method comprising: contacting an oil product feedstock with a hydrotreating catalyst described in the first or second aspect of the present invention under hydrotreating reaction conditions; wherein the oil product feedstock is selected from at least one of benzene, alkylbenzene, naphthalene, alkylnaphthalene, anthracene, alkylanthracene, crude oil, gasoline, diesel, wax oil, slurry oil, residual oil, coal tar, and biomass oil.

[0065] The conditions for the hydrogenation reaction include: based on the weight of the oil feedstock and calculated in metals, the amount of the hydrogenation catalyst is 50-10000 μg / g, preferably 50-3000 μg / g; the initial hydrogen pressure is 1-20 MPa, preferably 3-15 MPa; the reaction temperature is 300-500℃, preferably 350-450℃; and the liquid hourly space velocity is 0.05-5.0 h⁻¹. -1 Preferably, it is 0.05-1.0h. -1 The hydrogen-to-oil volume ratio is 100-3000, preferably 200-2000.

[0066] The present invention will be further described in detail below through examples, but the present invention is not limited thereto.

[0067] Unless otherwise specified, all raw materials used in the embodiments can be obtained through commercial purchase.

[0068] Examples 1-4

[0069] Examples 1-4: Preparation of hydrogenation catalysts C1-C4.

[0070] The raw materials, reaction conditions, and experimental results used in Examples 1-4 are shown in Table 1. The corresponding weights of the organometallic acid complex and organic treatment agent were weighed according to Table 1 and added to a three-necked flask. The reaction was then carried out under the conditions shown in Table 1. The gases produced during the reaction were separated. After the reaction was completed, the liquid product in the flask was poured out to obtain the hydrogenation catalyst. The resulting liquid product is generally solid at room temperature after cooling. The metal content and infrared spectrum of the obtained product were determined, and the composition of the obtained product was determined based on the measured results.

[0071] The preparation method of the metal-organic acid complexes used in Examples 1-4 includes: adding a metal-containing compound to a three-necked flask, then adding an organic carboxylic acid in a molar ratio of 1-10 times to the metal and mixing them, reacting at 160-260°C for 5 hours to obtain an oily metal-organic acid complex.

[0072] Methods for determining the metal content in the hydrogenation catalysts C1-C4 and the metal-organic acid complexes of the raw materials obtained in Examples 1-4: The test samples were diluted 200 times with organic solvent and then measured using inductively coupled plasma optical emission spectrometry (ICP-OES) with a SPECTRO ARCOS SOP plasma optical emission spectrometer. The measurement conditions were: the optical chamber was sealed and filled with argon gas, vertical observation was performed, and the wavelength range was 130-770 nm.

[0073] Method for determining the infrared spectra of C1-C4 hydrogenation catalysts obtained in Examples 1-4: The infrared spectra of the obtained solid catalyst products were determined using a Thermo Fisher NICOLET IS50 spectrometer. The measurement conditions were a scanning wavelength of 400-4000 cm⁻¹. -1 The number of scans was 16. A ZnSe crystal and a mercury cadmium telluride infrared detector were used together to measure the attenuated total reflectance (ATR) of the sample, with a resolution of 4 cm⁻¹. -1 .

[0074] The thermal analysis method for the raw material organometallic acid complexes used in Examples 1-4 and the C1-C4 hydrogenation catalysts obtained in Examples 1-4 was as follows: The obtained solid catalyst products were analyzed using a STA 499C thermal analyzer (NETZSCH, Germany). The analysis was conducted under N2 atmosphere, with a test range of 50-600℃ and a heating rate of 10℃ / min.

[0075] Table 1

[0076]

[0077] Figure 1 The thermogravimetric analysis (TGA) diagram of the hydrogenation catalyst C1 obtained in Example 1 is shown below. Figure 2 This is a thermogravimetric analysis (TGA) chart of the organometallic acid complex used in Example 1. (The data is presented in the original text.) Figure 1 and Figure 2 It is known that organometallic acid complexes undergo severe weight loss at 160℃, and the weight loss reaches more than 60% at 200℃, while the weight loss of hydrogenation catalyst C1 is less than 20% at 300℃. This shows that the thermal stability of organometallic acid complexes is greatly improved after treatment with organic treatment agents, which has a beneficial effect on the storage stability and in-situ activation of hydrogenation catalysts.

