Unsupported catalyst compositions for heavy oil hydrotreating and their applications

Abstract

This application relates to an unsupported catalyst composition suitable for heavy oil hydrotreating and its application. By weight, the composition comprises 10-45% unsupported hydrotreating catalyst, 45-80% dispersion medium, and 1.0-10% activator. The unsupported hydrotreating catalyst consists of a metal-organic complex formed by coordination bonding between a metal central atom or central ion and an organic ligand, and optionally an organic ligand compound. The infrared spectrum of the catalyst is in the range of 700-1000 cm⁻¹. ‑1 1350-1450cm ‑1 and 1500-1610cm ‑1 The location exhibits a characteristic peak. When used in processes such as heavy and residual oil hydrotreating and hydrocracking, the unsupported catalyst composition can significantly inhibit condensation reactions, enhance asphaltene lightening, and improve system stability. It has the advantages of low coke production rate, high residual oil conversion rate, and high asphaltene lightening rate, while also helping to improve system stability and extend the unit's operating cycle.

Description

Technical Field

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

[0002] In 2020, China's dependence on imported crude oil exceeded 70%, with most of the imported crude oil being low-quality and heavy crude oil from the Middle East and South America, of which residual oil accounted for more than 50%. Therefore, effectively utilizing petroleum resources, especially achieving deep processing of residual oil, not only improves the utilization rate of petroleum resources, but also alleviates my country's energy security crisis.

[0003] To better process low-quality residual oil, Chinese patent application CN102989493A discloses a composite catalyst for heavy oil hydrotreating. This catalyst contains 2.5-12% support, on which metal sulfides and phosphides are loaded. However, when the supported catalyst catalyzes the hydrotreating process of heavy oil and residual oil, large molecules such as heavy gums and asphaltenes in the feedstock are difficult to diffuse to the active centers of the catalyst located in the pores, affecting the probability and efficiency of the catalytic reaction. In addition, the coke, removed metals, and other heteroatoms generated during the reaction can easily cause catalyst pore blockage and catalyst poisoning and deactivation.

[0004] To improve the dispersibility and oil solubility of catalysts, and to enhance the accessibility of heavy and residual oils to the active sites of the catalyst, numerous researchers both domestically and internationally have conducted related research. Chinese patent application CN110813295A discloses a method for preparing and applying a slurry-bed hydrogenation catalyst. This method involves contacting a solution of a compound containing a metallic active element with a dust-laden gas stream, followed by gas-solid separation and drying. By controlling the average particle size of the particles in the dust-laden gas stream, the dispersion of the active components in the catalyst is improved, ultimately resulting in a slurry-bed hydrogenation catalyst with an average particle size of 10-100 μm.

[0005] Chinese patent CN107866278B discloses an organomolybdenum heavy oil hydrocracking catalyst and its preparation method. The catalyst contains molybdenum ions and C1-C16 organic anions bound to the molybdenum ions. The organic anions contain oxygen atoms, and the molar ratio of +4 molybdenum ions to +5 molybdenum ions to +6 molybdenum ions is (0.1-25.0):(10.0-40.0):(45.0-85.0). The catalyst preparation method is a two-step process. The first step involves dissolving and dispersing molybdenum oxide in water, adding an inorganic acid catalyst, and then adding a small-molecule organic acid, reacting at 40-150℃. The second step involves adding a large-molecule organic acid or ester to the product of the first step, reacting at 160-320℃ for 2-22 hours to form an organometallic compound. This catalyst preparation method requires a variety of raw materials, involves multiple synthesis steps, and requires an inorganic acid as a catalyst, resulting in high material and energy consumption. Furthermore, the multi-step synthesis process generates waste products. Summary of the Invention

[0006] To address the problems existing in the prior art, this application provides a novel unsupported catalyst composition. When used in processes such as heavy oil hydrotreating and hydrocracking, this composition can significantly inhibit condensation reactions, enhance asphaltene conversion, and help improve system stability and extend the operating cycle of the unit.

