Unsupported hydrogenation catalysts, their compositions and applications

Abstract

This application relates to an unsupported hydrogenation catalyst, its composition, and its uses. The unsupported hydrogenation catalyst comprises a complex formed by a metal central atom or central ion and an organic ligand bonded together via coordination bonds. The metal is selected from Group VB, Group VIB, Group VIII, Group IB metals, or various combinations thereof, all possessing hydrogenation properties. The organic ligand comprises a hydrocarbon moiety and a coordinating group moiety, and forms a coordination bond with the metal central atom or central ion via an oxygen atom. When used to catalyze the hydrogenation reaction of hydrocarbon feedstocks, this unsupported hydrogenation catalyst and its composition exhibit high oil-phase dispersibility and hydrogenation activity.

Description

Technical Field

[0001] This application relates to the technical field of hydrogenation catalysts, specifically to an unsupported hydrogenation catalyst, its composition, and its use. Background Technology

[0002] Currently, supported catalysts are the earliest studied, most widely used, and most extensive hydrogenation catalysts in the processing of hydrocarbon compounds. Supported catalysts consist of 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 aluminosilicate materials or porous materials such as alumina, silica, kaolin, or molecular sieves. For example, in a bimetallic reforming catalyst, Pt is the active component, Re or Sn is the co-catalytic component, and Al₂O₃ is the support. Research shows that the support is a crucial component of supported catalysts and one of the important factors affecting catalyst performance. In the hydrotreating process of oil products, in order to meet the requirements of the process and reaction for catalyst fluidization performance, mechanical strength, etc., the support acts as the skeleton of the active components, thus processing catalysts with shapes, particle sizes, and mechanical strengths that meet the requirements of the hydrotreating process. Secondly, since the specific surface area of ​​the active centers is relatively small, while the support has a large specific surface area, in order to improve the utilization rate of the active components, many researchers have uniformly dispersed the active components on the surface of the support with a large specific surface area, which can significantly increase the surface area per unit mass of active components and give full play to the role of active components. Thirdly, there is an interaction between the support and the active components, which can affect the geometry and catalytic activity of the active components and form new active structures, thereby generating species spillover, etc. Therefore, in recent years, the study of the interaction between metal components and the support has become a hot topic in the research and development of hydrotreating catalysts for distillate oils or heavy oils, in order to improve the catalytic effect of catalysts by modulating the influencing factors.

[0003] 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: 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 liquid phase; and diffusion of reaction products from the catalyst surface into the liquid phase. The diffusion step is essential for supported catalysts catalyzing hydrocarbon compounds or mixtures, influencing the probability and efficiency of the catalytic reaction. Therefore, many researchers focus on modifying the performance of the support and the interaction between the support and the active metal to improve the accessibility of feed molecules to the active components of the catalyst, and to develop hydrogenation catalysts that meet reaction requirements or improve the yield and selectivity of target products.

[0004] International application publication WO200528106A1 discloses an alumina support with a large pore volume, a large specific surface area and a large number of mesopores. After loading active metals Mo, W, Ni and Co onto it, it can significantly improve the cracking reaction of heavy hydrocarbons into light hydrocarbons.

[0005] Chinese patent application CN101632938A discloses a high-silica β-zeolite synthesized efficiently by plate-like micelle method and a modified Y-type zeolite as an acidic component and support. The β-zeolite is modified and supported by Group IA metals to obtain a hydrocracking catalyst. This catalyst is used in heavy oil hydrocracking process and exhibits high hydrocracking activity and selectivity for middle distillate oil.

[0006] Since supported catalysts and hydrocarbon feedstocks are two-phase, their catalytic reaction always involves seven steps, which limits the catalyst's reaction performance. Summary of the Invention

[0007] The purpose of this application is to provide an unsupported hydrogenation catalyst, its composition, and its use. This catalyst has high oil phase dispersibility and its hydrogenation reaction of hydrocarbon compounds is a homogeneous catalytic reaction, eliminating the diffusion step of heterogeneous catalytic reactions, thereby improving hydrogenation activity.

