Preparation method of unsupported multimetal hydrogenation catalysts

Abstract

This application relates to a method for preparing an unsupported multimetal hydrogenation catalyst, comprising the following steps: 1) mixing a first metal source or its dispersion with an organic ligand compound; 2) reacting the mixture obtained in step 1) at temperature T1 for time t1; 3) reacting the material obtained in step 2) at temperature T2 for time t2; 4) optionally, adding a second metal source or its dispersion to the material obtained in step 3), and reacting the resulting material at temperature T2 for time t3; and 5) collecting the resulting liquid product. This preparation method requires few raw materials, has a simple preparation process, low material and energy consumption, and is green and efficient. The prepared unsupported multimetal hydrogenation catalyst exhibits high oil-phase dispersibility and hydrogenation activity when used in the hydrogenation reaction of hydrocarbon-containing feedstocks.

Description

Technical Field

[0001] This application relates to the technical field of hydrogenation catalysts, specifically to a method for preparing an unsupported multimetal hydrogenation catalyst, the prepared catalyst, and its application. 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 reaction is a heterogeneous catalytic reaction, requiring seven steps. Among these, the diffusion step is essential for the catalytic catalysis of hydrocarbon compounds or mixtures by supported catalysts, influencing the probability and efficiency of the catalytic reaction.

[0003] To improve the dispersion and oil solubility of catalysts, numerous researchers both domestically and internationally have conducted related research. Chinese Patent Announcement CN104888796B discloses an oil-soluble Mo-Ni bimetallic catalyst, its preparation method, and its applications. The method involves dissolving nickel nitrate and ammonium molybdate in 15-25 times their mass of distilled water, adding a small amount of ethylene glycol; then adjusting the pH to alkaline by adding ammonia; heating the solution at 130-160℃ for 3-5 hours with stirring; filtering the product to obtain a solid intermediate; drying the solid intermediate at 100℃ under normal pressure; mixing it with oleic acid; and reacting it at 230-260℃ for 2-4 hours to obtain the oil-soluble Mo-Ni bimetallic catalyst. The catalyst exhibits a flexible and adjustable bimetallic mass ratio, high hydrogenation activity, and good coking suppression effect. However, this method requires the addition of extra ethylene glycol and ammonia in the first step, and the reaction product obtained in the first step needs to be filtered to obtain an intermediate product. The intermediate product is then dried before the second step reaction is carried out. The preparation process is complicated, filtration generates waste, and the target product has a low metal content.

[0004] Chinese Patent Publication CN107866279B discloses a molybdenum-nickel catalyst for hydrocracking and its preparation method. The preparation method involves dissolving and dispersing a hexavalent molybdenum source compound in a solvent, adding an inorganic acid catalyst and C1-C5 organic acid, and reacting at 40-150℃ for 0.5-10 h. Then, C6-C16 organic acid or C6-C16 ester is added to the reaction product from step (1), and the reaction is carried out at 160-320℃ for 2-22 h. The product from step (2) is cooled to 20-80℃, and nickel-containing inorganic material is added, reacting at 50-95℃ for 3-10 h, followed by a further increase in temperature to 100-180℃ for 1-8 h. The product obtained in step (3) is separated, the solvent phase is removed, the oil phase is washed with water, and light components are removed by vacuum distillation to obtain the hydrocracking molybdenum-nickel catalyst. This catalyst exhibits high conversion rate and high light oil yield in heavy oil hydrocracking reactions. However, this preparation method involves many steps, is complex, uses expensive raw materials, and requires washing the reaction products with water, which generates a large amount of wastewater and has poor environmental performance. Furthermore, the two metals are added at different times and steps during the synthesis process, and it is impossible to confirm whether the final synthesized product is a mixture of two organometallic compounds or a single organobimetallic compound.

