Unsupported bimetallic hydrogenation catalysts, their compositions and applications

Abstract

This application relates to an unsupported bimetallic hydrogenation catalyst, its composition, and its application. The catalyst is composed of a complex formed by coordination bonding between a metal central atom or central ion and an organic ligand. The catalyst has a schematic composition shown in general formula (I): M 1 M 2 O a [R(COO) x ] b (I), where M 1 M 2 Represents a metal, R(COO) x The catalyst 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 metal, and b represents the molar ratio of the organic ligand to the total metal. When used in the hydrogenation reaction of hydrocarbon feedstocks, this catalyst and its composition exhibit high oil-phase dispersibility, hydrogenation activity, and selectivity for the target product.

Description

Technical Field

[0001] This application relates to the technical field of hydrogenation catalysts, specifically to an unsupported bimetallic hydrogenation catalyst, its composition, 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. They consist of three components: a catalytically active component, a co-catalytically active component, and a support. The active and co-catalytically active components are primarily metals, while the support is typically alumina, silica, kaolin, molecular sieves, or other porous materials. To improve the properties of the metal active sites on the catalyst, making them more conducive to enhancing the catalyst's activity, selectivity, and stability, hydrogenation catalysts have evolved into bimetallic and multimetallic catalysts. For example, the widely used reforming catalysts fall into two main series: Pt-Re and Pt-Sn. Regarding the second component, Re or Sn, researchers currently believe that rhenium is preferred over Re. 4+ Existence, tin with Sn 2+ or Sn 4+ The presence of cofactors primarily involves their interaction with the support, altering its acidity. Mo-Ni and W-Ni hydrorefining catalysts are commonly used for distillate oil hydrorefining, while W-Mo-Ni catalysts are frequently used for vacuum distillate oil hydropretreatment. Non-precious metal hydrorefining catalysts such as Mo, W, and Ni often exist as sulfides, supported within the pores of the support. Regarding the role of cofactors, theories such as the intercalation model (Co or Ni intercalating into MoS2 or WS2), the synergistic model (Co existing as Co958), and the monolayer model (MoO3 or WO3 distributed in a monolayer on the support) explain the influence of cofactors on the structure of the main metal sulfide or the distribution of the main metal on the support.

[0003] Since existing bimetallic catalysts are all supported catalysts, their hydrogenation reactions in hydrocarbons are heterogeneous catalytic reactions, requiring seven steps: diffusion of feed molecules to the catalyst surface; diffusion of feed molecules into the catalyst channels; adsorption of feed molecules onto the catalyst active sites; surface catalytic reaction between feed molecules and catalyst activity; desorption of reaction products from the catalyst active site surface; diffusion of reaction products from the catalyst channels to the outside; and diffusion of reaction products from the catalyst surface into the liquid phase system. The diffusion step significantly affects the probability and efficiency of hydrogenation reactions in supported bimetallic catalysts, limiting their catalytic activity. Summary of the Invention

[0004] The purpose of this application is to provide a novel unsupported bimetallic hydrogenation catalyst, its composition, and its application. The catalyst contains an organometallic complex, which has high oil phase dispersibility and is a homogeneous catalytic reaction when catalyzing the hydrogenation of hydrocarbon compounds. This eliminates the diffusion step in heterogeneous catalytic reactions, thereby improving hydrogenation activity.

[0005] To achieve the above objectives, this application provides, on the one hand, a non-supported bimetallic hydrogenation catalyst, which 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 illustrative composition shown in general formula (I):

[0006] M 1 M 2 O a [R(COO) x ] b (I),

[0007] 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:

[0008] 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;

[0009] R is a C3-C19 hydrocarbon group;

[0010] x is 1, 2 or 3, preferably 1 or 2;

[0011] a is a positive number from 0 to 5, preferably a positive number from 1 to 3; and

[0012] b is a positive number from 1 to 6, preferably a positive number from 2 to 5.

[0013] 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.