[0008] To achieve the above objectives, this application provides, on the one hand, a non-supported hydrogenation catalyst, comprising a complex formed by a metal central atom or central ion and an organic ligand bonded together via coordination bonds. The metal is selected from Group VB, Group VIB, Group VIII, Group IB metals, or various combinations thereof, all possessing 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 via an oxygen atom. 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.

[0009] On the other hand, this application provides a hydrogenation catalyst composition comprising a non-supported 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, 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.

[0010] Furthermore, the application of the unsupported hydrogenation catalyst or hydrogenation catalyst composition according to this application in the hydrogenation reaction of hydrocarbon feedstock is provided.

[0011] The unsupported hydrogenation catalyst and its composition of this application exhibit high oil phase dispersibility and hydrogenation activity when used in the hydrogenation reaction of hydrocarbon feedstocks.

[0012] Other features and advantages of this application will be described in detail in the following detailed description section. Attached Figure Description

[0013] 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:

[0014] Figure 1 The positive ion ESI high-resolution mass spectra of the catalyst obtained in Example 3 are shown.

[0015] Figure 2 The infrared spectrum of the catalyst obtained in Example 1 is shown;

[0016] Figure 3 The infrared spectrum of the catalyst obtained in Example 2 is shown; and

[0017] Figure 4 Infrared spectra of the catalysts obtained in Examples 3-5 are shown. Detailed Implementation

[0018] 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.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] As described above, in a first aspect, this application provides a non-supported hydrogenation catalyst, which is composed of 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 Group VB, Group VIB, Group VIII, Group IB metals, or various combinations thereof, all possessing hydrogenation properties. The organic ligand comprises a hydrocarbon moiety and a coordinating group moiety, wherein the coordinating group is composed of carbon and oxygen atoms, and forms a coordination bond with the metal central atom or central ion through the oxygen atom. 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.

[0024] According to this application, the unsupported hydrogenation catalyst consists only of the complex and contains no solid support component. However, as needed, the unsupported 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.

[0025] 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.

[0026] In a preferred embodiment, the coordinating group may be a -C(=O)-O group.

[0027] In a preferred embodiment, the catalyst has the illustrative composition shown in formula (I):

[0028] MO a [R(COO) x ] b (I),

[0029] Where M represents the metal, and R(COO) x Let R represent the organic ligand, COO represent the coordinating group in the organic ligand, x represent the number of coordinating groups in the organic ligand, a represent the molar ratio of noncoordinated oxygen atoms bonded to metal M to metal M, and b represent the molar ratio of the organic ligand to metal M, wherein:

[0030] 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;

[0031] x is the number of coordinating groups in the organic ligand, and is 1, 2 or 3, preferably 1 or 2;

[0032] a is a positive number between 0 and 3, preferably a positive number between 1 and 3; and

[0033] b is a positive number from 1 to 6, preferably a positive number from 2 to 5.

[0034] According to this application, the unsupported hydrogenation catalyst can be a mixture of various complexes. The molar ratios a and b of oxygen atoms and organic ligands to the metal M in the catalyst composition are calculated values ​​based on metal content and elemental composition analysis, and therefore can be non-integers. When M is a single metal, the molar ratios a and b are relative to that metal; when M is a combination of two or more metals, the molar ratios a and b are relative to the total amount of all metals. Furthermore, the metal M portion (such as MoNi, MoCoV, etc.) in the catalyst composition only indicates which metals are present and does not indicate the molar ratio between the metals.