[0005] US Patent 7842635 B2 discloses a method for preparing an oil-soluble bimetallic catalyst. This method involves reacting a molybdenum source compound with an organic carboxylic acid in a mixed gas stream of N2 and H2 to obtain an organomolybdenum compound; reacting another metal compound with the organic carboxylic acid to obtain its organometallic compound; and then mixing the two metals in a certain proportion to obtain a bimetallic organometallic mixture. However, this preparation method involves a gas-liquid-solid three-phase reaction, resulting in low conversion rates, high energy consumption, and the generation of a large amount of waste products. Summary of the Invention

[0006] The purpose of this application is to provide a method for preparing an unsupported multimetal 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 multimetal hydrogenation catalyst can be used for hydrogenation reactions of hydrocarbon-containing raw materials and has high oil solubility, dispersibility and hydrogenation activity.

[0007] To achieve the above objectives, this application provides a method for preparing an unsupported multimetal hydrogenation catalyst, comprising the following steps:

[0008] A method for preparing an unsupported multimetal hydrogenation catalyst includes the following steps:

[0009] 1) Mix the first metal source or its dispersion with the organic ligand compound;

[0010] 2) Allow the mixture obtained in step 1) to react at temperature T1 for time t1;

[0011] 3) Allow the material obtained in step 2) to react at temperature T2 for time t2;

[0012] 4) Optionally, a second metal source or its dispersion is added to the material obtained in step 3), and the resulting material is reacted at temperature T2 for time t3; and

[0013] 5) Collect the obtained liquid product.

[0014] The first and second metal sources are each independently selected from elemental metals, metal oxides, metal hydroxides, metal oxyacids, inorganic metal salts, or combinations thereof. The metals in the first and second metal sources may be the same or different from each other, and each is independently at least one of Group VB, Group VIB, Group VIII, and Group IB metals with hydrogenation properties.

[0015] The organic ligand compound is selected from C4-C20 organic carboxylic acids or their anhydrides.

[0016] The molar ratio of the organic ligand compound to the total amount of metal in the first and second metal sources is 1-10:1.

[0017] The temperature T1 is 50-150℃, and the time t1 is 5-180min.

[0018] The temperature T2 is 100-350℃, and the time t2 is 1-8h.

[0019] The time t3 is 1-8 hours.

[0020] The condition is that when only the first metal source is used or the second metal source is the same as the metal in the first metal source, the metal in the first metal source is at least two of the group VB metals, group VIB metals, group VIII metals and group IB metals that have hydrogenation properties.

[0021] On the other hand, an unsupported multimetal hydrogenation catalyst prepared by the method of this application is provided.

[0022] On the other hand, the application of the unsupported multimetal hydrogenation catalyst according to this application in the hydrogenation reaction of hydrocarbon feedstock is provided.

[0023] 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 multi-metal hydrogenation catalyst is used in the hydrogenation reaction of hydrocarbon-containing raw materials, it has high oil solubility, dispersibility and hydrogenation activity.

[0024] Other features and advantages of this application will be described in detail in the following detailed description section. Attached Figure Description

[0025] 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:

[0026] Figure 1 The IR spectrum of the Mo-Ni bimetallic catalyst prepared in Example 1 is shown.

[0027] Figure 2 The IR spectrum of the Mo-Co bimetallic catalyst prepared in Example 2 is shown; and

[0028] Figure 3 The IR spectrum of the Mo-Fe bimetallic catalyst prepared in Example 3 is shown. Detailed Implementation

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] As described above, in a first aspect, this application provides a method for preparing an unsupported multimetal hydrogenation catalyst, comprising the following steps:

[0035] 1) Mix the first metal source or its dispersion with the organic ligand compound;

[0036] 2) Allow the mixture obtained in step 1) to react at temperature T1 for time t1;

[0037] 3) Allow the material obtained in step 2) to react at temperature T2 for time t2;

[0038] 4) Optionally, a second metal source or its dispersion is added to the material obtained in step 3), and the resulting material is reacted at temperature T2 for time t3; and

[0039] 5) Collect the obtained liquid product.

[0040] The first and second metal sources are each independently selected from elemental metals, metal oxides, metal hydroxides, metal oxyacids, inorganic metal salts, or combinations thereof. The metals in the first and second metal sources may be the same or different from each other, and each is independently at least one of Group VB, Group VIB, Group VIII, and Group IB metals with hydrogenation properties.

[0041] The organic ligand compound is selected from C4-C20 organic carboxylic acids or their anhydrides.