[0014] On the other hand, this application provides a bimetallic hydrogenation catalyst composition comprising the aforementioned unsupported bimetallic hydrogenation catalyst and at least one organic ligand compound and / or organic solvent, wherein the organic ligand compound is selected from C4-C20 organic carboxylic acids, and the organic solvent is selected from aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohol solvents, ether solvents, ester solvents, ketone solvents, or combinations thereof.

[0015] On the other hand, a method for hydrogenating hydrocarbon feedstock is provided, including the step of contacting the hydrocarbon feedstock with a non-supported bimetallic hydrogenation catalyst or a bimetallic hydrogenation catalyst composition according to the present application to carry out a hydrogenation reaction.

[0016] When the unsupported bimetallic hydrogenation catalyst and its composition are used in the hydrogenation reaction of hydrocarbon feedstocks, the present application exhibits high oil phase dispersibility, stability, hydrogenation activity, and selectivity for the target product.

[0017] Other features and advantages of this application will be described in detail in the following detailed description section. Attached Figure Description

[0018] 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:

[0019] Figure 1 The infrared spectrum of the product obtained in Example 1 is shown;

[0020] Figure 2 The infrared spectrum of the product obtained in Example 2 is shown.

[0021] Figure 3 The infrared spectrum of the product obtained in Example 3 is shown;

[0022] Figure 4 The infrared spectrum of the product obtained in Example 4 is shown;

[0023] Figure 5 The infrared spectrum of the product obtained in Example 5 is shown; and

[0024] Figure 6 The infrared spectrum of the product obtained in Example 6 is shown; Detailed Implementation

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] As described above, in a first aspect, 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 via coordinate 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 coordinate bond with the metal central atom or central ion via an oxygen atom. The catalyst has the schematic composition shown in formula (I):

[0031] M 1 M 2 O a [R(COO) x ] b (I),

[0032] Where M 1 M 2 Represents a metal, R(COO) xRepresents 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:

[0033] 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;

[0034] R is a C3-C19 hydrocarbon group, preferably selected from C5-C11 normal alkyl, C5-C11 isoalkyl, C5-C12 cycloalkyl and C6-C12 aryl;

[0035] x is 1, 2 or 3, preferably 1 or 2;

[0036] a is a positive number from 0 to 5, preferably a positive number from 1 to 3; and

[0037] b is a positive number from 1 to 6, preferably a positive number from 2 to 5.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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 2It only indicates which metals are present, but not the molar ratio between the metals.

[0042] In a preferred embodiment, at least a portion of the complex in the catalyst has the structure shown in formula (I-1):

[0043]

[0044] 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.

[0045] → represents a coordinate bond;

[0046] R is a C3-C19 hydrocarbon group, preferably selected from C5-C11 normal alkyl, C5-C11 isoalkyl, C5-C12 cycloalkyl and C6-C12 aryl;

[0047] x is the number of coordinating groups in the organic ligand, and it is either 1 or 2, preferably 1;

[0048] n represents the coordination number, which is an integer from 1 to 6, preferably an integer from 2 to 5;

[0049] 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

[0050] 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.

[0051] 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 .

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] In a preferred embodiment, the organic ligand in the complex is derived from an organic carboxylic acid of C4-C20, preferably from one or more of the following: normal or isomeric alkyl carboxylic acids of C4-C20, cycloalkanic carboxylic acids containing a saturated carbide ring of C6-C20, and aromatic carboxylic acids containing an aromatic ring of C7-C20; more preferably from one or more of the following: normal or isomeric alkyl carboxylic acids of C6-C12, cycloalkanic carboxylic acids containing a saturated carbide ring of C6-C13, and aromatic carboxylic acids containing an aromatic ring of C7-C13; and even more preferably from one or more of the following: 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.

[0060] In a preferred embodiment, the metal content in the unsupported bimetallic 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 weight of the metal.

