Preparation method of unsupported single metal hydrogenation catalyst

Abstract

This application relates to a method for preparing an unsupported single-metal hydrogenation catalyst, comprising the following steps: 1) mixing a metal source or its dispersion system with an organic ligand compound; 2) reacting the mixture obtained in step 1) at 100-350°C for 1-8 hours; and 3) collecting the resulting liquid product. This preparation method requires few raw materials, has a simple process, low material and energy consumption, and is green and efficient. The prepared unsupported single-metal hydrogenation catalyst can be used for the hydrogenation reaction of hydrocarbon-containing feedstocks and exhibits high oil solubility, dispersibility, and hydrogenation activity.

Description

Technical Field

[0001] This application relates to the technical field of hydrogenation catalysts, specifically to a method for preparing an unsupported single-metal hydrogenation catalyst, the prepared catalyst, and its uses. Background Technology

[0002] Currently, supported catalysts are the earliest studied, most widely used, and most extensive hydrogenation catalysts for processing hydrocarbon compounds. Hydrocarbon compounds or mixtures exist as liquid oil phases under reaction conditions, while supported catalysts are typically solids. Their catalytic hydrogenation of hydrocarbon compounds or mixtures is a heterogeneous catalytic reaction requiring seven steps. The diffusion step is essential for the catalytic reaction of hydrocarbon compounds or mixtures by supported catalysts, influencing the probability and efficiency of the catalytic reaction. Furthermore, the coke, removed metals, and other heteroatoms generated during the reaction can easily cause catalyst pore blockage and catalyst poisoning / deactivation.

[0003] To improve the dispersibility and oil solubility of catalysts, numerous researchers both domestically and internationally have conducted related research. Chinese patent application CN111434380A discloses a method for preparing oil-soluble monodisperse metal oxide nanocatalysts, comprising dispersing metal oxides in an organic solvent and water with the addition of a promoter and a surfactant. Although the dispersed nano-metal oxides reach nanoscale sizes (approximately 2-35 nm), the active centers remain solid metal oxide particles. During the reaction, a solid-liquid interface still exists between the catalyst metal oxide solid particles and the reactant organic molecules, failing to eliminate the interfacial diffusion problem.

[0004] Chinese patent application CN107866278A discloses a method for preparing a heavy oil hydrocracking catalyst. The method involves first dissolving and dispersing a hexavalent molybdenum source compound in a solvent, adding an inorganic acid catalyst, then adding a small-molecule organic acid, and reacting at 40-150°C. Finally, a macromolecular organic acid or ester is added to the reaction product to form an organometallic compound. The heavy oil hydrocracking catalyst prepared by this method exhibits good solubility in oil and demonstrates good coking inhibition performance when directly applied in the hydrocracking process. However, this catalyst preparation method requires a variety of raw materials and involves multiple synthesis steps, including the need for an inorganic acid as a catalyst, resulting in high material and energy consumption. Furthermore, the multi-step synthesis process may generate waste products. Summary of the Invention

[0005] The purpose of this application is to provide a method for preparing an unsupported single-metal hydrogenation catalyst, the prepared catalyst and its uses. The preparation method requires few raw materials, has a simple preparation process, low material and energy consumption, and is green and efficient. The prepared unsupported single-metal hydrogenation catalyst can be used for hydrogenation reactions of hydrocarbon-containing raw materials and has high oil solubility, dispersibility and hydrogenation activity.

[0006] To achieve the above objectives, this application provides a method for preparing an unsupported single-metal hydrogenation catalyst, comprising the following steps:

[0007] 1) Mix the metal source or its dispersion system with an organic ligand compound;

[0008] 2) React the mixture obtained in step 1) at 100-350℃ for 1-8 hours; and

[0009] 3) Collect the obtained liquid product.

[0010] The metal source is selected from elemental metals, metal oxides, metal hydroxides, metal oxyacids, inorganic metal salts, or combinations thereof, and the metal in the metal source is one of Group VB, Group VIB, Group VIII, or Group IB metals with hydrogenation properties.

[0011] The organic ligand compound is selected from C4-C20 organic carboxylic acids or their anhydrides.

[0012] The molar ratio of the organic ligand compound to the metal in the metal source is 1-10:1.

[0013] On the other hand, an unsupported single-metal hydrogenation catalyst prepared by the method of this application is provided.

[0014] Furthermore, the application provides the use of unsupported single-metal hydrogenation catalysts according to this application in hydrogenation reactions of hydrocarbon feedstocks.

[0015] The catalyst preparation method of this application requires few raw materials, has a simple preparation process, low material and energy consumption, and is green and efficient. When the prepared unsupported single-metal hydrogenation catalyst is used in the hydrogenation reaction of hydrocarbon-containing raw materials, it has high oil solubility, dispersibility and hydrogenation activity.

[0016] Other features and advantages of this application will be described in detail in the following detailed description section. Attached Figure Description

[0017] The accompanying drawings are provided to further illustrate the present application and form part of the specification. They are used together with the following detailed description to explain the present application, but do not constitute a limitation thereof. In the drawings:

[0018] Figure 1 The infrared spectrum of the catalyst obtained in Example 1 is shown;

[0019] Figure 2 The infrared spectrum of the catalyst obtained in Example 2 is shown.

[0020] Figure 3The infrared spectrum of the catalyst obtained in Example 3 is shown;

[0021] Figure 4 The infrared spectrum of the catalyst obtained in Example 4 is shown; and

[0022] Figure 5 The infrared spectrum of the catalyst obtained in Example 8 is shown; Detailed Implementation

[0023] The specific embodiments of this application will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit this application.