[0042] The molar ratio of the organic ligand compound to the total amount of metal in the first and second metal sources is 1:1-10.

[0043] The temperature T1 is 50-150℃, preferably 80-120℃, and the time t1 is 5-180min, preferably 10-150min.

[0044] The temperature T2 is 100-350℃, preferably 160-260℃, and the time t2 is 1-8h, preferably 2-5h.

[0045] The time t3 is 1-8 hours, preferably 2-5 hours.

[0046] The condition is that when only the first metal source is used or the second metal source is the same as the metal in the first metal source, the metal in the first metal source is at least two of the group VB metals, group VIB metals, group VIII metals and group IB metals that have hydrogenation properties.

[0047] According to this application, there are no strict requirements on the pressure and reaction atmosphere used in steps 2), 3) and 4). For example, the reaction pressure can be atmospheric pressure, and the reaction atmosphere can be air, nitrogen or an inert atmosphere.

[0048] In a preferred embodiment, the mixture obtained in step 1) consists of the first metal source and the organic ligand compound; or consists of the first metal source, a dispersion medium for dispersing the first metal source, and the organic ligand compound.

[0049] According to this application, the first and second metal sources may each independently contain at least one Group VB, Group VIB, Group VIII, or Group IB metal with hydrogenation properties. When two or more of the metals are contained, the first and second metal sources may each be a single metal source containing the two or more metals, or a mixture of two or more metal sources each containing one or more of the metals.

[0050] In a preferred embodiment, when step 4) is used, at least some of the metals in the second metal source are different from the metals in the first metal source. For example, when the second metal source contains two or more metals, at least one of the metals is different from the metals contained in the first metal source. More preferably, the metals in the second metal source are different from the metals in the first metal source.

[0051] According to this application, the molar ratio of the first metal source and the second metal source can be any ratio, based on metal content. This application does not impose strict limitations on this. In a preferred embodiment, the ratio of the first metal source to the second metal source is 1:1-5.

[0052] In some specific embodiments, the method includes the following steps:

[0053] i) Disperse the first metal source into a dispersion medium to obtain a first metal source dispersion;

[0054] ii) Add an organic ligand compound to the dispersion obtained in step 1), heat to temperature T1, and react at temperature T1 for time t1.

[0055] iii) Heating the material obtained in step ii) to temperature T2 and reacting at temperature T2 for time t2; and

[0056] iv) After the reaction is complete, cool down and collect the resulting liquid product.

[0057] In some other embodiments, the method includes the following steps:

[0058] i) The first metal source is directly dispersed into the organic ligand compound;

[0059] ii) Heat the mixture obtained in step i) to temperature T1 and react at temperature T1 for time t1;

[0060] iii) Heating the material obtained in step ii) to temperature T2 and reacting at temperature T2 for time t2; and

[0061] iv) After the reaction is complete, cool down and collect the resulting liquid product.

[0062] In some other embodiments, the method includes the following steps:

[0063] a) Adding a first metal source or its dispersion to an organic ligand compound;

[0064] b) Heat the mixture obtained in step a) to temperature T1 and react at temperature T1 for time t1.

[0065] c) Heat the material obtained in step b) to temperature T2 and react at temperature T2 for time t2.

[0066] d) Add a second metal source to the material obtained in step c) and react at temperature T2 for time t3; and

[0067] e) After the reaction is complete, cool down and collect the resulting liquid product.

[0068] 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 are preferably selected from Mo, Ni, W, Fe, V and Co.

[0069] According to this application, the inorganic metal salt can be an inorganic acid salt of the metal, such as chloride, sulfide, sulfate, nitrate, carbonate, etc., or a metal oxyacid salt of the metal, such as ammonium metal oxyacid. In a preferred embodiment, the first and second metal sources are each independently selected from metal oxides, metal hydroxides, metal chlorides, metal sulfides, metal sulfates, metal nitrates, metal carbonates, metal oxyacids, metal oxyacid salts, or combinations thereof, for example, 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] In a preferred embodiment, the dispersion medium in the dispersion of the metal source 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.