[0061] In a preferred embodiment, the unsupported bimetallic hydrogenation catalyst is obtained by directly reacting a Group VB metal, Group VIB metal, Group VIII metal, Group IB metal, its oxide, its hydroxide, its metal oxyacid, and / or its metal inorganic salt with hydrogenation properties with an organic ligand compound, wherein the organic ligand compound is selected from C4-C20 organic carboxylic acids, preferably 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, or combinations thereof.

[0062] 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.

[0063] 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, and ethylhexanoic acid.

[0064] 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.

[0065] 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.

[0066] In a further preferred embodiment, the organic ligand compound is selected from C6-C12 normal or isomeric alkyl carboxylic acids, C6-C13 cycloalkane carboxylic acids containing a saturated carbide ring, C7-C13 aromatic carboxylic acids containing an aromatic ring, or combinations thereof, and even more preferably selected 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.

[0067] In a second aspect, a method for preparing a non-supported bimetallic hydrogenation catalyst according to the present application is provided, comprising the step of reacting a metal source with an organic ligand compound, wherein the metal source is selected from elemental metals, metal oxides, metal hydroxides, metal oxyacids, metal inorganic salts, or combinations thereof, the metal in the metal source is selected from two of Group VB, Group VIB, Group VIII, and Group IB metals having hydrogenation properties, and the organic ligand compound is selected from C4-C20 organic carboxylic acids.

[0068] 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 molybdate or ammonium metavanadate.

[0069] 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.

[0070] In a preferred embodiment, the reaction temperature is 100-350℃, preferably 160-280℃, and the reaction time is 1-8h, preferably 2-6h.

[0071] According to this application, the reaction step does not have strict requirements on the reaction pressure and reaction atmosphere. For example, the reaction pressure can be atmospheric pressure, and the reaction atmosphere can be air, nitrogen, or an inert atmosphere.

[0072] According to this application, the reaction can be carried out under conditions of anhydrousness or in the presence of water (e.g., water in amounts of 0-10 times the weight of the organic ligand compound).

[0073] According to this application, the reaction can be carried out in the absence of other components (such as catalysts, alkaline pH adjusters, etc.) other than the metal source, organic ligand compound, and optional solvents (such as water and organic solvents such as toluene, ethanol, diesel, etc.).

[0074] In a preferred embodiment, the organic ligand compound is selected from C4-C20 normal or isomeric alkyl carboxylic acids, C6-C20 cycloalkanic carboxylic acids containing a saturated carbide ring, C7-C20 aromatic carboxylic acids containing an aromatic ring, or combinations thereof, preferably selected from C6-C12 normal or isomeric alkyl carboxylic acids, C6-C13 cycloalkanic carboxylic acids containing a saturated carbide ring, C7-C13 aromatic carboxylic acids containing an aromatic ring, or combinations thereof, more preferably selected from succinic acid, hexanoic acid, adipic acid, heptanoic acid, octanoic acid, nonanoic acid, ethylhexanoic acid, oleic acid, petroleum ether, salicylic acid, benzoic acid, or combinations thereof.

[0075] In a third aspect, this application provides a bimetallic hydrogenation catalyst composition comprising a non-supported bimetallic hydrogenation catalyst according to this application and at least one organic ligand compound and / or organic solvent, wherein the organic ligand compound is selected from C4-C20 organic carboxylic acids.

[0076] 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 a saturated carbide ring, C7-C20 aromatic carboxylic acids containing an aromatic ring, or combinations thereof, preferably selected from C6-C12 normal or isomeric alkyl carboxylic acids, C6-C13 cycloalkane carboxylic acids containing a saturated carbide ring, C7-C13 aromatic carboxylic acids containing an aromatic ring, or combinations thereof, more preferably selected 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.

[0077] This application does not impose strict limitations on the organic solvent, as long as it can disperse the unsupported bimetallic hydrogenation catalyst or be miscible with the unsupported bimetallic hydrogenation catalyst. For example, it can be 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.