[0035] In some further preferred embodiments, at least a portion of the complex in the catalyst has the structure shown in formula (I-1):

[0036]

[0037] M1 represents a metal, and is selected from one of the Group VB, Group VIB, Group VIII and Group IB metals that have hydrogenation properties;

[0038] → represents a coordinate bond;

[0039] R represents a C3-C19 hydrocarbon group, preferably selected from C5-C11 normal alkyl, C5-C11 isoalkyl, C5-C12 cycloalkyl and C6-C12 aryl;

[0040] x represents the number of coordinating groups in the organic ligand, and is 1, 2 or 3, preferably 1 or 2;

[0041] n represents the coordination number, which is an integer from 1 to 6, preferably an integer from 2 to 5; and

[0042] y represents the number of non-coordinated oxygen atoms connected to metal M1, and is an integer from 0 to 3, preferably an integer from 1 to 3.

[0043] In a further 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 less than 145 cm. -1 .

[0044] In some further preferred embodiments, at least a portion of the complex in the catalyst has the structure shown in formula (I-2):

[0045]

[0046] M2 represents a metal, and is selected from at least two of the group VB, group VIB, group VIII and group IB metals that have hydrogenation properties;

[0047] → represents a coordinate bond;

[0048] R represents a C3-C19 hydrocarbon group, preferably selected from C5-C11 normal alkyl, C5-C11 isoalkyl, C5-C12 cycloalkyl and C6-C12 aryl;

[0049] x represents the number of coordinating groups in the organic ligand, and is 1 or 2, preferably 1;

[0050] n represents the coordination number, which is an integer from 1 to 6, preferably an integer from 2 to 5;

[0051] z represents the number of non-coordinated oxygen atoms connected to metal M2, and is an integer from 0 to 3, preferably an integer from 1 to 3.

[0052] According to this application, the non-coordinate bonded oxygen atom connected to metal M2 in formula (I-2) includes oxygen atoms that are only connected to one metal atom / ion in the complex molecule (such as oxygen atoms that form M=O bonds), and also oxygen atoms that are connected between two metal atoms / ions in the complex molecule (such as oxygen atoms that form MOM′ bonds).

[0053] In a further 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 .

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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, isoundecyl, and isoundecyl.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] In a preferred embodiment, the metal content in the unsupported 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.

[0063] In a preferred embodiment, the unsupported hydrogenation catalyst is obtained by directly reacting a metal, its oxide, its hydroxide, its metal oxyacid, and / or its metal inorganic salt selected from group VB metals, group VIB metals, group VIII metals, group IB metals, or various combinations thereof, with an organic ligand compound, wherein the organic ligand compound is selected from C4-C20 organic carboxylic acids, preferably from C4-C20 normal or isomeric alkyl carboxylic acids, C6-C20 cycloalkane carboxylic acids containing a saturated carbocyclic ring, C7-C20 aromatic carboxylic acids containing an aromatic ring, or combinations thereof.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] In a second aspect, a method for preparing an unsupported hydrogenation catalyst according to the present application is provided, comprising the step of reacting a metal, its oxide, its hydroxide, its metal oxyacid, and / or its metal inorganic salt selected from group VB metals, group VIB metals, group VIII metals, group IB metals, or various combinations thereof, with an organic ligand compound, wherein the organic ligand compound is selected from C4-C20 organic carboxylic acids.

[0070] 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.

[0071] 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.

[0072] In a preferred embodiment, the reaction temperature is 100-350℃, preferably 160-280℃, and the reaction time is 1-8h, preferably 2-6h.

[0073] 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.

[0074] 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).

[0075] According to this application, the reaction can be carried out in the absence of any other components (such as catalysts, alkaline pH adjusters, etc.) other than the metal with hydrogenation properties, its oxides, its hydroxides and / or its metal inorganic salts, organic ligand compounds and optional solvents (such as water and organic solvents such as toluene, ethanol, diesel, etc.).

[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] In a third aspect, this application provides a hydrogenation catalyst composition comprising an unsupported 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.

[0078] 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.

[0079] This application does not impose strict limitations on the organic solvent, as long as it can disperse or be miscible with the unsupported 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.