[0078] Figure 3 The image shows the infrared spectrum of the hydrogenation catalyst C1 obtained in Example 1. Figure 4 The image shows the infrared spectrum of the hydrogenation catalyst C2 obtained in Example 2. From... Figure 3 and Figure 4 It can be seen that the infrared spectra of C1 and C2 in the hydrogenation catalyst are at 1350 cm⁻¹ -1 -1450cm-1 With 1500cm -1 -1610cm -1 All showed obvious characteristic peaks, indicating that the binding mode between the metal and the organic ligand did not change after the metal-organic acid complex was treated with an organic treatment agent.

[0079] Examples 5-8

[0080] Raw material A is vacuum residue, with an asphaltene content of 12.7%, a carbon residue value of 19.8%, and a heavy metal (Ni+V) content of 371 μg / g.

[0081] Using A as raw material, the mixture was combined with hydrogenation catalysts C1-C4 in an intermittent high-pressure reactor and subjected to catalytic hydrothermal conversion of residue oil under hydrogenation conditions. The reaction products were analyzed and detected. The hydrogenation reaction conditions and experimental results are shown in Table 2.

[0082] Comparative Example 1

[0083] Comparative Example 1 was tested in accordance with Example 5, except that the catalyst used in Comparative Example 1 was the same oil-soluble molybdenum organic acid complex used in Example 1, while other experimental conditions remained the same. The experimental results are shown in Table 2.

[0084] Comparative Example 2

[0085] Comparative Example 2 was tested in accordance with Example 6, except that the catalyst used in Comparative Example 2 was the same oil-soluble molybdenum-nickel organic acid complex used in Example 2, while other experimental conditions remained the same. The experimental results are shown in Table 2.

[0086] Table 2

[0087]

[0088] By comparing the data of Examples 5-8 and Comparative Examples 1-2 in Table 2, it can be seen that the hydrogenation catalyst obtained by treating the metal-organic acid complex with an organic treatment agent has higher hydrogenation activity. When applied to oil hydrogenation, it can achieve higher residue cracking rate, lower condensation rate and higher distillate oil yield.

[0089] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0090] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0091] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A hydrogenation catalyst, characterized in that, Includes an organic treatment agent and an oil-soluble catalyst dispersed in the organic treatment agent; The oil-soluble catalyst comprises an active metal central atom or central ion and an organic ligand coordinated to the active metal central atom or central ion; the active metal is selected from one or more of Group VB, Group VIB, Group VIII, and Group IB metals with hydrogenation properties; the organic ligand comprises a hydrocarbon moiety and a coordinating group moiety, wherein the coordinating group is a -C(=O)-O group and forms a coordinate bond with the metal central atom or central ion through an oxygen atom; in the hydrogenation catalyst, the molar ratio between the active metal and the organic ligand is 1:(0.5-3.5), and the mass ratio between the active metal and the organic treatment agent is 1:(0.1-10). The infrared spectrum of the oil-soluble catalyst is in the range of 700-1000 cm⁻¹. -1 1350-1450 cm -1 and 1500-1610cm -1 It has a characteristic peak at the location; The initial boiling point of the organic treatment agent is 10-150°C higher than the boiling point of the organic ligand; the organic treatment agent is selected from one or more of the following: alkanes with C>17, monocyclic aromatic hydrocarbons with side chains C>14, aromatic hydrocarbons with not less than 2 aromatic rings, dodecylbenzene sulfonic acid, oleic acid, oleylamine, stearic acid, hexadecyltrimethylammonium bromide, ethylenediaminetetraacetic acid, diesel oil, paraffin wax, ceresin wax, oil slurry, residual oil, asphalt, and coal tar. The preparation method of the hydrogenation catalyst includes: mixing a metal-organic acid complex and an organic treatment agent to obtain a mixture; heating the mixture to remove some of the organic ligands in the metal-organic acid complex and retaining the organic treatment agent to obtain the remaining material; the metal-organic acid complex comprises an active metal central atom or central ion and an organic ligand coordinated with the active metal central atom or central ion; the active metal is selected from one or more of Group VB, Group VIB, Group VIII and Group IB metals with hydrogenation properties; the organic ligand comprises a hydrocarbon moiety and a coordinating group moiety, wherein the coordinating group is a -C(=O)-O group and forms a coordinate bond with the metal central atom or central ion through an oxygen atom; in the metal-organic acid complex, the molar ratio between the active metal and the organic ligand is 1:(1-10).