[0024] Any specific numerical values ​​disclosed herein (including the endpoints of numerical ranges) are not limited to their exact values, but should be understood to also include values ​​close to the exact value, such as all possible values ​​within ±5% of the exact value. Furthermore, with respect to the disclosed numerical ranges, one or more new numerical ranges can be obtained by arbitrarily combining the endpoint values ​​of the range, the endpoint values ​​with specific point values ​​within the range, and the specific point values ​​themselves; these new numerical ranges should also be considered as specifically disclosed herein.

[0025] Unless otherwise stated, the terms used herein have the same meaning as commonly understood by those skilled in the art, and if a term is defined herein and its definition differs from the common understanding in the art, the definition herein shall prevail.

[0026] In this application, except where expressly stated, any matters or issues not mentioned are directly applicable to aspects known in the art without any modification. Furthermore, any implementation described herein can be freely combined with one or more other implementations described herein, and the resulting technical solutions or concepts are considered part of the original disclosure or original record of this application, and should not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider the combination manifestly unreasonable.

[0027] All patent and non-patent literature mentioned in this article, including but not limited to textbooks and journal articles, are incorporated in full by way of citation.

[0028] As described above, in a first aspect, this application provides a method for preparing an unsupported single-metal hydrogenation catalyst, comprising the following steps:

[0029] 1) Mix the metal source or its dispersion system with an organic ligand compound;

[0030] 2) React the mixture obtained in step 1) at 100-350℃ for 1-8 hours; and

[0031] 3) Collect the obtained liquid product.

[0032] The metal source is selected from elemental metals, metal oxides, metal hydroxides, metal oxyacids, inorganic metal salts, or combinations thereof, and the metal in the metal source is one of Group VB, Group VIB, Group VIII, or Group IB metals with hydrogenation properties.

[0033] The organic ligand compound is selected from C4-C20 organic carboxylic acids or their anhydrides.

[0034] The molar ratio of the organic ligand compound to the metal in the metal source is 1-10:1.

[0035] In a preferred embodiment, the mixture obtained in step 1) consists of the metal source and the organic ligand compound; or consists of the metal source, a dispersion medium for dispersing the metal source, and the organic ligand compound.

[0036] In some specific embodiments, the method includes the following steps:

[0037] i) Disperse the metal source into a dispersion medium to obtain a metal source dispersion system;

[0038] ii) Add an organic ligand compound to the obtained metal source dispersion system, heat to 100-350℃, and react for 1-8 hours; and

[0039] iii) After the reaction is complete, cool down and collect the resulting liquid product.

[0040] In some other embodiments, the method includes the following steps:

[0041] i) Directly disperse the metal source into the organic ligand compound;

[0042] ii) Heat to 100-350℃ and react for 1-8 hours; and

[0043] iii) After the reaction is complete, cool down and collect the resulting liquid product.

[0044] In a preferred embodiment, 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 Pd, and more preferably from Mo, Ni, W, Fe, V and Co.

[0045] According to this application, the inorganic metal salt can be an inorganic acid salt of the metal, such as nitrate, sulfate, or chloride; or it can be a metal oxyacid salt of the metal, such as ammonium metal oxyacid.

[0046] In a preferred embodiment, the metal source is selected from metal oxides, metal hydroxides, metal chlorides, metal sulfides, metal sulfates, metal nitrates, metal carbonates, metal oxyacids, metal oxyacid salts, or combinations thereof, such as oxides, hydroxides, chlorides, sulfides, sulfates, nitrates, and carbonates of V, Mo, W, Fe, Co, Ni, Cu, and Zn, molybdic acid, tungstic acid, various forms of ammonium molybdate, ammonium tungstate, or combinations thereof.

[0047] In a preferred embodiment, the organic ligand compound is selected from C4-C20 normal or isomeric alkyl carboxylic acids, C6-C20 cycloalkane carboxylic acids containing saturated carbocyclic rings, C7-C20 aromatic carboxylic acids containing aromatic rings, their anhydrides, or combinations thereof.

[0048] According to this application, the "C4-C20 n-alkyl carboxylic acid" refers to a carboxylic acid with 4-20 carbon atoms obtained by linking one or more carboxyl groups to a straight-chain alkane, such as butyric acid, succinic acid, valeric acid, hexanoic acid, adipic acid, heptanoic acid, octanoic acid, nonanoic acid, ethylhexanoic acid, tridecanoic acid, oleic acid, etc.

[0049] According to this application, the "C4-C20 isomeric alkyl carboxylic acid" refers to a carboxylic acid with 4-20 carbon atoms obtained by linking one or more carboxyl groups to a branched alkane, such as isobutyric acid, isovaleric acid, isohexanoic acid, ethylhexanoic acid, methylhexanoic acid, propylhexanoic acid, ethylheptanoic acid, ethyloctanoic acid, ethylnonanoic acid, etc.

[0050] According to this application, the "C6-C20 cycloalkane carboxylic acid containing a saturated carbon ring" refers to a carboxylic acid having 6-20 carbon atoms obtained by linking one or more carboxyl groups to an alkane compound containing a saturated carbon ring, such as cyclohexanoic acid, cyclohexyl diacid, decahydronaphthalic acid, and decahydronaphthalic acid.

[0051] According to this application, the "C7-C20 aromatic carboxylic acid containing an aromatic ring" refers to a carboxylic acid having 7-20 carbon atoms obtained by linking one or more carboxyl groups to an aromatic hydrocarbon, i.e., a hydrocarbon compound containing an aromatic ring, such as benzoic acid, phenylacetic acid, phthalic acid, and phenylpropionic acid.