[0007] To address the aforementioned technical problems, in one aspect, this application provides a non-supported catalyst composition suitable for heavy oil hydrotreating. By weight, the composition comprises 10-45% non-supported hydrotreating catalyst, 45-80% dispersion medium, and 1.0-10% activator, wherein:

[0008] The unsupported hydrogenation catalyst comprises a metal-organic complex formed by coordination bonds between a metal central atom or central ion and an organic ligand, and an optional organic ligand compound. 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 through 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] The organic ligand compound is selected from C4-C20 organic carboxylic acids.

[0010] The dispersion medium is selected from organic solvents, petroleum fractions, or combinations thereof. 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. The petroleum fraction is selected from distillate oils with a boiling range of 150-524℃ or residue oil components with a boiling point >524℃.

[0011] The activator is selected from elemental sulfur, sulfur-containing compounds, or combinations thereof.

[0012] On the other hand, the application of the unsupported catalyst composition of this application in the hydrorefining reaction of heavy oil is provided.

[0013] On the other hand, this application provides a method for hydrotreating heavy oil, comprising the step of subjecting a heavy oil feedstock to a hydrotreating reaction in the presence of hydrogen and optionally a pre-sulfurized unsupported catalyst composition of this application under heating conditions.

[0014] The unsupported catalyst composition of this application comprises a complex formed by coordination bonding between a metal central atom or central ion and an organic ligand, and optionally an organic ligand compound, forming an unsupported hydrogenation catalyst. This catalyst can be prepared in a one-step process, which is simple and environmentally friendly. Simultaneously, the catalyst exhibits oil solubility and high dispersibility, significantly enhancing the conversion of residue oil and asphaltenes. The catalyst composition of this application also possesses oil solubility and high dispersibility, and further contains a complex activator. When used in processes such as heavy and residue oil hydrogenation and hydrocracking, this composition can generate nano-sized hydrogenation active centers in situ, significantly inhibiting condensation reactions, enhancing asphaltenes lightening, and improving system stability. It has the advantages of low coke production, high residue oil conversion rate, and high asphaltenes lightening rate, while also contributing to improved system stability and long-term stable operation of the unit.

[0015] Other features and advantages of this application will be described in detail in the following detailed description section. Attached Figure Description

[0016] 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:

[0017] Figure 1 The infrared spectrum of the catalyst obtained in Example 1 is shown;

[0018] Figure 2 The infrared spectrum of the catalyst obtained in Example 2 is shown.

[0019] Figure 3 The infrared spectrum of the catalyst obtained in Example 3 is shown;

[0020] Figure 4 The infrared spectrum of the catalyst obtained in Example 4 is shown;

[0021] Figure 5 The infrared spectrum of the catalyst obtained in Example 7 is shown;

[0022] Figure 6 The diagram shows a comparison of the dispersion of the catalyst obtained in Example 1 in diesel fuel; and

[0023] Figure 7 The diagram shows a comparison of the dispersion of the catalyst obtained in Example 3 in toluene. Detailed Implementation

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] As described above, in a first aspect, this application provides a non-supported catalyst composition suitable for heavy oil hydrotreating. By weight, the composition comprises 10-45% of a non-supported hydrotreating catalyst, 45-80% of a dispersion medium, and 1.0-10% of an activator. The non-supported hydrotreating catalyst consists of a metal-organic complex formed by coordination bonds between a metal central atom or central ion and an organic ligand, and optionally an organic ligand compound. The metal is selected from Group VB, Group VIB, Group VIII, Group IB metals, or various combinations thereof, all possessing hydrotreating properties. The organic ligand comprises a hydrocarbon moiety and a coordinating group moiety, wherein the coordinating group consists of carbon and oxygen atoms, 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.

[0030] According to this application, the unsupported hydrogenation catalyst consists only of the metal-organic complex and optional organic ligand compounds, without any solid support components, and correspondingly, the unsupported catalyst composition also does not contain any solid support components.