[0078] In a preferred embodiment, based on the weight of the composition, the content of the unsupported bimetallic hydrogenation catalyst is 50-95%, preferably 80-95%; and the total content of the organic ligand compound and the organic solvent is 5-50%, preferably 5-20%.

[0079] In a preferred embodiment, the composition comprises at least one organic ligand compound, and the infrared spectrum of the composition is in the range of 700-1000 cm⁻¹. -1 1350-1450cm -1 1500-1100cm -1 and 1700-1750cm -1 It has characteristic peaks at the location, especially in the 700-1000 cm⁻¹ region. -1 1350-1450cm -1 and 1500-1610cm -1 The characteristic peak at position 1700-1750 cm⁻¹ is a characteristic peak of the coordination compound. -1 The characteristic peak at the position is a characteristic peak of the organic ligand compound.

[0080] In a further preferred embodiment, the hydrogenation catalyst composition comprises the unsupported bimetallic hydrogenation catalyst and at least one organic ligand compound. In this case, the composition of the hydrogenation catalyst composition can also be schematically represented by formula (I), M 1 M 2 O a [R(COO) x ] b , to represent, where b represents the total amount of organic ligands and organic ligand compounds relative to metal M. 1 and M 2 In addition to the total molar ratio, M 1 M 2 The definitions of a, R, and x are as described above.

[0081] In some embodiments, the hydrogenation catalyst composition may also include other components that improve oil solubility, storage stability and antioxidant properties, such as organic compounds with reducing functions, such as formic acid, oxalic acid, formaldehyde, ethylenediamine, oleylamine, etc. The content of the other components may be 0-80% based on the weight of the composition, preferably 0-50%.

[0082] In a fourth aspect, the application of a non-supported bimetallic hydrogenation catalyst or hydrogenation catalyst composition according to the present application in the hydrogenation reaction of hydrocarbon feedstock is provided.

[0083] In a fifth aspect, a method for hydrogenating a hydrocarbon feedstock is provided, comprising the step of contacting the hydrocarbon feedstock with a non-supported bimetallic hydrogenation catalyst or a hydrogenation catalyst composition according to the present application to carry out a hydrogenation reaction.

[0084] 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.

[0085] 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.

[0086] Example

[0087] 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.

[0088] In the following examples, the metal content of the obtained products was determined using an inductively coupled plasma optical emission spectrometer (ICP-OES) on a SPECTRO ARCOS SOP instrument. The measurement conditions were a sealed optical chamber filled with argon gas, vertical observation, and a wavelength range of 130-770 nm.

[0089] In the following examples, the elemental composition of the obtained products was determined as follows: the contents of elements C and H were determined by an Italian Cara Erba EA1110 elemental analyzer using the SH0656 method; the contents of element S were determined by energy dispersive X-ray fluorescence spectroscopy using the GB17040 method; and the contents of element O were determined by the O-content method.

[0090] In the following examples, the infrared spectra of the obtained products were measured using a Thermo Fisher NICOLET IS50 spectrometer, with measurement conditions of scanning wavelengths from 400 to 4000 enm. -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 .

[0091] Examples 1-6

[0092] 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 1-5 were completely dissolved, while unreacted metal compounds remained in the flask of Example 6. The liquid reaction products in the flasks of Examples 1-5 were poured out to obtain the target product; the product of Example 6 was filtered to remove the unreacted metal compounds, and the resulting liquid product was the target product. The metal content of the obtained product was determined by inductively coupled plasma optical emission spectrometry (ICP-OES), and the elemental composition of the obtained product was measured using appropriate methods. The composition of the product was obtained based on the measured metal content and elemental composition results. The reaction raw materials, reaction conditions, and experimental results used in Examples 1-6 are shown in Table 1.

[0093]

[0094] As shown in Table 1, the metal content of the non-supported bimetallic catalyst or bimetallic hydrogenation catalyst composition of this application can reach 9.17-33.3%, and the molar ratio of organic ligands to the total metal in the catalyst composition or the molar ratio of organic ligands to the total organic ligand compound in the catalyst composition to the total metal is 2.0-4.27.