[0052] In a further preferred embodiment, the organic ligand compound is selected from one or more of C6-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, and even more preferably selected from one or more of 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.

[0053] In a preferred embodiment, the dispersion medium in the metal source dispersion system can be an inorganic dispersion medium or an organic dispersion medium. The inorganic dispersion medium can be selected from water, carbonic acid, hydrochloric acid, sulfuric acid, or phosphoric acid. The organic dispersion medium can be selected from aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohol solvents, ether solvents, ester solvents, ketone solvents, or combinations thereof, and more preferably from ethanol, toluene, xylene, petroleum ether, gasoline, diesel, or combinations thereof.

[0054] In a further preferred embodiment, the weight ratio of the dispersion medium to the metal source in the dispersion system is 1-25:1, more preferably 2-8:1.

[0055] In a preferred embodiment, the reaction temperature in step 2) is 160-260°C and the reaction time is 2-5 hours.

[0056] According to this application, step 2) does not have strict requirements on the pressure and reaction atmosphere used. For example, the reaction pressure can be atmospheric pressure, and the reaction atmosphere can be air, nitrogen, or an inert atmosphere.

[0057] In a preferred embodiment, the infrared spectrum of the unsupported single-metal hydrogenation catalyst is in the range of 1350-1450 cm⁻¹. -1 With 1500-1610cm -1 There are characteristic peaks at certain locations, such as 700-1000 cm⁻¹. -1 1350-1450cm -1 1500-1610cm -1 and 1700-1750cm -1 It has a characteristic peak at the location.

[0058] In a preferred embodiment, the unsupported single-metal hydrogenation catalyst comprises a complex formed by coordination bonding of a metal from the metal source with an organic ligand derived from the organic ligand compound, and optionally an unreacted organic ligand compound, wherein the complex has the composition shown in formula (I):

[0059] MO y [R(COO) x ] n (I),

[0060] Where M represents the metal, and R(COO) x Representing 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, y represents the number of non-coordinated oxygen atoms connected to the metal M, and n represents the coordination number, wherein:

[0061] R is a C3-C19 hydrocarbon group, preferably selected from C5-C11 normal alkyl, C5-C11 isoalkyl, C5-C12 cycloalkyl, C6-C12 aryl or a combination thereof;

[0062] x is 1, 2 or 3, preferably 1 or 2;

[0063] y is a positive number from 0 to 3, preferably a positive number from 1 to 3; and

[0064] n is a positive number from 1 to 6, preferably a positive number from 2 to 5.

[0065] In some further preferred embodiments, at least a portion of the complex in the unsupported single-metal hydrogenation catalyst has the structure shown in formula (I-1):

[0066]

[0067] Where M represents the metal;

[0068] → represents a coordinate bond;

[0069] R represents a C3-C19 hydrocarbon group, preferably selected from C5-C11 normal alkyl, C5-C11 isoalkyl, C5-C12 cycloalkyl and C6-C12 aryl;

[0070] x represents the number of coordinating groups in the organic ligand, and is 1, 2 or 3, preferably 1 or 2;

[0071] n represents the coordination number, which is an integer from 1 to 6, preferably an integer from 2 to 5; and

[0072] y represents the number of non-coordinated oxygen atoms connected to metal M, and is an integer from 0 to 3, preferably an integer from 1 to 3.

[0073] In a further preferred embodiment, the infrared spectrum of the unsupported single-metal hydrogenation catalyst is in the range of 1350-1450 cm⁻¹. -1 A characteristic peak at the location is located at 1500-1610 cm⁻¹ -1 The distance between the peaks of a characteristic peak at a given location is less than 145 cm. -1 .

[0074] In some further preferred embodiments, at least a portion of the complex in the unsupported monometallic catalyst has the structure shown in formula (I-2):

[0075]

[0076] Where M represents the metal;

[0077] → represents a coordinate bond;

[0078] R represents a C3-C19 hydrocarbon group, preferably selected from C5-C11 normal alkyl, C5-C11 isoalkyl, C5-C12 cycloalkyl and C6-C12 aryl;

[0079] x represents the number of coordinating groups in the organic ligand, and is 1 or 2, preferably 1;

[0080] n represents the coordination number, which is an integer from 1 to 6, preferably an integer from 2 to 5; and

[0081] z represents the number of non-coordinated oxygen atoms bonded to metal M, and is an integer from 0 to 3, preferably an integer from 1 to 3.

[0082] According to this application, the non-coordinate bonded oxygen atom connected to metal M in formula (I-2) includes oxygen atoms that are only connected to one metal atom / ion in the complex molecule (such as oxygen atoms that form M=O bonds), and also oxygen atoms that are connected between two metal atoms / ions in the dimer of the complex molecule (such as oxygen atoms that form MOM bonds).

[0083] In a further preferred embodiment, the infrared spectrum of the unsupported single-metal hydrogenation catalyst is in the range of 1350-1450 cm⁻¹. -1 A characteristic peak at the location is located at 1500-1610 cm⁻¹ -1 The distance between the peaks of a characteristic peak at a given location is greater than 145 cm. -1 .

[0084] In some further preferred embodiments, the unsupported single-metal hydrogenation catalyst comprises the complex and optionally an unreacted organic ligand compound, and the unsupported single-metal hydrogenation catalyst has the illustrative composition shown in formula (II).