[0080] In a preferred embodiment, based on the weight of the composition, the content of the unsupported 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%.

[0081] 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 1500-1610cm -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 this location is characteristic of organometallic complexes, 1700-1750 cm⁻¹. -1 The characteristic peak at the location is the characteristic peak of the organic ligand compound.

[0082] In a further preferred embodiment, the hydrogenation catalyst composition comprises the unsupported 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), MO a [R(COO) x ] b , where b represents the molar ratio of the total amount of organic ligands and organic ligand compounds to metal M, and the definitions of M, a, R and x are as described above.

[0083] In some embodiments, the hydrogenation catalyst composition may further contain other components for improving oil solubility, storage stability and antioxidant properties, such as organic compounds with reduction stabilizing 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%.

[0084] In a fourth aspect, the use of an unsupported hydrogenation catalyst or hydrogenation catalyst composition according to the present application in a hydrogenation reaction of a hydrocarbon feedstock is provided.

[0085] In a fifth aspect, a method for hydrogenating a hydrocarbon feedstock is provided, comprising the step of contacting the hydrocarbon feedstock with an unsupported hydrogenation catalyst or a hydrogenation catalyst composition according to the present application to carry out a hydrogenation reaction.

[0086] 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.

[0087] In a preferred embodiment, the conditions for the hydrogenation reaction include a reaction temperature of 380-430°C, an initial hydrogen pressure of 5-20 MPa, and a fresh feed liquid hourly space velocity of 0.05-1.0 h⁻¹. -1 The catalyst concentration (in metals) relative to the total feed is 50-10000 μg / g.

[0088] Example

[0089] 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.

[0090] 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.

[0091] 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.

[0092] In the following examples, the positive ion ESI high-resolution mass spectra of the obtained products were measured using a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) from Bruker. The measurement conditions were: magnetic field strength 15T, electrospray ionization source, negative ion mode.

[0093] 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 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 .

[0094] Examples 1-7

[0095] 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 flasks of Examples 6-7. The liquid reaction products in the flasks of Examples 1-5 were poured out to obtain the target product; the products of Examples 6-7 were filtered to remove the unreacted metal compounds, and the resulting liquid product was the target product. The metal content of the obtained products was determined by inductively coupled plasma optical emission spectrometry (ICP-OES), and the elemental composition of the obtained products was measured using appropriate methods. The composition of the products was obtained based on the measured metal content and elemental composition results. The reaction raw materials, reaction conditions, and experimental results used in Examples 1-7 are shown in Table 1.

[0096]

[0097]

[0098] As shown in Table 1, the metal content of the unsupported hydrogenation catalyst or hydrogenation catalyst composition of this application can reach 12.75-33.3%, and the molar ratio of organic ligands to metals in the catalyst composition or the molar ratio of organic ligands and the total amount of organic ligand compounds to metals in the catalyst composition is 2.0-3.56.

[0099] The positive ion ESI high-resolution mass spectrometry spectrum of the product obtained in Example 3 was determined by FT-ICR MS analysis to characterize the molecular weight distribution of the ethylhexanoate molybdenum nickel complex in the prepared product. The results are as follows: Figure 1 As shown. Molecular weight fitting reveals that the product obtained in Example 3 contains a molybdenum nickel ethylhexanoate complex (MoNi)O3(i-C7H) with a coordination number of 2. 16 COO)2 also contains the molybdenum nickel ethylhexanoate complex (MoNi)O3(i-C7H) with a coordination number of 4. 16 COO)4.

[0100] The infrared spectra of the products obtained in Examples 1-5 are as follows: Figure 2-4 As shown. From Figure 2-4 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.