[0095] The elemental analysis results of the product obtained in Example 1 are shown in Table 2. The product composition (MoNi)O calculated from the data in Table 2 is...a (i-C7H 16 COO) b The values ​​of a and b in the equation are given, where b = 0.54 / (0.10+0.10) = 2.70 and a = (1.26-2.0×0.54) / 0.20 = 0.9.

[0096] Table 2 Elemental analysis results of the products obtained in Example 1

[0097] element mass content / % Molar content / % Moles of the corresponding groups C 51.84 4.32 4.32 / 8＝0.54 H 8.74 8.74 8.74 / 16＝0.54 O 20.23 1.26 1.26 Mo 9.94 0.10 0.10 Ni 6.01 0.10 0.10

[0098] The elemental analysis results of the product obtained in Example 2 are shown in Table 3. The product composition (MoCo)O calculated from the data in Table 3 is shown in Table 3. a (C7H 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.

[0099] Table 3. Elemental analysis results of the products obtained in Example 2

[0100] 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

[0101] The infrared spectra of the products obtained in Examples 1-6 were measured using a Thermo Fisher NICOLET IS50 spectrometer, and the results are as follows: Figure 1 As shown. From Figure 1 It can be clearly seen that the products in all embodiments are between 700-1000cm -1 1350-1450cm -1 and 1500-1610cm -1 It has a characteristic peak at the location.

[0102] The products in Examples 1-6 were respectively 700-1000cm -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 A characteristic peak at the location is 1500-1610 cm⁻¹ -1 The distance between the peak positions of a characteristic peak at a given location (i.e., the difference in wavenumbers corresponding to the peak positions) is greater than 145 cm. -1 This indicates that at least some of the complexes in the product have a bimetallic single-tooth mating structure, and the structural formula of the corresponding complex is:

[0103]

[0104] Examples 7-8

[0105] The products prepared in Examples 1 and 4 were used as catalysts in the hydrogenation reaction of the aromatic hydrocarbon phenanthrene, with 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 420℃, and a reaction time of 60min. The catalyst concentration (based on the weight of the total reactants) was 2500μg / g (as metal). The experimental results are shown in Table 4.

[0106] Comparative Example 1

[0107] The experiment was conducted according to Example 7, except that a conventional supported catalyst (Ni-Mo supported catalyst for residue hydrotreating, Mo content 9.3% and Ni content 2.52%) was used instead of the product prepared in Example 1, with the metal content replaced by an equal amount. The experimental results are shown in Table 4.

[0108] Table 4 shows the reaction results of Examples 7-8 and Comparative Example 1.

[0109] project Example 7 Example 8 Comparative Example 1 catalyst Product of Example 1 Product of Example 4 Ni-Mo supported catalyst Test results Fibre conversion rate / % 56.98 49.56 28.48 Product distribution / % Dihydrophenanthrene 23.00 23.12 23.23 Tetrahydrophenanthrene 19.05 14.69 5.25 Octahydrophenanthrene 14.93 11.75 0 Change in the number of hydrogenated moles / % +98.10 +72.15 benchmark

[0110] As shown in Table 4, compared with the supported catalyst, the unsupported bimetallic catalyst of this application has a higher phenanthrene conversion and a higher yield of deep hydrogenation products; compared with the supported catalyst, the molar number of phenanthrene hydrogenation increases by 72-98%.

[0111] Examples 9-10

[0112] The product prepared in Example 1 was combined with an organic ligand compound (ethylhexanoic acid) at a mass ratio of 95:5 to form a composition. This composition and the product prepared in Example 6 were used as catalysts 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 under the following conditions: initial hydrogen pressure 9MPa, reaction temperature 420℃, and reaction time 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 5.