[0085] MO a [R(COO) x ] b (II),

[0086] Where M represents the metal, and R(COO) x The organic ligands and organic ligand compounds are represented (the H atoms on the carboxyl groups in the organic ligand compounds are omitted for simplification), a represents the molar ratio of noncoordinated oxygen atoms bonded to metal M to metal M, and b represents the molar ratio of the total amount of organic ligands and organic ligand compounds to metal M, wherein:

[0087] R is a C3-C19 hydrocarbon group, preferably selected from C5-C11 normal alkyl, C5-C11 isoalkyl, C5-C12 cycloalkyl, C6-C12 aryl or a combination thereof;

[0088] x is 1, 2 or 3, more preferably 1 or 2;

[0089] a is a positive number between 0 and 3, preferably a positive number between 1 and 3; and

[0090] b is a positive number from 1 to 6, preferably a positive number from 2 to 5.

[0091] In a preferred embodiment, the metal content in the unsupported single-metal hydrogenation catalyst is 5-35% based on the weight of the catalyst, preferably 8-30%, more preferably 10%-25%, and particularly preferably 10-20%.

[0092] In this application, the term "C3-C19 hydrocarbon group" refers to a hydrocarbon group having 3-19 carbon atoms. The hydrocarbon group may be saturated or unsaturated, straight-chain, branched, or have a carbocyclic structure, including but not limited to C3-C19 normal alkyl, C3-C19 isoalkyl, C5-C19 cycloalkyl, and C6-C19 aryl.

[0093] In this application, the term "C3-C19 n-alkyl" refers to a straight-chain alkyl group having 3-19 carbon atoms, preferably 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.

[0094] In this application, the term "C3-C19 isoalkyl" refers to a branched alkyl group having 3-19 carbon atoms, preferably an isoalkyl group having 5-11 carbon atoms, such as isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, and isoundecyl.

[0095] In this application, the term "C5-C19 cycloalkyl group" refers to a saturated hydrocarbon group containing a saturated carbon ring having 5-19 carbon atoms, preferably a cycloalkyl group with 5-12 carbon atoms, such as cyclopentyl, cyclohexyl, methylcyclohexyl, decahydronaphthyl, methyldecahydronaphthyl, ethyldecahydronaphthyl, etc.

[0096] In this application, the term "C6-C19 aryl" refers to a group containing an aromatic ring having 6-19 carbon atoms, such as phenyl, naphthyl, anthracene, p-tolyl, benzyl, methylnaphthyl, methylanthrayl, etc., preferably an aryl group with 6-12 carbon atoms.

[0097] According to this application, the C3-C19 hydrocarbon group, C3-C19 normal alkyl group, C3-C19 isoalkyl group, C5-C19 cycloalkyl group and C6-C19 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.

[0098] In some preferred embodiments, step 3) further includes adding at least one organic ligand compound and / or organic solvent to the resulting liquid product, wherein:

[0099] The organic ligand compound added in step 3) is selected from C4-C20 organic carboxylic acids, preferably from C4-C20 normal or isomeric alkyl carboxylic acids, C6-C20 cycloalkane carboxylic acids containing saturated carbocyclic rings, C7-C20 aromatic carboxylic acids containing aromatic rings, or combinations thereof, more preferably from C6-C12 normal or isomeric alkyl carboxylic acids, C6-C13 cycloalkane carboxylic acids containing saturated carbocyclic rings, C7-C13 aromatic carboxylic acids containing aromatic rings, or combinations thereof, and even more preferably from succinic acid, hexanoic acid, adipic acid, heptanoic acid, octanoic acid, nonanoic acid, ethylhexanoic acid, oleic acid, petroleum ether, salicylic acid, benzoic acid, phenylacetic acid, or combinations thereof;

[0100] The organic solvent added in step 3) is selected from aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohol solvents, ether solvents, ester solvents, ketone solvents, or combinations thereof, preferably selected from toluene, gasoline, ethanol, diesel, or combinations thereof.

[0101] In a further preferred embodiment, based on the weight of the final product obtained in step 3), the amount of organic ligand compound and organic solvent added in step 3) is such that the total amount of organic ligand compound, dispersion medium and organic solvent in the final product is 5-50%, preferably 5-20%.

[0102] In some further preferred embodiments, step 3) further includes adding at least one other component to the resulting liquid product that can improve oil solubility, storage stability and / or antioxidant properties, such as organic compounds with reducing function, such as formic acid, oxalic acid, formaldehyde, ethylenediamine, oleylamine, etc. The amount of the other component added can be 0-80%, preferably 0-50%, based on the weight of the final product.

[0103] In a second aspect, a non-supported single-metal hydrogenation catalyst is provided, comprising or consisting of a complex formed by a metal central atom or central ion and an organic ligand bonded by coordination bonds, wherein the metal is one of a Group VB, Group VIB, Group VIII, or Group IB metal with hydrogenation properties, and the organic ligand comprises a hydrocarbon moiety and a coordinating group moiety, wherein the coordinating group is composed of carbon atoms and oxygen atoms, and forms a coordination bond with the metal central atom or central ion through the oxygen atom, wherein the infrared spectrum of the catalyst is in the range of 1350-1450 cm⁻¹. -1 and 1500-1610cm -1 It has a characteristic peak at the location.

[0104] In a preferred embodiment, the coordinating group may be a -C(=O)-O group.

[0105] In a further preferred embodiment, the complex has the composition shown in formula (I):

[0106] MO y [R(COO) x ] n (I),

[0107] The definitions of M, R, x, y, and n are as described above.

[0108] In some further preferred embodiments, at least a portion of the complex has the structure shown in formula (I-1):

[0109]

[0110] The definitions of M, R, x, y, and n are as described above.