[0077] In a preferred embodiment, the weight ratio of the dispersion medium to the first metal source dispersion and the weight ratio of the dispersion medium to the other metal sources in the second metal source dispersion are each independently 1-25:1, more preferably 2-8:1.

[0078] In a preferred embodiment, the molar ratio of the first metal source to the second metal source, calculated as metal, is 1:1-5.

[0079] The IR spectrum of the unsupported multimetal hydrogenation catalyst is in the range of 1350-1450 cm⁻¹. -1 and 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.

[0080] Secondly, this application provides a non-supported bimetallic hydrogenation catalyst, comprising a complex formed by a metal central atom or central ion and an organic ligand bonded together by coordination bonds. The metal is selected from two of Group VB, Group VIB, Group VIII, and Group IB metals, which possess 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 coordination bond with the metal central atom or central ion through an oxygen atom. The catalyst has the schematic composition shown in formula (I):

[0081] M 1 M 2 O a [R(COO) x ] b (I),

[0082] Where M 1 M 2 Represents a metal, 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 the metal to the total amount of metal, and b represents the molar ratio of the organic ligand to the total amount of metal, where:

[0083] M 1 and M 2 They are selected independently from one of the Group VB, Group VIB, Group VIII and Group IB metals that have hydrogenation properties;

[0084] R is a C3-C19 hydrocarbon group, preferably selected from C5-C11 normal alkyl, C5-C11 isoalkyl, C5-C12 cycloalkyl and C6-C12 aryl;

[0085] x is 1, 2 or 3, preferably 1 or 2;

[0086] a is a positive number from 0 to 5, preferably a positive number from 1 to 3; and

[0087] b is a positive number from 1 to 6, preferably a positive number from 2 to 5.

[0088] The infrared spectrum of the 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.

[0089] According to this application, the unsupported bimetallic hydrogenation catalyst consists only of the complex and contains no solid support component. However, if desired, the unsupported bimetallic hydrogenation catalyst of this application may also exist and be used in the form of a composition with a liquid component capable of dispersing the catalyst, such as an organic solvent and an organic ligand compound.

[0090] According to this application, depending on the metal used, the group VB, group VIB, group VIII and group IB metals with hydrogenation properties in the complexes of this application can be in the form of a central atom or a central ion or a central ion.

[0091] According to this application, the unsupported bimetallic hydrogenation catalyst can be a mixture of various different complexes, wherein the total amount of oxygen atoms and organic ligands in the catalyst composition relative to the total amount of metal (i.e., metal M) is... 1 and M 2 The molar ratios a and b of the total amount are calculated based on metal content and elemental composition analysis, and therefore can be non-integer. Furthermore, M in the composition... 1 and M 2 It only indicates which metals are present, but not the molar ratio between the metals.

[0092] In a preferred embodiment, at least a portion of the complex in the catalyst has the structure shown in formula (I-1):

[0093]

[0094] Where M 1 and M 2 The representative metals are selected independently from one of the Group VB, Group VIB, Group VIII and Group IB metals, which are capable of hydrogenation.

[0095] → represents a coordinate bond;

[0096] R is a C3-C19 hydrocarbon group, preferably selected from C5-C11 normal alkyl, C5-C11 isoalkyl, C5-C12 cycloalkyl and C6-C12 aryl;

[0097] x is the number of coordinating groups in the organic ligand, and it is either 1 or 2, preferably 1;

[0098] n represents the coordination number, which is an integer from 1 to 6, preferably an integer from 2 to 5;

[0099] y represents the connecting metal M 1 and metal M 2 The number of non-coordinated oxygen atoms, which is 0 or 1, preferably 1; and

[0100] z represents only with metal M 2 The number of connected non-coordinated oxygen atoms is an integer between 0 and 2, preferably 0 or 1.

[0101] In a preferred embodiment, the infrared spectrum of the 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 .

[0102] 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.

[0103] In some further preferred embodiments, the unsupported multimetal hydrogenation catalyst comprises the complex and optionally an unreacted organic ligand compound, and the unsupported multimetal hydrogenation catalyst has the illustrative composition shown in formula (II).