2. The hydrogenation catalyst according to claim 1, wherein, In the hydrogenation catalyst, the molar ratio between the active metal and the organic ligand is 1:(1.5-2.5), and the mass ratio between the active metal and the organic treatment agent is 1:(0.5-5).

3. The hydrogenation catalyst according to claim 1 or 2, wherein, The oil-soluble catalyst has the schematic composition shown in general formula (I): MO a [R(COO) x ] b (I), Where M represents metal, and R(COO) x Represents the organic ligand, R represents the hydrocarbon group in the organic ligand, COO represents the coordinating group in the organic ligand, x represents the number of coordinating groups in the organic ligand, a represents the molar ratio of non-coordinated oxygen atoms bonded to metal M to metal M, and b represents the molar ratio of the organic ligand to metal M, where: R is a C3-C19 hydrocarbon group; x is 1, 2, or 3; a is a positive number between 0 and 5; The group VB, group VIB, group VIII and group IB metals with hydrogenation properties are selected from V, Cr, Mo, W, Fe, Co, Ru, Ni, Cu and Zn; The organic ligand is derived from anhydrides of C4-C20 organic carboxylic acids and / or C4-C20 organic carboxylic acids, wherein the organic carboxylic acids are selected from one or more of C4-C20 normal or isomeric alkyl carboxylic acids, C6-C20 cycloalkane carboxylic acids containing saturated carbocyclic rings, and C7-C20 aromatic carboxylic acids containing aromatic rings.

4. The hydrogenation catalyst according to claim 3, wherein, R is selected from C5-C11 normal or isomeric alkyl, C5-C12 cycloalkyl and C6-C12 aryl; x is 1 or 2; a is a positive number between 1 and 3; The group VB, group VIB, group VIII and group IB metals with hydrogenation properties are selected from V, Mo, W, Fe, Co, Ni, Cu and Zn; The organic carboxylic acid is selected from one or more of the following: C4-C12 normal or isomeric alkyl carboxylic acids, C6-C13 cycloalkanic carboxylic acids containing saturated carbocyclic rings, and C7-C13 aromatic carboxylic acids containing aromatic rings.