[0111] In a further preferred embodiment, the infrared spectrum of the unsupported single-metal hydrogenation catalyst is in the range of 1350-1450 cm⁻¹. -1 A characteristic peak at the location is located at 1500-1610 cm⁻¹ -1 The distance between the peaks of a characteristic peak at a given location is less than 145 cm. -1 .

[0112] In some further preferred embodiments, at least a portion of the complex has the structure shown in formula (I-2):

[0113]

[0114] The definitions of M, R, x, z, and n are as described above.

[0115] In a further preferred embodiment, the infrared spectrum of the unsupported single-metal hydrogenation catalyst is in the range of 1350-1450 cm⁻¹. -1 A characteristic peak at the location is located at 1500-1610 cm⁻¹ -1 The distance between the peaks of a characteristic peak at a given location is greater than 145 cm. -1 .

[0116] In some preferred embodiments, the unsupported single-metal hydrogenation catalyst further comprises at least one organic ligand compound and / or a dispersion medium, wherein the organic ligand compound is selected from C4-C20 organic carboxylic acids or their anhydrides, preferably from C4-C20 n- or isomeric alkyl carboxylic acids, C6-C20 cycloalkane carboxylic acids containing a saturated carbocyclic ring, C7-C20 aromatic carboxylic acids containing an aromatic ring, their anhydrides, or combinations thereof, more preferably from C6-C12 n- or isomeric alkyl carboxylic acids, C6-C13 cycloalkane carboxylic acids containing a saturated carbocyclic ring, and C7-C13 aromatic carboxylic acids containing an aromatic ring. One or more of the aromatic carboxylic acids, more preferably selected from one or more of 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; the dispersion medium can be an inorganic dispersion medium or an organic dispersion medium, wherein the inorganic dispersion medium is selected from water, carbonic acid, hydrochloric acid, sulfuric acid, or phosphoric acid; the organic dispersion medium is selected from aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohol solvents, ether solvents, ester solvents, ketone solvents, or combinations thereof, more preferably selected from ethanol, toluene, xylene, petroleum ether, gasoline, diesel, or combinations thereof.

[0117] In a further preferred embodiment, the total content of organic ligand compounds and dispersion medium in the unsupported single-metal hydrogenation catalyst is 5-50%, preferably 5-20%, based on the weight of the catalyst.

[0118] In some further preferred embodiments, the unsupported single-metal hydrogenation catalyst also contains at least one other component that can improve oil solubility, storage stability and / or antioxidant properties, such as an organic compound with reducing function. The content of the other component can be 0-80% based on the weight of the catalyst, preferably 0-50%.

[0119] In some preferred embodiments, the unsupported single-metal hydrogenation catalyst comprises the complex and optionally an organic ligand compound, and the unsupported single-metal hydrogenation catalyst has the illustrative composition shown in formula (II).

[0120] MO a [R(COO) x ] b (II),

[0121] The definitions of M, R, x, a, and b are as described above.

[0122] In a preferred embodiment, the metal content in the unsupported single-metal hydrogenation catalyst is 5-35% based on the weight of the catalyst, preferably 8-30%, more preferably 10%-25%, and particularly preferably 10-20%.

[0123] In a particularly preferred embodiment, the unsupported single-metal hydrogenation catalyst is a catalyst prepared by the method of this application.

[0124] In a third aspect, the use of the unsupported single-metal hydrogenation catalyst according to this application in the hydrogenation reaction of hydrocarbon feedstock is provided.

[0125] In a fourth aspect, a method for hydrogenating a hydrocarbon feedstock is provided, comprising the step of contacting the hydrocarbon feedstock with a non-supported single-metal hydrogenation catalyst according to the present application to carry out a hydrogenation reaction.

[0126] According to this application, the hydrocarbon-containing raw material can be various unsaturated hydrocarbon compounds, such as benzene, alkylbenzene, naphthalene, alkylnaphthalene, anthracene, alkylanthracene, etc.; or it can be a mixture of various unsaturated hydrocarbon compounds, such as crude oil, gasoline, diesel, wax oil, residual oil, etc.

[0127] In a preferred embodiment, the conditions for the hydrogenation reaction include a reaction temperature of 380-430°C, an initial hydrogen pressure of 5-20 MPa, and a fresh feed liquid hourly space velocity of 0.05-1.0 h⁻¹. -1 The catalyst concentration (in metals) relative to the total feed is 50-10000 μg / g.

[0128] Example

[0129] The following examples provide a more detailed description of this application, but the application is not limited thereto. Unless otherwise specified, all reagents and raw materials used in the following examples are commercially available products of chemical purity.

[0130] In the following examples, the metal content of the obtained catalyst was determined using inductively coupled plasma optical emission spectrometry (ICP-OES) on a SPECTRO ARCOS SOP plasma optical emission spectrometer. The measurement conditions were a sealed optical chamber filled with argon gas, vertical observation, and a wavelength range of 130-770 nm.

[0131] In the following examples, the elemental composition of the obtained catalyst was determined as follows: the C and H contents were determined using an Italian Cara Erba EA1110 elemental analyzer using the SH0656 method; the S content was determined using energy dispersive X-ray fluorescence spectrometry (EDXRF) using the GB17040 method; and the O content was determined using the O-content method.

[0132] In the following examples, the infrared spectra of the obtained catalysts were measured using a Thermo Fisher NICOLET IS50 spectrometer, with measurement conditions of scanning wavelengths from 400 to 4000 cm⁻¹. -1The 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 .