[0104] MO a [R(COO) x ] b (II),

[0105] Where M represents the metal, and R(COO) x represents the organic ligand and organic ligand compound (in formula (II), the H atom in the carboxyl group of the organic ligand compound is simplified and omitted), a represents the molar ratio of noncoordinately bonded oxygen atoms connected to metal M to metal M, and b represents the molar ratio of the total amount of organic ligand and organic ligand compound to metal M, wherein:

[0106] 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;

[0107] x is 1, 2 or 3, more preferably 1 or 2;

[0108] a is a positive number between 0 and 3, preferably between 1 and 3; and

[0109] b is a positive number from 1 to 6, preferably a positive number from 2 to 5.

[0110] In a preferred embodiment, the metal content in the unsupported multimetal hydrogenation catalyst is 5-35% based on the weight of the catalyst, preferably 8-30%, more preferably 10-25%, and particularly preferably 10-20%.

[0111] In some preferred embodiments, the method further includes adding an additional metal source or dispersion thereof to the material obtained in step 4) after step 4) and before step 5), and further reacting the material at temperature T2, wherein the type of metal source, the metal in the metal source, and the dispersion medium in the dispersion are selected as described above for the first and second metal sources, and will not be repeated here.

[0112] In some preferred embodiments, step 5) further includes adding at least one organic ligand compound and / or organic solvent to the resulting liquid product, wherein:

[0113] The organic ligand compound added in step 5) 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;

[0114] The organic solvent added in step 5) 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.

[0115] Preferably, based on the weight of the final product, the amount of organic ligand compound and organic solvent added in step 5) 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%.

[0116] In some further preferred embodiments, step 5) 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.

[0117] In a preferred embodiment, the metal content in the unsupported multimetal hydrogenation catalyst is 5-35% based on the weight of the catalyst, preferably 8-30%, more preferably 10-25%, and particularly preferably 10-20%, calculated by metal content and based on the weight of the catalyst.

[0118] In a third aspect, the use of the unsupported multimetal hydrogenation catalyst according to this application in the hydrogenation reaction of hydrocarbon feedstock is provided.

[0119] 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 multimetallic hydrogenation catalyst according to the present application to carry out a hydrogenation reaction.

[0120] 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.

[0121] 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 Based on the overall feed catalyst concentration (in metals) of 50-10000 μg / g.

[0122] Example

[0123] 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.

[0124] 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.

[0125] 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.

[0126] In the following examples, the positive ion ESI high-resolution mass spectra of the obtained catalyst were measured by a Bruker Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) under the following conditions: magnetic field strength 15T, electrospray ionization source, negative ion mode.

[0127] In the following examples, the IR 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. -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 .

[0128] Examples 1-7

[0129] 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 1-6 were completely dissolved, while unreacted metal compounds remained in the flask of Example 7. The liquid reaction products in the flasks of Examples 1-6 were poured out to obtain the target catalyst product; the product of Example 7 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.

[0130] The reaction materials, reaction conditions and experimental results used in Examples 1-7 are shown in Table 1.

[0131]

[0132]

[0133] As shown in Table 1, the metal content of the unsupported multimetal catalyst of this application can reach 23.9%, and the molar ratio of the total amount of organic ligands and organic ligand compounds in the catalyst to the metal is 1.7-4.3.

[0134] The elemental analysis results of the catalyst obtained in Example 2 are shown in Table 2. The catalyst composition (MoCo)O can be calculated from the data in Table 2. a (C4H 16 COO) b The values ​​of a and b in the equation are given, where b = 0.54 / (0.11+0.11) = 2.45 and a = (1.36-2.0×0.54) / 0.22 = 1.27.

[0135] Table 2. Elemental analysis results of the catalyst obtained in Example 2

[0136] element mass content / % Molar content / % Moles of the corresponding groups C 51.85 4.32 4.32 / 8＝0.54 H 8.64 8.64 8.64 / 16＝0.54 O 21.79 1.36 1.36 Mo 10.56 0.11 0.11 Co 6.38 0.11 0.11

[0137] The elemental analysis results of the catalyst obtained in Example 4 are shown in Table 3. The catalyst composition (MoCoV)O can be calculated from the data in Table 3. a (C6H 14 COO) b The values ​​of a and b in the equation are given, where b = 0.57 / (0.05+0.05+0.13) = 2.48 and a = (1.80-2.0×0.57) / (0.05+0.05+0.13) = 2.87.