[0031] 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 organometallic complex of this application can be in the form of a central atom or a central ion.

[0032] In a preferred embodiment, the coordinating group in the organic ligand of the organometallic complex can be a -C(=O)-O group.

[0033] According to this application, based on the weight of the catalyst, the unsupported hydrogenation catalyst may contain 0-50%, preferably 5-50%, more preferably 5-20% of an organic ligand compound. Preferably, the unsupported hydrogenation catalyst contains an organic ligand compound, and the infrared spectrum of the unsupported hydrogenation catalyst is in the range of 700-1000 cm⁻¹. -1 1350-1450cm -1 1500-1610cm -1 and 1700-1750cm -1 It has a characteristic peak at the location.

[0034] According to this application, the organic ligand compound contained in the unsupported hydrogenation catalyst can be a variety of liquid organic carboxylic acids, preferably C4-C20 organic carboxylic acids, more preferably 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] In a preferred embodiment, the organic ligand in the organometallic complex is an organic ligand derived from the organic ligand compound, i.e., an organic ligand obtained by removing a hydrogen atom from the carboxyl group of the organic ligand compound. In this case, the composition of the unsupported hydrogenation catalyst can be schematically represented in the form of formula (I):

[0041] MO a [R(COO) x ] b (I),

[0042] Where M represents the metal, and R(COO) x The organic ligand and organic ligand compound are represented by R, COO, x, a, and b. R represents the hydrocarbon group in the organic ligand, COO represents the coordinating group in the organic ligand, x represents the number of coordinating groups in the organic ligand, a represents the molar ratio of non-coordinated oxygen atoms bonded to metal M to metal M, and b represents the molar ratio of the total amount of organic ligand and organic ligand compound to metal M.

[0043] 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;

[0044] x is 1, 2 or 3, more preferably 1 or 2;

[0045] a is a positive number between 0 and 3, preferably between 1 and 3; and

[0046] b is a positive number from 1 to 6, preferably a positive number from 2 to 5.

[0047] In the above formula (I) of this application, the H atom on the carboxyl group in the organic ligand compound is simplified and omitted, and the organic ligand and organic ligand compound are uniformly referred to as organic ligand "R(COO)". x It is expressed in the form of "".

[0048] According to this application, the unsupported hydrogenation catalyst can be a mixture of various complexes and may also contain organic ligand compounds. The molar ratios a and b of the total amount of oxygen atoms, organic ligands, and organic ligand compounds in the catalyst composition relative to the metal M are calculated values ​​based on metal content and elemental composition analysis, and therefore may 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 (e.g., MoNi, MoCoV, etc.) in the catalyst composition only indicates which metals are present and does not indicate the molar ratio between the metals.

[0049] In some further preferred embodiments, at least a portion of the complex in the unsupported hydrogenation catalyst has the structure shown in formula (I-1):

[0050]

[0051] 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;

[0052] → represents a coordinate bond;

[0053] R represents a C3-C19 hydrocarbon group, preferably selected from C5-C11 normal alkyl, C5-C11 isoalkyl, C5-C12 cycloalkyl and C6-C12 aryl;

[0054] x represents the number of coordinating groups in the organic ligand, and is 1, 2 or 3, more preferably 1 or 2;

[0055] n represents the coordination number, which is an integer from 1 to 6, preferably an integer from 2 to 5; and

[0056] 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.

[0057] In a further preferred embodiment, the infrared spectrum of the unsupported hydrogenation catalyst is in the range of 1350-1450 cm⁻¹. -1 A characteristic peak at the location is located at 1500-1610 cm⁻¹ -1 The distance between the peaks of a characteristic peak at a given location is less than 145 cm. -1 .