5. The hydrogenation catalyst according to claim 4, wherein, The active metal is selected from Mo, Ni and Co.

6. A method for preparing a hydrogenation catalyst, characterized in that, The method includes: mixing a metal-organic acid complex and an organic treatment agent to obtain a mixture; heating the mixture to remove some of the organic ligands in the metal-organic acid complex and retain the organic treatment agent to obtain the remaining material; the heating temperature is 200-450℃ and the time is 0.5-8h. The metal-organic acid complex comprises an active metal central atom or central ion and an organic ligand coordinated to the active metal central atom or central ion; the active metal is selected from one or more of Group VB, Group VIB, Group VIII and Group IB metals with hydrogenation properties; the organic ligand comprises a hydrocarbon moiety and a coordinating group moiety, wherein the coordinating group is a -C(=O)-O group and forms a coordinate bond with the metal central atom or central ion through an oxygen atom; In the metal-organic acid complex, the molar ratio between the active metal and the organic ligand is 1:(1-10). The metal-organic acid complex has the schematic composition shown in general formula (I): MO a [R(COO) x ] b (I), Where M represents metal, and R(COO) x Represents the organic ligand, R represents the hydrocarbon group in the organic ligand, COO represents the coordinating group in the organic ligand, x represents the number of coordinating groups in the organic ligand, a represents the molar ratio of non-coordinated oxygen atoms bonded to metal M to metal M, and b represents the molar ratio of the organic ligand to metal M, where: R is a C3-C19 hydrocarbon group; x is 1, 2, or 3; a is a positive number between 0 and 5; The infrared spectra of the aforementioned organometallic acid complexes are in the range of 700-1000 cm⁻¹. -1 1350-1450 cm -1 and 1500-1610cm -1 The position has a characteristic peak; the group VB, group VIB, group VIII and group IB metals with hydrogenation properties are selected from V, Cr, Mo, W, Fe, Co, Ru, Ni, Cu and Zn; The organic ligand is derived from C4-C20 organic carboxylic acids and / or the anhydrides of C4-C20 organic carboxylic acids, wherein the organic carboxylic acids are selected from one or more of C4-C20 normal or isomeric alkyl carboxylic acids, C6-C20 cycloalkane carboxylic acids containing saturated carbocyclic rings, and C7-C20 aromatic carboxylic acids containing aromatic rings. The organic treatment agent is selected from one or more of the following: alkanes with C>17, monocyclic aromatic hydrocarbons with side chains C>14, aromatic hydrocarbons with not less than 2 aromatic rings, dodecylbenzene sulfonic acid, oleic acid, oleylamine, stearic acid, hexadecyltrimethylammonium bromide, ethylenediaminetetraacetic acid, diesel oil, paraffin wax, ceresin wax, oil slurry, residual oil, asphalt, and coal tar. In the metal-organic acid complex, the molar ratio between the active metal and the organic ligand is 1:(1-10).

7. The method according to claim 6, wherein, The mass ratio of the active metal in the metal-organic acid complex to the organic treatment agent is 1:(0.1-10).

8. The method according to claim 7, wherein, The mass ratio of the active metal in the metal-organic acid complex to the organic treatment agent is 1:(0.5-5).

9. The method according to claim 6, wherein, R is selected from C5-C11 normal or isoalkyl, C5-C12 cycloalkyl and C6-C12 aryl; x is 1 or 2; a is a positive number between 1 and 3; The group VB, group VIB, group VIII and group IB metals with hydrogenation properties are selected from V, Mo, W, Fe, Co, Ni, Cu and Zn; The organic carboxylic acid is selected from one or more of the following: C4-C12 normal or isomeric alkyl carboxylic acids, C6-C13 cycloalkanic carboxylic acids containing saturated carbocyclic rings, and C7-C13 aromatic carboxylic acids containing aromatic rings.

10. The method according to claim 9, wherein, The active metal is selected from Mo, Ni and Co.

11. A method for hydrogenating oil, characterized in that, The method includes: Under hydrogenation reaction conditions, the oil feedstock is brought into contact with the hydrogenation catalyst described in any one of claims 1-5; The oil raw materials are selected from at least one of benzene, alkylbenzene, naphthalene, alkylnaphthalene, anthracene, alkylanthracene, crude oil, gasoline, diesel, wax oil, oil slurry, residual oil, coal tar, and biomass oil.

12. The method according to claim 11, wherein, The conditions for the hydrogenation reaction include: Based on the weight of the oil feedstock and calculated in metals, the amount of hydrogenation catalyst used is 50-10000 μg / g; the initial hydrogen pressure is 1-20 MPa; the reaction temperature is 300-500℃; and the liquid hourly space velocity is 0.05-5.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is 100-3000.

13. The method according to claim 12, wherein, The conditions for the hydrogenation reaction include: Based on the weight of the oil feedstock and calculated as metal, the amount of hydrogenation catalyst used is 50-3000 μg / g; the initial hydrogen pressure is 3-15 MPa; the reaction temperature is 350-450℃; and the liquid hourly space velocity is 0.05-1.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is 200-2000.

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