[0113] Table 5 Reaction results of Examples 9-10

[0114]

[0115] As shown in Table 5, the unsupported bimetallic catalyst and its composition of this application can achieve 100% cracking conversion and zero condensation rate of dodecylpyrene. Compared with the product of Example 6, the catalyst composition with further added organic ligand compounds has higher hydrogen consumption, indicating that the catalyst composition of this application has higher catalytic activity than the catalyst itself and higher hydrogen consumption under the same conditions.

[0116] Examples 11-13 and Comparative Example 2

[0117] 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 6. The experimental results are shown in Table 6.

[0118] Table 6. Reaction results of Examples 11-13 and Comparative Example 2.

[0119]

[0120]

[0121] As shown in Table 6, under the same reaction conditions, the unsupported bimetallic hydrogenation catalyst and its composition of this application have higher residue cracking rate, lower condensation rate and higher distillate oil yield compared with conventional supported catalysts.

[0122] 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.

[0123] 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.

[0124] 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 non-supported bimetallic hydrogenation catalyst, comprising a complex formed by coordination bonding of a metal central atom or central ion with an organic ligand, wherein the catalyst has the illustrative 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. 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. 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 unsupported bimetallic hydrogenation catalyst 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.

3. The unsupported bimetallic hydrogenation catalyst according to claim 1 or 2, wherein 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 .

4. The unsupported bimetallic hydrogenation catalyst 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.

5. The unsupported bimetallic hydrogenation catalyst according to claim 1 or 2, wherein M 1 and M 2 Selected from Mo, Ni, W, Fe, V or Co.

6. The unsupported bimetallic hydrogenation catalyst according to claim 1, wherein the organic ligand is derived from C4-C20 organic carboxylic acids.

7. The unsupported bimetallic hydrogenation catalyst according to claim 1, wherein the organic ligand is derived from one or more of succinic acid, hexanoic acid, adipic acid, heptanoic acid, octanoic acid, nonanoic acid, ethylhexanoic acid, oleic acid, salicylic acid, benzoic acid and phenylacetic acid.

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

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

10. The unsupported bimetallic hydrogenation catalyst according to claim 1, which is obtained by directly reacting a Group VB metal, Group VIB metal, Group VIII metal, Group IB metal, its oxide, its hydroxide, its metal oxyacid and / or its metal inorganic salt with hydrogenation properties with an organic ligand compound, wherein the organic ligand compound is selected from C4-C20 organic carboxylic acids.

11. The unsupported bimetallic hydrogenation catalyst according to claim 10, wherein the organic ligand compound 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.

12. A bimetallic hydrogenation catalyst composition comprising a non-supported bimetallic hydrogenation catalyst according to any one of claims 1-11 and at least one organic ligand compound and / or organic solvent, wherein: The organic ligand compound is selected from C4-C20 organic carboxylic acids; The organic solvent is selected from aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohol solvents, ether solvents, ester solvents, ketone solvents, or combinations thereof.

13. The composition according to claim 12, wherein the organic ligand compound 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 is selected from toluene, ethanol, or a combination thereof.

14. The composition according to claim 12 or 13, wherein the composition comprises at least one of the said organic ligand compounds, and the infrared spectrum of the composition 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 composition according to claim 12 or 13, wherein, Based on the weight of the composition, the content of the unsupported bimetallic hydrogenation catalyst is 50-95%; the total content of the organic ligand compound and the organic solvent is 5-50%.

16. The composition according to claim 12 or 13, wherein, Based on the weight of the composition, the content of the unsupported bimetallic hydrogenation catalyst is 80-95%; the total content of the organic ligand compound and the organic solvent is 5-20%.

17. A method for hydrogenating a hydrocarbon feedstock, comprising the step of contacting the hydrocarbon feedstock with any one of the unsupported bimetallic hydrogenation catalysts of claims 1-11 or any one of the bimetallic hydrogenation catalyst compositions of claims 12-16 to carry out a hydrogenation reaction, wherein the hydrocarbon feedstock is an unsaturated hydrocarbon compound or a mixture containing unsaturated hydrocarbon compounds.

18. The method of claim 17, 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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