[0058] In some further preferred embodiments, at least a portion of the complex in the unsupported hydrogenation catalyst has the structure shown in formula (I-2):

[0059]

[0060] 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;

[0061] → represents a coordinate bond;

[0062] R represents a C3-C19 hydrocarbon group, preferably selected from C5-C11 normal alkyl, C5-C11 isoalkyl, C5-C12 cycloalkyl and C6-C12 aryl;

[0063] x represents the number of coordinating groups in the organic ligand, and is 1 or 2, more preferably 1;

[0064] n represents the coordination number, which is an integer from 1 to 6, preferably an integer from 2 to 5;

[0065] z represents the number of non-coordinated oxygen atoms bonded to metal M2, and is an integer from 0 to 3, preferably an integer from 1 to 3.

[0066] 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).

[0067] In a further preferred embodiment, the infrared spectrum of the unsupported hydrogenation catalyst is in the range of 1350-1450 cm⁻¹. -1 A characteristic peak at the location is located at 1500-1610 cm⁻¹ -1 The distance between the peaks of a characteristic peak at a given location is greater than 145 cm. -1 .

[0068] According to this application, the infrared spectrum of the unsupported catalyst composition may have characteristic peaks that are substantially corresponding to the infrared spectrum of the unsupported hydrogenation catalyst, which will not be elaborated here.

[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 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] In a preferred embodiment, the metal content in the unsupported hydrogenation catalyst is 5-35%, preferably 8-30%, more preferably 10-25%, and particularly preferably 10-20%, based on the weight of the metal and the unsupported hydrogenation catalyst.

[0077] In a preferred embodiment, the unsupported hydrogenation catalyst is obtained by directly reacting the group VB metal, group VIB metal, group VIII metal, group IB metal, their oxides, their hydroxides and / or their metal inorganic salts with the organic ligand compound.

[0078] In a preferred embodiment, the unsupported hydrogenation catalyst can be prepared by a method comprising the following steps: 1) mixing a metal source or a dispersion thereof with the organic ligand compound; 2) reacting the mixture obtained in step 1) at 100-350°C for 1-8 h; and 3) collecting the resulting liquid product.

[0079] According to this application, the metal source can be one or more of the following: oxides, hydroxides, chlorides, sulfides, sulfates, nitrates, carbonates, metal oxyacids (such as molybdic acid and tungstic acid), and metal oxyacids (such as ammonium molybdate and ammonium tungstate in various forms) of Group VB, Group VIB, Group VIII, or Group IB metals with hydrogenation properties.

[0080] According to this application, when the dispersion of the metal source is used in step 1) of the method for preparing the unsupported hydrogenation catalyst, the dispersion medium in the dispersion can be an inorganic dispersion medium selected from water, carbonic acid, hydrochloric acid, sulfuric acid or phosphoric acid, or an organic dispersion medium selected from ethanol, toluene, xylene, petroleum ether, gasoline, diesel, or combinations thereof.

[0081] In a preferred embodiment, the reaction temperature of step 2) of the preparation method of the unsupported hydrogenation catalyst is 160-260℃; the reaction time is 2-6h.

[0082] According to this application, step 2) of the preparation method of the unsupported hydrogenation catalyst does not have strict requirements on the pressure and reaction atmosphere used. For example, the reaction pressure can be atmospheric pressure, and the reaction atmosphere can be air, nitrogen or an inert atmosphere.

[0083] According to this application, the preparation of the unsupported hydrogenation catalyst can be carried out under anhydrous or aqueous conditions (e.g., water in the presence of 0-10 times the weight of the organic ligand compound).

[0084] According to this application, the preparation of the unsupported hydrogenation catalyst can be carried out under conditions where no other components (such as catalyst, alkaline pH adjuster, etc.) are present, except for the metal source, organic ligand compound and optional dispersion medium (such as water and organic solvents such as toluene, ethanol, diesel, etc.).