[0133] Examples 1-8

[0134] The corresponding weights of compounds were weighed according to Table 1 and placed in a three-necked flask. The reaction was then carried out under the conditions shown in Table 1. After the reaction, the metal compounds in the flasks of Examples 1-7 were completely dissolved, while unreacted metal compounds remained in the flask of Example 8. The liquid reaction products in the flasks of Examples 1-7 were poured out to obtain the target catalyst product; the product of Example 8 was filtered to remove the unreacted metal compounds, thus obtaining the target catalyst product. The metal content of the catalyst was determined by inductively coupled plasma optical emission spectrometry (ICP-OES), and the elemental composition of the catalyst was measured using appropriate methods. The composition of the catalyst was obtained based on the measured metal content and elemental composition results.

[0135] The reaction materials, reaction conditions and experimental results used in Examples 1-8 are shown in Table 1.

[0136]

[0137] As shown in Table 1, the metal content of the unsupported single-metal hydrogenation catalyst of this application can reach 6.95-20.4%, and the molar ratio of the total amount of organic ligands and organic ligand compounds in the catalyst to the metal is 2.0-4.

[0138] The elemental analysis results of the catalyst obtained in Example 1 are shown in Table 2. The catalyst composition (MoO) can be calculated from the data in Table 2. a (i-C7H 16 COO) b The values ​​of a and b in the equation are given, where b = 0.52 / 0.18 = 2.84 and a = (1.23 - 2.0 × 0.52) / 0.18 = 1.0.

[0139] Table 2 Elemental analysis results of the products obtained in Example 1

[0140] element mass content / % Molar content / % Moles of the corresponding groups C 49.96 4.16 4.16 / 8＝0.52 H 8.32 8.32 8.32 / 16＝0.52 O 19.68 1.23 1.23 Mo 17.66 0.18 0.18

[0141] The infrared spectra of the catalysts obtained in Examples 1-4 are as follows: Figure 1-4 As shown in the figure, it is clear that the catalysts in all embodiments are within the range of 700-1000 cm⁻¹. -1 1350-1450cm -1 and 1500-1610cm -1 It has a characteristic peak at the location.

[0142] Specifically, such as Figure 1 As shown, the catalysts obtained in Example 1 have a specific oxidation state of 700-1000 cm⁻¹. -1 It exhibits characteristic vibrational peaks of MO and M=O at the location, and at 1350-1450 cm⁻¹ -1 and 1500-1610cm -1 The position shows characteristic peaks of -C(=O)-O groups coordinated with metals, and the peaks are located at 1350-1450 cm⁻¹. -1 The characteristic peak at the location is 1500-1610 cm⁻¹ -1 The distance between the peaks of the characteristic peaks at the location (i.e., the difference in wavenumbers corresponding to the peak positions) is less than 145 cm. -1 This indicates that the catalyst contains a complex with a bidentate structure, and the corresponding structural formula is:

[0143]

[0144] like Figure 2 and Figure 4 As shown, the catalysts obtained in Examples 2 and 4 were in the range of 1350-1450 cm⁻¹. -1 and 1500-1610cm -1 The position shows characteristic peaks of -C(=O)-O groups coordinated with metals, and the peaks are located at 1350-1450 cm⁻¹. -1 The characteristic peak at the location is 1500-1610 cm⁻¹ -1 The difference between the characteristic peaks at different locations is greater than 145 cm⁻¹. -1 This indicates that the catalyst contains a complex with a monodentate complexing structure, and the corresponding structural formula is:

[0145]

[0146] like Figure 3 As shown, the catalyst obtained in Example 3 has a viscosity of 1350-1450 cm⁻¹. -1 and 1500-1610cm -1 The peaks at position 1500-1610 cm⁻¹ are characteristic of the coordination between the -C(=O)-O group and the metal. -1 There are two characteristic peaks at this location, one of which is at 1350-1450 cm⁻¹. -1 The difference between the characteristic peaks at different locations is less than 145 cm⁻¹. -1 Another one is 1350-1450cm -1 The difference between the characteristic peaks at different locations is greater than 145 cm⁻¹. -1 This indicates that the catalyst contains both complexes with a bidentate structure and complexes with a monodentate structure, and the corresponding structural formulas are shown above.

[0147] Example 9

[0148] The catalyst prepared in Example 1 was applied to the hydrogenation reaction of the aromatic hydrocarbon pyrene, using tetrahydronaphthalene as the solvent. The mass fraction of pyrene in 10g of total reactants (pyrene + solvent) was 10%. The reaction was carried out in a 100ml high-pressure reactor with complete backmixing. The experimental conditions included an initial hydrogen pressure of 9MPa, a reaction temperature of 380℃, and a reaction time of 60min. The catalyst concentration (based on the weight of the total reactants) was 2500μg / g (metal content). The experimental results are shown in Table 3.

[0149] Comparative Example 1

[0150] The experiment was conducted according to Example 9, except that a conventional supported catalyst (Ni-Mo supported catalyst for residue hydrotreating, with a Mo mass content of 9.3% and a Ni mass content of 2.52%) was used instead of the catalyst prepared in Example 1, with the metal content replaced by an equal amount. The experimental results are shown in Table 3.

[0151] Table 3. Reaction results of Example 9 and Comparative Example 1

[0152] project Example 9 Comparative Example 1 catalyst Catalyst of Example 1 Ni-Mo supported catalyst Test results Pyrene conversion rate / % 71.24 70.87 Product distribution / % dihydropyrene 0 23.11 Tetrahydropyrene 10.61 5.71 Hexahydropyrene + decahydropyrene 60.63 42.05 Hydrogen consumption / mmol 11.62 8.87

[0153] As shown in Table 3, compared with the supported catalyst, the unsupported catalyst of this application has a higher pyrene conversion rate, a higher yield of deep hydrogenation products, and a higher hydrogen consumption, indicating that the unsupported catalyst of this application has higher catalytic activity.