[0138] Table 3. Elemental analysis results of the catalyst obtained in Example 4

[0139] element mass content / % Molar content / % Moles of the corresponding groups C 47.88 3.99 3.99 / 7＝0.57 H 7.98 7.98 7.98 / 14＝0.57 O 28.86 1.80 1.80 Mo 5.15 0.05 0.05 Co 7.37 0.13 0.13 V 2.76 0.05 0.05

[0140] The IR spectra of the catalysts obtained in Examples 1-3 are as follows: Figure 1-3 As shown, from Figure 1-3 It can be clearly seen that the catalysts in all embodiments are in the range of 700-1000 cm⁻¹ -1 1350-1450cm -1 and 1500-1610cm -1 It has a characteristic peak at the location.

[0141] like Figure 1-2 As shown, the catalysts in Examples 1-2 were respectively at 700-1000 cm⁻¹ -1 It exhibits characteristic MO vibration peaks 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 a given location (i.e., the difference in wavenumbers corresponding to the peak positions) is greater than 145 cm. -1 This indicates that the catalyst contains a complex with a monodentate complexing structure, and the corresponding structural formula is:

[0142]

[0143] Examples 8-9

[0144] The catalysts prepared in Examples 1 and 3 were applied to the hydrocracking reaction of the alkyl aromatic hydrocarbon dodecylpyrene, respectively. Decahydronaphthalene was used as the solvent, and 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 under the following conditions: initial hydrogen pressure 9MPa, reaction temperature 420℃, and reaction time 60min. The catalyst concentration (based on metal content) was 2500μg / g, with the total reactant weight as the baseline. The experimental results are shown in Table 4.

[0145] Table 4 Reaction results of Examples 8-9

[0146] project Example 8 Example 9 catalyst Catalyst of Example 1 Catalyst of Example 3 Dodecylpyrene test results Cracking conversion rate / % 100 100 Condensation rate / % 0 0 Hydrogen consumption / mmol 2.24 2.05

[0147] As shown in Table 4, the unsupported multimetal hydrogenation catalyst of this application achieved 100% cracking conversion and zero condensation rate of dodecylpyrene, indicating that the catalyst of this application has good coke suppression and cracking promotion activity.

[0148] Examples 10-12

[0149] Using 200g of vacuum residue A with an asphaltene content of 14%, a carbon residue value of 26.4%, and a heavy metal (Ni+V) content of 210μg / 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.

[0150] Comparative Example 1

[0151] The experiment was conducted according to Example 10, using a conventional supported catalyst (Ni-Mo supported catalyst for residue hydrotreating, Mo content 9.3% and Ni content 2.52%) instead of the catalyst prepared in Example 1. The experimental results are shown in Table 5.

[0152] Table 5. Reaction results of Examples 10-12 and Comparative Example 1

[0153]

[0154] As shown in Table 5, under the same reaction conditions, the unsupported multimetal hydrogenation catalyst of this application has a higher residue cracking rate, a lower condensation rate, and a higher distillate yield compared to conventional supported catalysts.

[0155] 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.

[0156] 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.

[0157] 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 multimetal hydrogenation catalyst, comprising the following steps: 1) Mix the first metal source or its dispersion with the organic ligand compound; 2) Allow the mixture obtained in step 1) to react at temperature T1 for time t1; 3) Allow the material obtained in step 2) to react at temperature T2 for time t2; 4) Optionally, a second metal source or its dispersion is added to the material obtained in step 3), and the resulting material is reacted at temperature T2 for time t3; and 5) Collect the obtained liquid product. The first and second metal sources are each independently selected from elemental metals, metal oxides, metal hydroxides, metal oxyacids, inorganic metal salts, or combinations thereof. The metals in the first and second metal sources may be the same or different from each other, and each is independently at least one of Group VB, Group VIB, Group VIII, and 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 total amount of metal in the first and second metal sources is 1-10:

1. The temperature T1 is 50-150℃, and the time t1 is 5-180min. The temperature T2 is 100-350℃, and the time t2 is 1-8h. The time t3 is 1-8 hours. The condition is that when only the first metal source is used, or when the second metal source is the same as the metal in the first metal source, the metal in the first metal source is at least two of the group VB, group VIB, group VIII, and group IB metals that have hydrogenation properties. The prepared unsupported multimetallic catalyst is composed of a complex formed by the coordination bonding of a metal central atom or central ion with an organic ligand, and the catalyst has the schematic characteristics shown in general formula (I). composition: M 1 M 2 O a [R(COO) x ] b (I), Where M 1 M 2 Represents a metal, 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 the metal to the total amount of metal, and b represents the molar ratio of the organic ligand to the total amount of metal, where: M 1 and M 2 They are selected independently from one of the Group VB, Group VIB, Group VIII and Group IB metals that have hydrogenation properties; R is a C3-C19 hydrocarbon group; x is 1, 2, or 3; a is a positive number between 0 and 5; and b is a positive number between 1 and 6. At least a portion of the complex in the catalyst has the structure shown in formula (I-1): Where M 1 M 2 The definitions of R and x are as described above; → represents a coordinate bond; 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; y represents the connecting metal M 1 and metal M 2 The number of non-coordinated oxygen atoms, and is 0 or 1; as well as z represents only with metal M 2 The number of connected, non-coordinated oxygen atoms, which is an integer between 0 and 2.

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 carbide ring or their anhydrides, C7-C20 aromatic carboxylic acids containing an aromatic ring or their anhydrides, or combinations thereof. The temperature T1 is 80-120℃, and the time t1 is 10-150min. The temperature T2 is 160-260℃, and the time t2 is 2-5h. The time t3 is 2-5 hours.

3. The method according to claim 1, wherein R is selected from C5-C11 normal alkyl, C5-C11 isoalkyl, C5-C12 cycloalkyl, and C6-C12 aryl; In general formula (I), x is 1 or 2; a is a positive number between 1 and 3; and b is a positive number between 2 and 5. In equation (I-1), x is 1; n is an integer between 2 and 5; y is 1; and z is 0 or 1.

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

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

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

7. The method according to claim 1 or 2, wherein the first and second metal sources are each independently 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 when a metal source dispersion is used, the dispersion medium in the dispersion 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 first metal source in the dispersion of the first metal source and the weight ratio of the dispersion medium to the second metal source in the dispersion of the second metal source are each independently 1-25:

1.

11. The method of claim 10, wherein the weight ratio of the dispersion medium to the first metal source in the dispersion of the first metal source and the weight ratio of the dispersion medium to the second metal source in the dispersion of the second metal source are each independently 2-8:

1.

12. The method according to claim 1 or 2, wherein the molar ratio of the first metal source and the second metal source, based on metal content, is 1:1-5.

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

14. The method according to claim 1 or 2, wherein the IR spectrum of the unsupported multimetal 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 IR spectrum of the unsupported multimetal 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 .

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

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

18. The method according to claim 1 or 2, comprising, after step 4) and before step 5), adding an additional metal source or dispersion thereof to the material obtained in step 4), and further reacting the material at temperature T2, wherein the additional 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, wherein the metal in the additional metal source is at least one of Group VB, Group VIB, Group VIII, and Group IB metals with hydrogenation properties, and the dispersion medium in the dispersion 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.

19. The method according to claim 1 or 2, wherein step 5) 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 5) is selected from C4-C20 organic carboxylic acids; The organic solvent added in step 5) 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 5) is such that the total amount of organic ligand compound, dispersion medium and organic solvent in the final product is 5-50%.

20. The method according to claim 19, wherein the organic ligand compound added in step 5) 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 5) 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 5) is such that the total amount of organic ligand compound, dispersion medium and organic solvent in the final product is 5-20%.

21. Use of the unsupported multimetal hydrogenation catalyst prepared by any one of claims 1-20 in the hydrogenation reaction of hydrocarbon feedstock, wherein the hydrocarbon feedstock is an unsaturated hydrocarbon compound or a mixture containing unsaturated hydrocarbon compounds.

22. The use according to claim 21, 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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