[0085] According to this application, the dispersion medium suitable for the unsupported catalyst composition can be any liquid material capable of enhancing the dissolution and dispersion of the organometallic complex in the unsupported hydrogenation catalyst, including but not limited to organic solvents and petroleum fractions capable of dispersing or being miscible with the catalyst. The organic solvent can be selected from aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohol solvents, ether solvents, ester solvents, ketone solvents, or combinations thereof, preferably from aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, or combinations thereof, such as n-octane, cyclohexane, toluene, and decahydronaphthalene, more preferably aromatic solvents. The petroleum fraction can be selected from distillate oils with a boiling range of 150-524°C or residue components with a boiling point >524°C, such as solvent gasoline, AGO fraction, LCO, slurry oil, furfural extract oil, atmospheric residue, and vacuum residue, preferably petroleum fractions rich in aromatics.

[0086] According to this application, the activator suitable for the unsupported catalyst composition is a substance capable of activating the MO bond in the organometallic complex to form the MS bond of the hydrogenation active phase. For example, it can be elemental sulfur, sulfur-containing compounds, mixtures of sulfur-containing compounds, or combinations thereof, preferably selected from thiols, thioethers, carbon disulfide, sulfur, thiophene compounds, or combinations thereof.

[0087] In a preferred embodiment, based on the weight of the unsupported catalyst composition, the content of the unsupported hydrogenation catalyst is 10-45%, preferably 10-30%, the content of the dispersion medium is 45-80%, preferably 60-80%, and the content of the activator is 1.0-10%, preferably 3.0-10.0%.

[0088] In a second aspect, the application of the unsupported catalyst composition of this application in the hydrorefining reaction of heavy oil is provided.

[0089] In a third aspect, this application provides a method for hydrotreating heavy oil, comprising the step of subjecting a heavy oil feedstock to a hydrotreating reaction in the presence of hydrogen and optionally a pre-sulfurized unsupported catalyst composition of this application under heating conditions.

[0090] In a preferred embodiment, the conditions for the hydrotreating reaction include: the amount of the unsupported catalyst composition, based on the weight of the heavy oil feedstock and calculated as metal, is 50-10000 μg / g, preferably 50-3000 μg / g; the initial hydrogen pressure is 3-20 MPa, preferably 5-15 MPa; the reaction temperature is 360-480℃, preferably 390-450℃; and the liquid hourly space velocity is 0.05-2.0 h⁻¹. -1 Preferably 0.05-1.0h -1 The hydrogen-to-oil volume ratio is 300-2000, preferably 500-1500.

[0091] Example

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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 .

[0096] Examples 1-7

[0097] 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 catalyst product; the products of Examples 6-7 were filtered to remove the unreacted metal compounds, and the resulting liquid product was the target catalyst product. The metal content of the obtained catalyst products was determined by inductively coupled plasma optical emission spectrometry (ICP-OES), and the elemental composition of the obtained catalyst products was measured using appropriate methods. The composition of the catalyst 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.

[0098]

[0099] As shown in Table 1, the metal content of the unsupported catalyst products prepared by the one-step method in Examples 1-7 of this application can reach 6.95-33.3%, and the molar ratio of organic ligands to the total amount of organic ligand compounds relative to metals in the product composition is 2.0-4.0.

[0100] The infrared spectra of the catalyst products obtained in Examples 1-4 and Example 7 are as follows: Figure 1-5 As shown in the figure, it is clear that the products in all embodiments are between 700-1000cm. -1 1350-1450m -1 and 1500-1610cm -1 The presence of a characteristic peak at the location indicates that the obtained catalyst product contains an organometallic complex.

[0101] The size of the organometallic complex synthesized in Example 1 was determined by molecular simulation. The results showed that the size of the molybdenum ethylhexanoate synthesized in this example was (1.85 × 0.97 × 0.58) nm, indicating that the organometallic complex in the unsupported hydrogenation catalyst of this application has a nanoscale size.