[0154] Examples 10-11

[0155] The catalysts prepared in Examples 1 and 3 were used to catalyze the hydrocracking reaction of the alkyl aromatic hydrocarbon dodecylpyrene, with decahydronaphthalene as the solvent. The mass fraction of dodecylpyrene in 10g of total reactants (dodecylpyrene + solvent) was 10%. The reaction was carried out in a 100ml high-pressure reactor. The experimental conditions included an initial hydrogen pressure of 9MPa, a reaction temperature of 420℃, and a reaction time of 60min. The catalyst concentration (based on the weight of the total reactants) was 2500μg / g (calculated as metal). The experimental results are shown in Table 4.

[0156] Table 4 Reaction results of Examples 10-11

[0157] project Example 10 Example 11 catalyst Catalyst of Example 1 Catalyst of Example 3 Dodecylpyrene test results Cracking conversion rate / % 100 100 Condensation rate / % 0 0 Hydrogen consumption / mmol 2.34 1.38

[0158] As shown in Table 4, the unsupported catalyst of this application achieved 100% cracking conversion of dodecylpyrene and zero condensation rate, indicating that the unsupported catalyst of this application has high coke suppression and cracking promotion activity.

[0159] Examples 12-13 and Comparative Example 2

[0160] Using 200g of vacuum residue A with an asphaltene content of 12%, a carbon residue value of 23.2%, and a heavy metal (Ni+V) content of 200μg / g as raw material, a catalytic hydrothermal conversion experiment was conducted in a 2L intermittent high-pressure reactor under the catalyst and reaction conditions shown in Table 5. The experimental results are shown in Table 5.

[0161] Table 5. Reaction results of Examples 12-13 and Comparative Example 2

[0162]

[0163] As shown in Table 5, under the same reaction conditions, the unsupported catalyst of this application has a higher residue cracking rate, a lower condensation rate, and a higher distillate yield compared to conventional supported catalysts.

[0164] The preferred embodiments of this application have been described in detail above. However, this application is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this application, various simple modifications can be made to the technical solution of this application, and these simple modifications all fall within the protection scope of this application.

[0165] 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, this application will not describe the various possible combinations separately.

[0166] Furthermore, various different implementations of this application can be combined in any way, as long as they do not violate the spirit of this application, they should also be regarded as the content disclosed in this application.

Claims

1. A method for preparing an unsupported single-metal hydrogenation catalyst, comprising the following steps: 1) Mix the metal source or its dispersion system with an organic ligand compound; 2) React the mixture obtained in step 1) at 100-350℃ for 1-8 hours; and 3) Collect the obtained liquid product. The metal source is selected from elemental metals, metal oxides, metal hydroxides, metal oxyacids, inorganic metal salts, or combinations thereof, and the metal in the metal source is one of Group VB, Group VIB, Group VIII, or Group IB metals with hydrogenation properties. The organic ligand compound is selected from C4-C20 organic carboxylic acids or their anhydrides; The molar ratio of the organic ligand compound to the metal in the metal source is 1-10:

1. The unsupported single-metal hydrogenation catalyst comprises a complex formed by coordination bonding of a metal from the metal source with an organic ligand derived from the organic ligand compound, and optionally an unreacted organic ligand compound, wherein the complex has the formula shown in (I). composition: MO y [R(COO) x ] n (I), Where M represents the metal, and R(COO) x Representing 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, y represents the number of non-coordinated oxygen atoms connected to the metal M, and n represents the coordination number, wherein: R is a C3-C19 hydrocarbon group; x is 1, 2, or 3; y is a positive number between 0 and 3; and n is a positive number from 1 to 6. At least a portion of the complexes have the structure shown in formula (I-1): Where M represents the metal; → represents a coordinate bond; R represents a C3-C19 hydrocarbon group; x represents the number of coordinating groups in the organic ligand, and can be 1, 2 or 3; n represents the coordination number, which is an integer from 1 to 6; and y represents the number of non-coordinated oxygen atoms bonded to metal M, and is an integer between 0 and 3.

2. The method according to claim 1, wherein the organic ligand compound is selected from C4-C20 normal or isomeric alkyl carboxylic acids or their anhydrides, C6-C20 cycloalkane carboxylic acids containing a saturated carbocyclic ring or their anhydrides, C7-C20 aromatic carboxylic acids containing an aromatic ring or their anhydrides, or combinations thereof.

3. The method according to claim 1, wherein R is selected from C5-C11 normal alkyl, C5-C11 isoalkyl, C5-C12 cycloalkyl, C6-C12 aryl, or combinations thereof; In equation (I), x is 1 or 2; y is a positive number between 1 and 3; and n is a positive number between 2 and 5. In equation (I-1), x is 1 or 2; n is an integer between 2 and 5; and y is an integer from 1 to 3.

4. The method according to claim 1 or 2, wherein the mixture obtained in step 1) comprises the metal source and the organic ligand compound; or The mixture obtained in step 1) consists of the metal source, the dispersion medium for dispersing the metal source, and the organic ligand compound.

5. The method according to claim 1 or 2, wherein M is selected from V, Cr, Mo, W, Fe, Co, Ru, Ni, Cu or Pd.

6. The method according to claim 1 or 2, wherein M is selected from Mo, Ni, W, Fe, V or Co.

7. The method according to claim 1 or 2, wherein the metal source is selected from elemental metals, metal oxides, metal hydroxides, metal chlorides, metal sulfides, metal sulfates, metal nitrates, metal carbonates, metal oxyacids, metal oxyacid salts, or combinations thereof.