[0101] like Figure 2 As shown, the products of Example 1 are respectively 700-1000cm -1 It exhibits characteristic peaks of M-O and M=O vibrations at the location, and at 1350-1450 cm⁻¹-1 and 1500-1610cm -1 The position shows characteristic peaks of -C(=O)-O groups coordinated with metals, and the peaks are located at 1350-1450 cm⁻¹. -1 The characteristic peak at the location is 1500-1610 cm⁻¹ -1 The distance between the peaks of the characteristic peaks at the location (i.e., the difference in wavenumbers corresponding to the peak positions) is less than 145 cm. -1 This indicates that the product contains a complex with a single-metal double-tooth mating structure, and the corresponding structural formula is:

[0102]

[0103] like Figure 4 As shown, the catalysts in Examples 3-5 were at 700-1000 cm⁻¹ -1 The location exhibits characteristic vibrational peaks of MO and M=O, at 1350-1450 cm⁻¹. -1 and 1500-1610cm -1 The position shows characteristic peaks of -C(=O)-O groups coordinated with metals, and the peaks are located at 1350-1450 cm⁻¹. -1 The characteristic peak at the location is 1500-1610 cm⁻¹ -1 The distance between the peaks of the characteristic peaks at the location is greater than 145cm. -1 This indicates that the product contains a complex with a bimetallic or multimetallic single-tooth mating structure, and the corresponding structural formula is:

[0104]

[0105] like Figure 3 As shown, the catalyst obtained in Example 3 has a viscosity of 1350-1450 cm⁻¹. -1 and 1500-1610cm -1 The peaks at position 1500-1610 cm⁻¹ are characteristic of the coordination between the -C(=O)-O group and the metal. -1 There are two characteristic peaks at this location, one of which is at 1350-1450 cm⁻¹. -1 The difference between the characteristic peaks at different locations is less than 145 cm⁻¹. -1 Another one is 1350-1450cm -1 The difference between the characteristic peaks at different locations is greater than 145 cm⁻¹. -1 This indicates that the catalyst contains both complexes with a bidentate structure and complexes with a monodentate structure, and the corresponding structural formulas are shown above.

[0106] Examples 8-9

[0107] The products prepared in Examples 1 and 5 were used as catalysts in the hydrogenation reaction of the aromatic hydrocarbon pyrene, 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 180min. The catalyst concentration (based on the weight of the total reactants) was 2500μg / g (calculated as metal). The experimental results are shown in Table 2.

[0108] Comparative Example 1

[0109] The experiment was conducted according to Example 8, 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 2.

[0110] Table 2 shows the reaction results of Examples 8-9 and Comparative Example 1.

[0111]

[0112] As shown in Table 2, compared with the supported catalyst, the unsupported hydrogenation catalyst and the hydrogenation catalyst composition of this application have higher pyrene conversion and deep hydrogenation product yield, as well as higher hydrogen consumption, indicating that the catalyst of this application has higher catalytic activity.

[0113] Examples 10-12

[0114] The product prepared in Example 1 was formulated into a composition with an organic ligand compound (ethylhexanoic acid) at a mass ratio of 95:5. This composition, the product prepared in Example 3, 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 9 MPa, reaction temperature 420℃, and reaction time 60 min. The catalyst concentration (based on the weight of the total reactants) was 2500 μg / g (calculated as metal). The experimental results are shown in Table 3.

[0115] Table 3 Reaction results of Examples 10-12

[0116]

[0117] As shown in Table 3, the unsupported hydrogenation catalyst and its composition of this application both achieved a cracking conversion of >97% for dodecylpyrene and zero condensation rate. Compared with the unsupported hydrogenation catalyst product of Example 6, the catalyst composition containing or further adding organic ligand compounds has a higher dodecylpyrene conversion and hydrogen consumption, indicating that the catalyst composition of this application has better coke suppression and cracking promotion activity than the catalyst itself.

[0118] Examples 13-15 and Comparative Example 2

[0119] 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 4. The experimental results are shown in Table 4.

[0120] Table 4. Reaction results of Examples 13-15 and Comparative Example 2

[0121]

[0122] As shown in Table 4, under the same reaction conditions, the unsupported 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.