[0102] Examples 8-9

[0103] The catalyst products obtained in Examples 1 and 3 were dispersed in diesel and toluene, respectively, to investigate the oil solubility of the unsupported hydrogenation catalyst prepared by the method of this application. The solubility and dispersion of the products of Examples 1 and 3 in diesel and toluene are shown in the figures. Figure 6 and Figure 7 The left side of the figure shows diesel and toluene before dissolution, while the right side shows diesel and toluene after dissolving the product of Example 1 and the product of Example 3. Figure 6 , Figure 7It is known that the unsupported hydrogenation catalyst synthesized in this application is completely miscible with diesel and toluene, indicating that it has good oil solubility.

[0104] Examples 10-11

[0105] Using 200g of vacuum residue A with an asphaltene content of 12%, a carbon residue value of 23.2%, and a heavy metal (Ni+V) content of 200μg / g as raw material, a catalytic hydrothermal conversion experiment was conducted in a 2L intermittent high-pressure reactor under the catalyst and reaction conditions shown in Table 2. The experimental results are shown in Table 2.

[0106] Comparative Example 1

[0107] The experiment was conducted according to Example 11, in which a conventional supported catalyst (Ni-Mo supported catalyst for residue hydrotreating, Mo content 9.3% by mass, Ni content 2.52%) was used instead of the product obtained in Example 3. The experimental results are shown in Table 2.

[0108] Table 2. Reaction conditions and results of Examples 10-11 and Comparative Example 1.

[0109]

[0110] As shown in Table 2, under the same reaction conditions, the unsupported catalyst of this application has a higher residue cracking rate, a lower insoluble matter yield, and a higher distillate oil yield compared to the supported catalyst.

[0111] Examples 12-14

[0112] Unsupported catalyst compositions were formed using the catalyst products of Examples 1 and 7, dispersion media, and activators. The content of each component in the resulting unsupported catalyst compositions is detailed in Table 3.

[0113] Table 3. Composition of the catalyst compositions obtained in Examples 12-14

[0114]

[0115] Example 15

[0116] The catalyst composition obtained in Example 13 was subjected to pre-sulfurization treatment at a reaction temperature of 360°C, an initial hydrogen pressure of 5 MPa, and a reaction time of 30 min. The reaction products were collected after the experiment.

[0117] Examples 16-19

[0118] The catalyst composition products of Examples 13, 14 and 15, as well as the catalyst product of Example 1, were mixed with 200g of vacuum residue B feedstock with an asphaltene content of 12.8%, a carbon residue value of 26.3%, and a heavy metal (Ni+V) content of 220μg / g. The vacuum residue was subjected to hydrothermal conversion tests in a 2L intermittent high-pressure reactor at a reaction temperature of 425℃, an initial hydrogen pressure of 9MPa, and a reaction time of 130min. The test results are listed in Table 4.

[0119] Table 4 Reaction conditions and results of Examples 16-19

[0120]

[0121] As shown in Table 4, compared with the product of Example 1 which does not contain an activator, the unsupported catalyst composition product of Example 13 containing an activator has a slightly higher residue oil conversion rate, a higher asphaltene lightening rate and a lower condensation rate, and the condensation rate is reduced by 48%, indicating that it has a higher performance in inhibiting the asphaltene condensation reaction.

[0122] Meanwhile, as shown in Table 4, compared with the unsupported catalyst composition product of Example 14 which does not contain organic ligand compounds, the unsupported catalyst composition product of Example 13 containing organic ligand compounds (ethylhexanoic acid) has a higher residue oil conversion rate and asphaltene lightening rate, as well as a lower condensation rate.

[0123] Furthermore, as shown in Table 4, when the unsupported catalyst composition product undergoes pre-sulfurization treatment, the residue oil conversion rate and the asphaltene lightening rate can be further improved, while the condensation rate is also further reduced.

[0124] 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.

[0125] 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.