8. The method according to claim 1 or 2, wherein the organic ligand compound is selected from one or more of C6-C12 ortho- or iso-alkyl carboxylic acids, C6-C13 cycloalkane carboxylic acids containing a saturated carbocyclic ring, and C7-C13 aromatic carboxylic acids containing an aromatic ring.

9. The method according to claim 1 or 2, wherein the organic ligand compound is selected from one or more of the following: adipic acid, heptanoic acid, octanoic acid, nonanoic acid, ethylhexanoic acid, salicylic acid, benzoic acid, and phenylacetic acid.

10. The method according to claim 1 or 2, wherein in step 1), the dispersion system of the metal source is used, wherein the dispersion medium in the dispersion system is an inorganic dispersion medium selected from water, carbonic acid, hydrochloric acid, sulfuric acid or phosphoric acid, or an organic dispersion medium selected from ethanol, toluene, xylene, petroleum ether, gasoline, diesel, or combinations thereof. The weight ratio of the dispersion medium to the metal source in the dispersion system is 1-25:

1.

11. The method according to claim 10, wherein the weight ratio of the dispersion medium to the metal source in the dispersion system is 2-8:

1.

12. The method according to claim 1 or 2, wherein the reaction temperature in step 2) is 160-260°C and the reaction time is 2-5 h.

13. The method according to claim 1 or 2, wherein the infrared spectrum of the unsupported single-metal hydrogenation catalyst is in the range of 1350-1450 cm⁻¹. -1 With 1500-1610cm -1 There is a characteristic peak at the location.

14. The method according to claim 13, wherein the infrared spectrum of the unsupported single-metal hydrogenation catalyst is in the range of 700-1000 cm⁻¹. -1 1350-1450cm -1 1500-1610cm -1 and 1700-1750cm -1 It has a characteristic peak at the location.

15. The method according to claim 1, wherein the infrared spectrum of the unsupported single-metal hydrogenation catalyst is in the range of 1350-1450 cm⁻¹. -1 A characteristic peak at the location is located at 1500-1610 cm⁻¹ -1 The distance between the peaks of a characteristic peak at a given location is less than 145 cm. -1 .

16. The method according to claim 1 or 2, wherein at least a portion of the complex has the structure shown in formula (I-2): Where M represents the metal; → represents a coordinate bond; R represents a C3-C19 hydrocarbon group; x represents the number of coordinating groups in the organic ligand, and is either 1 or 2; n represents the coordination number, which is an integer from 1 to 6; and z represents the number of non-coordinated oxygen atoms bonded to metal M, and is an integer between 0 and 3.

17. The method according to claim 16, wherein in formula (I-2), R is selected from C5-C11 normal alkyl, C5-C11 isoalkyl, C5-C12 cycloalkyl and C6-C12 aryl; x is 1; n is an integer between 2 and 5; and z is an integer between 1 and 3.

18. The method according to claim 16, wherein the infrared spectrum of the unsupported single-metal hydrogenation catalyst is in the range of 1350-1450 cm⁻¹. -1 A characteristic peak at the location is located at 1500-1610 cm⁻¹ -1 The distance between the peaks of a characteristic peak at a given location is greater than 145 cm. -1 .

19. The method according to claim 1 or 2, wherein, Based on the weight of the catalyst, the metal content in the unsupported single-metal hydrogenation catalyst is 5-35%.

20. The method according to claim 1 or 2, wherein, Based on the weight of the catalyst, the metal content in the unsupported single-metal hydrogenation catalyst is 10-20%.

21. The method according to claim 1 or 2, wherein step 3) further comprises adding at least one organic ligand compound and / or organic solvent to the resulting liquid product, wherein: The organic ligand compound added in step 3) is selected from C4-C20 organic carboxylic acids; The organic solvent added in step 3) is selected from aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohol solvents, ether solvents, ester solvents, ketone solvents, or combinations thereof. Based on the weight of the final product, the amount of organic ligand compound and organic solvent added in step 3) is such that the total amount of organic ligand compound, dispersion medium and organic solvent in the final product is 5-50%.

22. The method according to claim 21, wherein the organic ligand compound added in step 3) is selected from succinic acid, hexanoic acid, adipic acid, heptanoic acid, octanoic acid, nonanoic acid, ethylhexanoic acid, oleic acid, salicylic acid, benzoic acid, phenylacetic acid, or combinations thereof; The organic solvent added in step 3) is selected from toluene, ethanol, or a combination thereof. Based on the weight of the final product, the amount of organic ligand compound and organic solvent added in step 3) is such that the total amount of organic ligand compound, dispersion medium and organic solvent in the final product is 5-20%.

23. The unsupported single-metal hydrogenation catalyst prepared by any one of claims 1-22.

24. Use of the unsupported single-metal hydrogenation catalyst of claim 23 in the hydrogenation reaction of hydrocarbon feedstock, wherein the hydrocarbon feedstock is an unsaturated hydrocarbon compound or a mixture containing unsaturated hydrocarbon compounds.

25. The use according to claim 24, wherein the unsaturated hydrocarbon compound is selected from benzene, alkylbenzene, naphthalene, alkylnaphthalene, anthracene, or alkylanthracene; and the mixture comprising the unsaturated hydrocarbon compound is selected from crude oil, gasoline, diesel, wax oil, or residual oil.

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