[0123] 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.

[0124] 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.

[0125] 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 hydrogenation catalyst, comprising a complex formed by a metal central atom or central ion and an organic ligand bonded together via coordinate bonds, wherein the metal is selected from Group VB, Group VIB, Group VIII, Group IB metals, or various combinations thereof, and 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, and 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. The catalyst described herein has the schematic composition shown in formula (I): MO a [R(COO) x ] b (I), Where M represents the metal, and R(COO) x Let R represent the organic ligand, COO represent the coordinating group in the organic ligand, x represent the number of coordinating groups in the organic ligand, a represent the molar ratio of noncoordinated oxygen atoms bonded to metal M to metal M, and b represent the molar ratio of the organic ligand to metal M, wherein: R is a C3-C19 hydrocarbon group; x is 1, 2, or 3; a is a positive number between 0 and 3; 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): M1 represents a metal, and is selected from one of the Group VB, Group VIB, Group VIII and Group IB metals that have hydrogenation properties; → represents a coordinate bond; R represents a C3-C19 hydrocarbon group; x represents the number of coordinating groups in the organic ligand, and can be 1, 2 or 3; n represents the coordination number, which is an integer from 1 to 6; and y represents the number of non-coordinated oxygen atoms bonded to metal M1, and is an integer between 0 and 3.

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

3. The unsupported 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 less than 145 cm. -1 .

4. The unsupported hydrogenation catalyst according to claim 1, wherein at least a portion of the complex in the catalyst has the structure shown in formula (I-2): M2 represents a metal, and is selected from at least two of the group VB, group VIB, group VIII and group IB metals that have hydrogenation properties; → represents a coordinate bond; R represents a C3-C19 hydrocarbon group; x represents the number of coordinating groups in the organic ligand, and is either 1 or 2; n represents the coordination number, which is an integer from 1 to 6; z represents the number of non-coordinated oxygen atoms bonded to metal M2, and is an integer between 0 and 3.

5. The unsupported hydrogenation catalyst according to claim 4, wherein in formula (I-2), R is selected from C5-C11 normal alkyl, C5-C11 isoalkyl, C5-C12 cycloalkyl and C6-C12 aryl; x is 1; n is an integer between 2 and 5; z is an integer between 1 and 3.

6. The unsupported hydrogenation catalyst according to claim 4, 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 .

7. The unsupported hydrogenation catalyst according to claim 1, 2 or 4, wherein M, M1 and M2 are selected from V, Cr, Mo, W, Fe, Co, Ru, Ni, Cu or Pd.

8. The unsupported hydrogenation catalyst according to claim 1, 2 or 4, wherein M, M1 and M2 are selected from Mo, Ni, W, Fe, V or Co.

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

10. The unsupported 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.

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

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

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

14. The unsupported hydrogenation catalyst according to claim 13, 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.

15. A hydrogenation catalyst composition comprising an unsupported hydrogenation catalyst according to any one of claims 1-14 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.

16. The composition according to claim 15, 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.

17. The composition according to claim 15 or 16, 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.

18. The composition according to claim 15 or 16, wherein, Based on the weight of the composition, the content of the unsupported hydrogenation catalyst is 50-95%; the total content of the organic ligand compound and the organic solvent is 5-50%.

19. The composition according to claim 15 or 16, wherein, Based on the weight of the composition, the content of the unsupported hydrogenation catalyst is 80-95%; the total content of the organic ligand compound and the organic solvent is 5-20%.

20. Use of the unsupported hydrogenation catalyst of any one of claims 1-14 or the hydrogenation catalyst composition of any one of claims 15-19 in the hydrogenation reaction of a hydrocarbon feedstock, wherein the hydrocarbon feedstock is an unsaturated hydrocarbon compound or a mixture containing unsaturated hydrocarbon compounds.

21. The use according to claim 20, 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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