[0126] 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 catalyst composition suitable for heavy oil hydrotreating, comprising, by weight, 10-45% of a non-supported hydrotreating catalyst, 45-80% of a dispersion medium, and 1.0-10% of an activator, wherein: The unsupported hydrogenation catalyst comprises a metal-organic complex formed by coordination bonds between a metal central atom or central ion and an organic ligand, and an optional organic ligand compound. 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 through 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. The organic ligand compound is selected from C4-C20 organic carboxylic acids. The dispersion medium is selected from organic solvents, petroleum fractions, or combinations thereof. 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. The petroleum fraction is selected from distillate oils with a boiling range of 150-524℃ or residue oil components with a boiling point >524℃. The activator is selected from elemental sulfur, sulfur-containing compounds, or combinations thereof. The organic ligand in the aforementioned organometallic complex is an organic ligand obtained by removing hydrogen from the carboxyl group of the organic ligand compound, and the unsupported hydrogenation catalyst has the schematic composition shown in formula (I): MO a [R(COO) x ] b (I), Where M represents the metal, and R(COO) x The organic ligand and organic ligand compound are represented by R, COO, x, a, and b. R represents the hydrocarbon group in the organic ligand, COO represents the coordinating group in the organic ligand, x represents the number of coordinating groups in the organic ligand, a represents the molar ratio of non-coordinated oxygen atoms bonded to metal M to metal M, and b represents the molar ratio of the total amount of organic ligand and organic ligand compound to metal M. 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 organometallic complex in the unsupported hydrogenation 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 composition according to claim 1, wherein the activator is selected from thiols, thioethers, carbon disulfide, sulfur, thiophene compounds, or combinations thereof. 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 composition according to claim 1 or 2, wherein the infrared spectrum of the unsupported hydrogenation catalyst is in the range of 1350-1450 cm⁻¹. -1 A characteristic peak at the location is located at 1500-1610 cm⁻¹ -1 The distance between the peaks of a characteristic peak at a given location is less than 145 cm. -1 .

4. The composition according to claim 1, wherein at least a portion of the organometallic complex in the unsupported hydrogenation 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 composition 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 composition according to claim 4, wherein the infrared spectrum of the unsupported hydrogenation catalyst is in the range of 1350-1450 cm⁻¹. -1 A characteristic peak at the location is located at 1500-1610 cm⁻¹ -1 The distance between the peaks of a characteristic peak at a given location is greater than 145 cm. -1 .

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

9. The composition according to claim 1, wherein the organic ligand compound is selected 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.

10. The composition according to claim 1, 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.

11. The composition according to claim 1 or 2, wherein the unsupported hydrogenation catalyst has a metal content of 5-35% and an organic ligand compound content of 0-50% based on the weight of the catalyst.

12. The composition according to claim 1 or 2, wherein the unsupported hydrogenation catalyst has a metal content of 10-20% and an organic ligand compound content of 5-20% based on the weight of the catalyst.

13. The composition according to claim 1 or 2, wherein the unsupported 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 having hydrogenation properties with the organic ligand compound.

14. The use of the unsupported catalyst composition according to any one of claims 1-13 in the hydrorefining reaction of heavy oil.

15. A method for hydrotreating heavy oil, comprising the step of subjecting a heavy oil feedstock to a hydrotreating reaction in the presence of hydrogen and optionally a pre-sulfurized unsupported catalyst composition according to any one of claims 1-13 under heating conditions.

16. The application according to claim 14 or the method according to claim 15, wherein the conditions for the hydrogenation reaction include: Based on the weight of heavy oil feedstock and calculated using metals, the dosage of the unsupported catalyst composition is 50-10000 μg / g, the initial hydrogen pressure is 3-20 MPa, the reaction temperature is 360-480℃, and the liquid hourly space velocity is 0.05-2.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300-2000.

17. The application according to claim 14 or the method according to claim 15, wherein the conditions for the hydrogenation reaction include: Based on the weight of heavy oil feedstock and calculated using metals, the dosage of the unsupported catalyst composition is 50-3000 μg / g, the initial hydrogen pressure is 5-15 MPa, the reaction temperature is 390-450℃, and the liquid hourly space velocity is 0.05-1.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is 500-1500.

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